Chemical Engineering Journal 387 (2020) 123943

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Adsorption performance of standard biochar materials against volatile T

organic compounds in air: A case study using benzene and methyl ethyl
ketone
Kumar Vikranta, Ki-Hyun Kima,b, , Wanxi Pengb, , Shengbo Geb, Yong Sik Okc,
⁎ ⁎ ⁎

a
Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea
b
Henan Province Engineering Research Center for Forest Biomass Value-added Products, Henan Agricultural University, Zhengzhou 450002, China
c
Korea Biochar Research Center & Division of Environmental Science and Ecological Engineering, Korea University, Seoul 02841, Republic of Korea

HIGHLIGHTS

• Biochar is a carbon-based material that can be utilized as an adsorbent.

• 12 standard biochars were analyzed for the capture of gaseous benzene and MEK.
• Rice husk biochar prepared at 550 °C showed the highest capacity of 43 mg g for MEK. −1

• Soft wood pellet biochar prepared at 700 °C showed the best performance for benzene.
• Most of the analyzed biochars preferably adsorbed MEK as compared to benzene.

ARTICLE INFO ABSTRACT

Keywords: Recently, biochars have been proposed as highly efficient and low-cost media for the adsorptive removal of
Adsorption various hazardous compounds. However, there is a dearth of literature focusing on adsorption performance of
Biochars biochars against gaseous volatile organic compounds (VOCs). In light of this limitation, the adsorption perfor-
Pollution control mances of 12 standard biochars made of six different raw materials (i.e., Miscanthus straw pellets, oil seed rape
Volatile organic compounds
straw pellets, rice husk, sewage sludge, soft wood pellets, and wheat straw pellets) at two pyrolysis temperature
Air pollution
conditions (i.e., 550 °C and 700 °C) were investigated against two model gaseous VOCs (i.e., benzene and methyl
ethyl ketone (MEK)) at 1 Pa each. The breakthrough volume (BTV) and partition coefficient (PC) of benzene at
10% BTV, when measured for all these biochars, varied from 1.4 to 10 L atm g−1 and 6.E-04 to 1.4E-02 mol kg−1
Pa−1, respectively. Similarly, their counterpart values for MEK were 1.8 to 40 L atm g−1 and 1.E-03 to 2.E-
03 mol kg−1 Pa−1, respectively. The largest adsorption capacity values for benzene (2.9 mg g−1) and MEK
(43 mg g−1) were observed from the soft wood pellet biochar prepared at 700 °C (SWP700) and rice husk
biochar prepared at 550 °C (RH550), respectively. The results indicate that most biochars adsorbed MEK pre-
ferentially over benzene. The adsorption of MEK appeared to be primarily influenced by surface features and
composition of each specific biochar, while that of benzene was proportionate to their surface area. Overall, the
results of this investigation are expected to help establish technical standards for effective removal of gaseous
VOCs by biochars.

1. Introduction outdoor air can greatly contribute to the destruction of environment

The consensus has grown steadily on the proper management of air
quality with the recognition on the detrimental health effects (e.g., high
carcinogenicity and toxicity) of hazardous air pollutants including vo-
latile organic compounds (VOCs) [1–3]. It is identified that VOCs in
through depletion of the ozone layer and/or involvement in the for-
mation of secondary aerosols/photochemical smog [4–6]. Exposure to
VOCs, if occurring in residential and/or workplace indoor environment,
has also been reported to have great potentials to cause severe health
issues such as cerebral damage, headache, irritation of the eyes and

⁎
Corresponding authors at: Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea (K.H.
Kim).
E-mail addresses: kkim61@hanyang.ac.kr (K.-H. Kim), pengwanxi@163.com (W. Peng), yongsikok@korea.ac.kr (Y. Sik Ok).

https://doi.org/10.1016/j.cej.2019.123943

Available online 26 December 2019

1385-8947/ © 2019 Elsevier B.V. All rights reserved.
K. Vikrant, et al.
nose, nausea, dizziness, unconsciousness, narcosis, and even death
[7–9].
VOCs such as benzene and methyl ethyl ketone (MEK) are common
constituents in the indoor air environment of various locations (e.g.,
offices, hospitals, and residential/commercial buildings) as they are
frequently liberated from diverse sources (e.g., paints, varnishes, cos-
metics, glues, artificial leathers, synthetic rubbers, plastic casings,
printers, and other commodities) [10–12]. The concentrations of most
gaseous VOCs are usually reported in the sub-ppm or sub-ppb range in
indoor air. However, their concentrations can be much higher (ppm
range) if released as effluents from production processing of various
chemicals and consumer goods [1,13,14]. Likewise, various source
processes of VOCs have been identified to include animal feeding op-
erations [15,16], automotive painting [17,18], petroleum refining
[19,20], and wastewater treatment [21,22]. In light of the severe ad-
verse health effects of VOCs, the Occupational Safety and Health Ad-
ministration (OSHA) has set a permissible exposure limit of 1 ppm for
benzene on an 8 h time-weighted average basis [23]. Similarly, an 8-
hour time weighted average threshold limit of 200 ppm has been set for
MEK by the American Conference of Governmental Industrial Hygie-
nists (ACGIH) [24].
Among a myriad of VOC treatment approaches, adsorption has been
acknowledged as one of the most economical options due to facile
operation, large flexibility, and high efficiency under real-world con-
ditions [25–27]. To meet such conditions, use of an effective adsorbent
is essential for optimum adsorption. In this regard, various carbon-
based adsorbents such as activated carbon [28,29], carbon nanos-
tructures [30,31], and graphene-related materials [32,33] have been
explored extensively for removal of gaseous VOCs due to their nu-
merous merits (e.g., favorable porosity and high specific surface) and
proven performance.
Biochar is an emergent carbon-based material that has attracted
widespread research interests spanning across multiple scientific dis-
ciplines [34–36]. Biochars are usually synthesized through slow pyr-
olysis of feedstock biomass under an inert atmosphere at tempera-
tures ≤ 700 °C [37–39]. In recent years, biochar has been
recommended as a highly economical alternative to activated carbon as
its break-even price is approximately one-sixth of that of the commonly
used activated carbon [37,38,40]. Since biochars are usually prepared
from waste biomass under mild conditions, they provide a win–win
strategy to simultaneously manage generated biowaste and to mitigate
pollutant-rich environmental matrices [41–43]. In fact, many efforts
have been made to assess adsorptive removal of various hazardous
compounds by biochars. However, most research works were primarily
directed toward soil remediation and/or aqueous environments
[40,44,45]. At present, there is a dearth of literature analyzing the
potential applicability of biochars as adsorbents toward removal of
gaseous pollutants (e.g., VOCs) [35,37–39].
There is little information regarding the conditions of biochar pro-
duction and the related properties of synthesized materials [46,47].
Such a gap in information is expected to complicate replication of
biochars and associated specific findings from benchmarking studies
[46,47]. In this regard, the United Kingdom Biochar Research Centre
(UKBRC) located at the University of Edinburgh developed a set of 12
standard biochars with reproducible properties in 2012, and these
biochars were subsequently released to the scientific community in
2015 [46]. They were derived through pyrolysis (at 550 °C and 700 °C)
of Miscanthus straw pellets, oil seed rape straw pellets, rice husk,
sewage sludge, soft wood pellets, and wheat straw pellets. As such, they
can represent major sources of biomass encompassing a vast geographic
area [46,48]. Extensive interdisciplinary research has been undertaken
to analyze the performances of these 12 standard biochars to provide a
common reference point for scientists in various research areas
[46,49,50].
The present study aims at expanding the biochar database by ana-
lyzing the adsorption performances of 12 standard biochars (made
2
Chemical Engineering Journal 387 (2020) 123943
available by the UKBRC) against gaseous benzene and MEK as re-
presentative gaseous VOCs with contrasting properties of low polarity/
hydrophobicity (benzene) and high polarity/hydrophilicity (MEK)
[51]. As such, benzene and MEK were selected as the model VOCs in
this research in light of their contrasting characteristics (e.g., in terms
of polarities). Essentially, most gaseous VOCs are generally classified as
being polar or non-polar [51]. Thus, an in-depth inspection on nonpolar
(benzene) vs. highly polar VOC (MEK) will help us gain a better un-
derstanding on the adsorption performance of biochars (or other car-
bonaceous sorbents) against a broad class of VOCs in air. The con-
centrations of both the analyzed VOCs were maintained at 10 ppm
(1 Pa) to partly simulate their real-world levels in various industries.
Furthermore, detailed kinetic analyses were performed to gain insight
into the overall adsorption processes taking place between biochars and
gaseous VOC molecules. As mentioned earlier, there are a very few
studies in the literature that focused on adsorption performances of
biochars against gaseous VOCs. Consequently, the results of the present
study are expected to meet a dual purpose of (i) expanding the database
regarding 12 standard UKBRC biochars and (ii) providing new insights
into the applicability of biochars as potential adsorbents for different
types of gaseous VOCs. In addition, we believe that the present study is
the first detailed analysis of adsorptive removal of gaseous MEK by any
biochar.
2. Materials and methods
2.1. Biochar and VOC working standard preparation
A total of 12 standard biochars was produced through pyrolysis (at
550 °C and 700 °C) of Miscanthus straw pellets (MSP550 and MSP700),
oil seed rape straw pellets (OSR550 and OSR700), rice husk (RH550
and RH700), sewage sludge (SS550 and SS700), soft wood pellets
(SWP550 and SWP700), and wheat straw pellets (WSP550 and
WSP700) using a rotary kiln unit (pilot-scale) located at the UKBRC
(Table 1S). Detailed information of the operational conditions and
pyrolysis unit has been provided elsewhere [46,50,52]. In brief, the
dried precursor biomass samples were heated at a rate of
78–100 °C min−1 to maintain intermediate pyrolysis conditions. The
biomass samples were heated to 550 or 700 °C and held at this tem-
perature for about 5 min [52]. Subsequently, the obtained biochar
samples were subjected to various analyses. The surface areas of the
obtained biochar samples were also measured. A CHN analyzer was
employed to determine the hydrogen, nitrogen, and total carbon con-
tents of the biochar samples. Furthermore, the ash content of the pro-
duced biochars was determined using a dry combustion approach by
heating the samples in an open crucible for 6 h at 750 °C [52,53].
The liquid primary standards (L-PS) of benzene and MEK (both >
99% pure) were procured from Sigma-Aldrich (St. Louis, MO, USA).
The gaseous working standards (G-WS) of these VOCs were prepared at
concentrations of 10 ppm each by injecting 4 µL (liquid syringe (5 µL),
Trajan Scientific and Medical, Ringwood, Australia) of benzene and
MEK L-PS each into 100 L polyester aluminum (PEA) bags (Top Trading
Eng., Seoul, South Korea) filled with ultrapure N2 (99.999%). After
injecting the L-PS, the PEA bags were left for 60 min at room tem-
perature to ensure complete vaporization of each target inside the bag
[54]. In addition, possible contamination during preparation of G-WS
was avoided by flushing the PEA bags with ultrapure N2 (99.999%)
three times prior to injecting the L-PS.
2.2. Adsorption experiments and data analysis
The adsorption experiments using gaseous benzene and MEK were
conducted under continuous-mode operation by packing 5 mg of each
biochar sample in a quartz tube (4 mm inner diameter, 6 mm outer
diameter, and 89 mm length; Top Trading Eng., Seoul, South Korea).
The biochar samples were fixed in place inside the quartz tube using
K. Vikrant, et al.
quartz wool as end plugs. Each adsorption tube was conditioned for 3 h
at 300 °C under an inert atmosphere created by continuously flowing
(200 mL min−1) ultrapure N2 (99.999%) before beginning the ad-
sorption experiments. The conditioning step is important to remove any
impurities (e.g., pre-adsorbed pollutants and moisture) from the bio-
char surface [1,27].
The adsorption behavior of gaseous VOCs with biochar samples was
monitored by a gas chromatography/flame ionization detector (GC/
FID) system interfaced with a large volume injector (LVI) [1,54]. The
details regarding operation of the LVI-GC/FID system were reported in
our previous works [1,54]. Briefly, the LVI system employs a six-port
rotary valve fitted with a loop injector (PRG-2010, Shimadzu, Kyoto,
Japan) [1,55]. During sampling, the sample loop line is filled with G-
WS at a flow rate of 330 mL min−1 for varying intervals to monitor
adsorption (0.1 min for the first 5 samplings, 0.5 min for the next 5
samplings, 1 min for the next 5 samplings, and 5 min for the remaining
samplings until the end of experiment). An iterative sequential order
between sample-injection-sample was adopted for the LVI system [54].
The sample injection volume for the LVI-GC/FID system was fixed at
1 mL using a 1 mL loop system. A DB-WAX UI column (0.25 mm dia-
meter, 0.25 µm film thickness, and 60 m length) was procured from
Agilent Technologies, Inc., Santa Clara, CA, USA for use in GC-FID
analysis. The GC column was maintained at an isothermal condition
(oven temperature: 120 °C) with the detector system set at 250 °C.
Ultrapure N2 (99.999%) was utilized as the carrier gas (45 mL min−1)
for GC/FID operation. A schematic diagram of the experimental design
and procedures has been presented in Fig. 1S. All the experiments were
conducted under ambient conditions (~25 °C).
Five-point calibrations of each target VOC were prepared based on a
fixed standard volume (FSV) approach using the LVI-GC/FID system to
quantitatively analyze gaseous benzene and MEK [55,56]. The re-
producibility values of the system, if expressed in terms of relative
standard error (RSE) for benzene and MEK, were estimated to be 0.42%
and 0.49%, respectively. Their method detection limits (MDLs) were
estimated to be 0.95 and 0.17 ng, respectively. The quality assurance
(QA) data obtained for each VOC in this study are in line with those
reported previously [1,54,57]. The peak area obtained by the LVI-GC/
FID system was converted into a mass unit (ng) using a trapezoidal rule-
based integration operation (Eq. (1)) [27].
m
mn = [Cin 0.5([A](n + [A](n) )] Vn
1)
i=0
here ‘Δmn’ represents the mass of VOC adsorbed during the nth run, ‘Cin’
represents the VOC concentration at the adsorption tube inlet, ‘ΔVn’
represents the volume of G-WS puller per run, ‘A’ represents the VOC
being analyzed, and ‘n’ indicates the run number.
The breakthrough value, i.e., the ratio of VOC concentration at the
adsorption tube inlet (Cin) and outlet (Cout), can be described by Eq. (2)
[26].
Cout 0.5x [(Outlet concentration)n + (Outlet concentration)n 1]
= ratio. Such conditions induced a reduction in hydrophilicity while in-
Cin Inlet concentration
The partition coefficient (PC) values at a given BTV level can be
derived using Eq. (3). Note that the 10% breakthrough volume (BTV10)
was used as the basis for the computation of all performance metrics as
per the recommendations made elsewhere [28,58].
Adsorption capacity (at BTV 10)
Partition coefficient (PC ) at BTV 10 =
Cout (at BTV 10)
The pseudo-first-order (PFO), pseudo-second-order (PSO), and
Weber-Morris intra-particle diffusion (IPD) kinetic models are pre-
sented in terms of Eqs. (4)–(6), respectively. The linearized versions of
PFO, PSO, and IPD models can also be found elsewhere [59–61].
Chemical Engineering Journal 387 (2020) 123943
qt = qtL + qtH = qm L (1 e K1L t )
(
+ qm H 1 e K1H t
) (4)
K 2L qm2 L t K 2H qm2H t
qt = qtL + qtH = +
1 + K2 L qmL t 1 + K2 H qmH t (5)
qt = qtL + qtH = (KIDL t 0.5 + CL) + (KIDH t 0.5 + CH ) (6)
Here, qt implies the total adsorption capacity value at a given time
(t). The subscripts L and H represent the low pressure (first five sam-
pling points) and high pressure (remainder of sampling points) break-
through regions. The maximum adsorption capacity value predicted by
each kinetic model is denoted as qm. Furthermore, K1, K2, and KID de-
note the rate constants for PFO, PSO, and IPD models, respectively.
Also, C is a constant describing the thickness of the boundary layer.
Thus, a higher C value indicates an increased boundary layer effect in
the overall adsorption process.
3. Results and discussion
3.1. Physicochemical properties of biochars
The physicochemical properties of biochars are presented in
Table 1S. The properties varied among biochars due to differences in
inherent characteristics of the precursor biomass from which they were
prepared. The surface area of the analyzed biochars varied from 7.3 m2
g−1 (OSR550) to 162 m2 g−1 (SWP700) (Table 1S). In general, biochar
surface area increased with an increase in pyrolysis temperature from
550 to 700 °C (Table 1S). During pyrolysis, the hemicellulose and cel-
lulose contained in the precursor biomass were converted into lower
molecular weight compounds and liberated as pyrolytic vapor [37,62].
As pyrolysis temperature increases, the layered cellulose-like carbon
structure is converted into an amorphous char (through a phase tran-
sition mechanism) to increase the overall surface area [37,63]. In
general, the wide range of surface areas observed across biochars was
ascribed to the different levels of complex organic polymers among
precursor biomass samples (e.g., lignin, hemicellulose, and cellulose)
[62]. In general, precursor biomass with a higher lignin content is often
preferred for production of biochars because it facilitates production of
biochars with high porosity and large surface area [40,64,65].
The analyzed biochars were high in carbon (29.5–90.2%) and
oxygen (2.06–10.4%) and lower in nitrogen (0.1–3.79%) and hydrogen
(1) (0.63–2.77%) (Table 1S). Notably, increasing pyrolysis temperature
from 550 to 700 °C generally lowered the oxygen and hydrogen con-
tents, while the carbon ratio increased (Table 1S). The literature sug-
gests that most of the oxygen contained in biochar samples is present as
oxygenated functionalities (e.g., lactones, hydroxyls, carboxyls, anhy-
drides, and carbonyls) that can favorably participate in adsorbate-ad-
sorbent interactions [37,66,67]. In this regard, the oxygen to carbon
molar ratio is useful for characterizing the surface hydrophilicity of
biochars [68–70]. Table 1S shows that an increase in pyrolysis tem-
perature from 550 to 700 °C led to a decrease in oxygen to carbon molar
(2) creasing aromaticity for all the biochar samples. The lowest and highest
oxygen to carbon molar ratio values of 0.03 and 0.17 were recorded for
RH700 and SS550, respectively (Table 1S). In a general sense, biochars
with lower hydrophilicity are preferred for adsorption of hydrophobic
VOCs (e.g., non-polar aromatic hydrocarbons), whereas those with
higher hydrophilicity may favorably capture polar pollutants (e.g., al-
dehydes and ketones) [37,38,67]. However, such crude generalizations
(e.g., with respect to the effects of biochar hydrophilicity and polarity)
may only apply to part of the overall adsorption process because the
(3)
actual adsorption process is highly complex and involves multiple in-
teractions. The content of volatile matter in the analyzed biochars was
noted to vary from 4.99 to 21.4%, indicating incomplete carbonization
of the organic matter contained in precursor biomass (Table 1S). In-
terestingly, the surfaces of all the analyzed biochars were alkaline, with
3
K. Vikrant, et al.
pH ranging from 7.91 to 10.4 (Table 1S). The total ash content of the
analyzed biochars decreased in the range of 1.25 (SWP550) to 63.9%
(SS700) (Table 1S).
3.2. Adsorption performances of biochars against gaseous benzene and
MEK
Effective removal of gaseous VOCs under ambient conditions can
only be achieved by an adsorbent with a favorable breakthrough trend.
The maximum attainable breakthrough (BT) of a particular adsorbent
against a given set of VOCs can be defined as 100% (e.g., breakthrough
volume (BTV100)). Earlier trends in BT, such as the 10% level (BTV10),
have been widely acknowledged as a more realistic metric for perfor-
mance evaluations [26,71,72]. In essence, emission concentrations of
target VOCs measured at the outlet of the adsorption system (Cout)
should be maintained below the safe guidance levels as recommended
by the environmental/occupational protection agencies. In this regard,
the BTV10 value is very useful for projecting the life expectancy/service
life of a specific adsorbent as the material needs to be discarded when
exceeding specific values [73–75]. Hence, a good adsorbent should
possess enhanced BT capacity (e.g., higher BTV10).
The breakthrough trends of the selected biochars against gaseous
benzene and MEK are plotted in Fig. 1. Most biochars preferentially
adsorbed MEK over benzene (Fig. 1). The BTV10 values (L atm g−1) for
benzene decreased in the following order: SS550 (10) > WSP550
(8) > RH550 (2.6) > SWP700 (2.2) > SS700 (2) > SWP550/
MSP700 (1.8) > MSP550/OSR550/RH700/WSP700 (1.6) > OSR700
(1.4) (Table 1). Similarly, the BTV10 values (L atm g−1) for MEK de-
creased in the following order: RH550 (40) > SWP700 (26) > SS550
(22) > OSR700 (16) > SWP550 (14) > MSP700 (10) > MSP550
(9.7) > RH700 (8.9) > OSR550 (8.7) > SS700 (2) > WSP550/
WSP700 (1.8) (Table 1). Interestingly, a steeper slope (tangent) of the
breakthrough profile for a given adsorbate-adsorbent system indicates
rapid breakthrough, i.e., inferior performance [1,26,76]. For such ad-
sorbents, the adsorbing VOC molecules do not experience significant
resistance toward intraparticle mass transfer, leading to rapid satura-
tion of sorption sites, i.e., a low BTV10 value [26,76,77].
The BTV10 values increased by 504, 470, 444, 1021, 1448, 454,
120, 683, 1100, and 13% for MSP550, MSP700, OSR550, OSR700,
RH550, RH700, SS550, SWP550, SWP700, and WSP700, respectively,
when the target VOC changed from benzene to MEK (Table 1). In
contrast, the BTV10 value for WSP550 exhibited a 78% reduction for
MEK in the place of benzene (Table 1). Further, the results for SS700
were comparable for the two VOCs. Interestingly, the highest observed
BTV10 value toward MEK (40 L atm g−1 by RH550) was 4 times larger
than that for benzene (10 L atm g−1 by SS550) (Table 1).
To further analyze the performances of biochars against two VOCs,
the adsorption capacity values were plotted as a function of loaded G-
WS volume for both the adsorbates (Fig. 2). In addition, the adsorption
capacity values for all the analyzed biochars at different levels of
breakthrough (e.g., 5, 10, 50, and 100%) were summarized for com-
parison in Table 1. The maximum adsorption capacity values (mg g−1)
for benzene (measured at the 100% breakthrough level) decreased in
the following order: SWP700 (2.9) > SS700/RH550 (1.9) > SWP550
(1.5) > WSP700 (1.4) > SS550 (1.1) > MSP550 (0.71) > RH700
(0.5) > WSP550 (0.47) > MSP700 (0.35) > OSR550
(0.29) > OSR700 (0.05) (Table 1). Similarly, the maximum adsorption
capacity values (mg g−1) for MEK (measured at the 100% breakthrough
level) decreased in the following order: RH550 (43) > RH700
(24) > SWP700 (21) > SWP550 (17) > MSP700 (14) > MSP550
(8.9) > SS550 (6.4) > WSP700 (1.8) > OSR700 (1.6) > WSP550
(1.3) > OSR550 (1) > SS700 (0.67) (Table 1).
When the results are compared for MEK and benzene, the maximum
adsorption capacity values for MSP550, MSP700, OSR550, OSR700,
RH550, RH700, SS550, SWP550, SWP700, WSP550, and WSP700 in-
creased by 1154, 3843, 245, 3100, 2142, 4700, 482, 1033, 624, 177,
4
Chemical Engineering Journal 387 (2020) 123943
and 29%, respectively (Table 1). In contrast, SS700 showed a decrease
of 65% in the maximum adsorption capacity value for MEK relative to
benzene (Table 1). Interestingly, the highest observed maximum ad-
sorption capacity value (measured at 100% breakthrough) toward MEK
(43 mg g−1 by RH550) was 14.8 times larger than that for benzene
(2.9 mg g−1 by SWP700) (Table 1). Interestingly, RH550 displayed the
highest BTV10 as well as the maximum adsorption capacity value for
MEK (Table 1). Although SS550 displayed the highest BTV10 value of
benzene, the largest adsorption capacity value (measured at 100%
breakthrough level) was recorded for SWP700 (Table 1). This clearly
indicates that the initial breakthrough region for benzene (≤10%) was
highly dynamic in nature, resulting in initial superiority of SS550.
However, SWP700 outperformed SS550 in terms of overall adsorption
performance in the later breakthrough period (Figs. 1 and 2).
These observations suggest that SS550 is a better choice for treating
low or ambient level VOCs. In contrast, RH550 continued to perform
well for MEK throughout the entire breakthrough period (Figs. 1 and 2).
3.3. Evaluation of adsorption performance in terms of partition coefficient
values
Recent literature has elucidated the effective usage of PC as an
important metric for analyzing the performance of continuous-mode,
gas-phase adsorption processes [25–27]. (See below for details related
to the definition of PC.) Exclusive usage of conventional adsorption
capacity values to gauge the performance of adsorbents may not be
adequate from a comparative perspective as the capacity is generally
heavily dependent upon initial concentration (partial pressure) levels of
the gaseous pollutants loaded onto the adsorbents [71,78,79]. Conse-
quently, PC value (like PC at BTV10 or at BTV100) has been re-
commended as a less biased metric to gauge the performance of ad-
sorbents [25,27,80]. Fundamentally, PC value indicates the extent of
partitioning of the target VOC molecules between gaseous and solid
phases, i.e., degree of adsorbate captured by adsorbent [1,78,81].
Hence, a higher PC value is directly indicative of better adsorptive
performance. In this regard, PC at BTV10 has been effectively utilized
to meaningfully supplement the performance evaluation (in addition to
BTV10 and associated adsorption capacity values) [1,26,27] (Eq. (3)).
The variations in PC values as a function of loaded G-WS volume for
all the analyzed biochars are plotted in Fig. 2S. The PC at BTV10 (mol
kg−1 Pa−1) for benzene decreased in the following order: SS550 (1.4E-
02) > RH550 (3.E-03) > SS700/SWP700/WSP550 (2.E-
03) > MSP700/SWP550/WSP700 (1.E-03) > MSP550/RH700 (9.E-
04) > OSR550 (8.E-04) > OSR700 (6.E-04) (Table 1). Similarly, the
PC at BTV10 (mol kg−1 Pa−1) for MEK decreased in the following
order: RH550 (2.E-01) > SWP700 (9.9E-02) > OSR700 (7.9E-
02) > MSP550 (7.1E-02) > SWP550 (5.8E-02) > MSP700/OSR550
(4.8E-02) > RH700 (3.2E-02) > SS550 (1.5E-02) > SS700 (2.E-
03) > WSP550/WSP700 (1.E-03) (Table 1).
As the target VOC changed from benzene to MEK, the PC at BTV10
for MSP550, MSP700, OSR550, OSR700, RH550, RH700, SS550,
SWP550, and SWP700 increased by 7778; 4730; 5875; 13,050; 6697;
3456; 6.6; 5690; and 4850%, respectively (Table 1). These increases in
PC clearly indicate that most of the analyzed biochars preferentially
adsorbed MEK compared to benzene. Essentially, the biochar-MEK in-
teractions were more favorable than the biochar-benzene interactions.
In contrast, a 50% decrease in the PC (at BTV10) value was recorded for
WSP550 when the target VOC changed from benzene to MEK (Table 1).
Also, the PC at BTV10 value remained almost the same for SS700 and
WSP700 for the adsorption of MEK and benzene (Table 1). A similar
observation was made for the adsorption capacity values as well in case
of SS700 and WSP700. A possible explanation for such an observation
could be sought from the possibility that the adsorbate-adsorbent in-
teractions are less target specific for SS700 and WSP700. Furthermore,
the inherent molecular configuration of the precursor biomass utilized
for the production of biochars (e.g., SS700 and WSP700) could be
K. Vikrant, et al.
Fig. 1. Breakthrough profiles of the analyzed biochars against gaseous benzene and MEK.
primarily responsible for imparting their specific properties and pore
structures which in turn may induce less target-specific interactions
[37,39].
4. Adsorption kinetics analysis
Detailed analysis of net adsorption kinetics is essential for under-
standing the underlying processes and mechanisms during biochar-VOC
interactions [37,41,82]. The observed adsorption kinetics are usually
dictated by the prevailing mechanisms and physicochemical char-
acteristics of the biochar [83–85]. Thus, a suitable mathematical model
of the net adsorption process may be useful to assess the underlying
mechanisms. Use of such a model can save experimental effort, cost,
and time to ultimately pursue scale-up [41,86,87]. Various kinetic
5
Chemical Engineering Journal 387 (2020) 123943
models (linear as well as non-linear) have been reported to mathema-
tically describe adsorbent-adsorbate relationships [59,61,88]. Some
models (e.g., PFO, PSO, and IPD) have commonly been utilized for
analyzing adsorption kinetics due to their simplified mathematics,
better fitting results, and easy interpretability [59,60,89].
In general, a single kinetic model may not fit the entire set of
sorption data if the overall kinetic profile is best accounted for through
a multilinearity trend [41,59,61]. The adsorption process is usually
very fast in the beginning but slows over time as surface active sites
become saturated [37,41,89]. Thus, the net processes governing bio-
char-pollutant interactions change as adsorption proceeds. Conse-
quently, overall adsorption kinetic data can be effectively divided into
two parts as initial stage (low pressure region) and later stage (high
pressure region) [61]. As a result, the dual-surface theory is typically
K. Vikrant, et al. Chemical Engineering Journal 387 (2020) 123943

Table 1
Adsorption performances of the analyzed biochars against gaseous benzene and MEK.
Order VOC Biochar

MSP550 MSP700 OSR550 OSR700 RH550 RH700 SS550 SS700 SWP550 SWP700 WSP550 WSP700

−1
[A] 10% breakthrough volume (BTV10, L atm g )
1 Benzene 1.6 1.8 1.6 1.4 2.6 1.6 10 2 1.8 2.2 8 1.6
2 MEK 9.7 10 8.7 16 40 8.9 22 2 14 26 1.8 1.8

[B] Adsorption capacity (mg g−1)

At 5% breakthrough
1 Benzene 1.E-02 1.8E-02 1.4E-02 1.1E-02 3.E-02 2.E-02 2.6E-01 2.2E-02 1.9E-02 2.6E-02 2.2E-01 1.6E-02
2 MEK 0.22 0.21 0.19 0.38 0.94 0.12 0.61 0.02 0.31 0.42 0.02 0.02

At 10% breakthrough
1 Benzene 3.E-02 3.5E-02 2.7E-02 2.2E-02 6.E-02 3.E-02 3.E-01 4.3E-02 3.7E-02 5.1E-02 2.4E-01 3.2E-02
2 MEK 0.26 0.28 0.23 0.44 1.1 0.23 0.64 0.04 1 0.73 0.04 0.04

At 50% breakthrough
1 Benzene 0.13 0.14 0.12 0.11 0.23 0.13 0.57 0.18 0.16 0.21 0.33 0.14
2 MEK 0.67 1.1 0.46 0.93 3.7 1.5 0.81 0.16 1.3 1.6 0.15 0.15

At 100% breakthrough
1 Benzene 0.71 0.35 0.29 0.05 1.9 0.5 1.1 1.9 1.5 2.9 0.47 1.4
2 MEK 8.9 14 1 1.6 43 24 6.4 0.67 17 21 1.3 1.8

[C] Partition coefficient (PC, mol kg−1 Pa−1) at BTV10

1 Benzene 9.E-04 1.E-03 8.E-04 6.E-04 3.E-03 9.E-04 1.4E-02 2.E-03 1.E-03 2.E-03 2.E-03 1.E-03
2 MEK 7.1E-02 4.8E-02 4.8E-02 7.9E-02 2.E-01 3.2E-02 1.5E-02 2.E-03 5.8E-02 9.9E-02 1.E-03 1.E-03

invoked to meaningfully fit adsorption kinetics data over the entire
range of breakthrough points using the PFO, PSO, and IPD models (Eqs.
(4)–(6), respectively) [59,61,88].
4.1. Comparative discussions on linear and non-linear kinetic models
Two of the best performing biochars (with respect to maximum
adsorption capacity and BTV10) were selected for evaluation of each
VOC using the kinetic analyses (refer to Section 3.2). In this respect,
SWP700 and RH550 were selected for benzene kinetic analysis, while
RH550 and RH700 were selected for MEK kinetic analysis. The ob-
tained kinetic results (linear as well as non-linear models) for both the
pressure regions are provided in Table 2. As elucidated in Fig. 3S and
4S, most of the applied kinetic models for benzene and MEK showed
quite large coefficients of determination (R2 > 0.92) for both the
pressure regions. Due to the closeness of simulated linear modelling
results (Fig. 3S and 4S), R2 values could not be utilized as a suitable
basis for determining the best fitting kinetic model. As a result, corre-
lation coefficient (r2) and non-linear chi-square error (χ2) were em-
ployed to ascertain the best fitting kinetic model and relative errors
linking the experimental and simulated data [1,59,90].
The non-linear kinetic models superimpose well onto the experi-
mental data without much difference between benzene and MEK, in-
dicating their validity in both low and high pressure regions (Figs. 3
and 4). On the other hand, the simulated linear kinetic models diverged
from the experimental data, indicating their relatively inferior perfor-
mance (Figs. 3 and 4). The r2 values for non-linear PFO and PSO models
were 1 for benzene as well as MEK for all the analyzed biochars in the
low and high pressure regions (Table 2). In contrast, the linear PFO and
PSO models displayed a relatively inferior fitting result for benzene
(0.5 < r2 < 0.8 for SWP700 and 0.8 < r2 < 1 for RH550) (Table 2).
However, the linear PFO and PSO models fit the MEK data well, with
0.9 < r2 < 1, as observed from all the analyzed biochars in both
pressure regions (Table 2). The r2 values for the IPD model were con-
stantly 1 in the high pressure region for both the linear and non-linear
models of benzene and MEK (Table 2). Interestingly, in the low pressure
region (for all the analyzed biochars), the r2 values for the non-linear
IPD model were 0.9 (benzene) and 0.8 (MEK) (Table 2). These patterns
suggest that the initial breakthrough for both VOCs proceeds very dy-
namically.
Similar to r2, the χ2 values for non-linear PFO and PSO models were
consistently lower than those of the linear models, resulting in a su-
perior fit, i.e., less error between the simulated and experimental results
(Table 2). In the case of benzene, the χ2 values for non-linear PFO and
PSO models ranged from 0.003 to 0.05 for SWP700, while those for
RH550 were 0.002–0.05 (Table 2). Similarly, in the case of MEK, the χ2
values for non-linear PFO and PSO models ranged from 0.00004 to 5.9
for RH550, while those for RH700 were in the range of 0.0001–8.3
(Table 2). In contrast, the linear PFO and PSO models displayed a re-
latively inferior fitting result for benzene (0.1 < χ2 < 6.6 for
SWP700 and 0.002 < χ2 < 0.1 for RH550) (Table 2). For MEK, the
linear PFO and PSO models displayed χ2 values ranging from 0.00004
to 6.2 for RH550 and 0.0001–14.5 for RH700 across both pressure re-
gions (Table 2). Using the IPD model, the χ2 values for linear models
were consistently lower than those for non-linear models in both
pressure regions and for all the analyzed biochars (Table 2). However,
the C values obtained for all the analyzed biochars from the linear IPD
model were negative in both pressure regions (refer to Section 4.2)
(Table 2). Such negative C values indicate complex involvement of
multiple kinetic processes (surface reaction and film diffusion), as dis-
cussed in the subsequent subsection [59,91]. Given the superior
quantitative and qualitative fitting results provided by non-linear
models, further discussions will not include the linear kinetic models.
Nevertheless, the interested reader can refer to Table 2 for the corre-
sponding data obtained through linear models.
4.2. Adsorption kinetics modelling
Both the PFO and PSO models well fit the benzene adsorption data
onto the analyzed biochars (r2 = 1) in low and high pressure regions
(Table 2). The PFO model provided a superior fit as evidenced by the
similarity of qm values predicted by the kinetic equation and the ex-
perimentally obtained values (Table 2). The K1 value for benzene ad-
sorption onto SWP700 decreased from 1.9 to 0.2 min−1 (89%

6
K. Vikrant, et al.
Fig. 2. Evolution of adsorption capacity with loaded VOC G-WS volume for all the analyzed biochars.
reduction) when the pressure region changed from low to high
(Table 2). This is in line with the reported literature that the adsorption
process slows as the material becomes saturated [41,59,92].
The sorbent surface is relatively clean at the beginning of adsorp-
tion, which results in swift capture of incoming VOC molecules. As the
adsorption process progresses, the active sites of the sorbent surface are
occupied, resulting in increased repulsion between incoming and ad-
sorbed pollutant molecules. Similarly, the K1 value for benzene ad-
sorption onto RH550 decreased from 1.9 to 0.4 min−1 (79% reduction)
when the pressure region changed from low to high (Table 2). This
indicates equal initial rates of benzene adsorption onto SWP700 and
RH550. However, the kinetics become slower for SWP700 compared to
RH550 in the later stages of adsorption. Interestingly, the prevalence of
7
Chemical Engineering Journal 387 (2020) 123943
the PFO model indicates that adsorption of benzene onto the analyzed
biochars was largely physical in nature [60,93].
The K2 values for benzene adsorption onto the biochars also de-
creased when the pressure region changed from low to high (0.9 to
0.02 g mg−1 min−1 for SWP700 and 1 to 0.1 g mg−1 min−1 for RH550)
(Table 2). This observation indicates that the rate of benzene adsorption
onto SWP700 and RH550 decreased by 97 and 90%, respectively, when
the pressure region changed from low to high (Table 2). Furthermore,
the initial benzene sorption rates (h0, i.e., K2qm2) for SWP700 and
RH550 decreased by 54 and 57%, respectively, when the pressure re-
gion changed from low to high. Such an observation clearly indicates a
decrease in adsorption rate as the material approaches saturation
(Table 2). Notably, the relatively poor prediction of the benzene qm
K. Vikrant, et al. Chemical Engineering Journal 387 (2020) 123943

Table 2
Summary of the kinetic fitting results obtained for adsorption of benzene and MEK onto selected biochars.
Order Pressure Experimental Model Kinetic model constants Predicted Fitting parameters
region maximum maximum
capacity capacity
(qe, mg g−1) (qm, mg g−1)
a 2 b
r Non-linear Chi-square test (χ2)

K1 (min−1) K2 (g K2qm2 KID (mg C PFO PSO PFO PSO IPD PFO PSO IPD
mg−1 (mg g−1 g−1
min−1) min−1) min−0.5)

Benzene
[A] SWP700
1 Low 0.5 Linear 0.3 1.3 1.6 0.8 −0.1 2.8 1.1 0.8 0.5 1 0.1 1 0.004
2 Non-linear 1.9 0.9 1.3 0.6 0 0.8 1.2 1 1 0.9 0.003 0.003 0.02
3 High 2.9 Linear 0.4 0.03 0.8 1.2 −0.5 3.4 5.1 0.7 0.6 1 1.4 6.6 0.01
4 Non-linear 0.2 0.02 0.6 0.9 0 3.6 5.4 1 1 1 0.05 0.03 0.2

[B] RH550
1 Low 0.5 Linear 0.5 1.4 1.7 0.9 −0.1 1.8 1.1 0.8 1 1 0.1 0.002 0.001
2 Non-linear 1.9 1 1.4 0.6 0 0.8 1.2 1 1 0.9 0.002 0.002 0.02
3 High 1.9 Linear 0.4 0.1 0.6 0.6 0.1 1.9 2.5 0.9 1 1 0.1 0.02 0.001
4 Non-linear 0.4 0.1 0.6 0.6 0.1 1.9 2.5 1 1 1 0.05 0.02 0.001

Methyl ethyl ketone (MEK)

[A] RH550
1 Low 0.96 Linear 0.05 0.0003 2.2 1.9 −0.46 41.5 86 1 1 1 0.002 0.00004 0.01
2 Non-linear 0.08 0.001 2.0 1.2 0 23.7 45 1 1 0.8 0.00004 0.00004 0.22
3 High 42.6 Linear 0.02 0.0004 1.1 3.6 −1.6 41.9 52 1 1 1 6.2 2.5 3.4
4 Non-linear 0.02 0.0003 0.9 3.4 0 41.9 55 1 1 1 5.9 2.5 13

[B] RH700
1 Low 0.8 Linear 0.07 0.01 1.8 1.7 −0.4 23.7 12.6 1 1 1 0.004 0.0001 0.01
2 Non-linear 0.18 0.005 1.8 1 0 9.81 19.1 1 1 0.8 0.0001 0.0001 0.17
3 High 24.2 Linear 0.02 0.0007 0.6 2.1 −1.8 25.6 29.1 0.9 1 1 14.5 6.9 2.6
4 Non-linear 0.01 0.0002 0.3 1.9 0 28.3 41.4 1 1 1 8.3 6.9 5.7

a 2
r is the correlation coefficient to determine the best-fitting isotherm. r2 =
(qe qa )2
, where qc and qe are the calculated and experimental adsorption
(qe qa )2 + (qe qc )2
capacities, respectively. qa is the average of qc values.
b 2 (qc qe )2
χ is a statistical test to calculate the error between predicted and experimental data. χ2 =
n
i=1 qe
, where 'n' is the run number.

Fig. 3. Kinetic fitting plots for adsorption of benzene onto selected biochars. (a) Linear models for SWP700. (b) Non-linear models for SWP700. (c) Linear models for
RH550. (d) Non-linear models for RH550.

8
K. Vikrant, et al.
Fig. 4. Kinetic fitting plots for adsorption of MEK onto the selected biochars. (a) Linear models for RH550. (b) Non-linear models for RH550. (c) Linear models for
RH700. (d) Non-linear models for RH700.
values by the PSO model can be explained by the assumption of che-
misorption as the rate limiting step, although it is not important in
interactions between aromatic hydrocarbon and carbonaceous sorbent
[41,60]. In addition, the PSO model is useful to describe the valence
forces between the electrons shared by adsorbent and adsorbate [60].
Such a characteristic chemisorption process is not likely prevalent for
benzene-biochar interactions, and the PSO model cannot accurately
predict qm [27,35,57].
Adsorption of MEK onto the biochars followed a similar mechanistic
trend as noted for benzene. Interestingly, r2 values were 1 in both the
PFO and PSO model for both low and high pressure regions.
Subsequently, the qm values predicted by PFO were relatively close to
the experimental result (e.g., unlike PSO) (Table 2). The K1 value for
MEK adsorption onto RH550 decreased from 0.08 to 0.02 min−1 (75%
reduction) when the pressure region changed from low to high
(Table 2). For MEK adsorption onto RH700, the K1 value decreased
from 0.18 to 0.01 min−1 (94% reduction) with the same pressure
change conditions (Table 2). The K2 values for MEK under such chan-
ging conditions of adsorption onto RH550 and RH700 dropped from
0.001 to 0.0003 g mg−1 min−1 (70% reduction) and from 0.005 to
0.0002 g mg−1 min−1 (96% reduction), respectively (Table 2). Ad-
ditionally, the initial MEK sorption rates (h0) for RH550 and RH700
were noted to decrease by 55 and 83%, respectively, when the pressure
region changed from low to high (Table 2). The results indicate that
adsorption of MEK onto the biochars was largely controlled by physical
forces [59,60,93]. In addition, the adsorption kinetics become slower as
the biochar surface reached saturation due to the factors discussed
above. Interestingly, the observed kinetic parameters were smaller for
MEK than benzene (Table 2). This observation indicates that a longer
time was required to reach saturation for adsorption of MEK in com-
parison to benzene, which is in line with the experimental observations
(Figs. 3 and 4).
The feasibility of using the IPD model to fit the experimental data
was relatively good for both benzene and MEK. Hence, boundary layer
effects are likely to significantly contribute to biochar-VOC interactions
[59,60] (Table 2). However, the lower r2 values (0.8–0.9) of the IPD
9
Chemical Engineering Journal 387 (2020) 123943
model (compared to PFO and PSO models) in the low pressure region
indicate that this model is less suitable for describing the initial ad-
sorption process for both benzene and MEK (Table 2). Interestingly, the
C values obtained from a linear IPD model were negative for both
benzene and MEK (Table 2). Such an observation indicates that both
surface reaction and film/pore diffusion processes are dominant in the
overall adsorption phenomenon [59,91]. This is in line with the ob-
servation that PFO and PSO models provide a better match with the
experimental data than the IPD model, particularly in the low pressure
region (Table 2). Thus, it is reasonable to infer that the boundary layer
effect did not play a major role in the initial stages of benzene and MEK
adsorption onto the utilized biochars. In the high pressure region, the C
values obtained from the non-linear IPD model were consistently 0
(Table 2). This observation indicates that the thickness of the boundary
layer was the rate determining step for adsorption of benzene and MEK
onto the biochars [59,60,94]. However, as the PFO and PSO models
also demonstrated appreciable fits along with the negative C values
obtained from the linear IPD model, we concluded that the overall
adsorption process is a complex combination of various kinetic phe-
nomena including (i) diffusion into biochar pores (boundary layer ef-
fect) and (ii) physisorption on surface active sites, which play a major
role in capture of benzene and MEK molecules by analyzed biochars.
5. Influence of volatile matter, surface area, and adsorption
mechanisms
To analyze the influence of biochar surface area on net VOC ad-
sorption capacity, the maximum adsorption capacity values were
plotted as a function of total surface area for all the utilized biochars
(Fig. 5S(a)). No appreciable correlation was noted between surface area
and maximum adsorption capacity for both benzene (R2 of 0.2645) and
MEK (R2 of 0.0137) (Fig. 5S(a)). Nevertheless, the R2 value for benzene
was ~19 times larger than that for MEK, indicating that a higher sur-
face area favored adsorption of benzene (relative to MEK) onto the
biochars to a certain extent. According to a biochar-based adsorption of
three gaseous VOCs (i.e., acetone, cyclohexane, and toluene), the
K. Vikrant, et al.
overall adsorption mechanism primarily involved a combination of
physical adsorption and partitioning processes [37]. The physical ad-
sorption process is typically controlled by biochar surface area, whereas
the partitioning process is primarily governed by volatile matter con-
tent [37,38]. Note that in this study the term physical adsorption refers
to a number of processes and or interactions such as the Van der Waals
interactions, π-π electron donor–acceptor interactions, and pore-filling
processes taking place between the VOC molecules and biochar surface.
The partitioning mechanism could be understood as the capture of VOC
molecules on the biochar surface due primarily to the influence of vo-
latile matter content in the biochar structure [37,39]. As the biochars
produced at lower temperatures contain a larger amount of volatile
matter (Table 1S), it is instructive to plot the adsorption capacity versus
surface area data separately for biochars produced at 550 °C and for
those produced at 700 °C.
The correlation between maximum adsorption capacity and total
surface area of the biochars produced at 550 °C was very low for both
benzene (R2 of 0.0378) and MEK (R2 of 0.0023) (Fig. 5S(b)). This ob-
servation clearly indicates that both volatile matter (partitioning) and
surface area (physical adsorption) played a synergistic role in the net
adsorption process for the biochars produced at low temperature.
Hence, there was no significant correlation for surface area alone. In-
terestingly, when the maximum adsorption capacity was plotted as a
function of total surface area for the biochars produced at higher
temperature (700 °C), a remarkably high R2 value of 0.7591 was noted
for benzene (Fig. 5S(c)). However, a relatively low R2 value of 0.0407
was noted for MEK for such biochars (Fig. 5S(c)). These contrasting
patterns clearly demonstrate that the adsorption of less polar VOCs, i.e.,
benzene, is affected more sensitively by the surface area of biochar
(e.g., relative to MEK). In fact, the largest adsorption capacity value for
benzene (2.9 mg g−1) was recorded by the biochar possessing the
highest surface area of 162 m2 g−1 (SWP700) (Tables 1S and 1).
Along similar lines, no significant correlation was noted between
maximum adsorption capacity values and volatile matter content if the
results are compared for both MEK and benzene (Fig. 5S(d)–(f)).
However, an R2 value of 0.5544 was observed when the maximum
adsorption capacity for benzene was plotted against the volatile matter
content for the biochars produced at 700 °C (Fig. 5S(e)). This ob-
servation suggests that benzene should favorably partition in addition
to the physisorption process. Although the presence of volatile matter
should facilitate the partitioning mechanism of adsorbates (e.g., VOC
molecules), such a process can also be restricted by the low surface area
of biochars [37,38]. Essentially, if the surface area is too low, the
probability of intensive contact between the VOC molecule and organic
matter may decrease to a large degree. Thus, a clear correlation may
not be observed [37]. Nevertheless, if the size of the VOC molecules is
small, then they could effectively penetrate into the porous network of
biochar and exhibit significant correlation between volatile matter
content and maximum adsorption capacity [37].
On the whole, we concluded that overall adsorption of VOCs onto
the biochars was a complex combination of pure physical adsorption
and partitioning due to the presence of volatile matter. However, the
process was largely controlled by physisorption, which is related to the
surface area of the biochar, particularly for less polar VOCs (e.g., ben-
zene). In contrast, adsorption of polar VOCs, i.e., MEK, was very dif-
ferent. It is intriguing to note that RH550 displayed a remarkable per-
formance towards MEK adsorption despite the fact that it does not
possess the largest surface area or volatile matter content. It is now
acknowledged that the inherent molecular configuration of the pre-
cursor biomass feedstock utilized for the production of biochar can
tightly control the adsorption behavior of biochars towards particular
target species [37,39,63]. Such precursor effect on biochar performance
could be highly selective depending upon the biochar-pollutant pair.
Additionally, the nature of pore structure (e.g., pore size, pore volume,
10
Chemical Engineering Journal 387 (2020) 123943
and tortuosity) could also play a major role in controlling the ad-
sorptive removal of various pollutants [52]. Thus, the superior perfor-
mance of RH550 towards MEK could stem from a complex combination
between the favorable nature of feedstock and advantageous physico-
chemical properties of the produced biochar (e.g., pore structure
alongside surface area and volatile matter content). Similar observa-
tions between various types of VOCs and biochars have been reported
in the literature [37,95]. In our previous work, we demonstrated that
the adsorption of gaseous VOCs onto a carbonaceous adsorbent pri-
marily involves formation of Van der Waals bonds, π-π electron do-
nor–acceptor interactions, and pore filling mechanisms [57].
6. Performance comparison and assessment
A comprehensive survey has been made to describe the adsorption
performances of some representative adsorbents toward the removal of
gaseous benzene and MEK as summarized in Table 3. Note that some
adsorption data in published articles were not considered for this
comparison as they lacked sufficient experimental details (e.g., applied
flow rate, mass of adsorbent, and other technicalities). Also, the per-
formance table for gaseous benzene has been partially derived from
more extensive lists recently published by our research group to include
the data from some representative adsorbents (metal–organic frame-
works (MOFs) as well as conventional materials) for comparison pur-
poses [1,28].
In many gas-phase continuous-mode adsorption studies, experi-
ments were conducted at unrealistically high concentration levels of the
VOC to yield abnormally large adsorption capacity values (e.g.,
1575 mg g−1 for NENU-513 (NENU = Northeast Normal University) at
12,700 Pa benzene) (Table 3) [71,96]. As such unusual capacity values
are mainly induced by the large influent concentration of VOCs, the
usage of adsorption capacity as a general performance metric is of
limited practicality [71,79,80]. In this regard, PC (Eq. (3)) has been
recognized as a less biased performance metric for gauging the true
performance of a particular adsorbent material [1,28,79]. As the PC
values effectively measure the extent of partitioning, i.e., separation of
a given analyte between gas and solid phases, PC can be used to esti-
mate the strength of adsorbate-adsorbent interactions quantitatively
[1,27]. Thus, in many recent studies, the use of PC as a multifaceted
performance metric has been made extensively alongside maximum
adsorption capacity values to offer more objective criteria for perfor-
mance evaluation between various adsorbents [1,79,97].
As can be seen from Table 3, the PC values for benzene ranged from
0.0002 mol kg−1 Pa−1 (zeolite and MOF-177) [98,99] to 1.81 mol kg−1
Pa−1 (biochar XC-1 (produced from mixed feedstock)) [35]. As such,
the XC-1 biochar and activated carbon displayed the best performance
towards the adsorption of gaseous benzene (maximum adsorption ca-
pacities of 144 and 93.5 mg g−1 and the corresponding PC values of
1.81 and 1.27 mol kg−1 Pa−1 for 5 Pa benzene, respectively) [1,35]
(Table 3). In contrast, the PC value of the best performing biochar for
benzene in the present study (SWP700) was only 0.014 mol kg−1 Pa−1
which is ~ 129 times smaller than that of the XC-1 biochar (Table 3).
Further, the maximum adsorption capacity obtained by SWP700 at 1 Pa
benzene (2.9 mg g−1) was 98% smaller than that of XC-1 biochar at
5 Pa benzene (Table 3). As such, the performance of SWP700 was in-
ferior to those of other carbonaceous materials tested for benzene (e.g.,
activated carbon and other biochars). Nonetheless, it was still com-
parable and somewhat better than those of MOFs (Table 3). Never-
theless, MOF-199 and UiO-66 (UiO = Universitetet i Oslo) still out-
performed SWP700 with PC values of 1.08 and 0.24 mol kg−1 Pa−1,
respectively [1] (Table 3).
In case of MEK, the maximum adsorption capacity values were
observed from such sorbents as MCM-41 silica (MCM = Mobil com-
position of matter) [100], activated carbon [101], and palygorskite clay
K. Vikrant, et al. Chemical Engineering Journal 387 (2020) 123943

Table 3
Performance comparison of various adsorbents applied for the removal of gaseous benzene and MEK. A certain fraction of benzene removal data has been taken from
our recent report made elsewhere [1,28].
Order Adsorbent Inlet partial pressure (Pa) Temperature (K) Maximum adsorption Partition Coefficient (mol kg−1 Pa−1) Reference
capacity (mg g−1) (derived assuming Henry's law)

A. Benzene
1 Activated Carbon 2.45 433 15.4 0.0804 [106]
2 Activated Carbon 5 298 93.5 1.27 [1]
3 Zeolite 1800 363 31 0.0002 [99]
4 MOF-199 5 298 94.8 1.08 [1]
5 UiO-66 5 298 27.1 0.24 [1]
6 IRMOF-3 44 298 6 0.0016 [98]
7 IRMOF-62 44 298 11 0.0031 [98]
8 MOF-5 3500 303 703 0.0007 [107]
9 MOF-74 44 298 10 0.0027 [98]
10 MOF-177 44 298 1 0.0002 [98]
11 NENU-513 12,700 298 1575 0.0182 [96]
12 Biochar (XC-1) 5 298 144 1.81 [35]
13 Biochar (SWP700) 1 298 2.9 0.014 This study

B. MEK
1 Activated Carbon 20 293 170 0.12 [101]
2 Palygorskite clay 100 298 67.7 0.01 [102]
3 MCM-41 silica 5490 (Extrapolated using the Antoine 313 588 0.0015 [100]
parameters for MEK [108])
4 Zeolite 0.031 (as a 13 component mixture) 318 0.00129 (at 50% 0.0003 [103]
breakthrough)
5 MOF-199 0.031 (as a 13 component mixture) 318 0.00252 (at 50% 0.0004 [103]
breakthrough)
6 Biochar (RH550) 1 298 43 0.2 This study

[102] to be 588, 170, and 67.7 mg g−1, respectively (Table 3). How-
ever, their performances were fairly poor in terms of PC values (0.0015,
0.12, and 0.01 mol kg−1 Pa−1 for MCM-41, respectively) [100–102]
(Table 3). The high adsorption capacity values for MEK were noted to
arise from the usage of substantially high inlet partial pressures
(20–5490 Pa) [100–102] which further indicated the biasness of ca-
pacity values as explained above (Table 3). In this respect, RH550
tested in this study was identified as the best performing biochar for
MEK with the highest PC value of 0.2 mol kg−1 Pa−1 which was 1.6
times larger than that for the second best material (activated carbon)
(Table 3). In comparison, zeolite and MOF-199 exhibited low PC values
of 0.0003 and 0.0004 mol kg−1 Pa−1, respectively towards 0.031 Pa
MEK in our previous study [103] (Table 3). However, such low per-
formance data for MEK is likely to reflect the competitive inhibition of
adsorption process as MEK was supplied as a part of mixture containing
13 different gaseous components [103–105]. Hence, it is reasonable to
infer much improved values for MOF-199 and zeolite if their perfor-
mance is derived against MEK as the single component.
As can be seen from the above discussions, the biochars utilized in
the present study performed reasonably well for gaseous MEK which
was selected to represent a polar VOC (Table 3). However, the perfor-
mance of these tested biochars was rather poor for less polar aromatic
hydrocarbon (benzene) when compared to some MOFs (e.g., MOF-199
and UiO-66) or conventional materials (e.g., activated carbon and
biochar XC-1) (Table 3). Hence, the use of biochars reported in this
study could be recommendable for the adsorptive removal of polar,
rather than nonpolar, gaseous VOCs. Nevertheless, for the removal of
gaseous aromatic hydrocarbons, biochars prepared from other bio-
masses (e.g., XC-1) should still be a promising option as reported in our
earlier study [35]. If the performance of these biochars is considered in
relation to the overall operational cost and figure of merit, the use of
these biochars could still be more favorable than that of MOFs for
capturing gaseous aromatic hydrocarbons [27,28]. Notably, the major
advantage of using biochars should be its cheap price (break-even price
is approximately one-sixth of that of the commonly used activated
carbon) [37,38,40]. Also, as the biochars are usually prepared from
waste biomass, they can provide a win–win strategy to simultaneously
control environmental pollution and to efficiently manage the gener-
ated biowaste [41–43].
7. Conclusions
Given the dearth of literature regarding the adsorption perfor-
mances of biochars against gaseous VOCs, we analyzed 12 standard
biochars derived through pyrolysis (at 550 °C and 700 °C) of various
feedstock as sorbents against benzene and MEK (1 Pa each). For ben-
zene, the BTV10 and PC measured at BTV10 values varied from 1.4 to
10 L atm g−1 and 6.E-04 to 1.4E-02 mol kg−1 Pa−1, respectively. In the
case of MEK, the BTV10 and PC at BTV10 values varied from 1.8 to 40 L
atm g−1 and 1.E-03 to 2.E-03 mol kg−1 Pa−1, respectively. The highest
adsorption capacity value for benzene (2.9 mg g−1) was observed for
SWP700, while that for MEK (43 mg g−1) was from RH550. Most
biochars adsorbed MEK preferentially to benzene. The adsorption ki-
netics results indicated that the adsorption process was largely physical
in nature, with a complex combination of surface control and boundary
layer effects. Interestingly, biochar surface area was a useful parameter
to explain the differences in adsorption behavior between VOCs when
speciation can distinguish based on polarity. Further, other variables
such as biochar composition and other surface features also controlled
adsorption of more polar species like MEK, to an extent. The results
presented in this study contribute to the biochar database and can ex-
pand the applications of biochar as adsorbents in environmental re-
mediation and pollution control.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
We would like to acknowledge support by the R&D Center for Green
Patrol Technologies through the R&D for Global Top Environmental

11
K. Vikrant, et al.
Technologies funded by the Ministry of Environment (MOE), as well as
by a grant from the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT, & Future Planning (Grant No:
2016R1E1A1A01940995). This study was supported by the Korea
Ministry of Environment (MOE)as part of the “Technology Program for
Establishing Biocide Safety Management” (2018002490001).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.123943.
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