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Environmental Chemistry Letters (2021) 19:2237–2259

https://doi.org/10.1007/s10311-020-01165-9

REVIEW

Biochar production, activation and adsorptive applications: a review


Biswa R. Patra1 · Alivia Mukherjee1 · Sonil Nanda1 · Ajay K. Dalai1

Received: 30 November 2020 / Accepted: 17 December 2020 / Published online: 17 February 2021
© The Author(s), under exclusive licence to Springer Nature Switzerland AG part of Springer Nature 2021

Abstract
Rising global population and urbanization are major causes of waste generation, energy demand and carbon emissions. The
atmospheric ­CO2 concentration has increased of 44% from 284 ppm in 1850 to 409 ppm in 2018. In 2017, the world energy
consumption was 582 quadrillion British thermal units (qBtu), including 495 qBtu of fossil fuels and 87 qBtu of renewable
and nuclear energy sources. Therefore, there is a need for new energies and methods of carbon sequestration, for instance by
recycling biomass into biochar. Here, we review the thermochemical valorization of waste biomass by pyrolysis, gasification,
torrefaction and carbonization to produce biochar with promising and environmental applications. We detail parameters that
control biochar yields, quality and composition. Physical and chemical routes of biochar activation are also described. We
focus on the utilization of biochar as soil amendment and for the adsorption of pollutants from wastewater. We conclude by
a discussion on the techno-economic and lifecycle assessment of biochar production technologies.

Keywords Biochar · Activated carbon · Adsorption · Soil amendment · Heavy metals · Pharmaceuticals · Dyes

Abbreviations Millimoles per kilogram Mmol/kg


Acetylene C2H2 Minutes Min
Ammonia NH3 Moles per kilogram Mol/kg
Carbon dioxide CO2 Nitrous oxide N2O
Carbon monoxide CO Oxygen O2
Cubic centimeter per min Cm3/min Phosphoric acid H3PO4
Degree Celsius °C Potassium carbonate K2CO3
Ethane C2H6 Potassium hydroxide KOH
Ethylene C2H4 Potential of hydrogen PH
Gram per hour G/h Second S
Gram per minute G/min Sodium hydroxide NaOH
Gram G Zinc chloride ZnCl2
Hour H
Hydrogen H2
Kilogram Kg Introduction
Mega joules per kilogram MJ/kg
Methane CH4 With currently 7.8 billion people, the global population
Milligram per gram Mg/g has undergone tremendous growth over the last few dec-
Milligram per liter Mg/L ades (Worldometer 2020). The rapid population growth has
Millilitre per minute ML/min driven the need for food, energy and materials. Energy is the
Millimoles per gram Mmol/g base for economic development and essential for power gen-
eration, agriculture, industry and transportation. Today, most
of the world’s energy demand is fulfilled by fossil fuels.
* Ajay K. Dalai Figure 1 reveals the trend of global energy consumption as
ajay.dalai@usask.ca fossil fuels, e.g., coal, natural gas, petroleum and other liq-
1
Department of Chemical and Biological Engineering,
uid fossil fuels, renewables and nuclear sources. The global
University of Saskatchewan, Saskatoon, Saskatchewan, energy consumption was nearly 582 quadrillion British
Canada

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2238 Environmental Chemistry Letters (2021) 19:2237–2259

Fig. 1  Global trend of primary


energy consumption. Note the
increase in total energy usage
over the years including that of
petroleum and other liquid fossil
fuels, coal, natural gas, renewa-
bles and nuclear sources. Data
source: U.S. Energy Information
Administration (2020a)

thermal units in 2017 compared to 292 quadrillion British climate change (Nanda et al. 2016d). According to the U.S.
thermal units in 1980 (U.S. Energy Information Adminis- Energy Information Administration (2020b), the global total
tration 2020a). From the worldwide total energy consump- ­CO2 emissions from fossil fuel was 36,061 million metric
tion of 582 quadrillion British thermal units in 2017, coal, tonnes in 2017 compared to 18,746 million metric tonnes
natural gas, petroleum and other fossil fuels contributed 495 in 1980 (Fig. 2). From the total C ­ O2 emissions of 36,061
quadrillion British thermal units, whereas renewable and million metric tonnes in 2017, coal and coke, natural gas as
nuclear energy sources attributed to merely 87 quadrillion well as petroleum and other liquid fossil fuels attributed to
British thermal units. 15,657, 7268 and 13,136 million metric tonnes, respectively.
Rapid industrialization, urbanization and automation have Such an alarming amplification in ­CO2 emissions from fos-
led to an unprecedented increase in fossil fuel consumption, sil fuels necessitates the use of carbon–neutral alternative
thereby deteriorating the environment due to pollution. For energy sources.
the past few decades, there is a steep increase in the level The atmospheric C ­ O2 concentration has increased from
of greenhouse gases such as carbon dioxide (­ CO2), fluori- 284 parts per million in 1850 to 409 parts per million in
nated gases, nitrous oxide (­ N2O) and methane (­ CH4) among 2018 indicating a 44% rise within 138 years (Fig. 3) (Our
which ­CO2 plays an immense role in global warming and World in Data 2020a). According to the Global Monitoring

Fig. 2  Global trend of C


­ O2
emissions from fossil fuels.
Note the increase in the ­CO2
emissions from coal, coke,
natural gas, petroleum and other
liquid fuels over the years. Data
source: U.S. Energy Information
Administration (2020b)

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Fig. 3  Global trend of atmospheric C


­ O2 concentration. Note the dra- Fig. 4  Global average median temperature anomaly. Note the gradual
matic increase in ­CO2 concentration over the years. According to Our increase in the global average temperature with years. According to
World in Data (2020a), the ­CO2 emissions are calculated and inte- Our World in Data (2020b), temperature anomalies are calculated
grated from multiple sources such as the Carbon Dioxide Information based on the measurements made by the Met Office Hadley Centre
Analysis Center in the U.S. and Global Carbon Project in Australia. for Climate Science and Services located in the U.K. Data source:
Data source: Our World in Data (2020a) Our World in Data (2020b)

Laboratory in Colorado, the atmospheric C ­ O2 emissions


are reported as a dry air mole fraction without water vapor
(National Oceanic and Atmospheric Administration 2020b).
It is defined as the number of C
­ O2 molecules divided by the
number of all molecules in the air (along with C ­ O2) after
the removal of water vapor. The resulting mole fraction is
expressed in parts per million.
The increase in the atmospheric levels of C ­ O2 and other
greenhouse gases has resulted in global warming (Osman
et al. 2020). Figure 4 illustrates the global average median
temperature anomaly from 1850 to 2019 (Our World in Data
2020b). Temperature anomaly is defined as a deviation from
a reference value or long-term average of temperature. A posi-
tive anomaly refers to the observed temperature being warmer
than the reference value or long-term average. On the con-
trary, a negative anomaly is denoted by the observed tempera-
ture being cooler than the reference value or long-term aver-
age. The datasets typically used in calculating average global
temperature anomaly are land and sea surface temperatures
(National Oceanic and Atmospheric Administration 2020a).
The global economy necessitates clean and alternative
Fig. 5  Common sources of waste biomass. Some abundantly availa-
sources of energy to tackle fossil fuel-related environmen- ble biomass sources across the world include lignocellulosic biomass,
tal issues. A wide variety of organic residues with promis- e.g., agricultural crop residues, forestry biomass and energy crops,
ing candidacy as resources for waste-to-energy conversion municipal solid waste, industrial effluents, sewage sludge and cattle
include lignocellulosic biomass (Nanda et al. 2013), food manure. Such organic residues have tremendous potential to be used
as precursors for waste-to-energy conversion
waste (Kosheleva et al. 2019, Nanda et al. 2016c, 2019),
municipal solid waste (Nanda and Berruti 2020a, 2021),
waste plastics (Nanda and Berruti 2020b), cattle manure organic residues have emerged as the most sustainable
(Nanda et al. 2016b), sewage sludge (Gong et al. 2017) energy resource in achieving global energy security with a
and industrial effluents (Reddy et al. 2016) (Fig. 5). Such remarkable reduction in greenhouse gas emissions.

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Lignocellulosic biomass is generally a carbonaceous chlorophyll, waxes, terpenes, terpenoids, resins and aromat-
non-edible plant residue, captures the solar energy in the ics (Nanda et al. 2013). Ash is generally composed of inor-
form of carbohydrates through photosynthesis. Examples of ganic matter in biomass, which might catalyze or retard the
lignocellulosic biomass include agricultural crop residues, conversion process, thus influencing the biofuel yield. Ash
forestry biomass, dedicated energy crops and invasive crops often induces reactor fouling and slagging, thereby requiring
(Okolie et al. 2020a). Through suitable thermochemical and frequent maintenance leading to high expenditures (Zacco
biological conversion technologies, the stored carbohydrates et al. 2014).
can be converted to bio-hydrocarbons such as biofuels and Biomass conversion technologies can be divided broadly
biochemicals as well as bio-products such as nutraceuticals, into three routes such as physicochemical, biochemical and
cosmeceuticals, flavoring agents, aromatic products, biochar, thermochemical. The physicochemical conversion involves
activated carbon and other value-added compounds (Nanda the application of mechanical forces for the extraction of
et al. 2016a; Okolie et al. 2020b; Tang et al. 2020). bioactive components from biomass, whereas the thermo-
Lignocellulosic biomass typically contains lignin chemical conversion involves heat, pressure and catalysis
(10–25 wt%), hemicellulose (20–40 wt%), cellulose to thermally breakdown the biomass into biofuels and bio-
(25–45 wt%) along with extractives and ash (Nanda et al. products. On the other hand, the biochemical conversion
2013). Cellulose is a hexose sugar composed of glucose involves microorganisms or enzymes for the biodegradation
monomers connected by β (1–4) glycoside linkages. Hemi- of biomass to bioproducts. The biological technologies for
cellulose is made up of sugar like hexose and pentose and waste-to-energy conversion encompass anaerobic digestion,
sugar acids, e.g., glucuronic acid and galacturonic acid. ethanol fermentation and acetone-butanol-ethanol fermenta-
Hemicellulose is an amorphous heteropolymer, which tion, dark/photo-fermentation to produce primarily biometh-
makes it more susceptible than cellulose. Lignin consists ane, bioethanol, biobutanol and biohydrogen, respectively
of phenylpropane polymers that render highly branched and (Nanda et al. 2017a; Sarangi and Nanda 2020). As shown
phenolic structures with recalcitrant carbon–carbon link- in Fig. 6, thermochemical technologies such as pyrolysis,
ages (Fougere et al. 2016). Being a source of aromatics or liquefaction, gasification and torrefaction convert waste bio-
beneficial phenolic by-products, lignin has a high energy mass to bio-oil, producer gas, synthesis gas, tar and biochar
density (Spiridon et al. 2020). Extractives are generally com- (Nanda et al. 2014).
prised of non-structural water-soluble sugars and proteins,

Fig. 6  Thermochemical pathways of biomass conversion. From this gas) biofuels are generated from the thermochemical waste-to-energy
figure, it is evident that a wide variety of solid (i.e., biochar), liquid technologies
(i.e., bio-oil and bio-crude oil) and gaseous (i.e., syngas and producer

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Biochar, a stable solid carbon-rich co-product produced its energy efficiency and its effectiveness to produce bio-
from pyrolysis and gasification of lignocellulosic biomass, fuel with uniform-quality energy carriers with coal-like
has numerous applications in wastewater treatment, car- properties (Barbanera and Muguerza 2020). It involves
bon sequestration, pollution remediation, soil enrichment, thermal dehydration of lignocellulosic biomass under an
pharmaceuticals, cosmetics, catalysis, gas storage, electron- inert atmosphere at a moderate temperature typically in
ics and biocomposites, to name a few (Nanda et al. 2016a; the range of 200–300 °C with a slow to moderate heating
Gunarathne et al. 2019; Balajii and Niju 2019; Gopinath rate (Buratti et al. 2018). The operating conditions and
et al. 2020). Biochar is a porous carbonized material com- biomass composition directly affect the efficacy of tor-
prising of highly stable aromatic carbon, which can be refaction. During torrefaction of lignocellulosic materi-
widely applied for the adsorption of heavy metals and pol- als, hemicellulose is mostly affected due to its amorphous
lutants from wastewater, soil and air, carbon sequestration nature and a lower degree of polymerization compared to
and soil conditioning for improving its physicochemical and cellulose and lignin (Chen et al. 2015). Since hemicellu-
organic properties (Randolph et al. 2017; Azargohar et al. lose degrades almost completely during torrefaction, this
2014, 2019a; Karthik et al. 2020). thermal treatment renders the properties of diverse types
There are some key parameters determining biochar of biomass more uniformly with the effects of enriching
properties, which include: (1) feedstock properties includ- and changing the form of inorganic species.
ing its biopolymeric composition, elemental composition, Torrefaction of lignocellulosic biomass results in tor-
ash content and particle size; (2) type of conversion process refied biomass or char, tar and volatile gases. It results in
and reactor technology; (3) reaction conditions, e.g., tem- the production of homogeneous solid fuels with partially
perature, heating rate, vapor residence time, reaction time, reduced biopolymers (e.g., hemicellulose, cellulose and
feed concentration, equivalence ratio and catalysts (Nanda lignin), volatile matter and moisture content and higher
et al. 2016a; Okolie et al. 2019). Because of such param- carbon content. Some of the advantages of torrefaction
eters, there are variabilities in the elemental composition, are: (1) lowering the moisture content of biomass, (2)
surface morphology and functionalities of biochar, which improving hydrophobicity of biomass, (3) enhancing the
affect its performance. Based on the physicochemical and energy density, (4) higher grindability, (5) higher reactiv-
structural properties of biochar, its potential application can ity, (6) resistance to microbial decomposition due to lower
be determined. moisture content, and (7) compacted storage and handling
Biochar and activated biochar has exceptional abilities (Chen et al. 2015, 2016b; Zhang et al. 2020). Furthermore,
in removing organic and inorganic contaminants, heavy the emission of greenhouse gas such as ­CO2 and volatile
metals, toxic and other pollutants from wastewater and soil. matter from the burning of torrefied char is significantly
Recently, environmental remediation using biochar has reduced (Sukiran et al. 2017; Olugbade and Ojo 2020).
evolved as a promising area. Therefore, further studies on Moreover, the torrefied char can be extruded into solid fuel
biochar application in various fields are required to increase pellets through densification and pelletization (Azargohar
its applicability in environmental remediation. Biochar, with et al. 2019b).
its wide range of applications, is considered a win–win sce- Strandberg et al. (2015) studied the impact of torrefac-
nario for both waste management and environmental reme- tion temperature and residence time on the Norway spruce
diation. With this objective, this article reviews the process wood. The authors found that the atomic ratios for hydro-
parameters that affect biochar yields, quality and compo- gen/carbon and oxygen/carbon in torrefied biomass were
sition during thermochemical conversion and activation of reduced with increasing temperature and residence time
waste biomass. Some notable applications of biochar, espe- compared to the raw biomass. At 310 °C and 25 min of
cially in soil amendment and wastewater reclamation are residence time, the hydrogen/carbon atomic ratio reduced
systematically reviewed. from 1.4 to 0.86, whereas the oxygen/carbon atomic ratio
lowered from 0.64 to 0.27.
Zhang et al. (2018) investigated the impact of torrefaction
Thermochemical technologies for biochar temperature at the range from 200 to 300 °C and residence
production time (15–60 min) on the mass and energy yield of spent cof-
fee grounds, Chinese medicine residue and microalga resi-
Torrefaction due. The authors reported that the mass yield and energy
yield reduced with increasing the severity of torrefaction
Torrefaction, a relatively mild thermochemical process, temperature and time. The mass yield and energy yield were
is often proposed as an alternate pretreatment method in in the range of 98.2–55.4% and 98.9–74.7% for all the pre-
upgrading the physiochemical properties of biomass. Tor- cursors tested.
refaction has attracted tremendous attention because of

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The performance indices used to assess the extent of and producer gas. On the other hand, fast pyrolysis involves
torrefaction performance are solid yield, improvement in a high heating rate (i.e., 10–1000 °C/s), high temperatures
calorific value and energy yield of the torrefied char in (i.e., 300–700 °C) and short vapor residence times (i.e., less
comparison with their precursor (Zhang et al. 2018). The than 2 s) to thermally degrade the biomass into high yields
solid yield of torrefied biochar represents a decreasing trend of bio-oil and producer gas with lower yields of biochar
with the increasing severity of torrefaction temperature and (Ahmad et al. 2014; Roy and Dias 2017). The authors also
vapor residence time inside the reactor. Similarly, the energy studied the effects of heating rate and as well as the resi-
yield lowers with increasing torrefaction severity (Chen dence time on the production of biochar using slow and fast
et al. 2015). In contrast, the calorific value of torrefied char pyrolysis process.
increases because of comparatively more carbon retained Slow pyrolysis is also referred to as carbonization because
due to dehydration and decarboxylation, which cause the it leads to a higher biochar yield. The stages of carbonization
removal of hydroxyl groups, e.g., moisture, volatiles and of biomass are categorized into four major steps such as (1)
carboxylic acids from biomass. dehydration, (2) thermal cracking of lighter molecules, (3)
thermal cracking of larger molecules, and (4) evolution of
Pyrolysis and carbonization aromatized and stable carbon with the removal of volatiles
(Puligundla et al. 2016). Lignite-like biochar with a high
Pyrolysis of biomass is an endothermic process, which grade of aromatization is generated from carbonization.
includes the thermal degradation of solid organic matter Hydrothermal carbonization is another emerging route for
under an inert atmosphere into bio-oil, biochar and pro- biochar production from high-moisture containing biomass
ducer gas (Aravind et al. 2020). Pyrolysis produces bio-oil, such as algae, municipal solid wastes, invasive crops, and
biochar and non-condensable gases like C ­ O2, CO, C­ H4 and sewage sludge (Smith et al. 2016; Kang et al. 2019). The
­H2, which can be utilized for combined heat and power gen- solid residue obtained because of hydrothermal carboniza-
eration. The liquid product or bio-oil generally consists of tion of waste biomass is often termed as hydrochar because
oxygenated hydrocarbons such as phenolic ethers, alkyls, of its generation under hydrothermal conditions. The pro-
esters, aldehydes, ketones, carboxylic acids, hydrocarbons cess involves heating the biomass material under hydro-
and a substantial amount of water. The liquid product from thermal conditions at lower temperatures, i.e., 180–260 °C
pyrolysis generally possesses a calorific value of 16–28 MJ/ under higher pressures of, i.e., 22 MPa for longer dura-
kg (Mohanty et al. 2013). The calorific value of biochar is tions (Mäkelä et al. 2015). The reaction medium in such
generally in the range of 25–30 MJ/kg depending on the processes is mostly water at its subcritical conditions. Sub-
amount of unconverted organic fraction (Jia et al. 2017). critical water exists at temperatures and pressures below the
During the process of pyrolysis, components like cellulose water’s critical points, i.e., 374 °C and 22.1 MPa, respec-
and hemicellulose mostly form volatile products, while bio- tively (Nanda et al. 2017a, b). Hydrothermal carbonization
char is formed from lignin due to its high stability to ther- results in friable, energy-dense and hydrophobic hydrochar
mal degradation. Biochar retains the stable carbon from the with the reduction in hydrophilic moieties in the biomass
biomass and possesses various uses such as a solid fuel, soil and denaturing its colloidal structures (Smith et al. 2016).
amendment agent, carbon sequestration and precursor for The method is relatively inexpensive and environmentally
manufacturing value-added products of industrial and com- benign because of the involvement of water as a green sol-
mercial interest (Hansen et al. 2015). vent. The liquid products such as phenolic compounds and
The rate and degree of thermal decomposition of biomass furan derivatives can also be extracted, which could be uti-
during pyrolysis depend on the variations in temperature, lized for chemical or biofuel production, while the spent
heating rate, pressure, vapor residence time, reactor con- water can be used in anaerobic digestion facilities to increase
figuration and feedstock properties (Mohanty et al. 2013). the process efficiency (Oliveira et al. 2013).
Based on temperature, heating rate and vapor residence Temperature plays a significant role in determining the
time, pyrolysis can be categorized typically into slow and physicochemical, morphological and structural properties of
fast pyrolysis (Jahirul et al. 2012). Slow heating rates (i.e., biochar. Temperature causes dehydration, decarboxylation,
0.1–1 °C/s), moderate temperatures (i.e., 300–600 °C) and a decarbonylation and deamination of biomass, which leads
longer vapor residence time (i.e., greater than 30 min) usu- to the evolution of sticking physicochemical features in bio-
ally categorize slow pyrolysis (Roy and Dias 2017; Senneca char (Kim et al. 2011). For example, a rise in temperature of
et al. 2018; Safdari et al. 2019). A longer vapor residence pyrolysis, gasification and carbonization leads to a decrease
time results in a secondary reaction such as polymerization in the biochar properties such as yield, moisture and volatile
to produce biochar with high carbon content (Yaashikaa contents, electrical conductivity and cation exchange capac-
et al. 2019). Slow pyrolysis is a preferred route for biochar ity (Nanda et al. 2016a). In contrast, a rise in temperature
production due to its high yields compared to that of bio-oil causes an increase in the aromatic carbon content of biochar

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along with its elemental or ash content, pH value, surface is disintegrated into permanent gases and biochar during
area and porosity (Fig. 7). Biochar produced at low-temper- supercritical gasification because of a series of hydrothermal
ature pyrolysis usually possesses a lower surface area, unde- reactions such as water–gas shift, hydrogenation, methana-
veloped porous structures, acidic pH and low carbon con- tion, steam reforming and Boudouard reaction (Okolie et al.
tent. The pores in the low-temperature biochar are usually 2020c, 2020d). Supercritical water demonstrates gas-like
blocked by the formation of tar. Therefore, biochar requires viscosities and liquid-like densities acting as a green sol-
chemical or physical activation to increase its surface area vent, catalyst and reactant to decompose highly recalcitrant
and porosity. The formation of biochar involves crosslink- organic matter (Nanda et al. 2017b). The hydrothermal gasi-
ing reactions through condensation and dehydration at low fication can also eliminate excess energy requirements for
temperatures (Heidari et al. 2019). Biochar becomes pro- the pre-drying of biomass feedstocks because of the aqueous
gressively more aromatic with higher carbon content as the reaction medium (Correa and Kruse 2018).
temperature increases by the elimination of hydroxyl, olefin, In the case of conventional thermochemical gasifica-
aliphatic and carbonyl groups. At higher temperatures, the tion, the primary oxygenated vapors and liquids comprise
volatile matter is released from biochar, which results in the of hemicellulose and cellulose-derived compounds, i.e.,
opening of its pore structures. hydroxyl acetaldehyde and levoglucosan as well as methoxy
phenols derived from lignin (De Lasa et al. 2011). At around
Gasification 350 °C, the aromatization process starts and continues until
higher temperatures are attained. At temperatures ranging
Gasification, an endothermic process, involves the thermal from 700 to 850 °C, the primary vapors and liquids are con-
decomposition of organic materials mainly to combustible verted to gaseous olefins, ­CO2, ­H2, CO, ­H2O and conden-
synthesis gas or syngas and biochar under reducing con- sable oils like phenols and aromatics. A further rise in the
ditions in the presence of gasifying agents like oxygen or temperature from 850 to 1000 °C involves the conversion of
steam. The gasifying agents are supplied in a sub-stoichi- secondary products to ­H2, ­CH4, CO, ­H2O, ­CO2, tar and bio-
ometric amount when compared with the amount required char. Steam gasification of biomass has emerged as an area
for complete combustion to C ­ O2 and water. The gaseous of interest because of its capability in producing hydrogen-
phase contains a mixture of ­H2, ­CO2, CO and ­CH4 as well containing gaseous fuel along with biochar of high quality.
as traces of ­C2H2, ­C2H4 and ­C2H6 (Okolie et al. 2019). The feedstock properties need to be taken into consid-
Hydrothermal gasification is also another iteration of gasi- eration during gasification. The properties of biomass that
fication that involves supercritical water as the reaction can affect gasification are its specific surface area, volatile
medium. Supercritical water is a fluid phase of water occur- matter, moisture levels, ash content, particle size and carbon
ring at temperatures and pressures beyond its critical points. content (Okolie et al. 2019). There are few other variables
The critical temperature and critical pressure of water are that also considerably impact the performance of gasifica-
374 °C and 22.1 MPa (Reddy et al. 2014). Complex biomass tion such as temperature, heating rate, pressure, equivalence
ratio, feed concentration, gasifier configuration, gasifying
agent and catalysts (Bocci et al. 2014; Jia et al. 2017).
The equivalence ratio is considered as a crucial param-
eter, which states the actual oxygen-to-biomass ratio divided
by the stoichiometric oxygen-to-biomass ratio (Bermudez
and Fidalgo 2016). The equivalence ratio affects the com-
position of gasification products. A higher equivalence ratio
lowers the concentration of H ­ 2 and CO while increasing the
content of ­CO2 (Liu et al. 2018). Thus, a higher equivalence
ratio results in gaseous products with lower heating value.
Nevertheless, a high equivalence ratio shows an advanta-
geous effect by reducing the formation of tar as the oxygen
present in the system reacts with the volatiles (Upadhyay
et al. 2019). With an increase in equivalence ratio, the gase-
Fig. 7  Evolution of physicochemical properties of biochar with tem- ous yield also increases and biochar yield decreases. This is
perature. Note the increasing trend for the levels of aromatic carbon, because with the increase in the concentration of oxidizing
ash, pH value, surface area and porosity of biochar at higher tempera- agents, the combustion rate increases, thus converting the
tures for pyrolysis, gasification, torrefaction and carbonization. On
biomass into gaseous products (Ismail and El-salam 2017).
the contrary, at low reaction temperatures, the yield, volatile matter,
moisture content, electrical conductivity and cation exchange capac- Moreover, the steam-to-biomass ratio possesses a higher
ity of biochar are greater limit set by the stoichiometry of gasification beyond which

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the resulting gas contains a high amount of steam. Thus, in from waste biomass along with the generation of combus-
steam gasification, the resulting issues reveal the importance tible syngas.
of the proper selection of steam-to-biomass ratio for attain-
ing high process competence (Jia et al. 2017).
Hansen et al. (2015) reported that reactions between bio- Activation of biochar
char and oxygen in the combustion zone of the gasification
system played a prominent role in determining the quality of Activated carbon is a carbonaceous material containing
the product gas. Other factors like tar composition, conver- mostly aromatic and graphite form of carbon thermally
sion of biochar, gas composition, and heating value require or physicochemically treated to have high porosity and
significant consideration as they determine the operation and larger specific-surface area due to a well-built internal pore
performance of gasification. The rise in gasification tem- structure (Yahya et al. 2015). Activated carbon is typically
perature results in enhancing the content of combustible gas, derived from coal-based precursor or thermally stable bio-
especially hydrogen along with a substantial increase in its mass-derived char to develop organized pore-structure, high
heating value, and the reduction in tar content (Ning et al. specific surface area, favorable pore size distributions, high
2018). Furthermore, with the rising temperature, hydrogen physiochemical stability, surface reactivity and high adsorp-
shows an initial increment at chemical equilibrium, reaching tive capacity (Danish and Ahmad 2018; Heidarinejad et al.
maximum at a particular temperature and gradually decreas- 2020). Activated carbon can have a surface area approaching
ing (Bocci et al. 2014; Ismail and El-salam 2017). From or more than 1500 m2/g, which is almost fifty-times greater
an overall processing perspective, higher temperatures are than that of a biomass-derived char (Azargohar and Dalai
found to be suitable for biomass gasification. However, in 2006). The development of a larger specific surface area in
the biomasses with high alkaline metal concentrations, the activated carbons is attributed to the presence of a greater
ash agglomeration requires a lower temperature, which may degree of microporosity and mesoporosity generated from
restrict gasification at temperatures approaching 750 °C the conventional heating techniques. It should be noted that
(Kittivech and Fukuda 2019). activated carbon is a product of biochar activation through
The gasification process usually undergoes in the pres- a physical or chemical approach.
ence of gasifying agents like air, steam, ­O2 and ­CO2. Usu- Presently, commercial activated carbons are derived from
ally, the gasifying agent used in the gasification governs the non-renewable precursors such as coke or coal-based precur-
calorific value and the syngas quality, i.e., ratio of ­H2/CO. sors, which limits their extensive use (Baytar et al. 2018).
Kim et al. (2013b) reported that air as a gasifying agent Although, the source of activated carbon could be non-con-
resulted in the production of syngas of low heating value. ventional and renewable sources such as lignocellulosic bio-
The dilution of syngas by nitrogen present in the air was the mass (e.g., wood, straw, husk, peel, distillery grains, kitchen
main reason behind its low heating value. However, Choi waste, shell, pith, etc.) and wastes materials such as scrap
et al. (2015) found that when steam or an amalgamation of tires (Rashidi and Yusup 2017). The non-renewable fossil
steam and oxygen was used for gasification, a mediocre calo- fuel-based precursors are gradually being replaced by waste
rific value syngas was produced. Moreover, the combination organic biomasses for the production of activated carbon
of steam and air for gasification produced high hydrogen because of economically feasibility, eco-friendliness, lower
yields when compared to the use of air alone. Such prac- regeneration cost, high renewable carbon content, lower pro-
tice also can lessen the energy required for the gasification duction costs and energy requirements (Hesas et al. 2015;
process, which is usually supplied by combusting biomass. Rashidi and Yusup 2017; Mukherjee et al. 2019).
In the gasification process, residence time has a substan- The demand for activated carbon is escalating every
tial impact on the production and composition of gases, char year. The global market of activated carbon reached the
and tar. According to Erkiaga et al. (2014), the increase in U.S. $4.72 billion in 2018 with a compound annual growth
residence time negatively impacts the occurrence of oxygen- rate increase of 17.5% until 2025 (Grand View Research
containing compounds. Additionally, the yields of some of 2020). The growing demand for activated carbon is due to
the aromatic ring compounds (except benzene and naphtha- the enormous applications in chemical processes, pharma-
lene) are reduced with increased residence time, while that ceuticals, biomedicine, environmental remediation, waste-
of three- and four-ring aromatic species increased. Longer water treatment, gas storage and purification, electrical
residence times enable the reduction in tar as well as biochar devices, cosmeceuticals, personal care products, carbon
production, but it increases gaseous product yield (Reddy capture and sequestration, and other value-added sectors
et al. 2014). The removal of volatiles and tar at increased (González-García et al. 2013; González-García 2018;
residence time enhances the biochar porosity and surface Nanda et al. 2016a; Wong et al. 2018).
area (Nanda et al. 2016a). Therefore, gasification is an effec- The preparation of activated carbon from bio-
tive thermochemical technology for production of biochar char through physical activation involves a dual-stage

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Environmental Chemistry Letters (2021) 19:2237–2259 2245

mechanism where the biomass is thermally treated at liquid and gaseous stream. The study showed that chemi-
600–900 °C under an inert atmosphere to produce bio- cally activated carbon recorded the highest surface area of
char for further activation at 800–1100 °C in the presence 696 m2/g in contrast to the activated carbon derived from
of suitable activating or oxidizing agents (Yahya et al. physical activation (641 m2/g).
2015; Hesas et al. 2015). The commonly used oxidizing or Kumar and Jena (2018) reported high yields (38.1 wt%)
physical activation agents are steam, ­CO2, air or a binary of activated carbon with a higher surface area (2869 m2/g)
mixture of ­CO2 and ­N2. During the pyrolysis process, the and total pore volume (1.96 cm3/g) produced from Z ­ nCl2—
surface chemical properties of biochar undergo a series of assisted chemical activation of Fox nutshell. However, the
complex and variable changes that further facilitate the use of Z
­ nCl2 has adverse impacts on the environment, which
activation process (Wang et al. 2019). Extensive research has limited use in chemical activation processes (Azargohar
has been conducted on C ­ O 2-based physical activation, and Dalai 2008). Shahkarami et al. (2015) used whitewood
which is preferred over steam due to its easy handling, biochar as a precursor for physical and chemical activation
the requirement of low activation temperature and car- processes. KOH (1400 m2/g) resulted in the highest sur-
bon recyclability approach (Yahya et al. 2015). However, face area for the activated carbon followed by that of steam
from an industrial perspective, using a purified stream of (840 m2/g) and ­CO2 (820 m2/g).
­CO2 can increase the process expenditures. Hence, it is Rambabu et al. (2015) used chemical activation agent
recommended to use the flue gas generated after the post- (i.e., KOH and N ­ H3) and physical activation agent (i.e.,
combustion, which contains a binary mixture of ­N2 and steam and ­CO2) of de-oiled canola meal. The authors found
­CO2 (Puligundla et al. 2016). Table 1 summarizes some KOH led activation of canola meal with the highest surface
recent studies on the physical activation of biochar. area (1230 m2/g) and pore volume (0.4 cm3/g). The surface
Chemical activation involves impregnation of the pre- area of the resulting activated carbon was highest in the case
cursor with a chemical activating agent under an inert of KOH (1230 m2/g) followed by steam (403 m2/g), ­CO2
atmosphere typically at 450–900 °C. The chemicals agents (320 m2/g) and ­NH3 (19 m2/g). Muniandy et al. (2014) also
having the potential as a strong dehydrating agent during reported KOH as a superior activating agent for produc-
activation can be categorized as: (1) acids, e.g., sulfuric acid ing activated carbon from rice husk over NaOH. The study
and phosphoric acid, (2) alkalis, e.g., potassium hydroxide, reported a higher surface area of activated carbon produce
potassium carbonate, sodium hydroxide, sodium carbon- from KOH (2696 m2/g) when compared to that of NaOH
ate, and (3) transition metal salts, e.g., aluminum chloride, (594.9 m2/g). KOH is extensively used as a chemical acti-
zinc chloride and magnesium chloride (Yahya et al. 2015; vation agent for producing activated carbon with enhanced
Nanda et al. 2016a). Chemical activation is considered eco- surface area and adsorption performance. When compared
nomically viable compared to physical activation since it to physical activation, chemical activation tremendously
requires shorter processing time, lowers the activation tem- enhances the surface area and porosity of the activated
perature, generates high-grade porous activated carbon, high carbon.
final carbon yields and one-step processing (Bergna et al.
2018). The technique of mixing the dehydrating agent and
precursor can significantly influence the properties of acti- Applications of biochar and activated
vated carbon such as the yield of solid and carbon along biochar
with the inhibition of tar formation. Crucial developments
in the production of activated carbon have been made over Removal of heavy metals from wastewater
the past few years concerning the type of activating agents,
mixing techniques, activation process optimization and uti- Wastewater is generated from domestic, municipal and
lization of inexpensive carbonaceous precursors (Mukherjee industrial activities, which consists of harmful pollutants
et al. 2019). Table 2 summarizes some recent studies on the such as organic substances, pharmaceuticals, hormones
chemical activation of biochar. and steroids, plastics, sediments, oil and grease, patho-
Tehrani et al. (2015) studied the effects of process condi- genic microorganisms, heavy metals, microplastics, hydro-
tions like temperature as well as a physical and chemical carbons, radioactive substances and other toxic substances
activating agent on the characteristics of activated carbon (Sun et al. 2019; Chen et al. 2019a; Nanda and Berruti
produced from chemical and physical activation of coffee 2020a). These contaminants have many adverse effects on
extract residue. The authors used H ­ 3PO4 and steam as an the environment and ecosystems by affecting the natural
activating agent for chemical and physical activation, respec- habitats and metabolism of plants, animals and human
tively. The obtained activated carbon with a highly devel- beings. The exposure or consumption of wastewater con-
oped porous structure and surface area enabled its potential taining heavy metals and other contaminants can cause
application for the removal of various contaminants from a serious health ailments in human beings including cancer

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Table 1  Recent studies on the physical activation of biochar precursors


Feedstock Physical Activation Reac- Key attrib- BET Total pore Average Yield (wt%) References
agent temperature tion time utes surface area volume pore size
(°C) (min) ­(m2/g) ­(cm3/g) (nm)

Almond shell Steam 950 60 Steam 1261 – – 50 Nazem et al.


flow rate: (2020)
130 cm3/
min
Canola meal Steam 800 90 Steam flow 403 0.18 2.07 69.5 Rambabu et al.
rate: 8 g/h (2015)
CO2 700 120 CO2 flow 320 0.30 3.67 –
rate:
24 mL/min
Coconut CO2 850 60 CO2 flow 1152 0.72 – 2.6 Tsai and Jiang
shell rate: (2018)
50 cm3/
min
Coffee resi- Steam 700 120 Steam/N2 641 0.33 2.06 13.4 Tehrani et al.
due ratio: 1:2 (2015)
Pine nutshell Steam 850 80 Steam/bio- 1058 – – 31.2 Chen et al.
mass ratio: (2016a)
1.5:1
Pistachio Steam 950 30 Steam 1196 – – 41.7 Nazem et al.
shell flow rate: (2020)
130 cm3/
min
Sewage CO2 700 60 CO2/N2 240 0.39 6.46 – Zhang et al.
sludge ratio: 1:3 (2019)
Spruce, fir, Steam 900 60 – 1025 0.77 3.0 8 Bardestani and
and pine Kaliaguine
stem (2018)
Tea waste Steam 800 30 Steam 995 0.68 2.73 22.42 Zhou et al.
flow rate: (2018)
0.075 g/
min
Walnut shell Steam 950 60 Steam 1248 – – 45.8 Nazem et al.
flow rate: (2020)
130 cm3/
min
Whitewood Steam 700 100 Steam/car- 840 0.55 – 59 Shahkarami
bon ratio: et al. (2015)
1:1.06
CO2 890 100 CO2 flow 820 0.45 – 55
rate:
130 mL/
min
Wood chips CO2 800 180 CO2 flow 590 0.34 3.44 – Kilpimaa et al.
rate: (2015)
90 cm3/
min

and cardiovascular, neurological and pulmonary disorders Many studies have reported that a wide range of biochar
(Guo et al. 2016). The treatment of wastewater is often can be used effectively in removing different contaminants
found to be inefficient to complete removal of the toxic (Mohan et al. 2014; Inyang and Dickenson 2015; Cha et al.
compounds, micro-contaminants and nanoparticles. There- 2016). Biochar is considered a promising absorbent that can
fore, advanced treatments are required specific to particu- remove contaminants like heavy metal and organic matter
lar contaminants in the wastewater for its reclamation. present in water and soil. Biochar and activated carbons
have a high surface area, microporosity and surface-active

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Table 2  Recent studies on the chemical activation of biochar precursors


Feedstock Chemical Activation Reac- Impregnation ratio BET sur- Total pore Average Yield References
agent temperature tion time (Chemical:feedstock) face area volume pore size (wt%)
(°C) (min) or Chemical concen- ­(m2/g) ­(cm3/g) (nm)
tration

Canola KOH 800 120 3:1 1230 0.46 1.51 – Rambabu


meal et al.
(2015)
Coffee H3PO4 600 60 40% 696 0.59 3.37 34.9 Tehrani et al.
residue (2015)
Fox nut- ZnCl2 600 60 2:1 2869 1.96 2.73 38.1 Kumar and
shell Jena (2015)
Golden K2CO3 800 240 1:1 1413 0.66 1.86 57.7 Tran et al.
shower (2018)
Pinewood ZnCl2 580 120 1:1 1081 0.37 0.57 28.8 Ahmed et al.
KOH 580 120 1:4 1185 0.35 0.52 19.5 (2019)
Pinewood H3PO4 600 120 2:1 1547 1.17 – 43.3 Cao et al.
sawdust (2018)
Pumpkin ZnCl2 500 60 3:1 1564 0.965 24.7 18.6 Demiral et al.
seed shell (2015)
Rice husk KOH 850 60 1:5 2696 1.29 2.63 17.1 Muniandy
NaOH 750 60 1:2 595 0.34 8.41 18.2 et al.
(2014)
Sewage KOH 700 60 2:1 908 0.83 3.68 – Zhang et al.
sludge (2019)
Whitewood KOH 775 120 0.81:1 1400 0.62 – 35 Shahkarami
et al.
(2015)

functional groups, which make them effective adsorbents produced from feedstocks like rice husk, sewage sludge and
to remove heavy metals from the environment. The adsorp- the organic waste of municipal solid waste using slow pyrol-
tion capability of biochar depends upon the properties of ysis. Their study also showed optimum adsorbent dose to
the precursor biomass, conversion technology and process remove heavy metals like chromium(III), chromium(VI) and
condition employed. arsenic(V). Sewage sludge derived biochar showed the high-
Ahmad et al. (2014) reported that increasing pyrolysis est removal of arsenic(V), chromium(III) and chromium(VI)
temperature increases the specific surface area, carbon con- as 13.4 mg/g, 94.3 mg/g and 64.1 mg/g, respectively at 25 °C
tent, microporosity and development of the oxygen-oriented and pH 7 compared to other biochars.
functional group in biochar, which enhances the adsorption According to Xu et al. (2013), biochar produced from rice
capacity of the contaminants. It was evident from many husks and feces showed effective results in removing heavy
studies that biochar produced at elevated temperature, i.e., metals such as cadmium, copper and zinc. When compared
more than 400 °C developed enhanced surface area and to rice husk biochar, the feces-derived biochar showed bet-
microporosity to act as superior adsorbent (Jin et al. 2014; ter removal rates. In feces-derived biochar, heavy metals
Tan et al. 2015). Biochar can effectively remove heavy met- were adsorbed on oxygenated functional groups, whereas
als (e.g., arsenic, aluminum, cadmium, chromium, copper, in the case of rice husk-derived biochar, the adsorption took
lead, mercury, nickel, uranium and zinc), organic pollutants place on phenolic functional groups. From this study, it was
(e.g., pesticides, herbicides, antibiotics and dyes), and other evident that the functional groups, especially the ones that
pollutants (e.g., ammonium, nitrate, phosphate, fluoride and are oxygenated play an immense role in the adsorption of
perchlorate) from aqueous solutions, thus preventing the risk heavy metals.
of water contamination (Tan et al. 2015; Zou et al. 2018; Park et al. (2016) investigated the removal of heavy met-
Chen et al. 2019b; Xu et al. 2019). als using biochar produced from slow pyrolysis of sesame
Table 3 summarizes some recent studies on the adsorption straw at temperature 700 °C. The adsorption capacities of
of heavy metals by biochars derived from a wide variety of heavy metals like lead (i.e., 11.8 and 2.8 mg/g), cadmium
waste resources. Agrafioti et al. (2014) studied the removal (i.e., 9.7 and 1.2 mg/g), chromium (8.4 and 1.8 mg/g), copper
of contaminants like arsenic and chromium using biochar (6 and 2.4 mg/g), zinc (3.7 and 1.4 mg/g) were determined

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Table 3  Adsorption characteristics of heavy metals by biochar


Feedstock Conversion Conversion Target contami- Adsorption Adsorption Adsorption Isotherm References
technology temperature nant temperature capacity pH
(°C) (°C) (mg/g)

Sewage sludge Pyrolysis 300 Arsenic(V) 25 13.4 7 Langmuir Agrafioti et al.


Chromium(III) 94.3 (2014)
Chromium(VI) 64.1
Miscanthus Pyrolysis 300 Cadmium(II) 25 11.4 7 Langmuir Kim et al.
sacchariflo- 400 12.0 (2013a)
rus
500 13.2
600 13.0
Soybean straw Pyrolysis 400 Copper(II) 25 ± 1 0.83 mol/kg 5 Langmuir Tong et al.
(2011)
Sugar beet Pyrolysis 300 Chromium(VI) 22 ± 0.5 123 2 Langmuir Dong et al.
tailing (2011)
Hardwood Pyrolysis 450 Copper(II) 22 ± 2 6.8 5 Langmuir Chen et al.
Zinc(II) 4.5 (2011)
Corn Straw 600 Copper(II) 12.5
Zinc(II) 11
Rapeseed Pyrolysis 500 Lead(II) 25 ± 2 184.1 5 Langmuir Gao et al.
(2019)
Orchard prun- Pyrolysis 500 Lead(II) 20 108.2 mmol/ 4.5 Langmuir Caporale et al.
ing kg (2014)
Chromium(III) 98.3 mmol/kg
Copper(II) 46.5 mmol/kg
Pig manure Carbonization 600 Lead(II) 60 230.7 6 Langmuir Kołodyńska
Zinc(II) 79.6 5 et al. (2012)
Cadmium(II) 117 6
Cow manure Copper(II) 88.5 5
Lead(II) 219.3 6
Zinc(II) 61.9 5
Cadmium(II) 118.4 6
Anaerobic Pyrolysis 600 Lead(II) 25 51.2 6 Langmuir Ho et al. (2017)
digestion
sludge
Sesame straw Pyrolysis 700 Lead(II) 25 102 7 Langmuir Park et al.
Cadmium(II) 86 (2016)
Chromium(III) 65
Copper(II) 55
Zinc(II) 34
Loofah Pyrolysis 700 Chromium(VI) 30 30.1 3 Freundlich Xiao et al.
Sponges Copper(II) 30 54.7 7 (2019)
Pine dust Pyrolysis 700 Copper(II) 25 8.9 5.5 Langmuir Poo et al.
Cadmium(II) 5 (2018)
Zinc(II) 5.2
Saccharina Pyrolysis 500 Copper(II) 25 98.6 11.3 Langmuir Poo et al.
japonica 700 Cadmium(II) 60.7 10.9 (2018)
(Kelp)
Zinc(II) 84.3
Sargassum Pyrolysis 600 Copper(II) 25 94.1 9.7 Langmuir Poo et al.
fusiform 700 Cadmium(II) 37.2 11.2 (2018)
(Hijikia)
Zinc(II) 43

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by using Freundlich isotherms under mono-metal and multi- found to be 184.1 mg/g at room temperature, i.e., 25 ± 2 °C
metal conditions. They found that the adsorption capacity of with pH 5. Similarly, Ho et al. (2017) studied the removal
sesame straw produced biochar showed better results when of lead(II) from wastewater by using pyrolyzed anaerobic
compared to other adsorbents like zeolite, sawdust and acti- digestion sludge-derived biochar. The adsorption capacity of
vated carbons. lead(II) determined by the Langmuir model was 51.2 mg/g.
Caporale et al. (2014) studied the removal of heavy metals
like lead, chromium and copper from water using pruning- Removal of dyes from wastewater
derived biochar produced through slow pyrolysis at 500 °C.
The biochar having an average specific surface area of The discharge of wastewater and effluents from dye indus-
410 ± 6 m2/g and functional groups like hydroxyl, carboxyl tries poses numerous threats to the ecosystems as they
and amino groups was found to be effective in the removal of contain toxic chemicals, organics, acids, bases and other
heavy metals. The authors found the adsorption capacities of impurities. Textile dyes often show stability to the oxidiz-
lead (108.2 mmol/kg) and chromium (98.3 mmol/kg) to be ing agent and withstand aerobic digestion, which makes their
quite similar as both the heavy metals showed a higher affin- removal difficult (Mohan et al. 2014). Several researchers
ity toward biochar surface. However, copper (46.5 mmol/ have used various biochar samples derived from biomass
kg) showed lesser affinity. The highest adsorption of lead for the removal of dyes such as methylene blue, methyl vio-
metal at pH 4.5 was due to electrostatic attraction. The study let, Remazole orange and reactive red 141 (Xu et al. 2011;
also explored the role of pH in the adsorption process and Acemioğlu 2019; Gokulan et al. 2019). Table 4 summarizes
reported that the acidic conditions played a vital role in some notable studies on the adsorption of organic contami-
the adsorption of metal. The researcher adopted a fast field nants by biochars produced from several organic residues.
cycling nuclear magnetic resonance relaxometry method to Sun et al. (2013) used various biochar samples produced
study the essence of the bonds at the solid–liquid interface from pyrolysis of Eucalyptus, anaerobic digestion residues
of the biochar and metal. (or municipal organic waste) and palm bark at 400 °C to
Gao et al. (2019) used rape straw-derived biochar pyro- study the adsorption of methylene blue dye. The efficien-
lyzed at 500 °C for removing lead(II) from water. The max- cies for methylene blue removal by biochars derived from
imum adsorption capacity with the Langmuir model was anaerobic digestion residues, palm bark and Eucalyptus were

Table 4  Adsorption characteristics of dyes by biochar


Feedstock Conversion Conversion Target con- Adsorption Adsorption Adsorption pH Isotherm References
technology temperature taminant temperature capacity
(°C) (°C) (mg/g)

Rice husk Liquefaction 340 Malachite 30 67.6 9 Freundlich Leng et al.


green (2015)
Peanut straw Pyrolysis 350 Methyl violet 25 256.4 mmol/g 9.4 Langmuir Xu et al. (2011)
Soybean straw 178.6 mmol/g 8.4
Rice hull 123.5 mmol/g 8.3
Eucalyptus Pyrolysis 400 Methylene 40 2.1 7 Langmuir Sun et al.
Municipal blue dye 9.5 (2013)
organic
waste
Palm bark 2.7
Blue-green Pyrolysis 450 Congo red 30 51.3 2 Langmuir Nautiyal et al.
algae (2016)
(Spirulina
platensis)
Sugarcane Pyrolysis 800 Malachite 60 3000 mg/L 7.5 – Vyavahare et
bagasse green al. (2018)
Wood waste Gasification 700 Indosol Black 28 185 2 Langmuir Kelm et al.
­NF1200 (2019)
Green algae Pyrolysis 800 Malachite 35 5306.2 12.3 Freundlich Chen et al.
(Ulothrix green (2018)
zonata) Crystal violet 1222.5
Congo red 345.2

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2250 Environmental Chemistry Letters (2021) 19:2237–2259

found to be 99.5%, 99.3% and 86.1%, respectively, at opti- (Rajapaksha et al. 2019; Shi et al. 2020). Such wastes com-
mum conditions, i.e., 40 °C, 5 mg/L concentration and pH prise a wide range of organic chemicals, which include anti-
7. The municipal organic waste-derived biochar showed a biotics, therapeutic drugs, contraceptive pills, natural and
maximum adsorption capacity of 9.5 mg/g. synthetic hormones, cosmetics, nutraceuticals, veterinary
Leng et al. (2015) also studied the adsorption of mala- drugs, health supplements and other complex organic prod-
chite green using biochar produced from the liquefaction of ucts. Among the many hazardous and carcinogenic contami-
rice husk using ethanol as a solvent. The adsorption capac- nants, endocrine-disrupting chemicals are one of the emerg-
ity of malachite green was found to be between 32.5 and ing concerns. Endocrine-disrupting chemicals adversely affect
67.6 mg/g. Vyavahare et al. (2018) studied the removal of the physiological and metabolic pathways of humans, animals
malachite green dye using biochar produced from differ- and plants by causing disorders in hormonal development and
ent biomasses such as paper waste, cotton waste, rice husk, reproduction (Wang et al. 2015; Adeel et al. 2017).
sugarcane bagasse and groundnut shells. Among varying Steroid estrogen is a natural or synthetic hormone,
pyrolysis temperatures studied, the authors found that pyrol- which acts as an endocrine-disrupting chemical. It includes
ysis of sugarcane bagasse at 800 °C for 60 min showed better estriol, estrone and estradiol, which have adverse impacts on
performance resulting in maximum sorption of malachite humans and animals once they end up in soil and water bod-
green, i.e., 3000 mg/L. ies. It is estimated that approximately 30,000 kg and 700 kg
Nautiyal et al. (2016) used Spirulina platensis algae as of natural estrogen and synthetic estrogens are annually dis-
a feedstock for producing biochar for dye removal. The charged into the environment, respectively, at a global scale
researcher explored the use of algae residues after in situ (Adeel et al. 2017). The synthetic estrogen comes mainly
transesterification from biodiesel industries to examine the from birth control pills. Natural estrogens from both human
adsorption of Congo red dye from its resulting biochar. and animal waste results in adverse risks to the environ-
The authors reported that algae biochar showed 76.6% dye ment. Estrogen in the form of estradiol is found predomi-
removal with an adsorption dosage of 0.2 g per 100 mL. nantly in wastewater, which biomagnifies in aquatic plants
The study ascertained that biochar derived from algae pos- and animals and eventually enters the human food chain.
sesses a high adsorption capacity to treat wastewater from Both drinking water and seafood (e.g., fish and aquatic plant-
dye industries. based foods) consumed by humans could contain estrogen,
Chen et al. (2018) used pyrolyzed microalgae (Ulothrix thus affecting puberty and fertility (Gonsioroski et al. 2020).
zonata) derived biochar for the adsorption of various dyes Estrogen exposure also impairs fertility in fishes (Spivey
from wastewater. The study also investigated the influence of 2004). Estrogen, endocrine-disrupting chemicals and many
different pyrolysis temperatures of biochar on the adsorption other pharmaceutical drugs are unregulated compounds in
of dyes. The target dyes were crystal violet, Congo red and most developing and developed countries.
malachite green. Microalgae-derived biochar showed highly Many researchers have reported biomass-derived biochar
porous structures and thermal stability with developed surface to be an effective adsorbent for the removal of such potent
chemical characteristics, which resulted in the removal of the pharmaceutically active compounds from wastewater (Petrie
aforementioned dyes from the aqueous solution. The optimum et al. 2015; Fernandez et al. 2015; Ahmed et al. 2016; Sophia
adsorption capacity achieved for the removal of malachite and Lima 2018), a few of which have been summarized in
green dye was 5306.2 mg/g with biochar produced at 800 °C Table 5. Ahmed et al. (2018) investigated the removal of
while for crystal violet and Congo red, the maximum adsorp- phenolic endocrine-disrupting chemicals using functional-
tion capacities were 1222.5 and 345.2 mg/g, respectively. ized biochar. The functionalized biochar produced from the
Kelm et al. (2019) used biochar produced from the gasi- pyrolysis of Eucalyptus was used to investigate the adsorp-
fication of wood waste to remove azo dye (Indosol Black tion of six phenolic endocrine-disrupting chemicals such as
­NF1200) from an aqueous solution. The batch adsorption estriol, estrone, estradiol, 4-tert-butylphenol, bisphenol and
was performed at 28 °C for 3 h at a speed of 200 rpm. The 17α-ethynylestradiol. The researchers reported that at a pH
study showed that at lower pH, the experimental adsorption range of 3–3.5, the hydrogen bond formation and electron-
efficiency was found to be 185 mg/g using the Freundlich donor acceptor interaction are predominant, thus leading to
model. Thus, wood waste-derived biochar was reported as maximum sorption of endocrine-disrupting chemicals. The
an efficient adsorbent from the removal of individual azo dye study showed that the composition of water played a signifi-
contaminated wastewater. cant role in the sorption capacity of endocrine-disrupting
chemicals. Estrone was found to have the highest sorption,
Removal of pharmaceutical drugs from wastewater while estriol had the least sorption. The complete removal
of estrone in sewage effluent was observed at 300 mg/L of
For many years, water bodies are constantly getting con- biochar dosage, while other compounds were removed at a
taminated with pharmaceutical and personal care products dosage of 400 mg/L.

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Table 5  Adsorption characteristics of pharmaceutical compounds by biochar


Feedstock Conversion Conversion Target con- Adsorption Adsorption Adsorption Isotherm References
technology temperature taminant temperature capacity pH
(°C) (°C) (mg/g)

Peanut shells Pyrolysis 300 Trichloroeth- 25 12.1 7.7 Langmuir Ahmad et al.
Soybean ylene 12.5 7.2 (2012)
stover
Peanut shells 700 31.7 11.3
Soybean 32 10.5
Stover
Maize straw Pyrolysis 300 Oxytetracy- 25 ± 0.5 759.4 5.5 Freundlich Jia et al. (2013)
cline
Oil palm fiber Pyrolysis 500 Ethylparaben 25 349.7 6 Langmuir Zhou et al.
(2019)
Bagasse Pyrolysis 600 Sulfamethoxa- 25 54.4 6 Langmuir Yao et al. (2018)
zole
Sulfapyridine 8.6 8.4
Pomelo peels Pyrolysis 700 Paracetamol 25 147 7 Langmuir Tran et al.
waste (2020)
Pure glucose 900 286
Wood waste Gasification 900 Rhodamine B 25 189.8 7 Langmuir Maneerung
et al. (2016)

Zhou et al. (2019) used oil palm fiber-derived activated matter, altered soil structure, reduced water holding capac-
biochar to study the adsorption of ethylparaben. Ethylpara- ity, high heavy metal content, fluctuating soil pH and salin-
ben, an endocrine-disrupting compound, was adsorbed onto ity as well as lower nutrient retention capacity of the soil
activated biochar with an adsorption capacity of 349.7 mg/g (Randolph et al. 2017). The enhancement of the soil quality
at room temperature. To et al. (2017) used palm kernel shell- and augmentation of organic matter can lower the exposure
derived activated carbon for the adsorption of pharmaceu- and susceptibility of the crops to drought and soil infertility.
tical drugs like atenolol, carbamazepine and acetobutolol Windeatt et al. (2014) reported soil application of biochar
with the maximum adsorption capacities of 0.69 mmol/g, derived from crop residues as one of the prominent advan-
0.72 mmol/g and 0.72 mmol/g, respectively. tageous tools available for enhancing soil organic matter.
Tran et al. (2020) used spherical and non-spherical bio- Sohi et al. (2009) reported that biochar has the potential in
char derived from pure glucose and pomelo peel wastes, enhancing the organic carbon content of the soil, thus bene-
respectively, for removing pharmaceutical pollutants from fiting the environment and soil quality. According to Hansen
water. The researcher pyrolyzed pomelo peel wastes at et al. (2015), the conversion of organic residues via gasi-
700 °C to generate non-spherical biochar and used hydro- fication could produce environmentally benign bioenergy
thermal carbonization of glucose at 190 °C, followed by along with biochar as a by-product for soil amendment and
pyrolysis at 900 °C to produce spherical biochar. Both the carbon sequestration. The authors reported that gasification
biochar was used to study the adsorption of paracetamol. biochar has extensive potential for increasing the production
The adsorption capacities for spherical and non-spherical of crops in coarse sandy soils. Crop production is enhanced
biochar samples were 286 mg/g and 147 mg/g, respectively, due to increased water retention capacity of the soil and the
at 25 °C and pH 7. development of root systems. It was suggested that depend-
ing on the precursors and the conversion technology used,
Soil amendment biochar could comprise 60% carbon with demonstrated sta-
bility toward microbial degradation. The post-soil applica-
The agricultural crop production has been gradually rising to tion can enable the soil carbon pool to sustain for decades.
meet the overwhelming demand of the growing population. Brewer et al. (2009) prepared several biochar samples
Moreover, the usage of chemical fertilizers and agricultural from pyrolysis and gasification of different biomasses such
products has put the soil at risk, leading to soil degrada- as corn stover, switchgrass, and wood biomass. The obtained
tion and subsequent reduction in crop production (Karthik biochar was then subjected to an eight-week soil incuba-
et al. 2020). The conventional agricultural practices of using tion field trial for studying the improvement in the treated
chemical fertilizers could result in the loss of soil organic soil as well as for measuring the plant growth. The authors

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2252 Environmental Chemistry Letters (2021) 19:2237–2259

reported that biochar properties and their impacts on soil technologies such as combustion, pyrolysis and gasification
vary extensively with various biochar feedstocks and oper- for power generation. The researchers developed an equa-
ating conditions. They also found that gasification-derived tion for evaluating operating cost and capital cost for all the
biochar showed favorable results in terms of carbon stability conversion technologies. The assessment was performed
indicators, determining the pH and cation exchange capacity starting from feedstock processing to its conversion for
of the soil. electricity generation using dual-fuel diesel engines. Fast
Shaaban et al. (2018) reviewed the application of bio- pyrolysis showed better performance for power generation
char in enhancing soil properties and mitigation of environ- in diesel engines among other technologies. The technol-
mental pollutions. The review demonstrated the economic ogy was also deemed profitable by involving low initial
and agronomic importance of biochar application to soil. investment for plant setup. Profitability in the long- or
According to the authors, the biochar plays an indispensable short-term is dependent on several factors, which include:
role in enhancing soil pH by reducing metal toxicity. The
increased soil pH enables the retention of essential elements 1. Transportation majorly affects the product cost of
by enhancing its anion exchange capacity. Because of the biofuels. Therefore, biorefineries established near the
enhanced cation exchange capacity of the soil, the water and agricultural farms or forested areas could significantly
nutrients retention capacities can be improved significantly. reduce the cost of biomass transportation and storage.
Biochar produced from different biomass and varied tem- The location of the biorefinery is also dependent on the
peratures could show broadly developed surface functional local market demand and existing competitors (Parker
groups, which help in the retention of nitrate compounds. et al. 2010; Ulonska et al. 2018).
The researchers also reported that biochar also has a positive 2. The integration of different processing plants for the
impact on soil fertility by improving the macro-elements utilization of co-products or intermediate products can
(e.g., nitrogen, potassium, magnesium, calcium, phospho- reduce the overall process expenditure. For example,
rous and sulfur) and microelements (e.g., zinc, manganese, biological and thermochemical technologies could be
boron, iron, bromine, copper, cobalt and molybdenum) in consolidated to reduce waste generation, enhance recy-
the soil. Biochar has a significant application in alleviating cling of materials, improve cogeneration and promote a
soil pollution as the carbonaceous product can reduce the circular economy (Nanda and Berruti 2020b; Wu et al.
soil’s metal toxicity and remediate heavy metals content. 2021).
The study showed that biochar restricts the bioavailability of 3. Determination of the potential market for every product
previously mentioned heavy metals and can enhance nitro- (Ulonska et al. 2018).
gen fixation and microbial activity to make the soil suitable 4. Recycling of wastewater generated during biorefinery
for high crop production. processing to recover value-added products can bring
profit and contribute toward establishing a clean envi-
ronment (Tobin et al. 2020).
Techno‑economic analysis 5. Evaluation of different subsidy and incentive schemes by
of thermochemical conversion the government for bioproduct generation could reduce
the operational cost of biorefineries and low-cost prod-
Biomass-derived biofuels are evolving as a potential uct development (Kangas et al. 2011; Pérez et al. 2017).
replacement for fossil fuel. The recent trend in biomass
utilization for the production of biochar followed by acti- It is, therefore, evident that techno-economic analysis of
vation for various valuable applications is also gaining a biomass conversion technology could play a prodigious
wide attention. However, the diverse utilization of biochar role in governing its commercialization and directing the
as a fuel, adsorbent, catalyst, soil conditioner and electro- market value of the co-products.
catalytic precursor material is dependent on its cost com-
petitiveness, energy efficiency and marketability. Techno-
economic analysis can help in determining the energy Lifecycle assessment
input and output as well as the production cost of biofuels,
biochemicals and value-added bioproducts (Borugadda The anthropogenic activities have emerged as a burden
et al. 2020). The economic and financial performances for the environment, which can be assessed by analyz-
of the biomass processing plants can also be determined ing the consumed resources and energy during the life-
by developing discounted cash flow rate models through time of a product and the resulting pollution and waste
techno-economic analysis. emissions. Lifecycle assessment is a method to assess the
Bridgwater et al. (2002) performed a comparative qualitative and quantitative environmental impacts of the
techno-economic analysis of thermochemical conversion end-products at different stages of their life (Lozano and

13
Environmental Chemistry Letters (2021) 19:2237–2259 2253

Lozano 2018). Lifecycle studies are used to analyze the Conclusion


lifecycle of a product from the cradle to the grave, which
starts with the extraction and processing of raw materials The anthropogenic activities have caused irreversible deterio-
or feedstocks followed by manufacturing, distribution and ration of the environment. Biochar is a thermally stable and
supply, and ending with consumption (Nanda et al. 2015). inexpensive carbon product, which can be synthesized from
In lifecycle analysis, overall priority is given to enhance different waste organic residues through thermochemical
the process involved or its product and involves mainly technology such as pyrolysis, carbonization, gasification and
four stages (Li and Mupondwa 2014). In the first stage, it torrefaction. The processing conditions such as temperature,
explains the goal and scope of the assessment. In the next heating rate, pressure, reaction time, vapor residence time,
step, inventory analysis is done, which gives a constructive equivalence ration, feedstock concentration, inherent feed-
explanation of the product system and about the material stock properties, catalysts and reactor configuration largely
and energy flows. Furthermore, it also sheds light on their influence the operation of the conversion technology as well
interactions with the environment. The third step involves as product yield and composition. Biochar can be activated
the assessment of the impact, which is performed by nor- to produce activated carbon for several value-added indus-
malization and by weighting. The final stage involves the trial and environmental applications. Compared to physical
critical review, sensitivity analysis and presentation of the activation, chemical activation is cost-effective and produces
outcomes. activated carbon with greater solid yield, higher carbon con-
Biochar and other value-added products from biomass tent, larger specific surface area and well-developed porosity.
conversion technologies have emerged as an effective way to Biochar and activated carbon have a wide range of appli-
mitigate various environmental challenges. Many research- cations, which help in mitigating several environmental
ers have extended their research on the lifecycle assessment challenges. The potential applications of biochar include its
of biochar production technologies to explore their environ- usage for preparing activated carbon, enhancing soil qual-
mental risks and impacts. Dutta and Raghavan (2014) stud- ity and removing pollutants from soil, air and wastewater,
ied lifecycle assessment for biochar systems using agricul- developing catalyst supports, carbon sequestration and
tural and forestry residues as feedstocks to determine their manufacturing numerous carbon-based specialty materials
environmental impacts. The results showed a reduction in such as biocomposites, electrochemical devices, biomedical
the emission of greenhouse gases when both agricultural products and cosmeceuticals.
and forestry residues were used as feedstocks for biorefinery. It is noteworthy that the usage of biochar depends on its
The reduction in gaseous carbon emissions, i.e., C ­ O2, CO physicochemical properties and economic feasibility. There-
and ­CH4 was mainly because of the formation of stable solid fore, techno-economic and lifecycle analyses are key tools in
carbon, i.e., biochar. The authors also reported that biochar estimating the market value of biochar along with major co-
production from biomass pyrolysis is more suitable for car- products of thermochemical conversion technologies such
bon sequestration rather than for solid fuel applications. as bio-oil, producer gas and syngas. All the main products
Ibarrola et al. (2012) studied the generation of bio- of interest along with the co-products generated during bio-
char and bioenergy through the different thermochemical mass conversion have their discrete importance and market
conversions of biodegradable wastes. The study showed value. Therefore, biochar production for various applications
slow pyrolysis as the optimal process based on carbon like wastewater treatment, soil amendment, solid fuels and
abatement (0.07 to 1.25 tons of C ­ O2 equivalent per ton of carbon sequestration can be profitable when bio-oil and gas
precursor treated), while the gasification method showed products are utilized within a biorefinery framework.
better performance based on electricity generation (i.e.,
0.9 megawatt-hours per ton of precursor).
Alhashimi and Aktas (2017) studied the performance Funding The authors would like to thank the Natural Sciences and
as well as the lifecycle and economic assessment of bio- Engineering Research Council of Canada (NSERC), Canada Research
Chairs (CRC) Program, Agriculture and Agri-Food Canada (AAFC)
char and activated carbon using meta-analysis. The energy and BioFuelNet Canada for funding this bioenergy research.
demands for biochar and activated carbon were 6.1 MJ/
kg and 9.7 MJ/kg, respectively. On the other hand, the Compliance with ethical standards
average greenhouse gas emissions from biochar and acti-
vated carbon were 0.9 kg C ­ O2 equivalent/kg and 6.6 kg Conflicts of interest None declared.
­CO2 equivalent/kg, respectively. The adsorption capacity
of zinc and chromium showed biochar as the least energy- Consent for publication All authors agree to publish this article in
Environmental Chemistry Letters.
consuming agent with reduced global warming potential
when compared to activated carbon. Human or animal rights No conflicts, informed consent, and human or
animal rights applicable.

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2254 Environmental Chemistry Letters (2021) 19:2237–2259

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and decreases the risk of phosphate contamination of waters.

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