Journal of Industrial and Engineering Chemistry 40 (2016) 1–15

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Journal of Industrial and Engineering Chemistry

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

Review

Production and utilization of biochar: A review

Jin Sun Cha a,b, Sung Hoon Park c, Sang-Chul Jung c, Changkook Ryu d, Jong-Ki Jeon e,
Min-Chul Shin b, Young-Kwon Park a,*
a
School of Environmental Engineering, University of Seoul, Seoul, 02504, Republic of Korea
b
Korea Testing Laboratory, Seoul, 08389, Republic of Korea
c
Department of Environmental Engineering, Sunchon National University, Suncheon, 57922, Republic of Korea
d
School of Mechanical Engineering, Sungkyunkwan University, Suwon, 16419, Republic of Korea
e
Department of Chemical Engineering, Kongju National University, Cheonan, 31080, Republic of Korea

A R T I C L E I N F O A B S T R A C T

Article history: Biochar produced during the thermochemical decomposition of biomass not only reduces the amount of
Received 20 April 2016 carbon emitted into the atmosphere, but it is also an environment-friendly replacement for activated
Received in revised form 5 June 2016 carbon and other carbon materials. In this review paper, researches on biochar are discussed in terms of
Accepted 6 June 2016
production method and application. Different processes for biochar production, such as pyrolysis,
Available online 15 June 2016
gasification, hydrothermal carbonization, etc., are compared. Physical and chemical activation methods
used to improve the physicochemical properties of biochar and their effects are also compared. Various
Keywords:
environmental application fields of biochar including adsorption (for water pollutants and for air
Biochar
pollutants), catalysis (for syngas upgrading, for biodiesel production, and for air pollutant treatment),
Biochar activation
Biochar application and soil conditioning are discussed. Recent research trend of biochar in other applications, such as fuel
Adsorbent cell, supercapacitor, and hydrogen storage, is also reviewed.
Catalyst ß 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Soil amendment reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Production of biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Hydrothermal carbonization (HTC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Other thermochemical technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Modification of biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Physical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Chemical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Application of biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Adsorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Soil amendment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Other applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

* Corresponding author. Tel.: +82 2 6490 2870; fax: +82 2 6490 2859.
E-mail address: [email protected] (Y.-K. Park).

http://dx.doi.org/10.1016/j.jiec.2016.06.002
1226-086X/ß 2016 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
2 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15

Introduction hemicellulose and lignin that comprise biomass undergo their

own reaction pathways, including cross-linking, depolymeriza-
The combustion of fossil fuels emits CO2, which causes global tion and fragmentation at their own temperature, producing solid,
warming and climate change as well as the production of air liquid and gaseous products. The solid and liquid products are
pollutants, such as the oxides of sulfur and nitrogen [1]. Fossil fuel referred to as char and bio-oil, respectively, whereas the gaseous
exhaustion, increasing oil price, and the rise of global environ- mixture containing CO, CO2, H2, and C1–C2 hydrocarbons are
mental problems are calling for the development of alternative called syngas. The yields of the pyrolysis products depend on the
energy resources to replace conventional fossil fuels. Organic characteristics of the raw biomass materials and the pyrolysis
materials originating from living matter or complexes of organic processes adapted.
and inorganic materials from said sources are referred to The parameters that influence the products of the pyrolysis
collectively as biomass. Biomass includes not only living organ- processes include the reaction temperature, heating rate, and
isms, such as plants and animals, but also the excrement of residence time. In general, the biochar yield decreases and the
animals, sludge, and waste wood [2]. Thermochemical decompo- syngas yield increases with increasing pyrolysis temperature [32–
sition processes convert biomass materials to syngas, bio-oil, and 35]. Mohammad et al. [35] and Zhang et al. [36] reported that the
biochar. The gas product syngas and the liquid product bio-oil are yields of biochar and acidic functional groups decreased with
regarded as alternative fuels to fossil fuels, and extensive research increasing pyrolysis temperature, whereas those of the basic
is being conducted on their formation, upgrading, and applications functional groups, ash content, pH, and carbon stability increased.
[3–7]. Biomass is considered carbon neural because the carbon The increase in pH with increasing pyrolysis temperature was
dioxide emitted from biomass is compensated for by the carbon attributed to the reduction of organic functional groups, such as –
assimilation occurring during the photosynthesis of biomass. COOH and –OH. The bio-oil yield was reportedly highest at
Biomass is also known to have fewer adverse effects on the approximately 500 8C because cracking takes place at higher
atmosphere because it contains less S and N, resulting in lower SOx temperatures [34]. Fig. 1 shows the elemental compositions of
and NOx emissions than fossil fuels [1]. biochar produced at different pyrolysis temperatures [37]. Pyroly-
Biochar, the solid material formed during the thermochemical sis processes are divided into slow pyrolysis and fast pyrolysis
decomposition of biomass, is defined, by the International Biochar depending on the rate of the increase in temperature. In a slow
Initiative (http://www.biochar-international.org/biochar), as ‘‘a pyrolysis, in which the pyrolyzed vapors reside for a long time in
solid material obtained from the carbonization of biomass’’. As the reactor at low temperatures, continuing vapor-phase reactions
biochar is inexpensive, environment-friendly, and can be used for a increase the char yield [32,34,38]. Inguanzo et al. [39] evaluated
variety of purposes, such as soil remediation, waste management, the characteristics of the chars produced at two different
greenhouse gas reduction, and energy production, several studies temperature rising rates of 5 8C/min and 60 8C/min. They reported
have been conducted to develop new applications of biomass that the char produced at the higher temperature rising rate had a
[8]. Although the main element of biochar is carbon (C), it also lower volatile matter content and a higher ash (including fixed
contains hydrogen (H), oxygen (O), ash, and trace amounts of carbon) yield and concluded that a high temperature rising rate is
nitrogen (N) and sulfur (S) [9]. The elemental composition of preferable in terms of the quality of the product biochar. This effect
biochar varies according to the raw biomass material from which of the temperature rising rate was not observed at high pyrolysis
the biochar was produced and the characteristics of the temperatures [40]. Therefore, fast pyrolysis is generally aimed at
carbonization process [10–12]. Because of its large specific surface producing a liquid product in high yield [41,42]. To suppress the
area, porous structure, surface functional groups, and high mineral gas production due to secondary cracking, the vapor residence
content, biochar has been used as an adsorbent for water and air time is controlled short and rapid cooling is used to maximize the
pollutants [12,13], a catalyst to remove tar or produce biodiesel liquid product yield.
[14,15], and as a soil amendment [12,16]. Recently, the applica- Regarding the effects of the residence time on the product
tions of biochar to fuel cells [17,18] and supercapacitors [19,20] composition in a pyrolysis process, Zhang et al. [36] reported that
have also been reported. the biochar yield decreased with increasing residence time at the
In this article, before looking into the application instances of same pyrolysis temperature. In a study of the effects of the
biochar, the thermochemical decomposition processes for the residence time on the specific surface area and pore character-
production of biochar and previous studies on the biochar istics of biochar, Lu et al. [43] reported that the specific surface
modification to improve its properties are reviewed to enhance area and pore area increased with increasing residence time up to
the understanding of biochar formation. Most previous review 2 h at 500–900 8C but they decreased when the residence time
articles on biochar application discussed the removal of pollutants exceeded 2 h. In particular, the specific surface area and pore area
in water [13,21,22] and soil [23–27] using biochar. Only recent decreased rapidly when the residence time exceeded 2 h at high
research trend in those fields is briefly presented in this article, temperatures. Bandosz et al. observed in a study of the pyrolysis
whereas the applications of biochar to the removal of hazardous of sewage sludge that the specific surface area decreased from
pollutants (including air pollutants and tar) and other recently 141 m2/g to 125 m2/g and the pore volume decreased from
developed application fields, such as fuel cell, supercapacitor, and 0.209 cm3/g to 0.187 cm3/g when the residence time was
hydrogen storage, are discussed in detail. increased from 30 min to 1 h at a pyrolysis temperature of 950 8C
[44]. Lu et al. attributed the results of Bandosz et al. to a
Production of biochar narrowing and closure of the pore entrances owing to the
sintering of char, resulting in a reduction of the specific surface
This section summarizes several different carbonization area [43]. Table 1 summarizes the characteristics of biochar
processes to produce biochar along with their characteristics. produced under various pyrolysis conditions.

Pyrolysis Gasification

Pyrolysis is a process for decomposing organic materials Gasification is a thermochemical partial oxidation process
thermally under oxygen-free conditions in the temperature range, converting carbonaceous materials, such as biomass, coals, and
300–900 8C [28–31]. During thermal decomposition, cellulose, plastic materials, to gaseous products using gasification agents (air,
 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15 3

The mechanism of gasification can be divided into several steps,

as shown below, but each step cannot be separated from the others
clearly in terms of temperature and pressure.

Drying ! Pyrolysis ! Oxidation=Combustion ! Gasification

(1) Drying
The moisture in biomass is evaporated in this step and the
energy used for drying is not recovered. The moisture content
of biomass varies according to the biomass material gasified.
A separate drying step is required before the biomass is
introduced into the gasifier when the moisture content is too
high.

(2) Pyrolysis
Pyrolysis takes place over the temperature range, 150–400 8C,
decomposing the thermally weak constituents of biomass, such as
lignin, and producing char, gases and liquids.
Fig. 1. Van Krevelen diagram for raw materials and biochars produced at different
pyrolysis temperatures [37]. Biomass þ Heat ! Char þ Gases þ Liquids

Gaseous products formed during the pyrolysis step include H2,

CO, CO2, H2O, and small-molecular-mass hydrocarbons, such as
steam, oxygen, CO2 or gas mixture). In a gasification process, CH4. The liquid product is mostly mucous tar composed of small-
gaseous products (H2, CO, CO2, N2, etc.), liquid products (tar and oil), molecular-mass organic matter. The product composition depends
and solid products (char and ash) are formed. Because gasification is on the reaction temperature, pressure, and temperature rising rate.
aimed at producing gaseous products, the yield of biochar is only (3) Oxidation/combustion
approximately 5–10% of the raw biomass material mass, which is Oxidation and combustion of some gas species and char are
lower than that of fast pyrolysis (15–20%) [13,46]. Fig. 2 compares important sources of energy required for gasification reactions.
the product yields of slow pyrolysis, fast pyrolysis, and gasification. The gasification agent provided into the gasifier reacts with

Table 1
Characteristics of biochar produced using different feedstock materials under different pyrolysis conditions.

Raw biomass Temperature Heating Residence Yield of pH Ash Fixed C C/H C/O Ref
( 8C) rate ( 8C/min) time (h) biochar (%) contents (%) carbon (%)

Sewage sludge 450 5 – 53.0 80 50.7 – 36.0 1.15 7.50 [32]

450 60 – 47.0 8.2 58.0 – 29.9 1.38 6.13
650 5 – 47.0 9.0 60.3 – 30.8 2.13 9.78
650 60 – 45.0 8.6 62.2 – 29.2 2.02 9.49
850 5 – 45.0 11.7 62.3 – 33.0 3.93 25.89
850 60 – 38.0 11.9 66.3 – 29.6 3.52 26.31

Conocarpus wastes 200 – 4 51.33 7.37 4.53 – 64.19 16.21 2.42 [35]
400 – 4 31.86 9.67 5.27 – 76.83 27.15 5.43
600 – 4 27.22 12.21 8.56 – 82.93 64.79 12.66
800 – 4 23.19 12.38 8.64 – 84.97 137.05 17.45

Straw 200 – 1 84.95 5.34 11.90 33.63 45.57 7.90 1.19 [36]
200 – 2 81.23 5.91 12.29 34.47 46.33 8.24 1.26
200 – 4 78.24 6.11 12.78 34.72 46.52 8.46 1.29
400 – 1 37.30 10.82 25.74 40.41 57.07 17.14 3.46
400 – 2 35.91 10.86 27.54 42.66 57.59 17.89 3.67
400 – 4 36.65 10.78 28.40 42.76 57.92 19.05 3.77
600 – 1 32.48 10.93 32.33 49.87 59.17 38.42 5.36
600 – 2 32.48 10.96 33.57 54.34 59.09 41.03 5.54
600 – 4 30.89 10.99 34.31 55.37 60.80 45.71 5.73
Lignosulfonate 200 – 1 81.99 4.18 35.86 29.06 30.33 7.96 0.87
200 – 2 78.93 4.56 36.15 28.79 31.07 8.61 0.95
200 – 4 74.97 4.34 36.93 28.64 31.94 10.34 1.00
400 – 1 58.51 9.75 45.61 33.56 33.58 18.45 1.20
400 – 2 57.80 9.65 47.61 34.13 33.67 19.24 1.23
400 – 4 57.24 9.35 49.83 32.28 33.60 21.27 1.25
600 – 1 52.99 10.68 56.13 36.83 34.52 31.67 1.35
600 2 48.12 12.5 58.12 35.56 34.60 31.45 1.24
600 4 43.85 12.95 59.69 35.05 36.81 29.21 1.24

Bagasse 500 10 1 43.7 9.3 8.57 80.97 85.59 30.35 8.17 [45]
Cocopeat 62.9 10.3 15.90 67.25 84.44 29.32 7.24
Paddy straw 49.6 10.5 52.37 39.10 86.28 27.65 11.74
Palm kernel shell 53.5 6.9 6.86 80.85 87.85 30.19 10.79
Wood stem 42.6 9.5 2.28 83.47 89.31 34.75 12.17
Wood bark 50.3 9.6 12.84 68.66 84.84 27.11 8.32
4 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15

Fig. 2. Comparison of the product distributions of pyrolysis and gasification of biomass [13].

combustible species, producing CO, CO2 and H2O, and with the char closed reactor and the temperature is raised after a certain time for
produced during the pyrolysis step, producing CO2. stabilization. The pressure is also raised for water to maintain a
liquid state above 100 8C. Depending on the temperature under
C þ O2 ! CO2 saturated pressure, biochar [50,51], bio-oil [52], and gaseous
products, such as CO, CO2, CH4, and H2 [53], are the main products
of a hydrothermal process below 250 8C, at 250–400 8C, and above
H2 þ 1=2O2 ! H2 O 400 8C, respectively. Therefore, the hydrothermal process at each
temperature range is called hydrothermal carbonization (HTC),
(4) Gasification
hydrothermal liquefaction (HTL), and hydrothermal gasification
The char produced during the pyrolysis step is converted to CO,
(HTG), respectively. The char produced from the HTC process has a
CH4, and H2 through various gasification reactions. The gasifiers, in
higher C content than the char produced from dry processes [54],
which the gasification reactions take place, are divided into fixed
and reaction temperature, pressure, residence time, and water-
bed reactors, moving bed reactors, fluidized bed reactors, and
biomass ratio are reportedly the main parameters determining the
entrained bed reactors depending on the way of contact between
characteristics of the products [23,50,54]. The yield and character-
gasification agent and biomass. The parameters affecting the
istics of biochar produced under different conditions (HTC
gasification reactions include the reaction temperature, gasifica-
temperature, time, biomass/water ratio) are summarized in Table 2.
tion agent type, gasification agent–biomass ratio, and pressure.
Taba et al. [47] suggested that the temperature is the most
Other thermochemical technologies
important among the parameters directly affecting the gasification
reactions. They reported that increasing temperature enhanced the
Besides pyrolysis, gasification, and hydrothermal carbonization
production of H2, CO, and carbon, while reducing the contents of
discussed in the foregoing, flash carbonization [55–57] and
CO2, CH4, hydrocarbons and tar. Gomez-Barea et al. [48] also
torrefaction [58–60] are another thermochemical biomass con-
reported that the reduction of the gasification temperature in
version processes. In the flash carbonization, flash fire is ignited on
fluidized bed gasification resulted in reduced carbon conversion
a packed bed of biomass at a high pressure (1–2 MPa) to convert
and an increased tar concentration in gas.
biomass into gas-phase and solid-phase products. Temperature
Carbon conversion as well as the composition and heating value
and reaction time used generally for flash carbonization are 300–
of the product gas also varies according to the gasification agent
600 8C and 30 min, respectively. It has been reported that about
used in the gasification process. Tay et al. [49] examined the effects
40% of biomass is converted into solid-phase product (biochar) at
of gasification agents on the characteristics of the char using a
1 MPa [55] and that the carbonization time decreases with
reducing gasification agent (H2O) and oxidizing gasification agents
increasing pressure [56]. Compared to other processes for biochar
(CO2 and O2). The ratio of the small and large aromatic ring
production, however, reports on flash carbonization found in the
structure of the aromatic compounds composing the char was
lower and the contents of alkaline metals, such as Mg and Ca, in
char were higher when H2O was used. Table 2
Yield and characteristics of biochar produced under different HTC operation
conditions [54].
Hydrothermal carbonization (HTC)
Temperature Biomass/Water Time (h) Biochar HHV
(8C) ratio yield (%) (MJ/kg)
Dry processes such as pyrolysis and gasification can achieve
170 3.3 5.0 64.6 26.4
high product yields with low energy loss when the moisture 170 3.3 15.0 60.8 27.4
content of the biomass is low. On the other hand, most biomass 170 10.0 5.0 68.0 26.7
materials have high moisture contents and thus a separate drying 170 10.0 15.0 61.3 29.0
step is required to obtain high product yields and reduce the process 200 1.1 10.0 49.8 29.1
200 6.7 10.0 62.0 29.2
energy. Hydrothermal processes are anticipated to be able to
200 12.3 10.0 61.5 31.1
remedy this shortcoming of dry processes. Although the char 230 3.3 5.0 49.6 31.2
produced from a hydrothermal process is often called hydrochar to 230 3.3 15.0 27.6 32.9
distinguish it from the biochar produced from dry processes, the 230 10.0 5.0 62.2 28.3
general term biochar is used for hydrochar in this article. In a 230 10.0 15.0 35.4 34.8
250 6.7 10.0 29.4 34.6
hydrothermal process, biomass mixed with water is placed in a
 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15 5

literature are limited. Torrefaction is a process in which moisture, The rate of formation of pores by physical activation depends on
carbon dioxide, and oxygen contained in biomass are removed the ash content in the carbonized material and the status of the
under an inert condition at 200–300 8C and long polysaccharide pores.
chains are depolymerized to produce hydrophobic solid product C þ H2 O $ CðH2 OÞ (e)
with a low O/C ratio. This process is generally operated with a slow
heating rate and hence is referred to as mild pyrolysis. Several CðH2 OÞ ! CðOÞ þ H2 (f)
researchers [61,62] have reported that torrefaction temperature is
a more important parameter, than residence time, that influences The parentheses appearing in Eqs. (e) and (f) represent the
the biomass weight loss and the chemical and thermophysical attachment to the solid carbon surface. Water vapor attached to the
properties of the product. Torrefaction is studied usually to carbon surface is decomposed to emit hydrogen gas, whereas the
improve the thermochemical properties of biomass used for oxygen attached to the carbon surface reacts with carbon forming
combustion, gasification, and co-combustion with coal; the focus is CO. The hydrogen gas formed may remain in the vicinity of the
on the gas production. Table 3 compares the typical operation carbon surface and retard the progress of the reactions as follows:
conditions and product properties of various processes for biochar C þ H2 $ CðH2 Þ (g)
production.
Under this condition, the rate of activation by H2O can be
Modification of biochar represented by the following equation:

k1 P H2 O
The biochar produced from thermal treatment processes is RateC-H2 O ¼ 1=2
(h)
often activated to increase its specific surface area and pore 1 þ k2 PH2 þ k3 PH2 O
fraction or to form functional groups in it prior to use. The The reaction equation of carbon activation using CO2 is given as
activation methods are divided into physical activation and
follows:
chemical activation [63–66]. The pore fraction and pore size
distribution of the activated biochar vary according to the type and C þ CO2 $ 2CO (i)
quantity of biomass and activating gas.
As in the activation process using steam, the CO formed by the
reaction shown in Eqs. (j)–(l) may remain in the vicinity of the
Physical activation
carbon surface to retard further reactions.

Physical activation, also called gas activation, uses gas, such as C þ CO2 ! CðOÞ þ CO (j)
steam [67–73], CO2 [63,74–78], and ozone [79,80], to activate
biochar at temperatures above 700 8C. Physical activation can be CðOÞ ! CO (k)
divided into two steps. In the first step, the unstructured parts of
the carbonized material are decomposed selectively while fine C þ CO $ CðCOÞ (l)
pores enclosed in the carbon structure are opened, thereby The CO formed during CO2 activation removes the oxide
increasing the internal surface area. In the second step, crystalloid complex from the carbon surface and causes non-uniform
carbon comprising carbonized material or carbon containing fine gasification, retarding the C–CO2 reaction. Under the assumption
pores are depleted by the activation reactions, forming larger of uniform gasification, however, the rate of the C–CO2 reaction can
pores. The procedure of pore formation in the physical activation be expressed as
is closely related to the depletion of carbon by reactions. The
reaction mechanism of carbon activation using steam is as k1 PCO2
RateC-CO2 ¼ (m)
follows: 1 þ k2 P CO þ k3 PCO2

Cf þ H2 O ! CðOÞ þ H2 (a) The characteristics of physical activation depend on the biochar

activated, activating gas, and reaction conditions. Nabais et al. [73]
CðOÞ ! CO (b) activated the biochar obtained from the pyrolysis of coffee
endocarp using steam and CO2. They reported that the activation
2Cf þ H2 $ 2CðHÞ (c) rate is higher when steam was used, whereas the specific surface
area and pore size were higher when CO2 was used.
In a study of the carbonization of olive seed to produce activated
Cf þ 2H2 O ! CO2 þ 2H2 (d)
carbon, Reinoso et al. [81] used CO2 and steam as the activating gas
Cf: carbon-free active site. and compared the results. The activated carbon produced using
C(O): oxygen surface complex. pure steam had a smaller micropore volume than that activated
C(H): chemisorbed hydrogen. using CO2 (CO2-activated carbon). When diluted steam was used at

Table 3
Comparison of the typical operation conditions and product properties of various processes for biochar production [62].

Process Process Residence Solid product yield Carbon content Carbon yield
temperature (8C) time on a dry wood of the solid (masscarbon,
feedstock basis product (mass%) product/masscarbon,
(mass%) feedstock)

Slow pyrolysis 400 Minutes to days 30 95 0.58

Fast pyrolysis 500 1 s 12–26 74 0.2–0.26
Gasification 800 10–20 s 10 – –
HTC 180–250 1–12 h <66% <70% 0.88
Flash carbonization 300–600 <30 min 37 85 0.65
Torrefaction 290 10–60 min 61–84 51–55 0.67–0.85
6 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15

high temperatures, however, a microporosity similar to that of Although chemical activation has several drawbacks, such as
CO2-activated carbon developed. They also reported that activa- corrosion of the apparatus by chemicals, difficult recovery of
tion using steam was superior to CO2-activation in developing chemicals, and high cost of chemicals, its activation efficiency is
meso- and macro-porosity, leading to a higher pore size. higher than that of physical activation.
Zhang et al. [77] examined the effects of temperature and Basic chemicals, such as KOH [8,67,69,75,83–85], NaOH
duration of CO2-activation on the characteristics of the biochar [8,75,86], NH3 [76], K2CO3 [83,87], and ZnCl2 [83,84,88] as well
produced from the fast pyrolysis of oak wood waste, corn hulls, and as acids, such as H3PO4 [8,68,75,89], H2SO4 [89], and HCl [90], are
corn stover. All three types of chars showed an increasing specific representative chemical agents used for the chemical activation of
surface area and micropore volume with increasing activation char. Eqs. (n) and (o) present the reaction of carbon with alkali
temperature. The effects of the activation duration, however, were metal activating agents [83].
different depending on the raw biomass material. The specific
6NaOH þ 2C $ 2Na þ 3H2 þ 2Na2 CO3 (n)
surface area increased with increasing activation duration in the
case of oak wood waste-derived char, whereas the other two chars
6KOH þ 2C $ 2K þ 3H2 þ 2K2 CO3 (o)
showed a decreasing specific surface area with increasing
activation duration. Guo et al. [78] generated char by pyrolyzing The parameters through which the chemical activation of
coconut shell at 600 8C and activated it using CO2 in the biochar is influenced include the type and dose of activating
temperature range, 750–950 8C, to examine the effects of the agent and activation temperature. Ros et al. [75] used CO2 as the
activation temperature and duration and CO2 flow rate on the activating agent for physical activation, and H3PO4, NaOH, and
specific surface area, total pore volume, micropore volume, and KOH as the activating agents for chemical activation to examine
carbon fraction of char. When the activation temperature was the effects of the activating agents on the activation of sewage
lower than 900 8C, the specific surface area and micropore volume sludge-derived char. According to their study, H3PO4 did not
of the char increased with increasing activation temperature. increase the specific surface area and pore volume of sludge char
When the activation temperature was higher than 900 8C, and activation using CO2 also provided much smaller increase in
however, the specific surface area and micopore volume decreased specific surface area and pore volume than the alkali metal
with increasing activation temperature above 900 8C, whereas the activating agents. When NaOH or KOH was used, the specific
mesopore volume increased. The specific surface area, micropore surface area and pore volume increased with increasing dose of
volume, and mesopore volume increased with increasing activa- activating agent; the specific surface area and pore volume
tion duration up to 5 h. Activation for more than 5 h, however, increased from 689 m2/g to 1,224 m2/g and from 0.29 cm3/g to
caused the pores to collapse, leading to a decrease in specific 0.44 cm3/g, respectively, when the NaOH:char ratio was
surface area and pore volume. The char yield decreased with increased from 1:1 to 1:3. In contrast, an increase in the
increasing CO2 flow rate due to the burn-out of carbon. A high CO2 KOH:char ratio from 1:1 to 1:3 resulted in an increase in specific
flow rate below a certain threshold promoted the formation of surface area and pore volume from 853 m2/g to 1686 m2/g and
pores but an excessive flow above a certain threshold decreased from 0.34 cm3/g to 0.64 cm3/g, respectively. KOH was more
the specific surface area and pore volume, indicating that char effective in improving the characteristics of sludge char than
activation is affected by the process parameters. Table 4 compares NaOH.
the characteristics of biochars produced from various feedstock Tay et al. [83] investigated the effects of the activation
biomass materials using different physical activation methods. temperature (600–800 8C) and activating agents (K2CO3 and KOH)
on the generation of activated carbon using soybean oil cake. They
Chemical activation reported that K2CO3 led to a larger activated carbon yield, a higher
pore fraction, and lower ash and sulfur contents than KOH.
In chemical activation, char is doped with a chemical agent and Although both activating agents produced a larger increase in
micropores are formed by subsequent dehydration and oxidation. specific surface area at a higher activation temperatures, the

Table 4
Characteristics of biochar activated using physical activation methods.

Raw material Activation method BET surface Pore volume Ave. pore Ref.
area (m2/g) (cm3/g) diameter (nm)

Rice straw 40% H2O for 1 h at 700 8C 363 0.164 1.81 [67]
Sewage sludge 64 0.039 2.45

Almond shell Steam for 0.5 h at 850 8C 601 0.375 – [70]

Walnut shell 792 0.524 –
Almond tree pruning 1080 0.95 –
Olive stone 813 0.545 –

Coffee endocarp Carbonization 600 8C for 30 min, CO2 activation at 700 8C 820 0.4 – [73]
Carbonization 600 8C for 60 min, CO2 activation at 700 8C 554 0.28 –
Carbonization 600 8C for 120 min, CO2 activation at 700 8C 919 0.49 –
Carbonization 600 8C for 60 min, steam at 700 8C 630 0.35 –

Sewage sludge CO2 at 670 8C 12 0.01 – [75]

CO2 at 750 8C 62 0.03 –
CO2 at 800 8C 7 – –

Palm oil shell O3 for 30 min at 33 g/m3 at 23 8C 1 ND – [79]

Posidonia oceanica (L.) fibers Pyrolyzed 375 0.056 13.03 [82]

at 600 8C for 1 h, steam activation at 600 8C for 20 min
Pyrolyzed at 600 8C for 1 h, steam activation at 600 8C for 120 min 496 0.086 13.26
Pyrolyzed at 600 8C for 1 h, steam activation at 600 8C for 300 min 615 0.160 13.09
Pyrolyzed at 600 8C for 1 h, steam activation at 600 8C for 720 min 313 0.707 17.16
 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15 7

effects of the activation temperature was much larger for K2CO3 Application of biochar
than for KOH; the pore volume, microporosity, and mesoporosity
increased with increasing activation temperature when K2CO3 Adsorbent
was used, whereas when KOH was used, the microporosity
decreased with increasing activation temperature. The maximum Activated carbon generally has a high specific surface area and
specific surface area of the activated carbon (1352.86 m2/g) was pore fraction and contains oxygen functional groups and aromatic
achieved using K2CO3 at 800 8C, which was comparable to those of compounds on its surface [91,92]. These characteristics of
commercial activated carbon. activated carbon have been utilized to adsorb various kinds of
Angın et al. [88] activated the biochar produced from the pollutants [93–97]. As mentioned above, biochars with various
pyrolysis of safflower seed press cake using ZnCl2 as the activating specific surface areas, pore structures, and functional groups have
agent to examine the effects of the activation temperature and been developed and used for the adsorption of a variety of
impregnation ratio on the characteristics of the char and its pollutants by taking advantage of these physical and chemical
adsorption of methylene blue dye. In that study, the porosity, characteristics [98–101].
surface area, and adsorption capacity of the activated char The adsorption characteristics of biochar depend on the raw
increased with increasing activation temperature (600–900 8C) material used for the production of char. Xu et al. [102] generated
and impregnation ratio (1:1–4:1). biochar from 4 different biomass materials (canola straw char,
Zhang et al. [76] activated the pyrolysis char produced from peanut straw char, soybean straw char, and rice hull char) and
cotton stalk using two different activating agents, CO2 and NH3, applied them to the adsorption of methyl violet. The methyl violet
and compared the CO2 adsorption capacities of the two activated adsorption capacities of the chars were in the order of canola straw
chars. CO2 adsorption increased with increasing activation char, peanut straw char, soybean straw char, and rice hull char.
temperature at an adsorption temperature of 20 8C and the They suggested that the adsorption characteristics of biochar were
CO2-activated char adsorbed more CO2 than the NH3– or influenced by the quantity of negative charges that it contained. Xu
CO2 + NH3-activated chars. This was attributed to the ability of et al. [103] produced biochar from rice husk and dairy manure
CO2 to upgrade the micropore structure and form heteroatom under the same conditions and used them for the adsorption of Pb,
groups, such as C–O and C5 5O, particularly at high activation Cu, Zn, and Cd in water. The adsorption capacity of biochar was
temperatures, which are stronger active sites than nitrogen strongly dependent on the biomass material used for the
functional groups. When the adsorption temperature was 120 8C, production of biochar because the quantity of the mineral
however, the char activated at 500–700 8C using CO2 + NH3 component, such as CO32 and PO42, in the biochar varied
showed the highest adsorption capacity, which was attributed to according the raw biomass material.
the nitrogen functional groups formed by the reaction of the C- The adsorption capacity of biochar also depends on the process
matrix of biochar with ammonia. When the activation tempera- conditions under which the biochar is produced. The effects of the
ture was higher than 700 8C, the formation of nitrogen functional pyrolysis temperature on the adsorption characteristics of biochar
groups was suppressed, resulting in lower CO2 adsorption have been investigated by a number of researchers [104–106]. An
capacity. Table 5 compares the characteristics of biochars increase in pyrolysis temperature results in an increase in carbon
produced from various feedstock biomass materials using content, specific surface area, and porosity of biochar and a
different chemical activation methods. decrease in the number of oxygen functional groups on the char

Table 5
Characteristics of biochar activated using chemical activation methods.

Raw material Activation method BET surface Pore volume Ave. pore Ref.
area (m2/g) (cm3/g) diameter (nm)

Rice straw Char/KOH = 1.0 for 2 h at 60 8C, heat treatment at 700 8C 772.3 0.422 2.185 [67]
Sewage sludge 782.6 0.606 3.096

Sewage sludge 30% H3PO4 at 450 8C 6 – – [72]

50% H3PO4 at 450 8C 17 – –
char/NaOH = 1.0 60 8C and heat treatment at 700 8C 689 0.29 –

Soybean oil cake Mixed with K2CO3 for 24 h, heat treatment at 600 8C for 1 h 643.54 0.336 1.04 [83]
Mixed with K2CO3 for 24 h, heat treatment at 800 8C for 1 h 1352.86 0.680 1.01
Mixed with KOH for 24 h, heat treatment at 600 8C for 1 h 600.05 0.299 0.99
Mixed with KOH for 24 h, heat treatment at 800 8C for 1 h 618.54 0.291 0.94

Safflower seed press cake Pyrolyzed at 500 8C (50 8C/min), ZnCl2/biochar = 4, heat treatment 249.3 0.151 2.42 [88]
at 600 8C for 1h
Pyrolyzed at 500 8C (50 8C/min), ZnCl2/biochar = 4, heat treatment 491.9 0.249 2.02
at 700 8C for 1h
Pyrolyzed at 500 8C (50 8C/min), ZnCl2/biochar = 4, heat treatment 772.0 0.358 1.85
at 800 8C for 1h
Pyrolyzed at 500 8C (50 8C/min), ZnCl2/biochar = 4, heat treatment 801.5 0.393 1.96
at 900 8C for 1h
Pyrolyzed at 500 8C (50 8C/min), ZnCl2/biochar = 3, heat treatment 719.3 0.371 2.23
at 900 8C for 1h
Pyrolyzed at 500 8C (50 8C/min), ZnCl2/biochar = 2, heat treatment 703.0 0.344 1.94
at 900 8C for 1h
Pyrolyzed at 500 8C (50 8C/min), ZnCl2/biochar = 1, heat treatment 619.8 0.330 2.13
at 900 8C for 1h

Organic sewage sludge 3 M H2SO4, 650 8C for 60 min 408 0.523 5.21 [89]
3 M H3PO4, 650 8C for 60 min 289 0.436 2.65
5 M ZnCl2, 650 8C for 60 min 555 0.752 2.26
8 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15

surface. Ahmad et al. [104] reported that an increase in pyrolysis

temperature led to an increase in specific surface area, micro-
porosity, and C content, leading to an increase in TCE removal
efficiency. Zhou et al. [105] also reported that the benzene and
nitrobenzene adsorption capacity of pine char increased with
increasing pyrolysis temperature. On the other hand, Ding et al.
[106] reported a decrease in Pb adsorption with an increase in
pyrolysis temperature. Sun et al. [107] produced biochar by
pyrolyzing grass and wood at 200–600 8C and applied them to the
adsorption of fluridone and norflurazon. In their experiments, the
adsorption capacity of the biochars increased with increasing
pyrolysis temperature below 400 8C; further increases in pyrolysis
temperature above 400 8C rather decreased the adsorption
capacity. This was attributed to the polarity of the pollutants
adsorbed; polar compounds, such as fluridone and norflurazon, are
adsorbed on H-bonding between the adsorbed substances or on O-
groups of biochar, whereas non-polar compounds, such as TCE are
adsorbed on the hydrophobic sites of the biochar surface.
The solution pH is another important parameter affecting the
adsorption process. Tan et al. [108] used the biochar produced from Fig. 3. Comparison of the Cu removal capacities of seaweed biochars [111].
municipal sewage sludge for the adsorption of Cd. The Cd
adsorption capacity was 20 mg/g when the solution pH was 2 or
lower, whereas it was 40 mg/g when the pH was 3 or higher. Xu Table 6
Physical characteristics of seaweed chars [111].
et al. [102] also reported that the methyl violet adsorption capacity
of the biochars produced from crop residue increased to a large BET surface Pore volume Ave. pore
extent when the solution pH was increased from 7.7 to 8.7. They area (m2/g) (cm3/g) diameter (nm)
suggested that an increase in pH enhanced the dissociation of U ND ND ND
phenolic–OH groups on the biochar surface, which in turn UW 57.9 0.02 1.25
increased the electrostatic attraction between adsorbent and UK 1287.0 0.64 2.00

adsorbate.
(1) Adsorbent for water pollutants
Heavy metals are important toxic water pollutants with adverse of U was not even measurable (see Fig. 3 and Table 6). The authors
effects on the metabolism of humans, animals and plants [109]. A measured the quantity of ion-exchangeable cations in each char
range of biochars have been applied to the removal of heavy metals and concluded that copper removal by biochar is dominated by ion
[71,103,110–116]. Xu et al. [103] used the chars produced from exchange rather than by adsorption. Despite its large specific
rice husk and feces to remove Pb, Cu, Zn, and Cd from aqueous surface area, the KOH-activated char (UK) showed the lowest
solutions. Feces-char had higher metal removal efficiencies than copper removal efficiency because it lost most of its ion-
rice husk-char for all the 4 heavy metals examined. When feces- exchangeable cations during the activation process.
char was used, heavy metals were not only adsorbed on the ionized Kim et al. [119] produced biochar from the pyrolysis of the
hydroxyl-O groups but also precipitated due to the reaction with green macroalga, Enteromorpha compressa. Steam activation
CO32 or PO43, whereas the adsorption on ionized phenolic O increased both the specific surface area and cation exchange
groups is the only heavy metal removal mechanism of rice husk- capacity (CEC), resulting in a huge increase in the copper removal
char. Their study indicated that oxygen-functional groups and efficiency of the char, whereas KOH activation, despite increasing
mineral compounds, such as CO32 and PO43, play important roles the specific surface area and pore fraction greatly, reduced the
in the sorption of heavy metals on biochar. Kim et al. [110] quantity of CEC and hence the copper removal efficiency. Ion
produced biochars from the slow pyrolysis of giant Miscanthus exchange was also shown to be the most important mechanism for
over the temperature range of 300–600 8C with an interval of copper removal in their study. Shim et al. [73] produced giant
100 8C. They reported that a higher pyrolysis temperature resulted Miscanthus char (BC) from slow pyrolysis at 500 8C and activated it
in a higher aromatic structure and a smaller quantity of polar with steam (ABC) to increase its specific surface area from 181 m2/
functional groups in biochar. In particular, when the pyrolysis g to 322 m2/g. On the other hand, activation did not improve the
temperature was higher than 500 8C, the pH and specific surface copper removal by fast sorption significantly and rather reduced
area of the biochar increased considerably and the Cd sorption the copper removal by slow sorption. They concluded that the
capacity also increased. Based on the results obtained, the authors specific surface area was not an important factor for copper ion
suggested that the main mechanisms for the removal of aqueous sorption. They also found that ABC exhibited high toxicity to
Cd were sorption due to large specific surface area of char and Daphnia magna. Therefore, they concluded that BC is a more
precipitation due to the high pH. Cho et al. [111] and Kim et al. adequate sorbent for toxic pollutant removal than ABC. Samsuri
[117] generated chars from marine macroalgae and applied them et al. [112] produced biochar from oil palm empty fruit bunches
to the removal of aqueous copper. They reported different results (EFB) and compared it with commercial rice husk char (RHB) in
from the above-mentioned previous studies. Cho et al. [111] terms of their adsorption capacities for Zn, Cu, and Pb. The two
pyrolyzed Undaria pinnatifida at 500 8C to produce biochar (U) and chars had similar carbon contents but EFB had higher O, H, S, N and
activated the char physically with 40 wt.% steam (UW) or K contents than RHB. Despite its lower specific surface area, EFB
chemically using a 1.0 M KOH solution (UK). UW exhibited the exhibited higher Zn, Cu and Pb adsorption efficiencies than RHB.
largest copper adsorption capacity, followed by U and UK, which The authors attributed the higher metal removal efficiency of EFB
was not in agreement with the order of the specific surface area of to its large content of oxygen-containing functional groups, high
the chars; the specific surface area of UK was quite large O/C ratio, and high polarity index [(O + N)/C]. They concluded that
(1287.0 m2/g), whereas that of UW was only 57.9 m2/g and that the chemical properties of biochar were more important factors in
 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15 9

Table 7
Maximum Cu adsorption quantities of pyrolytic biochars [117].

Pyrolytic biochar source Maximum Cu

adsorption
quantity (mg/g)

Hardwood 7.44
Switch grass 31.0
Corn straw 12.52
Amino-modified biochar 17.01
Spartina alterniflora 48.49
Peanut straw 88.9
Soybean straw 50.2
Composted swine manure 20.11
Sewage sludge 10.56
Commercial activated carbon 11.4
Commercial powdered activated carbon 1.80
Undaria pinnatifida 125.8
Enteromorpha compressa 75.1
Fig. 4. Adsorption of formaldehyde over chars treated using various methods [124].

the adsorption of heavy metals than specific surface area. Table 7

lists the maximum Cu adsorption quantities of pyrolytic biochars CO2 is the most important global warming gas, even though its
found in the literature. direct health impact is not large. Adsorption is one of the most
Organic matter is another important target water pollutants to widely used methods to capture and store CO2. The adsorbents
remove using biochar [118–122]. Many studies applied biochar to used widely to capture CO2 include carbon materials (e.g.
the adsorption of tetracycline (TC), which is used as antibiotic for activated-carbon, carbon molecular sieve, and carbon nanotube),
animals and plants. Zhu et al. [118] activated char thermally over zeolites, and MOFs (metal-organic frameworks) [125]. Extensive
the temperature range of 300–700 8C by injecting N2 gas to a studies have been conducted to develop new carbon adsorbents
hydrochar produced from 300 8C HTC. They reported that the pH, from biochar. Creamer et al. [126] produced biochar from the
ash content, specific surface area, pore volume, and aromaticity pyrolysis of sugarcane bagasse (BG) and hickory wood (HW) at 300,
increased with increasing activation temperature, whereas the 450 and 600 8C and used them for the adsorption of CO2 at 25 8C
polarity decreased. A high activation temperature led to a large TC and 75 8C. The biochar produced at high temperatures showed a
adsorption capacity. The authors concluded that the organic very large CO2 adsorption capacity (73.55 mg/g at 25 8C), which
matter adsorption on biochar is correlated closely with aromaticity was attributed to the physisorption of CO2 of which the efficiency
index (H/C), polarity index (O/C and (O + N)/C), and porosity is proportional to the specific surface area of the char. When the
(specific surface area, total pore volume, and micropore volume). char specific surface area was sufficiently large, however, the
Liu et al. [119] activated crude bio-char with acid and alkali and quantity of nitrogenous groups played a more important role in the
used it for the adsorption of tetracycline. The alkali-activated char adsorption of CO2 on the biochar surface. Huang et al. [127]
had a larger specific surface area and exerted a larger adsorption pyrolyzed rice straw using microwaves to produce biochar and
capacity (58.8 mg/g) than acid-activated char. They suggested that used it to adsorb CO2. They reported that the specific surface area is
the specific surface area and O-functional groups are important the most important characteristic of biochar in CO2 adsorption. In
factors affecting the adsorption of TC, whereas the effect of solution general, the CO2 adsorption capacity increased with increasing
pH on TC adsorption was not large. Sun et al. [120] produced pyrolysis temperature. Compared to the biochar produced using a
biochar from eucalyptus saw dust and activated it using citric conventional pyrolysis process at the same temperature, the
acids, tartaric acids, and acetic acids. When the activated chars biochar produced using microwave pyrolysis showed a higher CO2
were used for the removal of aqueous methylene blue (MB), the adsorption capacity when the pyrolysis temperature was 400 8C or
citric acid-activated char (BC-CA) showed the largest adsorption lower, demonstrating the merits of microwave pyrolysis in terms
capacity despite having the lowest specific surface area. Fourier of cost and time. Creamer et al. [128] pyrolyzed cottonwood at
transform infrared spectroscopy showed that BC-CA contained the 600 8C after pretreating it with various concentrations of metal
largest quantity of carboxyl groups (COOH), indicating that the ions (Al, Mg and Fe) to generate metal oxyhydroxide–biochar
quantity of oxygen functional groups is another important factor composites. The modified biochar showed a higher CO2 adsorption
for the adsorption of organic pollutants. capacity than the unmodified biochar. The Fe2O3–biochar compo-
(2) Adsorbent for air pollutants sites showed the largest specific surface area but the AlOOH–
Air pollutants have adverse acute or chronic impacts on human biochar composite showed the largest CO2 adsorption capacity,
health depending on their type, concentration, and exposure indicating that the CO2 adsorption capacity is affected not only by
duration [123]. Lee et al. [124] activated sludge char using 20% the specific surface area, but also by metal oxyhydroxides. The
steam gas, KOH and ammonia, and used it for the adsorption of an maximum adsorption capacity was 71 mg/g by AlOOH–biochar at
indoor air pollutant, formaldehyde, at low concentrations. As 25 8C, which was similar to those of commercial adsorbents. The
shown in Fig. 4, the biochar showed a higher adsorption capacity desorption efficiency at 120 8C was 90–99%, showing that the
than the commercial activated carbon even before activation, biochar-based composites are very efficient and economical CO2
which was attributed to the basicity of the char surface due to the capturing adsorbents.
abundant metal species. KOH- and ammonia-activation increased
the formaldehyde adsorption capacity even further by increasing Catalysts
the number of oxygen and nitrogen functional groups as well as the
specific surface area. They concluded that the basicity due to metal (1) Catalysts for syngas cleaning
species and oxygen and nitrogen functional groups are important As mentioned above, mucous tar produced during the pyrolysis
factors that improve the formaldehyde adsorption capacity of the step of the gasification processes is composed of organic
biochar. components of the raw material. Being a mixture including 1–5
10 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15

ring aromatic organic compounds, oxygenated hydrocarbons, and tar. They reported that the type of char had little effects on tar
polycyclic aromatic hydrocarbons (PAHs), tar exhibits toxicity due reduction, whereas the tar reduction efficiency decreased with
to aromatic compounds, such as PAHs and benzene, and produces increasing char particle size. They attributed this to a reduction of
aerosols and soot that may block the filter, reactor and line of the specific surface area by the increase in particle size. On the
gasification processes [129]. Therefore, the removal of tar is other hand, the effects of char particle size decreased when the
important in gasification. A range of physical and chemical tar reaction temperature was increased from 700 8C to 1000 8C.
reduction methods are summarized in Table 8 [130–134]. Qian et al. [137] examined the effects of various factors on tar
Catalytic reforming is a method to convert tar catalytically to H2 cracking using the char produced from the gasification of red cedar
and CO. In a review paper by Han et al. [135] the catalysts used for as a tar cracking catalyst. They reported that the char-based
tar cracking were divided into Ni-based catalysts, alkali metal catalyst was quite effective in removing lignin tar. The reaction
catalysts, dolomite catalysts, and novel metal catalysts. In recent temperature, injection of moisture, and pressure influenced tar
studies, char has also been used as a support material for tar- removal. The removal efficiencies of most tar components except
removing catalysts [14]. for naphthalene increased with increasing reaction temperature.
Abu El-Rub et al. [40] compared biomass char with other The high pressure also enhanced the catalytic conversion of tar.
catalysts (calcined dolomite, olivine, fluid catalytic cracking (FCC) Excess moisture, however, was reported to reduce the tar removal
catalyst, biomass ash, and commercial nickel catalyst) with respect efficiency.
to their tar removal capability. Among the tar components, the (2) Catalyst for biodiesel production
inlet and outlet concentrations of phenol and naphthalene were Biodiesel is a mixture of methyl ester compounds produced
measured to determine the tar conversion. The results are from the reaction (transesterification or esterification) of alcohol
summarized in Table 9. Most phenol (98%) was converted at with vegetable oil or animal fat composed of triglycerides and free
900 8C even without a catalyst (with only thermal cracking), fatty acids. As shown in Fig. 5, transesterification is a reaction, in
whereas naphthalene was converted only when the catalysts were which the main component of fat and oil, triglyceride, reacts with
used. With the exception of a commercialized nickel catalyst, alcohol over a catalyst producing fatty acid methyl ester and
biomass char showed the highest naphthalene conversion. The glycerol [138,139].
authors argued that gasification-derived biomass char is a good In esterification, free fatty acids (FFAs) and alcohol react to
candidate catalyst for tar reduction because char can be produced produce biodiesel and water (Fig. 6).
continuously from gasification and the by-products, CO2 and Although solid-phase acid catalysts have been used widely as
steam, can be used to activate the char. the catalyst for biodiesel production, biochar has recently been
Chen et al. [136] used rice straw char, corn straw char, and fir applied to biodiesel production.
sawdust char particles with a size range of 100–150 mm to reduce Dehkhoda et al. [140] sulfonated hardwood char using
concentrated sulfuric acid and fuming sulfuric acid, activated it
chemically with 10 M KOH to increase the specific surface area, and
Table 8 applied it to the transesterification of vegetable oil and the
Reduction of tars in various tar reduction systems.
esterification of FFA. Concentrated sulfonated biochar exhibited
Method Temperature Tar high activity only for the esterification of free fatty acid, whereas
(8C) reduction (%) fuming sulfonated char showed a higher transesterification
Physical Sand bed filter 10–20 50–97 activity than concentrated sulfonated biochar. The authors
Fabric filter 130 0–50 reported that a large specific surface area and high acid density
Wash tower 50–60 10–25 led to a high biodiesel production yield, whereas high transester-
Oil scrubber [132,133] 27–28 50–90
ification activity was accompanied by a high specific surface area
Water scrubber [134] 28–28.5 20–40
Wet electrostatic 40–50 0–60 when the acid density was similar. They also reported that the FFA
precipitator conversion increased with increasing alcohol to oil ratio, reaction
Thermal cracking [40,133] 800 78 duration, and catalyst dose. Kastner et al. [141] pyrolyzed
800–900 >98
pelletized peanut hulls, pine logging residues, and wood chips
Chemical Catalytic tar cracker 900 >95, >98 at 400–500 8C to produce biochar. They sulfonated those biochars
Pulse corona discharge 200 8–44 and commercial activated carbon using H2SO4 at 100, 150, and
[135]
200 8C for 12 h and using SO3 gas at 23 8C. They applied the
sulfonated carbon to the esterification of vegetable oil and animal
fat (5–15 wt.% FFA) with methanol. The esterification of fatty acids
for 30–60 min resulted in 90–100% conversion at 55–60 8C. When
Table 9 the catalysts were reused, the char sulfonated at 100 8C exhibited
Thermal and catalytic conversion of phenol and naphthalene [40]. the highest reaction rate and the lowest conversion reduction,
Catalyst T (8C) Conversion (%)

Phenol Naphthalene

Empty reactor 700 6.0

(thermal cracking) 800 98.2
900 98.4 2
Olivine 700 34.5
900 100 55.0
Biomass char 700 42.7
900 100 94.4 Fig. 5. Production of biodiesel by transesterification reaction.
FCC 700 81.6
900 100 60.3
Dolomite 700 90.0
900 100 61.0
Nickel 700 91.0
900 100 100
Fig. 6. Production of biodiesel by esterification reaction.
 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15 11

demonstrating its potential as an acid catalyst for biodiesel Table 10

pH and base cation content of biochar [144].
production.
(3) Catalyst for air pollution control Source of biochar pH Base cation content (cmol/kg)
Several studies have investigated the application of activated Ca2+ Mg2+ K+ Na+
biochars as low-temperature SCR (selective catalytic reduction)
Rice 7.69 32.8 11.4 92.2 5
catalysts [67,68,90,142]. Cha et al. [67] pyrolyzed rice straw and Corn 9.24 26.5 10.5 188.4 2.6
sewage sludge, whereas Jo et al. [142] pyrolyzed sewage sludge, to Peanut 8.88 90.8 46.9 21.3 1.5
generate biochar and use them as a low-temperature SCR catalyst. Faba bean 10.33 35.7 8.7 111.1 64.4
Ammonia was used as a reducing agent. Each char was activated Mung bean 10.35 74.9 12.3 178.2 1.5
physically or chemically and their characteristics and NOx removal
efficiencies were examined. The chemically activated char
exhibited a higher NOx removal efficiency than the physically ammonia conversion at low ozone concentrations, whereas the
activated char, indicating that the chemical properties, such as steam-activated char showed a higher ammonia conversion when
oxygen functional groups and NH3 adsorption sites, were more the ozone concentration was higher than 500 ppm. Ammonia
important factors for NOx removal than the physical properties, conversion by char was very low at low air humidity, whereas it
such as specific surface area and pore size. Cha et al. also reported increased considerably at high humidity. In addition, the steam-
that the impregnation of 3 wt.% manganese on chemically activated char produced little NO2 by-product, which was another
activated char enhanced its NOx removal activity even further. merit.
Ko et al. [90] activated municipal waste char and RDF (refuse
derived fuel) char physically using steam or chemically using HCl Soil amendment
and KOH, and used them as low-temperature SCR catalysts. The
NOx removal efficiency of KOH-activated char was higher than Application of biochar to soil can not only isolate carbon in soil,
those of the other chars, suggesting that the increased oxygen but also improve the soil quality by neutralizing acidic soil,
functional groups, specific surface area, and pore size increased the enhancing the CEC of soil, and increasing the activity of soil
quantity of active sites on the char surface, leading to improved microorganisms. As shown in Table 10, biochars are basic.
NH3 adsorption ability. The impregnation of MnOx on the KOH- Therefore, the use of biochar as a soil amendment can neutralize
activated catalyst resulted in an even higher adsorption efficiency acidic soils [143,144].
than the commercial carbon SCR catalyst, demonstrating the high In addition, biochar has phenolic, carboxyl and hydroxyl
feasibility of municipal waste char and RDF char as de-NOx functional groups, which react with H+ ions in the soil to reduce
catalysts (Fig. 7). Shen et al. [68] impregnated a Mn-CeOx base the H+ ion concentration and increase the soil pH. Silicates,
catalyst on modified cotton biochar and activated carbon and used carbonates and bicarbonates in biochar can also combine with H+,
them for the low-temperature SCR reaction. The modified cotton controlling the soil pH [23]. Yuan et al. [144] applied 10 g/kg of
biochar exhibited a higher potential as a low-temperature SCR 9 different kinds of biochars to soil and found that in 60 days, the
catalyst support material than the commercial activated carbon. In soil pH increased by 0.59–1.05 depending on the biochar applied.
particular, the biochar activated physically and chemically and Biomass materials, which are used as raw materials to produce
impregnated with Mn-CeOx had the highest specific surface area, biochar, contain many basic cations. As shown in Table 11, the
surface acidity, and Mn4+/Mn3+ ratio. The Mn-CeOx dispersion was cations in the biomass reside in biochar after the biochar
good and there were large quantities of adsorbed oxygen and production processes [145,146]. When biochar is applied to soil,
oxygen functional groups, which promoted the oxidation of NO to the basic cations contained in the biochar are discharged into the
NO2 and hence improved the SCR activity. soil, replacing Al and H+ and enhancing the CEC of soil. The CEC of
Kastner et al. [69] used the pyrolysis char produced from pellet- the soil increases with increasing charge density in soil (per unit
type peanut hull and wood fly ash as the catalyst for the catalytic surface area) and with increasing soil surface area that can adsorb
ozonation of gas-phase ammonia. Wood fly ash showed the highest cations [147]. In general, the CEC increases with increasing pH. Lee

Fig. 7. NOx conversion as a function of reaction temperature over municipal solid waste char (YC) and RDF char (RC). W: H2O activation, H: HCl activation, K: KOH activation
[90].
12 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15

Table 11
Concentrations of metal elements in biochar [143,144] (unit: ppm).

Poplar wood Poplar wood char-750 Wheat straw char-475 Poultry litter char-475 Sawdust char-475 Flax straw char-475

Ca 5200 10,900 42,293 161,395 11,423 41,479

K 1200 7200 33,899 67,798 3928 13,384
Na <50 64 264 14,624 238 2027
Mg 340 1200 2418 19,255 1419 5846

et al. [148] reported that the CEC of char increased when the pH effects of reducing the global warming gas emissions using biochar
was increased from 5.0 to 8.5. In particular, CEC was negative when as a soil amendment have been reported [150–152]. Spokas et al.
the pH was low, which was attributed to the discharge of bound [151] reported that the amendment of soil using biochar
cations. Liang et al. [147] reported a 1.9-fold increase in CEC by the suppressed the decomposition activity of microorganisms, result-
injection of black carbon in soil. ing in reduced CO2 emissions by 2–60%, depending on the area of
Biochar contains high concentrations of N, P, Ca, and K, which biochar application, reduced N2O emission by 60%, and reduced
may provide soil with nutrients directly or may be used as CH4 oxidation. They also reported that the application of 5% (w/w)
nutrients of microorganisms. When biochar is used as a soil of biochar to soil enhanced the sorption of atrazine and acetochlor
amendment, the pore fraction of soil is increased by biochar. Each and reduced the dissipation rate of herbicides. Overall, the authors
pore provides the space in which the microorganisms can grow and concluded that the application of biochar to soil is an effective
increases the quantity of air and moisture and the residence time of carbon isolation strategy and an effective way of reducing global
nutrients, resulting in the enhanced activity of microorganisms warming gas emissions if the continuous reduction of N2O is
and increased growth rate of plants in that soil. possible. Yanai et al. [150] also reported up to 89% reductions in
The use of biochar as a soil amendment can also reduce the N2O emissions by adding 10% biochar to re-wetted soil.
global warming gas emissions. Although the direct combustion of
biomass emits carbon in biomass to the atmosphere as CO2, the Other applications
pyrolysis or gasification of biomass converts C to biochar, which
can be stored in soil (Fig. 8). The isolation of biochar in soil can In addition to the fields discussed in the previous sections,
reduce the carbon emissions because biochar is barely decom- biochar has been used in other applications. A number of different
posed by microorganisms or through mineralization. types of fuel cells exist, depending on the kinds of fuels and
Lehmann et al. [24] reported that the conversion of biomass electrolytes used and operation temperature, even though their
carbon to biochar can isolate 50% of the initial carbon quantity in principles are the same. Among others, the fuel cells that use the
soil. This is much higher than those obtained from combustion (3%) largest quantity of carbon materials are the phosphoric acid fuel
or from biological decomposition (10–20% in 5–10 years). The cell and direct carbon fuel cell (DCFC) [153]. Ahn et al. [154]

Fig. 8. The global carbon cycle of net primary productivity and release to the atmosphere from soil [149].
 J.S. Cha et al. / Journal of Industrial and Engineering Chemistry 40 (2016) 1–15 13

examined the effects of the type of fuel on the cell performance and applications. According to previous studies, the characteristics of
the characteristics of electrochemical reactions between the fuel biochar are influenced by the raw biomass material and the
and electrolyte using wood biomass char as the fuel for DCFC. The process used to produce it as well as the process parameters.
maximum power density obtained using biomass char was 60–70% Biochar has been utilized in a variety of applications, such as
of that obtained using coal, which was attributed to the low carbon adsorbents, catalysts, and soil amendments, depending on their
content and high ash content of biomass char. Nevertheless, they characteristics. Modification of char, e.g. by increasing the specific
argued that biomass char has potential as a DCFC fuel because the surface area and pore fraction or by forming functional groups,
porous characteristics of biomass char and the functional groups depending on the application purpose, is important for increasing
on the char surface promote the electrochemical reactions in the the reaction activity of biochar, even though mineral components
low current density region. in biochar itself are sometimes used. Biochars are being used in an
Supercapacitors are used for energy storage for portable increasing number of fields. The establishment of a continuous
electrical devices and hybrid vehicles. Supercapacitors have been supply system will be needed to promote the application of biochar
reported to have higher power, higher energy density, higher to higher value-added areas.
chemical stability, and longer life cycle than secondary batteries
[155]. Various carbon materials have recently been used as the Acknowledgement
electrodes of supercapacitors because carbon materials exert high
electric conductivity and a large pseudo capacitance. A number of This work was supported by the National Research Foundation
studies reported biochar as an electrode in supercapacitors of Korea (NRF) grant funded by the Korea Government (MSIP) (No.
[156,157]. Those studies reported that the capacitive performance 2015R1A2A2A11001193).
of biochar electrode was influenced by surface functional groups,
electric conductivity, and pore structure and distribution as well as
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