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Renewable and Sustainable Energy Reviews 92 (2018) 958–979

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Renewable and Sustainable Energy Reviews


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

Microwave assisted preparation of activated carbon from biomass: A review T


a a a a a a a
Wenya Ao , Jie Fu , Xiao Mao , Qinhao Kang , Chunmei Ran , Yang Liu , Hedong Zhang ,

Zuopeng Gaoa, Jing Lia,b, Guangqing Liua, Jianjun Daia,
a
College of Chemical Engineering, Beijing University of Chemical Technology, 15 Beisanhuan East Road, Chaoyang District, Beijing 10029, China
b
GreenGenTech Energy Inc., 18 Gardengate Way, Ottawa, Ontario, Canada K2H 5Z2

A R T I C LE I N FO A B S T R A C T

Keywords: Activated carbon has been widely used as adsorbents, catalyst support and energy storage materials. Microwave
Microwave heating is a promising technique for thermochemical treatment and activation of activated carbons due to its
Activated carbon fast, selective, uniform and volumetric heating. Previous reviews mainly focused on specific feedstocks (e.g.
Biomass agricultural biomass or oil palm wastes) or ignored important parameters for microwave activation (e.g. mass of
Activation
activated carbon precursor). Characteristics of activated carbons prepared from conventional and microwave
treatment were not compared and economics of microwave activation were not described in previous studies.
This paper presentst a state of the art review of activation under microwave irradiation for various biomass
sources (e.g. agricultural wastes, woody biomass and sewage sludge). Characteristics of microwave heating,
main activation parameters, research progress and technology status of activated carbon preparation and re-
generation under microwave irradiation are investigated with key challenges and economics being addressed.
Characteristics of activated carbons made from microwave irradiation and conventional activation are compared
and the advantages of microwave-assisted preparation are highlighted. It shows that the BET
(Brunauer–Emmett–Teller) surface area, iodine number, methylene blue adsorption capacity and the yield of
activated carbons under microwave irradiation are up to 2500–3000 m2/g, 1800–2200 mg/g, 500–700 mg/g and
13–96 wt%, respectively, competitive with conventional methods on the quality of activated carbons and process
economics. Potential applications and future perspectives are described with pertinent information on activated
carbon preparation under microwave irradiation.

1. Introduction such as sawdust [20], coconut shells, fruit stones and peels [21–26],
peat [27] and bituminous coal [28].
Activated carbon (AC) has been proven to be an effective adsorbent AC consists of functional groups bonded to fused-aromatic rings,
for removing a wide variety of organic and inorganic pollutants, polar which would be expected to possess chemical properties similar to
and non-polar compounds in the aqueous phase or from gaseous en- those in the aromatic hydrocarbons. Surface functional groups on the
vironment [1,2], and has also been used in energy storage fields [3]. AC carbon matrix can be manipulated and adjusted by thermal, hydro-
has large porous surface area, tunable pore structure and surface thermal or chemical treatments for particular functions. Pyrolysing
chemistry, good thermostability at high temperatures in inert or re- hydrothermal char in the presence of KOH increased the surface area
duction atmospheres, low acid-base reactivity and receives much at- from 10 m2/g to > 1200 m2/g, due mainly to removal of acidic side
tention owing to its superior and efficient ability in air pollution control chains that would block pore access [29]. Hydrothermal chars have
[4–6], solvent recovery [7], food processing [8], wastewater treatment higher oxygen content than pyrolysis chars and have shown promises
(e.g. dyes, heavy metals, detergents, herbicides, pesticides and poly- for adsorption of metal cations from aqueous solutions (e.g. Cu and Cd),
aromatic hydrocarbons) [4,9–12], metal recovery [13], catalysis [29]. However, ACs prepared from hydrothermal chars were not sys-
[14–16], electrode materials for supercapacitors, porous matrix to host tematically investigated in previous studies. The sorption performance
active substances for cathodes [17], as well as improving odor and taste and pore characteristics of ACs depend on the physical and chemical
[18,19]. AC is generally produced from woody biomass, agricultural properties of precursors as well as activation techniques [30]. Various
wastes and coal by pyrolysis and activation at elevated temperatures, carbonaceous solids, either natural or synthetic, can be used as


Corresponding author.
E-mail addresses: 2015210059@mail.buct.edu.cn (W. Ao), 2016200226@mail.buct.edu.cn (J. Fu), 2016200223@mail.buct.edu.cn (X. Mao),
jjdai@mail.buct.edu.cn, daijianjun@hotmail.com (J. Dai).

https://doi.org/10.1016/j.rser.2018.04.051
Received 11 July 2017; Received in revised form 9 April 2018; Accepted 14 April 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
W. Ao et al. Renewable and Sustainable Energy Reviews 92 (2018) 958–979

Nomenclature DS Date stones


MB Methylene blue
AC Activated carbon MSW Municipal solid waste
BET Brunauer–Emmett–Teller MW Microwave
BUCT Beijing University of Chemical Technology MWA Microwave-assisted absorbers
C-C JCBERI The China-Canada Joint Centre for BioEnergy Research MWP Microwave-assisted pyrolysis
& Innovation NG Natural gas
DLTP Dielectric loss tangent parameter UBC University of British Columbia, Canada

precursors for preparation of ACs. The choice of precursor is largely development of porosity and favorable surface functionalities [44].
dependent on its availability, cost, purity, manufacturing processes and Conventional activation techniques, kinetic models for pyrolysis and
intended application of the product. Agricultural residues, forestry activation, applications and uses of agricultural residues based ACs are
wastes and sewage sludge are considered as important precursors be- reviewed [45]. However, the textural properties and characteristics of
cause they are cheap, renewable and available in large quantities [31]. ACs (e.g. specific surface area) are not linked to the corresponding
In addition, agricultural and forestry wastes have high carbon and low process parameters. The modification of AC surface chemistry has been
ash contents (0.2–10 wt%) [32–34]. frequently the target of a variety of AC beneficiation treatments. Oxi-
Physical and chemical activations are common techniques to pre- dation is one of the most conventional modifications used for ACs.
pare ACs. Chemical activation is usually preferred due to the simplicity, Oxidation methods involve the utilization of oxidizing gases or oxi-
shorter activation time, higher yield, lower temperature and better dizing solutions (i.e. nitric acid, hydrogen peroxide, chlorine water,
development of the porous structure. Recently, microwave (MW) acti- etc.) to introduce carbon–oxygen surface groups in ACs [46]. Research
vation becomes a viable alternative to conventional methods in pre- aiming at modifying the surface chemistry of ACs should pay much
paration of ACs, due mainly to its unique characteristics such as fast, attention to a parallel study of the porous structure since porous
selective, uniform and volumetric heating, instant and accurate control, structure considerably affects the behavior and performance of ACs.
non-direct contact between the heating source and heated materials. Textural characteristics, surface chemistry and oxidation of ACs have
The equipment size is reduced owing to the fast reaction rate under MW been reviewed and interpreted by Daud and Houshamnd [47]. It was
irradiation [35]. MW heating increases the carbon yield, improves the reported that the changes in surface chemistry and textural character-
AC quality, provides high energy efficiency, minimizes formations and istics of ACs treated by a specified oxidant were not similar, and in some
emissions of hazardous materials, thereby rendering the technique en- cases, were in conflict. The inconsistencies were possibly attributed to
vironmentally friendly [36–39]. the diversity of used ACs, oxidants, oxidation methods, treating pro-
Detailed comparisons of characteristics of ACs made from MW ac- cedures, as well as analysis methods [47].
tivation and conventional techniques are not provided and economics
of MW activation are not addressed in previous studies. Previous re-
2.2. Heating rate and non-uniformity of heating
views either focuses on specific feedstocks (e.g. agricultural biomass or
oil palm wastes) or ignores important parameters of MW activation
The heating techniques strongly affect the physical and chemical
(e.g. mass of AC precursor activated in the reactor under MW irradia-
characteristics of ACs. For conventional heating (e.g. electric, steam and
tion). This paper presents a comprehensive review of AC activation
flue gas heating), the heat source heats the carbon bed from outer
under MW irradiation for different biomass sources (e.g. agricultural
surface to its interior through convection, conduction, and radiation
wastes, woody biomass and sewage sludge), and summarizes research
mechanisms, and results in surface heating of the bed and different
progress and technology status of AC preparation under MW irradia-
temperature distribution for particles of different shapes and sizes,
tion. The review compares characteristics of ACs made from conven-
generating a temperature gradient from the hot surface to the interior
tional methods and MW activation and the advantages of MW-assisted
[81]. Some authors provided information of particle size, shape and
preparation of ACs are highlighted. The MW heating characteristics,
moisture content of AC precursors, others didn’t even mention these
main activation parameters, key challenges and future perspectives are
parameters [82]. Particle size, shape and moisture content affect
described, providing the readers with pertinent information on MW-
heating rate and temperature profile of bulk solids and the individual
assisted preparation of ACs.
particles. The surfaces, edges and corners are generally hotter than the
inside of the particle. Small particle size (e.g. < 0.2 mm) and dry AC
2. Activated carbon from conventional methods and the precursors are beneficial to avoid uneven heating. However, size re-
drawbacks duction and drying are energy intensive processes and increase the total
cost of ACs production. Gas-solid contacting characteristics of fixed bed
2.1. Conventional methods for activated carbon preparation and peculiar properties of AC precursors always lead to non-uniform
heating of bulk solids and individual particles.
Carbon materials with low oxygen content, basic properties, highly To avoid this thermal gradient, a slower heating rate at intermediate
hydrophobic characteristics and resistance to aging can be obtained by final temperatures with isothermal holding is generally used, increasing
appropriate thermal treatments in different gaseous environments the duration of the preparation process, thereby resulting in greater
[40–42], which is usually achieved by convective, conductive and ra- energy consumption and higher expenses [81,83,84]. The thermal
diative heating of the AC precursor in fixed bed (e.g. tube reactor and gradient impedes the release of pyrolysis gases to the surroundings.
vertical shaft kiln), moving bed (e.g. rotary kiln and multiple hearth Hence some volatile components may remain inside the particles,
furnace) or fluidized bed reactors. Conventional AC preparation giving rise to carbon deposition problems. The deposited carbon is
methods are mainly physical activation, chemical activation and com- possible to obstruct the microporous network, leading to distortion and
binations of the above techniques ( Table 1). The temperature, reaction inhomogeneous microstructure, low values of total pore volume and
time and impregnation ratio are all important variables for the extent of BET surface area [19,85–87]. Consequently, the quality of AC products
carbonization reactions, and the textures and properties of the pro- is frequently inferior to the desired result [35,85]. Fast firing is also a
duced ACs [43]. Selection of appropriate activation techniques and disadvantage of the conventional heating method, depending on dif-
optimization of parameters could improve AC properties via ferent AC precursors, process configurations, reactor types and

959
Table 1
Conventional activation methods and main process parameters.
W. Ao et al.

Conventional methods Description Advantages Disadvantages Ref.

Physical activation One-step or two-step; carbonization/pyrolysis and activation; CO2, steam or Environmentally friendly and there are no specific High activation temperature, long activation time, low [48,49]
oxygen as oxidizing gases requirements for the construction materials carbon yield, low quality of ACs (e.g. low specific surface
areas), and large energy consumptions
Chemical activation One-step or two-step; precursor materials are impregnated with chemical reagents Lower carbonization and activation temperatures, Severe corrosion to the equipment, strict requirements [44,50–59]
and heated in an inert or oxidizing gas atmosphere; Steam is usually preferred due shorter carbonization and activation times, thus for washing to remove excessive residues of activation
mainly to smaller molecules and larger diffusion rate. Main activation reagents are requiring smaller energy consumption. Activation reagents, and adverse effects on the environment and
alkali metals (e.g. KOH, K2CO3, NaOH, and Na2CO3), alkaline earth metals (e.g. reagents promote pyrolytic decomposition, inhibit tar public health
AlCl3, FeCl3, and ZnCl2) and some acids (e.g. H3PO4 and H2SO4) formation and increase carbon yields.
Physiochemical Combination of physical and chemical activation: 1) carbonization with chemical Applied when chemical reagents were not fully More complex process and higher investment [60–69]
activation impregnation onto the raw precursors followed by physical activation; 2) eliminated even after washing, promoting pore
carbonization and activation of impregnated char in oxidizing gas or inert gas formation; development of unique textural and chemical
atmosphere characteristics of ACs
Main process parameters of conventional methods
Raw material Particle size (mm) Carbonization conditions (oC/ Activation condition oC/h Physical and chemical treatment Process information Ref.
h) (heating rate)
Olive 750/2 (10oC/min) 750/2 (10oC/min) Steam/N2 One-step physical pyrolysis/activation [70,71]
o
Straw 750/2 (10 C/min) 750/2 (10oC/min) Steam/N2 One-step physical pyrolysis/activation [70,71]
Birch 750/2 (10oC/min) 750/2 (10oC/min) Steam/N2 One-step physical pyrolysis/activation [70,71]
Bagasse 750/2 (10oC/min) 750/2 (10oC/min) Steam/N2 One-step physical pyrolysis/activation [70,71]
Miscanthus 750/2 (10oC/min) 750/2 (10oC/min) Steam/N2 One-step physical pyrolysis/activation [70,71]
Sunflower shell < 0.25 1000/0.5(20oC/min); 1000oC/10min(20oC/ Steam/N2 Two-step physical pyrolysis and activation [72]
min);
N2 of 40mL/min N2 and steam of 40mL/
min
o
Pinecone < 0.25 1000/0.5(20 C/min); 1000oC/10min(20oC/ Steam/N2 Two-step physical pyrolysis and activation [72]

960
min);
N2 of 40mL/min N2 and steam of 40mL/
min
Rapeseed < 0.25 1000/0.5(20oC/min); 1000oC/10min(20oC/ Steam/N2 Two-step physical pyrolysis and activation [72]
min);
N2 of 40mL/min N2 and steam of 40mL/
min
o
Cotton refuse < 0.25 1000/0.5(20 C/min); 1000oC/10min(20oC/ Steam/N2 Two-step physical pyrolysis and activation [72]
min);
N2 of 40mL/min N2 and steam of 40mL/
min
Olive refuse < 0.25 1000/0.5(20oC/min); 1000oC/10min(20oC/ Steam/N2 Two-step physical pyrolysis and activation [72]
min);
N2 of 40mL/min N2 and steam of 40mL/
min
Pistachio-nut shells 1–2 500/2(10oC/min); 800/2.5 (10oC/min); N2/CO2 Two-step physical activation [73]
N2 of 150mL/min CO2 of 100mL/min
Hazelnut shell 1–1.25 750/10-18; ZnCl2 (30 wt%) One-step chemical activation; Max. phenol [74]
N2 of 40mL/min adsorption=190 mg/g at 750oC/14h; Max. methylene
blue adsorption=5.1 mg/g at 750/850oC and 18h
Walnut shell 1–1.25 750/10; ZnCl2 (30 wt%) One-step chemical activation; Max. phenol [74]
N2 of 40mL/min adsorption=170 mg/g at 750oC/10h;Max. methylene
blue adsorption=9 mg/g at 750oC/10h or 850oC/6h
Apricot stone 1–1.25 750/18; ZnCl2 (30 wt%) One-step chemical activation; Max. methylene blue [74]
N2 of 40mL/min adsorption=2 mg/g at 750oC/18h
Almond shell 1–1.25 800/24; ZnCl2 (30 wt%) One-step chemical activation; Max. methylene blue [74]
N2 of 40mL/min adsorption=3 mg/g at 800oC/6h or 850oC/24h
o o
Corn cob 1.19–1.68 500-800 C (10 C/min); N2 of CO2 activation for 1 h and 15 wt% KOH and 37.5 wt% K2CO3 Impregnation of dry Two-step chemical and physical activation [75]
200mL/min; N2 cooling biomass with chemical reagents;
(continued on next page)
Renewable and Sustainable Energy Reviews 92 (2018) 958–979
W. Ao et al. Renewable and Sustainable Energy Reviews 92 (2018) 958–979

operating conditions [85] (Table 2).

[76]

[76]

[77]

[77]

[78]

[79]

[80]
Ref.

3. Characteristics of microwave heating

3.1. Classification of electromagnetic waves

MW is a form of electromagnetic radiation with wavelengths ran-

Two-step physical and chemical activation.

One-step physical and chemical activation.


ging from as long as 1 m to as short as 1 mm with frequencies between
0.3 and 300 GHz. These wavelengths are regulated for industrial, sci-
entific and medical purposes to avoid interference. For industrial MW
processing of various materials, the available frequencies are
Two-step chemical activation
One-step chemical activation

One-step chemical activation

One-step chemical activation

Two-step physical activation

0.915 GHz, 2.45 GHz, 5.8 GHz, and 24.124 GHz; For domestic purpose,
2.45 GHz is generally used [88]. However, 0.915 GHz domestic MW
ovens are also available in the markets. The corresponding wavelengths
used in domestic MW heating are 12 or 33 cm, providing highly effi-
Disadvantages

cient and less penetrative heating. More information about MW is


available in previous studies [32].

3.2. Heating mechanism


Impregnation ratio (KOH/char)=1.8, 2 h of incubation

MW heating is a sub-category of dielectric heating at certain fre-


Impregnation ratio (KOH/biomass)=1.8, 2 h of

quencies. The mechanism of dielectric heating relies on dipolar and


interfacial polarization effects, and the materials receive energy
through dipole rotation and ionic conduction. The electric field com-
ponent of MW causes polar molecules (e.g. water) to rotate and try to
align in both permanent and induced dipoles at certain frequency called
dipolar polarization. Friction and collision generated by the increased
K2CO3/dry biomass=1;

molecular rotation and moving result in heat loss and MW heating [98].
ZnCl2/dry biomass=1;

ZnCl2/grape stalk=2

In general, the higher of the induced polarity, the greater of the influ-
ence of MW, which indicates selective, uniform and volumetric heating
characteristics of MW irradiation [99,100].
Advantages

CO2/ZnCl2;
incubation

H2SO4/Air

Dielectric loss tangent parameter (DLTP) quantifies a dielectric


N2/CO2

material's inherent dissipation of electromagnetic energy into heat,


expressed by the ratio of dielectric loss factor (imaginary permittivity)
to dielectric constant (relative real permittivity), where dielectric con-
350/2;550/2 (10oC/min);

CO2 flow rate of 100mL/


CO2 flow of 500 mL/min

Air flow rate of 100 mL/


400-1000/1 (10oC/min);

400-1000/1 (10oC/min);

650/0.3;750/1; 850/2;

stant specifies the amount of electromagnetic incident energy reflected


550/1.5(12 C/min);

550/1.5(12oC/min);

700/2 (20oC/min);

and absorbed by the treated material and the dielectric loss factor
N2 of 100mL/min

N2 of 100mL/min

corresponds to the amount of electric energy dissipated in the form of


N2 atmosphere

N2 atmosphere
o

heat within the material. DLTP is used to characterize MW energy ab-


sorption and is useful in studying MW heating which is the non-contact
energy transfer process and uses electromagnetic wave of high-speed
min

min

alternating frequency to heat the object [32]. Large amounts of heat can
be transferred to the interior of the material as shown in Fig. 1. How-
CO2 flow rate of 100mL/min
N2 flow rate of 500 mL/min

N2 flow rate of 100mLmin

ever, most biomass materials show relatively low MW absorption ca-


pacity when subjected to MW radiation. These materials cannot be
550/1.5(12 C/min);

600/2 (10oC/min);

700/2 (20oC/min);

heated to the desired temperature owing to their inability to absorb


850/1 (4 C/min);
N2 atmosphere

sufficient amount of MW energy [34]. This problem can be solved by


o

addition of microwave absorbers (MWAs) into the heating system.


o

Carbon-based materials are effective MWAs and can be transformed


into new materials with modified properties under MW irradiation
[40]. MWAs may act as catalysts in different heterogeneous reactions
[32]. The chemical structure, shape and size of MWAs determine the
number and intensity of the tiny micro-plasma (small sparks or electric
arcs) spots generated during MW heating [101]. Micro-plasmas are of
Description

0.3–0.177

two types, depending on shape and nature: ball lighting and arc dis-
0.5–1.5
< 0.5

< 0.5

<4

<4

charge effects. The appearance of micro-plasmas is limited to tiny space


1-2

and lasts only for fractional second [40]. Hence MW heating may
Conventional methods

generate hot spots inside the carbon particles and inside the bulk solids.
Table 1 (continued)

More information about micro-plasmas was shown in previous litera-


Plane tree seed

tures [102]. Different mechanisms of MW heating and conventional


Cherry stones
Orange peel

Orange peel

Grape stalk
Corn stalks

Corn stalks

heating are the major reasons for different properties of ACs prepared
from conventional methods and under MW irradiation, depending on
different biomass types and properties, reactor types and additives to
biomass (Table 2).

961
W. Ao et al. Renewable and Sustainable Energy Reviews 92 (2018) 958–979

Table 2
Comparison of microwave and conventional heating for activated carbon preparation.
Heating methods Advantages Disadvantages References

MW heating Fast, volumetric and uniform heating; Non-contact technique; Hot spots caused by micro-plasma and non-uniformity of [19,89–94]
Lower activation temperature; Shorter processing time and materials; Inaccurate temperature measurement and control;
energy savings; Temperature gradient from the centre to the Thermal runaway; Possible leakage of MW; Economics needs to be
outer surface; Micro-plasmas thermal and catalysis effects; improved; Process scale-up is not mature.
Light components are easily released to create more pores;
Improved efficiency; Immediate start-up and shutdown;
Improved safety; Smaller equipment size and less feedstock
pre-treatment needed.
Conventional Relatively mature process and easy scale-up Relatively high thermal gradient inside the particle; non- [83,84,87,91,95–97]
heating effectiveness of removal of gaseous products; Carbon deposition
and obstruct microporous network; Low pore volume and BET
surface area; Distortion and inhomogeneous microstructure;
Longer treating time and high cost; Possible fast firing.

Fig. 1. Schematic of temperature profile and direction of heat transfer (a) Conventional heating (b) MW heating (red-high temperature, blue-low temperature). (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 2. Schematic of AC preparation from biomass under MW irradiation (CH-conventional heating, CR-chemical reagents, MW-microwave, PA-physical activation
agents, adapted from [97,110]).

962
Table 3
Comparison of ACs prepared from MW activation, conventional physical and chemical activation.
W. Ao et al.

Precursors Process parameters SBET (m2/g) Vtotal (cm3/g) Average pore Yield (wt%) Langmuir (m2/ Ref.
size (nm) g)

Peanut shells Two-step: MW treatment followed by carbonization; 2.50g of size < 0.2mm, mixed with 40 SBET=395.8 Vtotal=0.210 3.54 517.61 [82]
mL of 4N H2SO4 solution; MW power=700W, activation time=20 min; pyrolyzed (heating Sexternal=54.8
rate of 5oC/min from 25 to 800oC) at 800oC for 5 h under N2 flow of 100 ml/ min; Adsorption
capacity of direct black 38=110.6 mg/g; Adsorption capacity of reactive red=284.5 mg/g
Peanut shells One-step physical activation; 6g peanut shell of size < 0.2mm, heating rate=5°C/min from 25 SBET=370.1 Vtotal=0.174Sexternal=51.4 2.56 490.70 [82]
to 800°C; 5h at 800°C; N2 flow of 100 ml/min.
Coconut shell Two-step physical activation. Particles of < 2 mm; heating rate=10°C/min, hold at 1000°C for 901 Vtotal=0.618Vmicro=0.46 2.745 16 [114]
2h under N2 flow; 30g char, heating rate=50°C/min, activation temperature 900°C at 30min,
steam=1.35 g/min
Coconut Shells Two-step MW physical activation: Particle size 3.35–4.75mm; Carbonization: electric tube 1011 Vtotal=0.59Vmicro=0.52Vmeso=0.067 [115]
furnace, stainless steel reactor. 1000°C for 2 h at a heating rate of 10°C/min, N2 flow of 100ml/
min;
Activation: 25g char, maximum MW=3kW, tubular furnace, activation temperature=900°C
at 15min, steam=1.35g/min
Coconut Shells Two-step MW physical activation: same as above except MW activation time=75min 2079 Vtotal=1.21Vmicro=0.97Vmeso=0.24 42.2 [115]
Coconut Shells Two-step MW physical activation: same as above except MW activation time=60min and CO2 1162 Vtotal=0.72Vmicro=0.57Vmeso=0.15 [115]
activation (600ml/min)
Coconut Shells Two-step MW physical activation: same as above except MW activation time=210min and 2288 Vtotal=1.3Vmicro=1.01Vmeso=0.29 37.5 [115]
CO2 activation (600ml/min)
Coconut Shells Two-step MW physical activation: same as above except MW activation time=15min and CO2- 1139 Vtotal=0.69Vmicro=0.59Vmeso=0.1 [115]
steam mixture activation (600ml/min + 1.35g/min):
Coconut Shells Two-step MW physical activation: same as above except MW activation time=75min and CO2- 2194 Vtotal=1.29Vmicro=1.01Vmeso=0.28 - 39.2 - [115]
steam mixture activation (600ml/min + 1.35g/min)
Coconut shell Two-step chemical activation: Particles of 0.25-0.425mm, heating rate=20oC/min, 500°C for 2825 Vtotal=1.498Vmicro=1.143Vmeso=0.355 2.27 18.8 [57]

963
2h; NaOH:char=3(g/g), Activation time of 1.5h at 700°C; Adsorption of methylene
blue=916.26mg/g
Coconut shell Two-step chemical activation: same as above except NaOH:char=2 1842 Vtotal=0.927Vmicro=0.775Vmeso=0.152 1.8 23.4 [57]
Coconut shell Two-step chemical activation: same as above except NaOH:char=1 783 Vtotal=0.378Vmicro=0.356Vmeso=0.022 1.63 28.9 [57]
Coconut shell Two-step physical activation. 1926 Vtotal=1.26 2.616 9 [114]
Particles of < 2 mm; Vmicro=0.931
heating rate=10◦C/min, hold at 1000oC for 2h under N2 flow;
30g char, heating rate=50 °C/min, steam=1.35 g/min, 900°C at 120min.
Coconut shell Two-step physical activation. 697 Vtotal=0.562 3.222 19 [114]
Particles of < 2 mm; Vmicro=0.331
heating rate=10◦C/min, hold at 600°C for 2h under N2 flow;
30g char, heating rate=50 °C/min, steam=1.35 g/min, 900°C at 30min.
Orange peels MW activation. 500g, particle size=1-2 mm, K2CO3 pellet/char)=1.25 Carbonization: SBET=1104.45 Vtotal=0.615 2.227 1661.04 [116]
T=700°C, N2 flow=150ml/min;MW=600W, microwave radiation time 6 min, N2 of 300ml/ Smiro=420.09 Vmicro=0.247
min for activation, Sexternal=420.09 Vmeso=0.368
Orange peels One-step chemical activation. SBET=477 Vtotal=0.23 1.8 20 [77]
Carbonization/activation: Smiro=422 Vmicro=0.21
K2CO3/biomass=1, heating rate=10°C/min, 700°C at 1 h. N2 of 100mL/min Sexternal=35 Vmeso=0.02
Orange peels One-step chemical activation. SBET=822 Vtotal=0.5 2.3 33 [77]
Carbonization/activation: Smiro=213 Vmicro=0.09
ZnCl2/biomass=1, heating rate=10°C/min, 700°C at 1 h. N2 of 100mL/min Sexternal=669 Vmeso=0.41
Orange peels One-step chemical activation. SBET=1352 Vtotal=0.79 2.3 11 [77]
Carbonization/activation: Smiro=505 Vmicro=0.22
K2CO3/biomass=1, heating rate=10°C/min, 950°C at 1 h. N2 of 100mL/min Sexternal=847 Vmeso=0.57
Cotton stalk One-step MW activation. 6g dry cotton stalk of size < 2mm, mixed with 30ml KOH solution at SBET=729.33 Vtotal=0.38 2.08 11 1015.46 [86]
ambient temperature for 24 h at KOH/cotton stalk =0.6, then activated at MW power=680W, Smiro=529.46 Vmicro=0.26
radiation time=10min; Iodine number=1100mg/g, MB=186mg/g (294.12mg/g- Langmuir) Sexternal=199.88 Vmeso=0.12
(continued on next page)
Renewable and Sustainable Energy Reviews 92 (2018) 958–979
Table 3 (continued)

Precursors Process parameters SBET (m2/g) Vtotal (cm3/g) Average pore Yield (wt%) Langmuir (m2/ Ref.
W. Ao et al.

size (nm) g)

Cotton stalk One-step MW activation. 6g dry cotton stalk of size < 2mm, mixed with 30ml K2CO3 solution SBET=621.74 Vtotal=0.38 2.43 869.70 [86]
at ambient temperature for 24 h at K2CO3/cotton stalk =0.8, activation MW power=660W, Smiro=384.67 Vmicro=0.11
radiation time=8min; Iodine number=820mg/g, MB=178mg/g (285.71mg/g- Langmuir) Sexternal=236.8 Vmeso=0.27
Cotton stalk One-step MW activation. Dry cotton stalk of size < 2mm, 1.6 g Zn/g precursor, 24 h SBET=794.84 Vtotal=0.63 3.2 37.92% - [117]
impregnation in ZnCl2 solution (20-50wt%) at room temperature, then activated at glass Smiro=156.69 Vmicro=0.083
reactor under MW=560W, activation time 9 min. Iodine number=972.92 mg/g, methylene Sexternal=638.15 Vmeso=0.55
blue adsorption=193.5 mg/g
Cotton stalk One-step MW activation. Particle size < 2mm, 6 g dried cotton stalk, mixed with 30mL of SBET=653.82 Vtotal=0.476 2.92 42.95 [118]
H3PO4 (concentrations in the range of 20-50v%), soaked for 20h. MW=400W, radiation time Smiro=127.18 Vmicro=0.058
8 min. Iodine number= 885.14mg/g Sexternal=525.64 Vmeso=0.419
Lotus stalks One-step MW activation. Particle size 0.5-1 mm, H3PO4/lotus stalk=2, after soaking SBET=1432 Vtotal=1.337 3.74 40.1 [119]
overnight, radiation power of 700W, radiation time 15 min Smiro=453.93 Vmicro=0.306
Sexternal=928.39 Vmeso=1.031
Lotus stalks One-step chemical activation. Particle size 0.5-1 mm, H3PO4/lotus stalk=2, after soaking SBET=1220 Vtotal=1.191 3.90 56.3 [119]
overnight, heated to 450°C for 1 h Smiro=502.71 Vmicro=0.286
Sexternal=717.29 Vmeso=0.905
Rice husk Two-step MW activation. Dried sample was carbonized at 700°C under N2 flow. Char produced SBET=752 Vtotal=0.64 3.414 1147 [120]
was soaked in KOH solution with an KOH/char impregnation ratio of 1:0.75 (wt%); Smiro=346 Vmicro=0.26
MW=600W, irradiation time 7 min; Washed by deionized water and 0.1 N HCl Sexternal=406 Vmeso=0.38
Rice husk Two-step MW activation. Dried sample was carbonized at 700°C under N2 flow; Char produced SBET=1165 Vtotal=0.78 2.689 1760 [120]
was soaked in K2CO3 solution with a K2CO3/char impregnation ratio of 1:0.75 (wt%); Smiro=607 Vmicro=0.33
MW=600W, irradiation time 7 min; Washed by deionized water and and 0.1 N HCl Sexternal=558 Vmeso=0.45
Rice husk Two-step chemical activation. 3 g of particle size of 2–5 mm and then dried further at 105°C SBET=2297 Vtotal=1.882 3.2 20.2 [121]
for 12 h, torrefaction temperature: 220°C, N2 150 ml/min flow rate; 20 min torrefaction time; Smiro=2164 Vmicro=0.906
then 550°C for 5 min; NaOH:char=3:1 (mass ratio), heating rate of 5°C/min, 400-800°C; wash

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by 10 wt% HCl and distilled water, dried at 105°C for 10h
Rice husk Torrefaction temperature: 250°C, others are the same as above SBET=2348 Vtotal=1.83 3.12 21.1 [121]
Smiro=2144 Vmicro=0.921
Rice husk Torrefaction temperature: 280°C, others are the same as above SBET=2679 Vtotal=1.888 2.82 23 [121]
Smiro=2494 Vmicro=1.053
Rice husk No torrefaction, others are the same as above SBET=2046 Vtotal=1.632 3.2 19.3 [121]
Smiro=1986 Vmicro=0.817
Sawdust pellets Two-step MW activation. 8X10mm pellets,7.6% moisture, N2 of 170ml/min at 400°C under SBET=387 Vtotal=0.24 2.0 24.7 [112]
MW irradiation, kept 60 min for char production; Physical activation of char at 600°C in CO2 Smiro=370 Vmicro=0.2
atmosphere of 250ml/min under MW irradiation for 60 min Sexternal=17
Sawdust pellets Two-step MW activation. Same as above except physical activation of char at 700°C. SBET=426 Vtotal=0.27 2.0 25 [112]
Smiro=408 Vmicro=0.22
Sexternal=18
Sawdust pellets One-step MW activation. 8X10mm pellets, 7.6% moisture, physical activation of sawdust SBET=367 Vtotal=0.23 2.56 [112]
pellet at 600°C for 60 min under MW irradiation Smiro=352 Vmicro=0.19
Sexternal=15
Wood sawdust Two-step activation. 500 g of dried sawdust into a tubular furnace and heating to a SBET=1496 Vtotal=0.864 2.3 80 2245.53 [122]
carbonization temperature of 700°C at N2 flow rate of 150 mi/min; K2CO3: Wood Vmicro=0.47
sawdust=1.26(g/g); activation MW power=600W, activation time=6 min; MB Vmeso=0.394
adsorption=423.2 mg/g
White pine wood One-step MW activation. Particle size 0.3-3.3mm, impregnated with a ZnCl2 aqueous solution SBET=1459 Vmeso=0.7 38.1 [20]
powders and dried at 110°C to obtain a mixture with a mass ratio of ZnCl2 to wood=2.5. 10g sample
placed at quartz reactor, and heated at MW=700W, activation time 10 min, N2 flow of 20 ml/
min
Iodine number=1050 mg/g, MB=200 mg/g
White pine wood One-step MW activation. Same as above except ZnCl2/wood=1.5. Iodine number=1100 mg/ SBET=1379 Vmeso=0.17 37 [20]
powders g, MB adsorption=160 mg/g.
White pine wood One-step MW activation. Same as above except ZnCl2/wood=0.75. Iodine number=1060 mg/ SBET=1048 Vmeso=0.12 36.2 [20]
powders g, MB adsorption=140 mg/g.
(continued on next page)
Renewable and Sustainable Energy Reviews 92 (2018) 958–979
Table 3 (continued)

Precursors Process parameters SBET (m2/g) Vtotal (cm3/g) Average pore Yield (wt%) Langmuir (m2/ Ref.
W. Ao et al.

size (nm) g)

Sapelli sawdust One-step MW activation. 100 g of Sapelli sawdust (< 300 μm), 100 g of inorganic components SBET=914.08 Vtotal=0.52 [108]
(20% lime + 80% ZnCl2) and 45.0 mL of water were added and thoroughly mixed to produce Smiro=518.65 Vmicro=0.25
a homogeneous paste at inorganic:organic ratio=1; 30.0 g of the sample was placed in a Sexternal=395.43 Vmeso=0.27
quartz reactor under MW=1200W for 320s with N2 of 200 ml/min
Sapelli sawdust One-step MW activation. Same as above except inorganic:organic ratio=1.5 SBET=874.72 Vtotal=0.55 [108]
Smiro=560.6 Vmicro=0.27
Sexternal=314.11 Vmeso=0.28
Sapelli sawdust One-step MW activation. Same as above except inorganic components are (20% lime+40% SBET=805.06 Vtotal=0.44 [108]
ZnCl2+40% FeCl3) and inorganic:organic ratio=1 Smiro=435.17 Vmicro=0.21
Sexternal=369.89 Vmeso=0.23
Sapelli sawdust One-step MW activation. Same as above except inorganic components are (20% lime+40% SBET=647.05 Vtotal=0.34 [108]
ZnCl2+40% FeCl3) and inorganic:organic ratio=1.5 Smiro=405.89 Vmicro=0.20
Sexternal=241.15 Vmeso=0.14
Woody biomass One-step chemical activation. Particle size of 0.5-1 mm, impregnation with 50% H3PO4, acid SBET=761 Vtotal=0.618 3.2 [123]
birch solution: biomass=1.5; Carbonization temperature 600°C in N2 for 1h at heating rate of 3°C/ Vmicro=0.297
min. Iodine number=900 mg/g Vmeso=0.321
Woody biomass One-step chemical activation. Same as above except nitrogen and steam (120 ml/min) gas SBET=1290 Vtotal=0.939 3.0 [123]
birch atmosphere. Iodine number=1200mg/g Vmicro=0.471
Vmeso=0.468
Woody biomass One-step chemical activation. Same as above except steam atmosphere and carbonization SBET=1360 Vtotal=1.026 3.0 [123]
birch temperature=700°C. Iodine number=1280mg/g Vmicro=0.485
Vmeso=0.541
Bamboo One-step MW and chemical activation. Dried particle size=1-2mm, 5.0 g precursor, soaked SBET=1432 Vtotal=0.696 47.8 [107]
with H3PO4 at room temperature for 48 h; activation MW=350W, radiation time 20min, Smiro=1112 Vmicro=0.503
H3PO4/carbon 1:1, quartz reactor, N2 of 40 mL/min Sexternal=320 Vmeso=0.193

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Bamboo Two-step MW activation. H3PO4/carbon precursor=1, activation in an electric furnace under SBET=1409 Vtotal=0.671 1.9 [124]
N2 flow of 100 mL/min at 600°C, heating rate of 5°C/min, activation time 90 min; Resultant Smiro=1075 Vmicro=0.49
AC particle size 1-2 mm; Modification: 2.0 g AC was placed in a tubular quartz reactor for Sexternal=334 Vmeso=0.181
modification, N2 flow of 150 mL/min, MW=200W, activation time 2 min; total amounts of the
acidic groups were 92.2% of AC; pHpzc value=3.45; MB adsorption=224 mg/g
Bamboo Two-step MW activation. Same as above except MW activation time of 5min. pHpzc SBET=1357 Vtotal=0.687 2.02 [124]
value=3.5, MB adsorption=241.7 mg/g Smiro=976 Vmicro=0.477
Sexternal=381 Vmeso=0.21
Bamboo Two-step MW activation. Same as above except MW activation time of 10min. pHpzc SBET=1323 Vtotal=0.699 2.11 [124]
value=3.6, MB adsorption=286.1 mg/g Smiro=920 Vmicro=0.448
Sexternal=403 Vmeso=0.236
Bamboo One-step chemical activation. 5 g precursor, electrical furnace, heating rate of 10°C/min, SBET=1215 Vtotal=0.56 46.9 [107]
T=600°C, H3PO4/carbon=1:1, activation time 30 min Smiro=986 Vmicro=0.448
Sexternal=229 Vmeso=0.112
Bamboo One-step chemical activation. Same as above except activation time 60 min SBET=1416 Vtotal=0.673 43.4 [107]
Smiro=1132 Vmicro=0.511
Sexternal=284 Vmeso=0.162
Industrial waste One-step MW activation. Lignin/ZnCl2=1.5, impregnation time=4 min, MW radiation SBET=1164 Vtotal=0.64 2.08 60.73 [125]
lignin time=4min; carbonized at 600°C for 1 h in a closed stainless-steel reactor placed in Smiro=1102 Vmicro=0.457
programmable furnace under self-generated environment Sexternal=162 Vmeso=0.174
Industrial waste One-step chemical activation. Lignin/ZnCl2=1.5, impregnation time=48 h; carbonized at SBET=921.2 Vtotal=0.506 2.248 60.49 [125]
lignin 600°C for 1 h in a closed stainless-steel reactor placed in programmable furnace under self- Smiro=702.2 Vmicro=0.329
generated environment Sexternal=218.5 Vmeso=0.155
Sewage sludge One-step MA chemical activation. A portion of 100 g sample was impregnated by certain SBET=377.1 Vtotal=0.243 2.78 [126]
amount of 5 M ZnCl2 solutions for 24 h. impregnation ratio (mass of activating agent/raw
material) of 1:1.5; Samples were subjected to vacuum drying at 105°C for 24 h, then placed in
a quartz reactor, and heated in a MW furnace with 800W power under N2 flow of 10 mL/min
for 10 min
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Renewable and Sustainable Energy Reviews 92 (2018) 958–979
Table 3 (continued)

Precursors Process parameters SBET (m2/g) Vtotal (cm3/g) Average pore Yield (wt%) Langmuir (m2/ Ref.
W. Ao et al.

size (nm) g)

Sewage sludge One-step MW chemical activation. A portion of 100 g sample was impregnated by certain SBET=290.6 Vtotal=0.168 2.56 [126]
amount of 3 M H2SO4 solutions for 24 h. impregnation ratio (mass of activating agent/raw
material) of 1:2; Samples were subjected to vacuum drying at 105°C for 24 h, then placed in a
quartz reactor, and heated in a MW furnace with 800W power under N2 flow of 10 ml/min for
10 min
Sewage sludge One-step MW chemical activation. Air-dried sewage sludge, impregnated with ZnCl2 (ZnCl2/ SBET=124.8 Vtotal=0.12 1.2 67 [111]
sludge=0.15:1), after drying and crushing, < 0.5mm sludge was collected. 4kg of the sample
was charged into the quartz kettle under 8kW MW irradiation at 5L/min N2 flow.
Carbonization T=600°C for 20 min, radiation time=106min; Iodine=148.2mg/g
Sewage sludge One-step MW chemical activation. Air-dried sewage sludge, impregnated with H3PO4 (H3PO4/ SBET=118.3 Vtotal=0.1 3.7 65 [111]
sludge=0.128), after drying and crushing, < 0.5mm sludge was collected. 4kg of the sample
was charged into the quartz kettle under 8kW MW irradiation at 5L/min N2 flow.
Carbonization T=600°C for 20 min, radiation time=103min; Iodine=246.3mg/g
Sewage sludge One-step MW chemical activation. Air-dried sewage sludge, impregnated with KOH (KOH/ SBET=130.7 Vtotal=0.13 3.6 66.4 [111]
sludge=0.093), after drying and crushing, < 0.5mm sludge was collected. 4kg of the sample
was charged into the quartz kettle under 8kW MW irradiation at 5L/min N2 flow.
Carbonization T=600°C for 20 min, radiation time=107min; Iodine=268.4mg/g
Sewage sludge One-step chemical activation. Dewatered sludge of 3-5mm, impregnated with chemicals for SBET=353.2 Vtotal=0.276 3.85 [127]
24h at sludge:activation solution= 1:3(w/v), 3mol/L ZnCl2; activation in tube reactor,
activation temperature=500°C, activation time=2h with a N2 flow rate of 0.5L/min
Sewage sludge One-step chemical activation. Dewatered sludge of 3-5mm, impregnated with chemicals for SBET=389.59 Vtotal=0.212 3.273 [127]
24h at sludge:activation solution=1:3(w/v), 3mol/L ZnCl2, ZnCl2/H2SO4=10:1 (v/v),
activation in tube reactor, activation temperature=500°C, activation time=2h with a N2 flow
rate of 0.5L/min
Sewage sludge One-step chemical activation. Sewage sludge, ZnCl2 of 3mol/L, sludge/ZnCl2=2.5(wt), SBET=299.59 Vmicro=0.299-0.562 2.486 [128]

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activation temperature=450°C, activation time=30min; Iodine number= 846.358mg/g Vmeso=0.137-0.199
Tobacco stems Particle size < 2mm, carbonization: 450°C, heating rate of 10°C/min, 2h at 450°C, N2 SBET=2557 Vtotal=1.647 0.6 16.7 517.5 [91]
atmosphere; activation MW=700W, radiation time=30min, N2 atmosphere, K2CO3/C(wt) Vmicro=0.988
=1.5; Iodine number=1834 mg/g, methylene blue=517.5 mg/g Vmeso=0.659
Renewable and Sustainable Energy Reviews 92 (2018) 958–979
W. Ao et al. Renewable and Sustainable Energy Reviews 92 (2018) 958–979

drying. For this case, the total MW radiation time is the summation of
treating times of drying, carbonization and activation. The main ad-
vantages of the one-step MW activation are more compact structure and
smaller footprint with simpler operation in comparison with traditional
two-step activation processes. Two-step MW activation processes typi-
cally consists of carbonization and activation of char, with either acti-
vation or carbonization being conducted under MW irradiation [91].
Sometimes both carbonization and activation were performed by MW
heating [112]. Drying may be a separate process, or combined into
carbonization, depending on different biomass types and properties.
Some research works adopt MW treatment followed by conventional
pyrolysis to make ACs of interesting characteristics [82,113] (Fig. 2 and
Table 3). The properties (e.g. BET surface area) of AC depend on
variables like feedstock types and sources, pyrolysis temperature and
radiation power, holding time and additives used. Because of these very
controllable parameters, MW heating is a highly versatile process and it
is possible to optimize these variables to make ACs with good pore
structure and surface characteristics [129,130].

Fig. 3. Effect of radiation power on yields and adsorption capacities of ACs


4.2. Microwave radiation power
(KEFB: AC made by empty fruit bunch, preparation conditions: impregnation
ratio (KOH/AC precursor) = 1, radiation time = 8 min; KCH: AC made by co-
conut husk, preparation conditions: impregnation ratio (KOH/AC pre- MW heating can be used for carbonization and/or activation, and is
cursor) = 1.25, radiation time= 5 min; KCS: AC made by cotton stalk, pre- usually beneficial for surface area and pore structure development
paration conditions: impregnation ratio (KOH/AC precursor) = 0.6, radiation (Table 3). MW power is closely related to sample temperature although
time = 10 min; KCCS: AC made by cotton stalk, preparation conditions: im- it is difficult to accurately measure the sample temperature. Previous
pregnation ratio (K2CO3/AC precursor) = 0.6, radiation time = 10 min; KCWS: studies tried to compare the difference between MW assisted activation
AC made by wood sawdust, preparation conditions: impregnation ratio (K2CO3/ and conventional activation methods on surface and pore character-
AC precursor) = 1.25, radiation time = 5 min)(MB-methylene blue, I-Iodine, K- istics of ACs [116,131,132]. However, it is impossible to compare these
KOH, KC-K2CO3, adapted from [86,91,122,131,133]). two techniques due mainly to unknown temperature of the sample and
different heat transfer mechanisms. MW can heat up MWAs quickly.
3.3. Penetration depth Whereas, materials with poor MW absorbing capacity cannot be easily
heated to the desired temperature. Additives are sometimes added to
For MW heating, penetration depth of 10–20 mm was reported and the samples to increase MW absorbing ability of the treated materials.
small penetration depth may limit MW application in diverse fields Sample mass is also an important parameter related to MW radiation
[34]. It should be noted that penetration depth of MW varies with power for activation as the heating rate and final temperature of the AC
material types, microstructure properties and temperature. For ex- precursor are affected by the total mass. For one-step MW induced
ample, water at 25.1 °C can absorb up to 14 mm MW at 2.45 GHz, K2CO3 activation of cotton stalks, increasing the power level and/or
whereas its penetration depth at the same MW frequency increases to activation time enhanced the AC yield until the optimum conditions.
57 mm at 90.1 °C [103]. The use of 0.915 GHz provides larger pene- After that, the yields of AC decreased with further increases of these
tration depth compared to 2.45 GHz. Depending upon the density and parameters due to greater gasification and burning [117]. However, it
water content, biomass shows variable penetration depth of MW. MW was also reported that the AC yields (two-step MW activation of orange
frequencies of 0.915 GHz and 2.45 GHz are preferred for laboratory peel with ZnCl2 as the chemical reagent) gradually decreased as the
reactions due to their good availability and adequate penetration depth power level and/or activation time increased. The AC yields are heavily
under most laboratory operating conditions [104]. The penetration dependent on properties of AC precursors, interactions between AC
depth is therefore an important parameter in the design of MW cavity precursors and chemical reagents, and secondary pyrolysis. Higher MW
size, process scale up and investigation of MW assimilation capacity of power levels led to larger energy input to the sample, and the more
materials. active sites and pores were generated on the samples. When MW power
reached a certain level, overfull energy could make a small quantity of
carbon burnt, and the structure of pores was destroyed
4. Operating parameters for microwave-assisted activation [86,91,122,131,133], as indicated in Fig. 3.
Cotton stalk was added to ZnCl2 solutions of different concentra-
4.1. Process configurations tions, and effects of MW radiation power on the adsorption capacity
and yield of ACs were evaluated at impregnation ratio of 1.2 g Zn/g
Traditionally physical and chemical activations of ACs are con- precursor and MW radiation time of 8 min. It showed that the yield of
ducted in a multiple hearth furnace, rotary kilns or fluidized bed fur- ACs increased gradually from 27.25% to 32.37% with MW power level
nace, etc. [105]. In recent years, MW irradiation has been widely in- increasing from 400 W to 560 W, and then decreased to 32.15% as MW
vestigated due to its capability of molecular level heating, which leads power increased to 640 W. There were similar tendency for the iodine
to homogeneous and quick thermal reactions [106]. MW treatment number and methylene blue (MB) adsorption value of ACs [117]. Ef-
combined with physical and/or chemical activation is employed to fects of MW power level on the adsorption capacity and yield of ACs
produce high quality ACs, using either one-step [86,107,108] or two- were closely related to the types of AC precursors, activation time, gas
step activation processes [109] as shown in Fig. 2. atmosphere (e.g. steam), additives added (e.g. chemical activation re-
One-step MW activation typically achieves two processes, i.e. car- agents) and impregnation ratios.
bonization and activation, simultaneously in one reactor (e.g. tube re-
actors, auger reactors) and is currently at demonstration scale for bio- 4.3. MW activation time
mass pyrolysis and AC regeneration [32,94,111]. Depending on
moisture contents of biomass, the one-step activation may also cover MW radiation time is another important factor influencing

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W. Ao et al. Renewable and Sustainable Energy Reviews 92 (2018) 958–979

activation of ACs, and the activation degree is strongly dependent on activation. While it increases the heating rate for MW activation be-
the MW radiation time [134–136]. The longer of the MW radiation cause of good MW absorbing capacity of water. For MW assisted car-
time, the more energy transferred to the AC precursor and the higher bonization or one-step MW activation, biomass is directly sent to a
temperature of the sample if MW power is set at the same level. With reactor under MW irradiation. Biomass is usually not a good MWA.
the prolongation of MW radiation time, much more active sites and Hence, at initial stage, biomass temperature may not increase to the
pores are initially formed on the surface of samples. Therefore, the desired temperature. Impregnation of the activation agents with bio-
adsorption capacity of ACs increased. However, when MW radiation mass could significantly increase MW absorbing capacity, indicating
time reached a certain value, the pores of carbon would be burnt off by that activation agents act as the main MWAs at the initial stage to
MW heating, which would lower the adsorption ability and reduce the achieve reliable carbonization or one-step activation under MW irra-
yield of the ACs as shown in Fig. 4 [117]. Due mainly to the unique diation [20]. Bio-char is also a good MWA, once it is formed, it will
characteristics of MW heating, MW irradiation significantly shorten the absorb MW energy and maintain the desired temperature for MW as-
activation time compared to conventional activation, reducing the en- sisted activation. However, high ash content may adversely affect the
ergy consumptions. surface and pore structure development [32,61].
5 g bamboo was used to prepare AC at H3PO4/C mass ratio of 1 and
MW power of 350 W. The AC yield gradually decreased from 58.6 wt%
to 45.3 wt% as the activation time increased from 5 to 30 min thanks to 4.5. Interactions between microwave and chemical reagents
the continuous mass loss as the pore structure was developed [107].
Effects of MW radiation time on the yield and adsorption capacities Chemical activation and regeneration are usually carried out by
(iodine and MB adsorption) of ACs from cotton stalk were evaluated at using specific chemical reagents and solvents, which involve low tem-
MW power of 560 W and ZnCl2 impregnation ratio of 1.2 [91,117]. The perature operation and high quality ACs. Chemical activation shortens
results showed that the yield of AC increased from 32.37 wt% to the activation time and reduces temperature due to impregnation of AC
34.39 wt% when MW radiation time was prolonged from 8 to 9 min and precursor with chemical activation reagents and interactions between
reached maximum, then decreased to 33.5 wt% when the radiation them. ZnCl2, K2CO3, KOH, NaOH, H3PO4 are among the most widely
time increased to 10 min. However, the sample mass treated was not used chemical activation reagents, mainly because it results in high
provided. The same tendency was obtained for the iodine number and surface areas and high AC yield [91,117,138–141]. MW irradiation
MB adsorption as shown in Fig. 4. The devolatilization and activation improves the heating rates and uniformity of temperature across the
reaction increased as activation time was initially prolonged. Hence the particles, leading to special characteristics of ACs. In chemical activa-
adsorption capacity increased as a result of porosity and pore structure tion, increasing the chemical reagent mass fraction could initially
development. As MW radiation time was further increased, a dramatic strengthen the activation until the optimum impregnation ratio was
temperature rise might occur and the average pore diameter might reached. Further increasing the reagent ratio could have adverse ef-
enlarge. The local hotspots generated by further MW heating led to the fects, leading to burning and making the pores blocked by excessive
ablation and shrinkage of the channels and skeleton of the AC. There- reagent (Fig. 5). Hence the accessible area could be reduced. The MW
fore, the accessibility of the AC sites was dramatically reduced, re- treatment has unique effects on the surface chemistry of prepared AC,
sulting in reduction of the adsorption capacity [116]. As above- increasing the carbon/oxygen ratio by eliminating acidic oxygen-con-
mentioned, the effects of MW power and MW activation time on the AC taining functional groups and resulting in basic ACs [132]. Different
yield are complex, depending on specific AC precursors, secondary
pyrolysis, interactions between AC precursors and additives, and op-
erating conditions.

4.4. Physical and chemical properties of biomass

MW radiation power and radiation time should match the total mass
of the AC precursor to avoid overheating or insufficient heating, de-
pending on the MW absorbing capacity of the sample. It is difficult to
measure the sample temperature under MW irradiation. Hence MW
assisted AC preparation should be tested first, including setup of MW
power levels and radiation times, in order to obtain ACs with acceptable
properties [119,137].
Biomass has peculiar physical properties (e.g. non-regular shape,
wide particle size distribution, large moisture content and low particle
density), and various chemical compositions and structures [33]. For
conventional heating, the heat is transferred from the surface to the
interior of the particle. Particle size and shape are very important for
heat transfer, and closely related to temperature gradient of the par-
ticle. The larger of the particle size, the greater temperature gradient Fig. 4. Effect of radiation time on yields and adsorption capacities of ACs
(KEFB: AC made by empty fruit bunch, preparation conditions: impregnation
inside the particle. The AC precursor particle of irregular shape (e.g.
ratio (KOH/AC precursor) = 1, MW power = 600 W; KCH: AC made by coconut
cube or long and thin) may have non-uniform temperature distribution
husk, preparation conditions: impregnation ratio (KOH/AC precursor) = 1.25,
in the electrical furnace, with some points burnt-off and other points MW power= 600 W; KCS: AC made by cotton stalk, preparation conditions:
less developed, affecting uniformity of AC surface characteristics and impregnation ratio (KOH/AC precursor) = 0.6, MW power = 600 W; KCCS: AC
pore structure development. For activation under MW radiation, heat made by cotton stalk, preparation conditions: impregnation ratio (K2CO3/AC
transfer relies on different mechanism in comparison to conventional precursor) = 0.8, MW power = 720 W; KCTS: AC made by tobacco stems,
heating, leading to unique characteristics of MW heating as mentioned preparation conditions: impregnation ratio (K2CO3/AC precursor) = 1.5, MW
in Section 3. MW absorbing capacity of the AC precursor is usually more power = 700 W; KCWS: AC made by wood sawdust, preparation conditions:
important than particle size and shape due mainly to selective and impregnation ratio (K2CO3/AC precursor) = 1.25, MW power = 600 W) (MB-
volumetric characteristics of MW heating. Moisture in the sample methylene blue, I-iodine, K-KOH, KC-K2CO3, adapted from
consumes more energy and decreases heating rate for conventional [86,91,122,131,133]).

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5.1. Agricultural residues

Agricultural residues are one of the most abundant biomass feed-


stocks in China and in the world, and many previous studies focused on
AC production from agricultural residues based on carbonization and
MW activation. The ACs prepared from cotton stalks with different
activation agents (KOH and K2CO3) under MW radiation were in-
vestigated. The results from the one-step MW activation showed that
MW radiation time and radiation power were the most significant
factors on adsorption capacities of the ACs. KOH generated a greater
micropore volume than K2CO3 did. Compared with conventional
heating methods, the one-step MW radiation could shorten the pro-
cessing time and reduce the consumption of chemical activation agents
[86].
Date stones (DS) were used to make ACs under MW irradiation with
K2CO3 as the activation reagent. 2 g date stone of particle size
300–600 µm was selected for one-step AC production under MW irra-
diation in a quartz reactor. The effects of radiation time (4–12 min),
radiation power (540–700 W) and impregnation ratio (0.5–2.5 g
K2CO3/g dry DS, impregnated for 24 h) on the yields and MB uptakes of
Fig. 5. Effect of impregnation ratio on yields and adsorption capacities of ACs ACs were investigated. AC yield of 20 wt% was reported at radiation
(KEFB: AC made by empty fruit bunch, preparation conditions: MW time of 8 min, MW power of 660 W and impregnation ratio of 1.5 g/g.
power = 360 W, radiation time = 8 min; KCH: AC made by coconut husk,
The BET surface area and total pore volume were 1144.25 m2/g and
preparation conditions: MW power = 360 W, radiation time = 5 min; KCS: AC
0.656 m3/g, respectively [109]. Date stones of particle size 1–2 mm
made by cotton stalk, preparation conditions: MW power = 680 W, radiation
time = 10 min; KCCS: activated carbon made by cotton stalk, preparation
were carbonized at 700 °C with N2 flowing in a tube furnace to make
conditions: MW power = 720 W, radiation time = 8 min; KCTS: AC made by char, which was then soaked in KOH solution with an impregnation
tobacco stems, preparation conditions: MW power = 700 W, radiation time = mass ratio (KOH:char) of 1.75:1. The activation step was conducted in a
30 min; KCWS: AC made by wood sawdust, preparation conditions: MW tubular glass reactor with a N2 flow rate of 300 ml/min and radiation
power = 360 W, radiation time = 5 min) (MB-methylene blue, I-iodine, K-KOH, time of 8 min under MW power of 600 W. The BET surface area,
KC-K2CO3, impregnation ratio (wt) = chemical reagents/AC precursor, adapted Langmuir surface area and total pore volume of ACs were 856 m2/g,
from [86,91,122,131,133]). 1275 m2/g and 0.4680 cm3/g, respectively [95]. However, the sample
mass was not mentioned. One-step activation under MW irradiation,
biomass types and operating conditions have been investigated for and two step AC production with conventional carbonization and MW
producing ACs as shown in Table 3. activation were both feasible with acceptable characteristics of ACs.
Orange peel of particle size 1–2 mm was carbonized at 700 °C under Although the same raw biomass materials were used for these two re-
N2 flow rate of 150 ml/min in a tubular furnace. The produced char was search works, the results may not be comparable due to different
mixed with K2CO3 pellets at different impregnation mass ratios of equipment and apparatus used, different operating conditions (e.g. MW
K2CO3/char. The mixture was then activated at MW power of 360 W power levels, inert gas atmospheres and inert gas flow rates), different
and radiation time of 5 min. The MB adsorption capacity was increased particle size, different chemical activation reagents and impregnation
from 56.5 to 171.2 mg/g as the impregnation ratios increased from 0.25 ratios, and some unknown information (e.g. unknown sample mass
to 1.25, due mainly to the reduction of K2CO3 under inert condition to treated).
form K, K2O, CO and CO2, and MW absorbing and catalysis effects of MW-assisted KOH activation has been adopted to prepare AC from
K2CO3 during activation. At the impregnation ratio > 1.25, the pores Albizia lebbeck seed pods. 3 g of dried pods of average particle size
could be blocked by an excess of K2CO3 and metallic potassium that was 0.8 mm was mixed with 20 ml of KOH solution for 24 h at room tem-
left on the surface of the AC, leading to a reduction in the accessible perature to reach an impregnation ratio of 1.0 g dried pods/g KOH. A
area. Widening and burning of pores could be another reason for the quartz reactor under MW irradiation was employed for activation with
decreasing adsorption capacity [116]. The AC yield versus impregna- radiation power of 620 W and radiation time of 8 min. The surface area,
tion ratio showed the same trend as MB adsorption capacity. The microspores volume and mesoporous volume of the produced AC were
maximum AC yield was 85.1 wt%, corresponding to the impregnation 1824.88 m2/g, 0.645 cm3/g and 0.137 cm3/g, respectively [143]. The
ratio of 1.25. The identical results were obtained from the KOH acti- prepared AC exhibited efficient removal for ciprofloxacin and nor-
vation of fruit residue. At the optimum impregnation ratio, the carbons floxacin in aqueous solutions with removal efficiency up to 96.12% and
on the active sites reacted completely with the KOH and the adsorption 98.12%, respectively. Siris seed pods were also used as precursors for
capacity was maximized [131]. preparation of microporous AC by MW-assisted K2CO3 activation [144].
Dried pods (3 g) were mixed with 20 ml of K2CO3 solution for 24 h at
room temperature to obtain various impregnation ratios (0.5–2.5 g/g).
5. Activated carbon from microwave treatment The dried samples were directly activated in a quartz glass reactor
under MW irradiation with power level of 500–700 W and radiation
Due to the direct and uniform heating of the entire sample, MW time of 4–12 min (one-step activation). After washing and drying, the
heating can accelerate many processes and influence the properties of prepared AC has a structure with high microporous content, as in-
the treated materials [142]. The comparisons of MW assisted activation dicated from the high value of iodine number (1617.97 mg/g). The BET
and conventional activation methods were tabulated in Table 3 for surface area, micropores volume and mesopores volume of the prepared
agricultural residues, woody biomass, sewage sludge and industrial AC were 1676.61 m2/g, 0.527 cm3/g, and 0.181 cm3/g, respectively. It
wastes, including MW assisted chemical and physical activations indicated that the one-step MW activation without conventional car-
(Fig. 2). bonization generated ACs of good surface and pore characteristics
[144].
The MW-induced activation process for bamboo was compared with

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the conventional electrical furnace. 5.0 g dried bamboo precursor was characteristics. However, the sample mass corresponding to the op-
impregnated with phosphoric acid at H3PO4/carbon mass ratio of 1:1, timum operating conditions was not provided [91] and the MW energy
then the sample was placed in a quartz reactor for one-step activation consumption for activation per unit sample mass couldn’t be estimated.
under MW irradiation (350 W) with radiation time of 20 min and N2 Durian shell was used to prepare ACs in terms of two-step methods
flow rate of 40 ml/min. The one-step thermal activation (temperature including conventional carbonization and MW activation. After
600 °C at a heating rate 10 °C/min, H3PO4/carbon = 1:1, activation washing and drying, 500 g durian shell of particle size 1–2 mm was
time = 30 and 60 min) was compared with MW assisted activation. It placed in a vertical furnace for carbonization and the temperature in-
showed that the pore structure of the MW assisted AC was better de- creased to 700 °C at a heating rate of 10 °C/min under N2 flow rate of
veloped than that of the thermally activated carbon at 30 min, and 150 ml/min. Produced char was mixed with NaOH pellets with dif-
comparable to that of the thermally activated carbon at 60 min [107]. ferent impregnation mass ratios (NaOH:char). In terms of carbon yields
The MW assisted AC had a slightly higher portion of mesopores than and adsorption performance of the AC, the optimal combination of
those activated thermally in the electrical furnace, probably due to operating conditions was MW power of 600 W, activation time of 6 min
more intense activation reactions under MW irradiation. MW heating and impregnation ratio of 1.5. The BET surface area, micropore surface
can reach a high temperature (e.g. > 1000 °C) quickly and enhance the area and total pore volume were 1475.48 m2/g, 863.29 m2/g and
development of the pore structure if the heated materials contain 0.841 cm3/g, respectively. The results showed that integration of MW
considerable MW absorbing substances. Hence a shorter activation time heating promoted porosity development in a short heating period, in-
was required for MW assisted activation, indicating high efficiency and dicating the reduction of energy consumption and cost [24,132].
energy savings as demonstrated in previous works [20,42,107]. The The coconut shells were heated by electric furnace up to a carbo-
interior part of the carbon can be heated more favorably under MW nization temperature of 1000 °C at a heating rate of 10 °C/min in a
irradiation, creating a temperature gradient reducing from the centre to horizontal tube reactor and were held for 2 h at the carbonization
the surface [32]. Hence, the release of tar or volatile matter would be temperature under N2 gas flow of 100 ml/min. The produced char was
enhanced. In comparison to the conventional thermal activation, the utilized to prepare AC with steam, CO2 and a mixture of steam-CO2 as
MW induced activation led to slightly higher AC yield, due mainly to the activation agents under MW irradiation [115]. It showed that the
the longer activation time and larger mass loss of the AC precursor for BET surface areas of ACs could be > 2000 m2/g, depending on acti-
the conventional thermal method. However, the mass loss was alle- vation agents and activation time under MW irradiation. The activation
viated in the MW activation thanks to the shorter activation time [107]. time under MW heating was much shorter. While the yield of the AC is
6 g of dried cotton stalks was mixed with 30 ml of KOH and K2CO3 comparable to that from the conventional heating methods. The results
solutions for 24 h at ambient temperature, respectively. After mixing, showed that the prepared AC using CO2 activation has the largest BET
the slurries were placed in a glass reactor for one-step activation under surface area. However, the activation time was ~ 2.5 times longer than
MW irradiation. The effects of MW power levels on adsorption capa- the activation using steam or mixture of steam-CO2 as the activation
cities of ACs prepared by different activation agents were investigated agents. The chemical structure and surface functional groups of ACs did
[86]. The results showed that MW radiation time was the greatest factor not show much differences in terms of FTIR (Fourier-transform infrared
on adsorption capacities of the KOH activated carbon. While radiation spectroscopy) analysis although the ACs were prepared under different
power was the most significant factor on adsorption capacities of the gas atmospheres.
K2CO3 activated carbon. The iodine and MB numbers of the K2CO3 Jatropha hull was carbonized in a muffle furnace by heating to
activated carbon increased gradually with the increase of MW power 600 °C at a heating rate of 10 °C/min and N2 flow rate of 100 ml/min,
levels from 480 to 660 W, then decreased as MW power level further kept at 600 °C for 1 h. The produced char was activated using steam and
increased to 720 W. There were similar tendencies found for the KOH CO2 as the activation agents under MW irradiation [145]. The BET
activated carbon. Chemical activation could develop both micro- surface area, total pore volume and average pore size were 1350 m2/g,
porosity and mesoporosity. When KOH was used as the activation 1.07 cm3/g and 3.1 nm for steam activation and 1284 m2/g, 0.87 cm3/g
agent, a large quantity of micropores and some mesopores were formed. and 2.71 nm for CO2 activation under MW irradiation, respectively. For
Whereas, when K2CO3 was adopted, a larger number of mesopores were steam activation, the yield of AC (16.56 wt%) was slightly higher than
produced. Hence, the porosity and surface groups of the ACs could be that from conventional physical activation (13.32 wt%). However, the
controlled by using different activation agents under MW irradiation. At yield of AC from CO2 activation (36.6 wt%) was double compared to
low MW power, the pore structure was not adequately developed. conventional CO2 activation (18.02 wt%), which indicated possible
Higher MW power was beneficial for better pore structure and surface economic benefits from MW-assisted activation. The average pore size
characteristics. Therefore, the adsorption capacities of K2CO3 and KOH (i.e. 2.71 nm) from MW activation in CO2 atmosphere was slightly
activated carbon were increased with MW radiation power. However, smaller than that from conventional CO2 activation, leading to a mar-
higher MW radiation levels could make a small quantity of carbon burnt ginally higher surface area under MW heating [145]. The BET surface
off, destroying the pore structures and decreasing adsorption capacities area and the pore volume from steam activation under MW irradiation
as described in Section 4 [86]. were comparable to conventional steam activation. While the BET
The tobacco stems were heated to 450 °C in a stainless-steel tubular surface area and the pore volume from CO2 activation under MW ir-
reactor placed in an electrical furnace at a heating rate of 10 °C/min radiation were almost the same as those from conventional CO2 acti-
under N2 gas flow, and was held for at least 2 h at 450 °C. ACs from vation. However, CO2 activation under MW irradiation considerably
carbonized tobacco stems with K2CO3 as the chemical activation agent reduced the activation temperature and the flow rate of CO2, and
under MW irradiation were investigated [91]. Effects of MW power shorten activation time compared to conventional CO2 activation,
(80–700 W), radiation time (5–60 min) and K2CO3/C (0.5–3) ratios on rendering MW-assisted activation more economical than the conven-
the yields and adsorption capacities of ACs were evaluated. The results tional heating methods. It also indicated that physical activation using
indicated that the optimum conditions were as follow: MW power of CO2 as the oxidizing gas under MW irradiation might be more eco-
700 W; radiation time of 30 min; K2CO3/C ratio of 1.5:1. Iodine nomical than combination of steam activation and MW heating for
number, MB adsorption capacity and the yield of AC prepared under specific biomass feedstock in terms of AC yields, pore structure devel-
optimum conditions were 1834 mg/g, 517.5 mg/g and 16.65 wt%, re- opment and surface characteristics.
spectively. ACs had a micropore content ~59.98% and a small number Macadamia shell was first carbonized at temperature 500 °C for 1 h.
of mesopores and macropores; BET specific surface area and total pore The produced biochar samples were crushed and sieved to ensure the
volume were 2557 m2/g and 1.647 cm3/g, respectively. This research particle size in the range of 0.5–1.5 mm, then physical and chemical
provided a typical two-step process for preparation of ACs with good activation were combined with MW irradiation, respectively. MW

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power levels were set at 90–360 W and the radiation time at 1–5 min. results showed that AC prepared with (20%lime + 80%ZnCl2) at im-
For MW power of 90 W, the average iodine adsorption values of 680.8 pregnation ratio (inorganic:organic) of 1.5 worked best for removal of
and 672.4 mg/g were obtained from steam activation and ZnCl2 acti- phenol from aqueous solution (667.9 mg/g, 93.1% efficiency). The ef-
vation process, respectively. For MW power of 360 W, the average io- ficiencies of the prepared ACs to treat effluents were directly related to
dine adsorption from steam activation showed similar value (678.7 mg/ the textural properties of ACs [108].
g), whereas average iodine adsorption from ZnCl2 activation increased Coniferous wood pellets of 8 mm in diameter and 10 mm in length
by 5%. The H2O and 25 mol% ZnCl2 were mixed with biochar at 3:1 were pyrolyzed at 400 °C with N2 flow rate of 170 ml/min under MW
mass ratio to realize combination of steam activation and chemical irradiation, activation of pyrolysis char was then conducted at tem-
activation under MW irradiation. The results showed that AC could be perature of 600–700 °C for 60 min in CO2 atmosphere (250 ml/min)
activated within 1 min under MW irradiation. MW heating has the under MW irradiation [112]. Hence the two-step carbonization and
advantages of rapid temperature rise, uniform temperature distribution, activation were both conducted under MW irradiation with different
and energy savings over conventional thermal methods [141]. gas atmospheres. The effects of activation temperature on the textural
500 g of dried langsat empty fruit bunch waste was put into a muffle parameters, acid-base characteristics of the surface and sorption prop-
furnace, and heated to 700 °C for carbonization at a heating rate of erties of ACs were analyzed. The adsorption of NO2 and H2S was carried
10 °C/min and N2 flow rate of 150 ml/min. The produced char was used out from dry or moist (70% humidity) air. The results showed that NO2
for preparation of ACs by MW-induced activation. Activation was and H2S sorption properties of ACs depended on the temperature of
conducted at the impregnation mass ratio (NaOH/char) of 1.25, MW activation and the conditions of adsorption. AC obtained from direct
power of 600 W and radiation time of 6 min. The MB uptake was up to activation of sawdust pellets under MW irradiation without separate
302.48 mg/g [146]. It was reported that the AC yield was up to ~96 wt pyrolysis stage exhibited poorer developed surface area than that from
% at MW power of 90 W, impregnation ratio (NaOH/char) of 1.25 and two-step pyrolysis and CO2 activation under MW irradiation [112].
radiation time of 5 min. However, the MB adsorption was only 25 mg/g. However, previous studies also reported good pore structure and sur-
The carbon yield increased from 80.30 wt% to 88.67 wt% with in- face characteristics of ACs prepared by one-step activation under MW
creasing impregnation ratio (NaOH/char) from 0.25 to 1.25 at MW irradiation [107,144]. The results were heavily dependent on biomass
power of 360 W and radiation time of 5 min [146]. More information is types, reactor configurations, gas atmospheres, MW power level, MW
available in Table 3. radiation time and chemical reagents used for activation.
ACs made from conventional pyrolysis and MW treatment were Wood sawdust was washed, air-dried and sieved to obtain particle
compared using peanut shells as the raw material. 2.5 g peanut shells size of 1–2 mm. Two-step activation process was adopted. The carbo-
were treated under MW power of 700 W and radiation time of 20 min, nization process was carried out by loading 500 g of dried sawdust into
followed by conventional pyrolysis at 800 °C for 5 h. The results showed a tubular furnace and heating to a carbonization temperature of 700 °C
that the AC under MW irradiation exhibited superior characteristics at N2 flow rate of 150 mi/min [122]. The char was mixed with K2CO3
such as texture, surface area, pore volume and pore size in comparison pellets at different impregnation mass ratios of K2CO3/char. Activation
with conventional treatment. MW irradiation followed by conventional was performed in a reactor with N2 flow rate of 300 ml/min under MW
pyrolysis provided an alternative way to prepare an AC with acceptable irradiation. The optimal operating conditions based on carbon yield and
characteristics and high adsorption capacities for organic dyes [82]. adsorption performance were MW power of 600 W, activation time of
6 min and impregnation ratio of 1.25. The BET surface area, Langmuir
5.2. Woody biomass surface area, total pore volume, average pore size and the adsorption
capacity of MB were 1496.05 m2/g, 2245.53 m2/g, 0.864 cm3/g,
White pine wood powders of size 0.3–3.3 mm were impregnated 2.306 nm and 462.1 mg/g, respectively. This study highlighted the
with a ZnCl2 solution and dried at 110 °C to obtain a mixture with a feasibility of wood sawdust as a promising precursor for production of
mass ratio of ZnCl2 to wood in the range of 0:1–3:1. 10 g mixture was ACs with a considerable decolorization capacity. MW heating produced
placed in a quartz reactor under MW irradiation with MW power of a high-quality AC by opening of previously inaccessibly pores and
700 W and N2 flow of 20 ml/min for one-step MW activation [20]. The creation of new pores, due partly to the interior and volumetric heating
wood powder without ZnCl2 was hardly heated even after exposure of of MW irradiation. The results showed that MW heating was a pro-
10 min to the MW irradiation. The addition of ZnCl2 promoted pyrolysis mising way of producing ACs and represented savings of energy and
of wood powder due to the MW absorbing capacity and heat carrier cost.
properties of ZnCl2. Combination of MW and chemical activation en-
hanced porosity development of ACs. The BET surface areas for the 5.3. Sewage sludge and industrial wastes
samples of 0.75:1, 1.5:1, 2.5:1 ZnCl2/wood mass ratios were 1048,
1379 and 1459 m2/g, respectively. The AC prepared by the conven- Sewage sludge is a solid waste with high moisture content and high
tional activation method with ZnCl2/wood mass ratio of 2.5:1 had a contents of toxic substances. Sludge treatment, disposal and utilization
BET surface area of 1321 m2/g, lower than that under MW irradiation. has become a topic of growing interest in both research and industry in
The mesoporous volumes of the above three samples increased (0.12, the past decades. Pyrolysis treatment of sludge was considered as an
0.17, 0.70 cm3/g, respectively) with increasing ZnCl2/wood ratios, in- attractive technique in reducing sludge volume and its harm to the
dicating that ZnCl2/wood ratios can be used to adjust the mesoporosity. environment and public health. Meanwhile, sewage sludge can be re-
The results demonstrated that higher mass ratio of ZnCl2/wood and utilized as energy sources or sludge-based adsorbents. Thanks to the
longer MW activation time increased adsorption capacity of produced increasing demand of ACs, sewage sludge was becoming an important
ACs. MW-induced ZnCl2 activation required < 10 min for preparation source for production of ACs because of the high carbon content and
of ACs with good properties, whereas several hours were generally good availability [147,148]. The pyrolysis of sewage sludge was usually
needed for low-temperature carbonization and conventional chemical performed under inert atmosphere at 400–1000◦C. The methods to
activation [20]. activate ACs could be simply classified into physical activation and
Sapelli wood residue, inorganic additives (20% lime + 80% ZnCl2 chemical activation, same as woody biomass and agricultural residues
or 20% lime + 40% FeCl3 + 40% ZnCl2) and water were mixed at [111]. The ACs produced by activation generally exhibited a high metal
different ratios for making ACs. The paste mixture of 30 g was treated cation capacity, and thus can be used to remove heavy metal ions from
for 320 s at MW power of 1.2 kW. The inorganic compounds were wastewater [149–151]. Turning solid wastes into value-added and
MWAs, promoting energy transfer, and allowing MW induced pyrolysis useful AC products (e.g. wastewater treatment and gas purification) is
and activation to be carried out in one-step process. The experimental beneficial to protect environment and public heath [147].

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A portion of 100 g dried sewage sludge was impregnated by certain MW power of 90–800 W, radiation time of 5–10 min and N2 flow rate of
amount of 3 M H3PO4 or 5 M ZnCl2 solutions for 24 h. The amounts of 300 ml/min [131]. The BET surface area, total pore volume, average
H3PO4 and ZnCl2 solution used was adjusted to provide impregnation pore size and MB adsorption capacity were 1372 m2/g, 0.76 cm3/g,
ratios (mass of chemical activating agents/mass of raw material) of 1:2 2.206 nm and 395.30 mg/g, respectively. It showed that MW power and
and 1:1.5, respectively. After liquid-solid separation and vacuum drying radiation time had more significant effects on the adsorption capacity
at 105 °C for 24 h, the solid sample was placed in a quartz reactor and and carbon yield in comparison with KOH impregnation ratios.
heated by MW power of 800 W for 10 min with a N2 flow rate of 10 ml/ Tannery sludge, ZnCl2 and lime were mixed together at 50 wt%,
min. The addition of ZnCl2 or H3PO4 initialized the pyrolysis of sewage 40 wt% and 10 wt% mass fractions, respectively. ~10 g of the prepared
sludge due to their MW absorbing and heat carrier properties, and paste was crushed and placed in a quartz reactor at N2 flow rate of
promoted porosity development in the final AC. The experimental re- 100 ml/min under MW irradiation. Carbonization was conducted under
sults showed that the BET surface areas, total pore volumes and average MW power of 1200 W and irradiation time of 150 s. After cooling,
pore diameters were 290.6–377 m2/g, 0.168–0.243 cm3/g and complete pyrolysis was carried out for 20 min under MW irradiation
2.56–2.78 nm, respectively. The ACs produced from sewage sludge [152]. The BET surface area and total pore volume were 491.0 m2/g
have a lower BET surface area than most commercially available ACs and 0.440 cm3/g, respectively, with mesoporous pore size distribution.
(e.g. ~400–1500 m2/g). The lower specific surface area of the produced The maximum sorption capacities for acid red and acid black were
ACs was related to the little microporosity, which was primarily at- 589.5 mg/g and 1108 mg/g, respectively.
tributed to the properties of the precursor [126]. The paper mill sludge samples were dried and ground to produce
A pilot-scale MW heating device was use to treat sewage sludge to powder of particle size 150–600 µm. 5 g of dried and ground sludge was
make adsorbents [111]. The optimum carbonization temperature for mixed with ground NaOH particles (300–600 µm) to reach an impreg-
making sludge-based adsorbents was 600 °C. The increase of carboni- nation mass ratio (NaOH:sludge) of 1:1 and 1:2. The homogenous
zation temperature gave rise to the decrease in the quantity of polar mixture of powdered sludge and NaOH was subjected to one-step ac-
functional groups on the surface of resultant adsorbents, and a higher tivation under MW irradiation for 3–7 min in the quartz reactor. After
temperature (e.g. 700 °C) resulted in severe activation that had a det- washing and drying, the ACs produced were characterized. The BET
rimental impact on the quality of adsorbents in terms of specific surface surface area and the AC yield were 660 m2/g and 13 wt%, respectively,
area, total pore volume and iodine number. After impregnation and at impregnation ratio of 2:1 and MW radiation time of 5 min under MW
drying, the dried sludge was crushed to particle size of < 0.5 cm, and power of 1200 W [148]. It showed that 5 wt% KOH enabled a complete
then homogenized. ~4 kg of dried sludge was charged into the quartz pyrolysis of the sludge in a few minutes. In fact, both KOH and NaOH
kettle under MW irradiation (maximum MW power of 9.6 kW, 12 sets of were good MWAs for MW assisted pyrolysis [32]. KOH was well known
MW generators), then pyrolysis was performed at a N2 flow rate of 5 L/ for its effectiveness in creating porosity in AC precursors. While NaOH
min. The KOH activated sludge-based adsorbents (carbonization tem- has been used to chemically activate carbonaceous materials and was
perature of 600 °C for 20 min, MW power of 8 kW, radiation time = much cheaper than KOH. Moreover, NaOH was readily available in
107 min) had the highest BET surface area of 130.7 m2/g and the Kraft mills, leading to promising economics for AC preparation.
highest total pore volume of 0.13 ml/g, indicating that KOH was one of
the most effective chemical activators for better development of porous 5.4. Regeneration of ACs under MW irradiation
texture. However, the H3PO4-activated adsorbent acted as the best one
to adsorb Cu2+ and Pb2+ from aqueous solutions in terms of the ex- A wide variety of AC regeneration techniques has been suggested
perimental tests [111]. MW heating apparatus has a great potential to and applied in the past decades, including thermal, chemical and bio-
treat sewage sludge to produce adsorbents for removal of heavy metals regeneration technologies [19,153]. Nowadays the most extensively
from wastewater. used technique was the thermal regeneration processes (typically
For conventional pyrolysis of sewage sludge, the optimum para- 800–1000 °C) under mildly oxidizing gas atmospheres (e.g. CO2 and
meters have been identified as: pyrolysis temperature of 500 °C, holding steam). However, thermal regeneration processes may cause loss of a
time of 15 min, and an impregnation mass ratio of ZnCl2:sludge of 0.5 considerable amount of carbons (~5–15 wt%) and adsorption capa-
[97]. MW assisted pyrolysis was found to be optimal when operating at cities due to attrition, burn-off and washout [48]. Whereas, chemical
980 W for 12 min. The most significant factors affecting surface area for regeneration was usually carried out by the desorption of adsorbates
the conventional pyrolysis were the pyrolysis temperature and inter- using specific solvents or by decomposition of adsorbed species using
action between pyrolysis temperature, activation time and mass ratio of oxidizing chemical agents under either subcritical or supercritical
ZnCl2 to sludge. The most important parameters for the MW heating conditions, and a large investment cost was usually involved. The re-
were the interaction between MW power level, ratio of ZnCl2: sludge generation efficiency depended mainly on the solubility of the adsorbed
and the MW radiation time [97]. The results showed that all surface substances and the effect of pressure on the chemical structure of
area values derived from conventional pyrolysis were higher than those carbon [154]. Biological regeneration was generally slow and can only
of ACs made by MW pyrolysis over the whole set of conditions. The be applied to the biodegradable substances.
highest surface area was found for a sample made by conventional MW irradiation has been successfully applied for the preparation
method (i.e. 679 m2/g), which was about 35.52% higher than the and regeneration of ACs due to unique characteristic of MW heating.
highest surface area of a sample made by MW pyrolysis (501 m2/g). It MW application in the industrial regeneration of spent ACs has showed
indicated that, under these experimental conditions, conventional promising results [106,132]. The basic purpose of regeneration was to
pyrolysis was more efficient at generating high surface areas than MW provide used ACs with good adsorption capacity for reutilization. The
pyrolysis [97]. However, it may be too early to make a conclusion since main factors influencing regeneration of ACs were MW power level,
the activation time was not the same for conventional pyrolysis and temperature, radiation time, flow rate of regeneration agents and im-
MW pyrolysis processes, and the MW power level for MW pyrolysis and pregnation ratio, which required optimization. However, the optimi-
activation temperature for conventional pyrolysis may not be compar- zation for AC regeneration was complicated since there were more than
able. one characteristic parameter that needed to be considered. Hence re-
The biodiesel industry solid residue, oil palm empty fruit bunch, sponse surface methodology (RSM), one of the relevant multivariate
was reutilized for preparation of ACs using KOH as activating agent techniques, was sometimes used, performing multivariant experimental
under MW irradiation. Loading 500 g of dried precursor into a muffle design, statistical modeling and process optimization. In fact, RSM
furnace at N2 flow rate of 150 ml/min, and heated to 700 °C for car- technique has been widely employed for process optimization for both
bonization at heating rate of 10 °C/min. Activation was conducted at preparation and regeneration of ACs from different raw materials such

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as coconut shell and husk, oil palm fiber, Turkish lignite, sewage radiation time were usually used as process parameters to investigate
sludge, olive-waste cakes, Jatropha hull [106,124,126]. Regeneration the characteristics of MW heating [89]. However, they are not adequate
of ACs from spent catalysts made from vinyl acetate synthesis was also to be used as scale-up parameters. A thermocouple and an infrared
reported [106]. The efficiency of applying MW technology to re- pyrometer were used in combination to measure the sample and reactor
generate coal-based ACs saturated with phenol was investigated. The temperature under MW irradiation, providing a perspective to use dif-
results were very promising due to the rapid heating of the AC under ferent temperature measurement techniques to estimate the sample
MW irradiation. MW technology didn’t damage the carbon, and allowed temperature [32].
the carbon to be recycled and reused many times with acceptable sur-
face area and pore volume [155]. 6.2. Thermal runaway and temperature control
Oil palm fiber, empty fruit bunches and shells were air-dried, cru-
shed and sieved to obtain particle size of 1–2 mm. One sample was One of the main challenges in scaling-up the MW heating process is
carbonized at 700 °C in an electrical furnace under inert atmosphere. thermal runaway and instability of the temperature, usually deterior-
The generated char was mixed with KOH pellets with various impreg- ating into arcing, and adversely affecting MW oven performance and
nation ratios. The activation was conducted at MW power of 600 W and product quality [98]. The non-uniform energy distribution is analogous
irradiation time of 6–10 min [156]. The resulting ACs were immersed in to the hot spots and cold spots generated in the domestic MW oven,
500 mg/l of MB solution for 24 h to ensure that the active sites were which has become one of the primary technological drawbacks for MW
fully saturated. After washing and drying, regeneration was performed processing in industries. Heat absorbed under MW irradiation is pro-
in a glass reactor under 600 W MW irradiation and N2 flow rate of portional to the dielectric loss tangent. Rapid increase in dielectric loss
300 ml/min. The heating times were 3, 4 and 5 min for palm fiber AC, tangent with increasing temperature will provide a potential for tem-
empty fruit bunched AC and palm shell AC, respectively. The adsorp- perature rising and thermal runaway [98,160]. It becomes more critical
tion-regeneration process was repeated six times. The BET surface area if the reactant is impregnated with chemical reagents for chemical ac-
(1149–257 m2/g), micropore volume (0.126–0.021 cm3/g) and micro- tivation under MW irradiation because the value of dielectric loss
pore surface area (262–105 m2/g) of the MW treated samples de- tangent is not constant and varies not only with frequency, but also
creased, while the mesopore volume (0.134–0.051 cm3/g) and external with temperature, moisture content, physical state (solid or liquid) and
surface area, which was more accessible for the adsorbate molecules, composition [98,161]. A dynamic impedance matcher may be required
didn’t differ noticeably from the parent ACs [155,157]. After six cycles, to minimize the reflected power and improve the energy efficiency for
the adsorption capacity of phenol decreased by 70% and 82% for MW the MW-assisted AC preparation due to the dynamically changed di-
regeneration and conventional electrical furnace regeneration, respec- electric properties [161].
tively. Hence MW energy contributed to higher efficiency for re-
generation of saturated ACs with phenol and longer lifetime of the ACs 6.3. Database of dielectric properties
[131,158]. The textural properties of the MW-regenerated carbons were
better preserved. The decomposition of the adsorbed adsorbates inside There are little studies on dielectric properties in the field of AC
the carbon matrix was not favored under MW heating, which con- preparation. Previous literatures only focused on the dielectric prop-
tributed to the preservation of the porous structure [157]. erties of ACs, neglecting those of the AC precursors, chemical reagents
and reactants mixtures [161]. It is important to obtain the dielectric
6. Key challenges for microwave assisted activated carbon property data for each material and mixture involved in the MW-as-
production sisted activation, and build a database for commonly used AC pre-
cursors and additives. However, the dielectric property may change
6.1. Temperature measurement with frequency, temperature and activation atmosphere, which adds
complexity to analyze the performance of MW heating. Understanding
For conventional heating, the temperature of the gas atmosphere dielectric properties of reactants, additives and products, and how these
and/or the bulk temperature of the solids are measured, and the solid properties change during the course of activation is important to predict
average temperature could be estimated in terms of traditional heat the heating selectivity, heating rate and heat distribution [161,162],
transfer mechanisms (e.g. conduction, convention and radiation). which is crucial for reactor design and process scale-up.
However, it is almost impossible to accurately measure the temperature
of the sample under MW irradiation [90]. An infrared pyrometer is 6.4. Continuous operations
usually employed to measure the sample temperature in the MW field.
However, the infrared pyrometer only measures the surface tempera- Previous studies in MW heating mainly focused on glass or quartz
ture of the sample or the device under MW irradiation. There is tem- tube reactors of batch operation. Many studies provided the MW power,
perature gradient inside the sample and temperature gradient from the radiation timer and the sample mass treated by MW [20], other re-
sample to the reactor wall, limited by traditional heat transfer. In order search works didn’t mention the sample mass and only MW power level
to heat up the sample at a faster heating rate, the reactor is usually and radiation time were available, which was even harder to estimate
made by materials of low MW absorbing capacity (e.g. quartz or glass), the temperature of the sample and energy consumption of MW treat-
which increases the challenges to reach uniform temperature for the ment [91,106]. For continuous operation, the feeding rate instead of
sample of good MW absorbing capacity and the reactor wall under MW the total mass treated in the batch operation should be provided, to-
irradiation. Some infrared sensors have an adjustable emissivity setting, gether with MW input power and radiation time in order to investigate
which can be set to measure the temperature of lower emissivity and MW performance and product quality, as well as scale-up parameters
higher emissivity surfaces. Hence infrared pyrometer may be able to [94]. Biomass pre-treatment is an important step to realize smooth and
detect the sample surface temperature. However, there is temperature continuous feeding to the reactor under MW irradiation. Hence con-
gradient (e.g. tens of degrees) from the core to the outer surface of the tinuous operation usually has stricter requirements on properties of the
particle. There may be undetected overshoot of sample internal tem- feedstocks (e.g. particle size, shape, moisture content, etc) compared to
perature, especially for carbonaceous materials. The thermocouple may batch operations [33]. On the other hand, the AC products from con-
give rise to false reading thanks to the enhanced localized heating tinuous operations are supposed to be more uniform in size, shape and
around the tip of the thermocouple. Fiber optic temperature probes are other product qualities in comparison with batch operations. The seal
fragile and expensive, and can only measure temperature < 300 °C, not between the feeding system and the reactor is important to prevent
suitable for AC preparation [159]. Hence the MW input power and leakage of process gases and MW radiation, which follows different

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W. Ao et al. Renewable and Sustainable Energy Reviews 92 (2018) 958–979

mechanisms from that in batch operations [33]. Careful and innovative of biomass in China. Municipal solid waste (MSW), sewage sludge and
design of the feeding system and the reactor is required to ensure safety bamboo pole are chosen as the feedstocks. The purpose to treat MSW
and reliability. Penetration depth, temperature measurement and con- under MW irradiation (MW power = 75 kW, vertical fixed bed reactor)
trol, dielectric properties of the AC precursors and additives are all is to make this solid waste harmless and reduce the secondary pollu-
essential to achieve reliable continuous operations under MW irradia- tions to the environment and public health. However, there are not
tion. enough data and information to compare the products from MWP of
MSW with those from conventional pyrolysis. The leaching character-
6.5. Scale-up and equipment selections istics of solid residues from MWP were not available either. China has
the most abundant bamboo sources in the world. Conventional tech-
The scale-up of MW processing is not straightforward and needs to nologies making bamboo char include clay brick kiln, externally fired
consider many factors, such as penetration depth of MW, construction retort, vertical shaft continuous kiln. Due to unique characteristics of
materials of the reactor under MW irradiation, thermal insulation ma- MW heating, MWP has been used for production of bamboo char in the
terials, manufacturing capability of MW components, biomass types recent years in China. MWP of bamboo produces bamboo char of ex-
and properties, reactor types, operation modes (batch or continuous cellent quality, larger yield and lower production cost than those gen-
operations) and economics of the process [94]. Scale-up law of the erated from conventional technologies. The BET surface area of bamboo
specific reactor type (e.g. fixed beds, auger reactors and fluidized beds) char is up to 800 m2/g, equivalent to that of commercial ACs [163].
should be followed in terms of specific biomass feedstocks. However, MWP of bamboo is currently in batch operation mode and has the
process scale-up is also limited by unique characteristics of MW heating potential to achieve semi-continuous or continuous operation with less
and process economics. For example, penetration depth of MW is a pollutant emissions and ease of control in the future. The pilot plant for
function of MW frequency, temperature, dielectric properties of the AC preparation from sewage sludge under MW irradiation was de-
material being heated. Generally the higher of the MW frequency, the scribed in Section 5.3.
smaller of the penetration depth [32]. BUCT has a benchtop auger reactor for MWP of solid wastes and AC
It was reported that 0.915 GHz generators provided up to 100 kW preparation (e.g. agricultural residues, woody biomass, sewage sludge
from a single magnetron and the largest commercial 2.45 GHz units and textile dying sludge, etc). HY Microwave Technology, Ltd. China
used 30 kW magnetrons. A single magnetron of small MW power is built a demonstration plant in 2016 for regeneration of ACs (1 t AC/
usually at low price. The cost increases rapidly as the capacity of the day) contaminated by wastewater from printing and dyeing industries
magnetron increases in terms of communication with HY Microwave in collaboration with BUCT, showing promising prospects to use MW
Technology, Ltd. China. Hence the multiple magnetron systems are technology to produce and regenerate ACs in the auger reactor of
usually adopted for MW processing in industries. The commonly used continuous operation.
materials of construction for reactors under MW irradiation in lab and Canada built a distributed MW pyrolyser of domestic wastes [164].
benchtop facilities, and demonstration plants are quartz, glass, porce- This approach reduces the cost of waste transportation and collection,
lain and other materials of small dielectric loss factors. The more MW and offers alternative ways of valorizing the gas, bio-oil and char. There
energy the AC precursor absorbs, the less MW energy the reactor ma- are several companies in Canada developing pyrolysis technologies for
terial takes, the higher the system efficiency is. The reactor capacity is biochar production [32]. University of British Columbia (UBC), Canada,
limited by the available size (e.g. 0.5–1 m) of these tubes and vessels are actively investigating pyrolysis technologies, including MWP of
from commercial suppliers considering mechanical strength, manu- biomass, and biochar effects on carbon sequestration and soil fertility.
facturing ability and economics. If carbonization and activation under Comprehensive bio-oil, syngas and biochar applications has been con-
MW heating are performed at relatively high temperatures, the in- sidered and investigated. The China-Canada Joint Centre for BioEnergy
sulation materials of small dielectric loss factors become very important Research & Innovation (C-C JCBERI) opened on August 15, 2015 was
for higher energy efficiency. initiated in 2014 by UBC and BUCT. One of the research areas for the C-
All the factors are highly interacted each other. Biomass types and C JCBERI is bio-oil, biochar and AC production. Biochar and ACs can be
properties, reactor types, operation modes, MW heating configurations, used as adsorbents for wastewater treatment and gas cleanup. More
process configurations and capacities, additives (e.g. MWAs, catalysts, information about biochar and AC applications is available in previous
sorbents) should be integrated and combined to achieve a feasible and studies [165].
reliable design. Process parameters from the small equipment may be Three research performers (United Kingdom, Norway and Italy)
useful when the process is scaled up. However, the data from small tested MWP of wood wastes [166]. The overall technical goal of the
facilities may not be applicable for larger units. project is to build a scalable prototype plant that can turn 230 kg/h of
low value forest residues into char, as well as valuable bio-oil. However,
7. Technology status and economics of microwave assisted the operation is on a batch basis. A full-scale plant of continuous op-
activated carbon production eration is planned at a capacity of 2000 kg/h, using 400 kW MW power.
The recent pilot, demonstration and commercial projects at home and
7.1. Technology status and potential applications abroad for production of biochar and ACs, as well as regeneration of
ACs, under MW irradiation, provided meaningful experiences in de-
Biochar and ACs are important topics from academic and techno- signing and operating MW assisted activation units, improving AC
logical development point of view and closely related to pyrolysis qualities for various biomass feedstocks.
processes. Beijing Sino-Green Technology Co., Ltd. Beijing (China) has
cooperated with Beijing University of Chemical Technology (BUCT, 7.2. Economics of activated carbon production under microwave irradiation
China) in the past four years to develop a patented technology for
biomass carbonization (moving bed). Several demonstration plants The main advantage of MW heating in comparison to conventional
have been set up around Beijing, China to investigate biochar and AC heating is the shorter time of pyrolysis and activation (e.g. < 20 min),
applications. The joint centre of BUCT and Beijing Sino-Green as well as lower price of production and regeneration of ACs. Most of
Technology Co., Ltd. are further developing advanced pyrolysis tech- previous studies in preparation of ACs under MW irradiation used tube
nologies, including microwave-assisted pyrolysis (MWP) of biomass, to reactors or fixed beds of batch operation, and economics was seldom
improve biochar and AC qualities, maximizing the profits in terms of covered in these literatures. In fact, the MW power level and MW ra-
gas, liquid and solid products [32]. diation time determine the energy input to the AC precursor, depending
There are several pilot and demonstration plants investigating MWP on MW absorbing characteristics of the sample, reactor types and

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operating modes. For one-step MW activation, electricity consumption Table 4


can be estimated if MW power level, MW radiation time and sample Basic economics for AC preparation from biomass under MW irradiation in
mass are known. For example, 3 g of dried siris seed pods was mixed China.
with 20 ml of K2CO3 solution at an impregnation ratio of 1.5 g/g. After Items Values Unit
drying, the sample was placed in a quartz reactor under 540 W MW
irradiation. MW heating time was 8 min [144]. Assuming conversion Plant capacity 1 tonne air-dry biomass/day
Days per year 365 days/year
efficiency from electricity to MW energy was 70%, the electricity con-
Capacity factor (%) 90 –
sumption was 34,000 kWh/tonne dried biomass. For two-step carbo- AC yield 0.35 –
nization and MW activation processes, electricity consumption could be Capital charge rate (%) 10 –
calculated based on unit mass char or unit mass of dried biomass. For Initial capital cost 500,000 RMB
Annual capital charge 50,000 RMB/year
instance, 500 g dried raw materials was carbonized in a muffle furnace
O&M 2000 RMB/tonne air-dry biomass
at 700 °C and N2 flow rate of 150 ml/min, the char yield was 43.17 wt O&M 657,000 RMB/year
%; Activation was conducted in a glass reactor at MW of 600 W and Fuel cost 200 RMB/tonne air-dry biomass
activation time of 7 min [131], the electricity consumption was 200 Fuel cost 65,700 RMB/year
kWh/tonne dried biomass or 469 kWh/tonne char. Hence one-step Production cost 772,700 RMB/year
AC price 8000 RMB/tonne
processes corresponded to higher electrical consumptions due mainly to
Sales from AC 919,800 RMB/year
its simultaneous pyrolysis and activation in one single reactor. How- Profits from AC 147,100 RMB/year
ever, the electricity consumptions from different literatures differed
significantly for MW activation and was basically in the range of 200– Note: 1 US$ = 6.9 RMB.
40,000 kWh/tonne dried biomass, typically 2500–10,000 kWh(e)/
tonne dried biomass, depending on different feedstocks, reactor types, shown in Table 4. It showed that development of MW activation was of
chemical reagents used, gas atmospheres and operating conditions reasonable cost with considerable profits. The regeneration of ACs was
[82,137]. The above estimation was based on the tube reactors or fixed even more profitable, especially for contaminated ACs in printing and
beds of batch operation for MW activation in previous literatures, and dyeing industries. The printing and dyeing plants and the local gov-
may not be applicable for practical applications. It should be noted that ernments (e.g. Jiangsu Province) would like to pay ~RMB 4000 per
many previous studies only focused on parametric investigation and AC tonne used ACs in order to recycle and dispose these contaminated
characterization, and didn’t mention the mass of the AC precursors sorbents from printing and dyeing industries. On the other hand, steam
[91], which added uncertainty to the electricity consumption discussed generator required by conventional physical activation and equipment
above. An auger reactor of continuous operation under MW irradiation related to conventional chemical activation (e.g. mixing, washing and
was set up for pyrolysis and activation of biomass and industrial wastes, drying) are expensive and may be comparable to MW equipment.
the electricity consumption was in the range of 800–3000 kWh/tonne
dried raw material, depending on different temperatures and auger 8. Conclusions and future work
speeds [94]. Based on previous research works, we select 3000 kWh/
tonne dried raw material as the electricity consumption for one-step MW heating has many advantages over conventional heating, such
MW activation. Activation in the electrical furnace needs ~3–20 times as uniform and internal heating, fast and selective heating, ease of
longer activation time in comparison to MW activation. Hence the control, simple set-up, insensitive to particle size and shape, less pre-
electricity consumption for conventional electrical furnace activation is treatment requirements of the feedstocks. MW technology is a pro-
supposed to be much larger than that for MW activation. For compar- mising technique for thermochemical treatment and activation of ACs
ison purpose, we convert the above electricity consumption of MW owing to its unique characteristics. Previous reviews mainly focused on
activation to energy consumption based on natural gas (NG) assuming specific feedstocks (e.g. oil palm wastes) or ignored important para-
50% electrical efficiency of the NG power plant. The calculated energy meters for MW activation (e.g. mass of AC precursors). Comparison of
consumption for MW activation based on NG is 21,600 MJ/tonne dried characteristics of ACs prepared from conventional methods and MW
raw material. activation still lacked, and economics of MW activation were not de-
If NG was burned and the flue gas was used for activation, the en- scried in previous studies. This paper presented a comprehensive re-
ergy consumption based on NG is 26,000 MJ/tonne dried raw material, view of MW treatment for AC activation from various biomass sources
assuming the total mass flow rate of generated (CO2 + steam) is 2.4 (e.g. agricultural wastes, woody biomass sewage sludge).
times as large as that of the dried biomass in terms of industrial ex- Characteristics of ACs made from MW activation and conventional ac-
perience for conventional physical activation. Hence the energy con- tivation were compared and the advantages of MW-assisted preparation
sumption of one-step MW activation is lower than that of conventional of ACs were described. Based on previous research works, the max-
physical activation, indicating MW activation reduces greenhouse gas imum BET surface area, the maximum iodine number, the maximum
emissions. Conventional chemical activation lowers the energy con- MB adsorption and the range of AC yields from biomass under MW
sumption at the price of handing basic and/or acid solutions, and cor- irradiation were 2500–3000 m2/g, 1800–2200 mg/g, 500–700 mg/g
rosion problems. If carbonization was considered, the conventional and 13–96 wt%, respectively, competitive with conventional methods
technologies would consume more energy in comparison with one-step in the quality of ACs and process economics.
MW activation. MW heating is a mature technology. However, MW-assisted pre-
It was declared that the cost of producing 1 kg of AC by MW heating paration of ACs is still far from maturity although there are some pilot
was US$ 32.43, while production of 1 kg of AC by conventional heating and demonstration plants operating in China and overseas. Small-scale
would cost US$70.67. Therefore, the use of MW heating significantly reactors provide little information about how this technology would
reduced the total production cost of AC [152]. However, cost analysis of scale up and how large-scale MW equipment perform. Dielectric prop-
ACs strongly depends on specific biomass feedstock, process config- erties measurement on precursors, chemical reagents, reactants mix-
urations and locations. In terms of communication with HY Microwave tures and products (final and intermediate) involved in producing ACs
Technology Company in China, the investment cost of the auger reactor is crucial for MW treatment and scale-up. A continuous and reliable AC
system of 1 t/day capacity under MW irradiation was about preparation system under MW irradiation deserves more studies and
RMB500,000. Assuming the capital charge rate of 10% and the plant energy consumption for producing ACs under MW irradiation should be
lifetime of 10 years, the basic economics of one-step AC preparation further investigated. There are few published data and information in
using biomass as the feedstock under MW irradiation was estimated as these fields, and more research and process development are still

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required. Technol 2010;91:1345–54. http://dx.doi.org/10.1016/j.fuproc.2010.05.006.


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