Menya 2018

Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296
Contents lists available at ScienceDirect
Chemical Engineering Research and Design
journal homepage: www.elsevier.com/locate/cherd
Review
Production and performance of activated carbon

from rice husks for removal of natural organic
matter from water: A review
E. Menya a,b,∗ , P.W. Olupot a , H. Storz c , M. Lubwama a , Y. Kiros d

a Department of Mechanical Engineering, College of Engineering, Design, Art and Technology, Makerere University,
P.O. Box 7062, Kampala, Uganda
b Department of Biosystems Engineering, Gulu University, P.O. Box 166, Gulu, Uganda
c Thuenen Institute of Agricultural Technology, Bundesallee 50, 38116 Braunschweig, Germany
d Department of Chemical Engineering, KTH Royal Institute of Technology, SE 100 44 Stockholm, Sweden
a r t i c l e i n f o a b s t r a c t
Article history: Adsorption by activated carbon has great potential to improve natural organic matter (NOM)
Received 23 July 2017 removal from water. However, the high production and regeneration costs limit its wide
Received in revised form 26 October scale application. To address these limitations, research efforts have been focused on find-
2017 ing low cost materials that can be transformed into activated carbon. Rice husk is one of
Accepted 2 November 2017 such materials of research focus, especially in the developing countries, where over 96%
Available online 11 November 2017 of rice husks are generated globally. Although numerous investigations have been made
concerning the production of activated carbon from rice husks, the existing scientific infor-
Keywords: mation still remains widely scattered in literature. Furthermore, the scientific information
Rice husk regarding performance of rice husk activated carbon during NOM removal from water still
Activation remains poorly documented. This review article therefore provides ample information on
Activated carbon efforts made by various researchers concerning production of activated carbon from rice
Natural organic matter husks and its adsorption performance in relation to NOM removal from water. Properties
Water and pretreatment of rice husks in relation to production of activated carbon are discussed.
Activation of rice husks by physical and chemical methods under numerous conditions
is reviewed. Factors affecting NOM adsorption by activated carbon are briefly discussed.
Adsorption performance of rice husk activated carbon is also reviewed with respect to NOM
removal from water, and where possible compared with other source derived activated car-
bons. The data from literature revealed that NOM removal by rice husk activated carbon can
be as effective as commercial activated carbon. Consequently, rice husk activated carbon
has potential to serve as an alternative to commercial activated carbon.
© 2017 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.
∗
Corresponding author at: Department of Mechanical Engineering, College of Engineering, Design, Art and Technology, Makerere Univer-
sity, P.O. Box 7062, Kampala, Uganda.
E-mail addresses: [email protected], [email protected] (E. Menya).
https://doi.org/10.1016/j.cherd.2017.11.008
0263-8762/© 2017 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.
272 Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
2. Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
3. Properties of rice husk as a precursor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
4. Pretreatment of rice husks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
5. Activation of rice husks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
5.1. Physical or thermal activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
5.2. Chemical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
5.3. Washing of activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
5.4. Comparison of physical and chemical activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
5.5. Comparison of textural properties of rice husk activated carbon with other source-derived activated carbon . . . . 281
5.6. Cost comparison of rice husk activated carbon with other activated carbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
6. Mechanism of NOM removal by activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
7. Factors affecting NOM adsorption by activated carbon. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .284
7.1. Physicochemical properties of activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
7.2. NOM characteristics and competing organic species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
7.3. Solution pH and charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
7.4. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
7.5. Contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
8. NOM removal using raw and pyrolyzed rice husks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
9. NOM adsorption by rice husk activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
9.1. Powdered activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
9.2. Granular activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
9.3. Adsorption isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
10. Future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
11. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
Conflicts of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
1. Introduction
indicates that NOM is mainly composed of hydrophilic, low molec-
Natural organic matter (NOM) is a complex matrix of heterogeneous ular mass organic compounds (Edzwald and Tobiason, 1999). The
organic material present in all natural waters (Matilainen et al., 2010). hydrophobic NOM primarily consists of humic and fulvic acids (humic
It is derived from decaying terrestrial plants and as a byproduct of substances) (Parson et al., 2004; Swietlik et al., 2004), which are rich in
bacteria, algae, and aquatic plants (Chow et al., 2008). It can be clas- aromatic carbon, phenolic structures and conjugated bonds (Bhatnagar
sified as either particulate organic matter, retained by a 0.45 ␮m filter, and Sillanpää, 2017). On the other hand, the hydrophilic NOM consists
or dissolved organic matter which is NOM passing through a 0.45 ␮m of higher proportions of aliphatic carbon and nitrogenous compounds,
filter (Szymczycha et al., 2017). NOM is introduced in water sources such as carboxylic acids, carbohydrates and proteins (Matilainen et al.,
through interactions between the hydrologic cycle, biosphere and geo- 2010).
sphere (Matilainen et al., 2010). The amount and characteristics of The presence of NOM causes numerous problems in water treat-
NOM vary with source, level of degradation, season, climate and geol- ment and distribution systems. NOM interacts with disinfectants
ogy (Golfinopoulos, 2000; Owen et al., 1995; So et al., 2017; Wei et al., forming harmful disinfection by-products (DBPs) (Golea et al., 2017; Rao
2008; Szymczycha et al., 2017). To better understand the role of NOM in et al., 2011; Tubić et al., 2013), reduces water quality by causing unpleas-
water treatment, characterization of NOM in the raw water is necessary. ant odors, tastes and color in raw drinking water, promotes bacterial
Simple techniques such as color, total organic carbon (TOC), dissolved reproduction and biofilm formation within drinking water distribution
organic carbon (DOC), chemical oxygen demand (COD), pH, turbidity, systems (Korotta-Gamage and Sathasivan, 2017; Metsämuuronen et al.,
and ultraviolet (UV254 ) absorbance are commonly employed by water 2014), increases the solubility of heavy metals due to complexation with
treatment facilities in their quality control (Chow et al., 2008). However, metal ions and minerals (Iriarte-Velasco et al., 2008; Rao et al., 2011),
these do not give information about their molecular weight distribution causes fouling of membranes (Drikas et al., 2011; Zularisam et al., 2010),
and hydrophobicity. Instead, high performance size exclusion chro- reduces water treatment efficiency during flocculation/coagulation
matography (HPSEC) analysis is often employed to determine NOM’s (Rao et al., 2011), increases coagulant and disinfectant doses, which
molecular weight distribution (Chow et al., 2008). On the other hand, consequently increases sludge volumes and production of DBPs. The
fractionation techniques are employed to determine the hydrophilic latter poses numerous public health concerns to water utilities, since
and hydrophobic fractions of NOM (Sharp et al., 2006; Soh et al., 2008; their consumption in drinking water is linked to development of var-
Swietlik et al., 2004). Specific ultraviolet absorbance (SUVA254 ) can also ious cancers and a variety of adverse reproductive outcomes (Singer,
be used to define the hydrophobicity of NOM (Matilainen et al., 2010), 1999). This has prompted major international regulatory agencies such
as well as its aromatic character (Cheng et al., 2005; Chow et al., 2008). as the United States Environmental Protection Agency (US EPA), and
SUVA254 is obtained as the UV254 absorbance divided by the DOC con- the World Health Organization (WHO) to develop a number of reg-
centration of the sample and is reported in units of L(mg-m)−1 (Cheng ulations for DBPs like trihalomethanes (THMs) and haloacetic acids
et al., 2005; Chow et al., 2008; Metsämuuronen et al., 2014). SUVA254 (HAAs). For instance, the United States Environment Protection Agency
value (>4) indicates that NOM is largely composed of hydrophobic, high (US EPA) limits total THMs and the sum of five HAAs in drinking water
molecular mass organic compounds, while a low SUVA254 value (<2) treatment to 80 and 60 ␮g L−1 , respectively as Stage 1 of the disinfec-
Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296 273
tants/disinfection by-product (D/DBP) rule (US EPA, 1998). In Stage 2, materials have been listed elsewhere (Ali et al., 2012; Bhatnagar et al.,
these limits are halved to 40 and 30 ␮g L−1 for total THMs and sum of five 2015; Dias et al., 2007; Grace et al., 2016; Pollard et al., 1992; Tran et al.,
HAAs respectively (Najm et al., 1998). The World Health Organization 2015). Out of these, rice husk is the least utilized (Quispe et al., 2017),
(WHO) set the guideline value for DBPs in drinking water not to exceed and therefore more abundantly available in the developing countries,
100 ␮g L−1 (Gordon et al., 2008). The European community (EC) also set where over 96% of rice husks are produced globally (FAO, 2015). About
the quality standard for total THMs in drinking water to be 100 ␮g L−1 20% of paddy weight is rice husk (Kumagai et al., 2007), translating
(EECD, 1997). However, these maximum contaminant levels are some- to over 148 million metric tonnes of rice husk produced globally per
times exceeded at some drinking water treatment plants (García and year. Out of these, about 17% find an application per year, suggest-
Moreno, 2009; Golfinopoulos, 2000; Kalibbala, 2007). To lower the risks ing that very huge volumes of rice husks become waste (Ankur, 2010).
of DBP formation in drinking water treatment, TOC and SUVA254 need These usually end up either being openly dumped or merely burnt in
not to exceed 2.0 mg L−1 and 2.0 L(mg-m)−1 respectively prior to primary open space, causing environmental pollution. Moreover, with a 65% (3.7
disinfection using chlorine (US EPA, 2012). billion) projected increase in the world’s population by 2050 (Wallace,
Numerous methods are available for NOM removal from water, such 2000), global paddy production is expected to increase if the popula-
as coagulation (Heiderscheidt et al., 2016; Tubić et al., 2013), membrane tion’s demand for food is to be sufficiently met. This will exacerbate
separation (Metsämuuronen et al., 2014), ion exchange (Heijman et al., the disposal challenges of rice husks in the developing countries, since
1999), biological, advanced oxidation processes (AOPs) (Matilainen and even with the current paddy production, rice husk is usually in excess
Sillanpää, 2010), adsorption (Yan and Bai, 2005) or a combination of of any local application. Transformation of rice husks into activated car-
these methods (Humbert et al., 2008; Joseph et al., 2012). Each of the bon therefore adds considerable economic value to a product hitherto
methods has its own advantages and shortcomings as reported else- considered waste, helps reduce the cost of waste disposal, and most
where (Bhatnagar and Sillanpää, 2017; Dewil et al., 2017; Rao et al., importantly provides a potentially inexpensive alternative to the exist-
2011; Ribau Teixeira et al., 2017; Zhao et al., 2014). Coagulation and ing commercial activated carbons for numerous applications, including
flocculation followed by sedimentation/flotation and filtration is the water treatment.
most commonly employed and economically feasible process for NOM Despite the numerous investigations made concerning the produc-
removal from water (Bhatnagar and Sillanpää, 2017; Ghernaout, 2014; tion of activated carbon from rice husks, the existing reviews mostly
Sillanpää et al., 2015). However, the hydrophilic fraction and the low concern the application of rice husk activated carbon for removal of
molar mass compounds of NOM are less effectively removed by coagu- heavy metals (Chuah et al., 2005; Kumar and Bandyopadhyay, 2006;
lation than the hydrophobic fraction and high molar mass compounds Mohan and Sreelakshmi, 2008; Sobhanardakani et al., 2013), pesticides
of NOM (Johnson et al., 2016). Consequently, the less efficiently removed (Foo and Hameed, 2010; Njoku et al., 2014), and dyes (Guo et al., 2005;
NOM fraction contribute to the formation of DBPs and other related Malik, 2003) from water and wastewater. To the best of our knowledge,
problems in drinking water treatment. To address these concerns, no review has been made to document the numerous investigations
numerous research efforts have been undertaken to increase the extent by various researchers on the production of activated carbon from rice
of NOM removal through enhanced coagulation (Liu et al., 2012; Hong husks, and their potential application for NOM removal from water.
et al., 2009), where the coagulant dose is significantly increased, cou- This review article is therefore aimed at providing ample informa-
pled with pH adjustment to optimum ranges. For instance, a study by tion on efforts made by various researchers regarding production of
Liu et al. (2012) revealed that enhanced coagulation potentially reduced activated carbon from rice husks and its adsorption performance in
the total THMs formation by 24.8%. A study by Hendricks (2006) revealed relation to NOM removal from water. Properties and pretreatment
that about 40–60% of humic substances can be removed in the incom- of rice husks in relation to production of activated carbon are dis-
ing ambient water by enhanced coagulation. A study by Hong et al. cussed. Activation of rice husks by physical and chemical methods
(2009), revealed that enhanced coagulation potentially reduced 10–30% under numerous conditions is reviewed. Factors affecting NOM adsorp-
more of DOC than via conventional coagulation. At the drinking water tion by activated carbon are discussed. Adsorption performance of rice
treatment plant of Boaco in the central region of Nicaragua, 50% of husk activated carbon is also reviewed with respect to NOM removal
NOM was removed by enhanced coagulation (García and Moreno, 2009). from water, and where possible compared with other source derived
Despite the promising results regarding improvements in NOM removal activated carbons. More specifically, the removal of NOM from water
through enhanced coagulation, some water treatment plants may still focussed on the removal of humic substances (humic and fulvic acids),
need additional NOM removal to comply with the more stringent DBP since these produce high concentrations of DBPs in water (Singer, 1999),
regulations even after enhanced coagulation (Dastgheib et al., 2004; accounting for over 50% of the TOC content in water (Matilainen et al.,
Sillanpää et al., 2015). Adsorption has been regarded as a promis- 2010).
ing method for removal of the NOM fraction that is poorly removed
via coagulation (Johnson et al., 2016; Hong et al., 2009). More specif-
ically, adsorption by activated carbon is most preferred not only due 2. Methodology
to its highly developed internal surface area, porosity, and conse-
quently a large adsorption capacity, but also due to its simplicity in
Original research articles, review articles, reports and books
design, and ease of operation (Bhatnagar and Sillanpää, 2017). How-
were searched from various sources such as Scopus, Google
ever, commercial activated carbons are expensive (Dias et al., 2007),
and are commonly derived from non-renewable materials such as Scholar, and publisher-specific search engines especially Sci-
bituminous coal, anthracite, lignite and peat (Ali et al., 2012). In addi- enceDirect, Taylor and Francis, American Chemical Society
tion to being environmentally unfriendly, the high production and and Royal Society of Chemistry. The Boolean operator “AND”
regeneration costs associated with commercial activated carbons limit was also used to include several key words in a single
their extensive use at large scale water treatment plants (Ali et al., search. Search terms included NOM characteristics; NOM
2012; Lin and Juang, 2009). Consequently, this has prompted numerous measurement; mechanism of NOM removal; activated car-
research efforts with the aim of finding low cost as well as environ- bon; problems of NOM in drinking water treatment; natural
mentally friendly alternative materials that can be transformed into
organic matter removal in drinking water treatment; factors
low cost activated carbons. Such low cost materials include animal
affecting NOM removal by activated carbon; low cost mate-
bones (Cechinel et al., 2014), waste bamboo cums (Wang, 2012), sludge
rials; production of activated carbon; activated carbon from
(Bjorklund and Li, 2017), waste tires (Betancur et al., 2009), coconut
shell (Iriarte-Velasco et al., 2008), rice husks (Ahmedna et al., 2000;
rice husks; adsorption isotherms; NOM removal by low cost
Chen et al., 2011; Foo and Hameed, 2011; Liou and Wu, 2009), sugar activated carbons; NOM removal by activated carbon from low
cane bagasse (Gonçalves et al., 2016), sugar cane bagasse ash (Kaushik cost materials; properties of rice husks; pretreatment of rice
et al., 2017), molasses (Gonçalves et al., 2016), almond shell (Omri et al., husks; disinfection by-products; NOM removal by coagulation;
2014), and orange peel (Hashemian et al., 2014). Several other low cost physical activation of rice husks; chemical activation of rice
husks; and leaching of rice husks among others. Commercial to specific rice husk materials based on their properties and
activated carbons and other low cost adsorbents were also on the intended application.
included in the search for comparison with rice husk derived
activated carbon. References from selected papers were also 4. Pretreatment of rice husks
explored to obtain the relevant information. The articles were
selected based on their relevance to the review; with a pri- Rice husk is unusually high in ash content, for which 76–99%
mary focus on NOM removal from water. Where possible; of the total weight is silica (SiO2 ), while the rest of the metallic
the search was limited to papers published within the last impurities exist in low concentrations. Similar to proper-
ten years. Exceptions were only made for areas with limited ties of rice husks, the properties of rice husk ash may also
research available. No geographical limitations were applied vary with geographical location of growth (Benassi et al.,
in the search. A total of 217 references were selected; and out 2015), as highlighted in Table 2. The high ash content in
of these; majority are journal articles within research areas of rice husks is not desired in the preparation of activated car-
materials science; chemistry and engineering. bon, since it obstructs pore development, which consequently
leads to activated carbon with both low mechanical strength
and adsorption capacity (Yeganeh et al., 2006). Besides, dur-
3. Properties of rice husk as a precursor ing chemical activation, the activating agent is consumed
when it reacts with silica in the ash, reducing the activating
Rice husk has physico- and bio-chemical properties, which agent/carbon ratio. For this reason, under similar preparation
suit it as a potential precursor in the production of activated conditions, the Brunauer–Emmett–Teller (BET) surface area of
carbon. It is one of the lignocellulosic biomass, constituting of activated carbon derived from raw rice husks is reported to
lignin, cellulose and hemicellulose (Liou and Wu, 2009; Olupot be lower than activated carbon from lignocellulosic materi-
et al., 2016). Out of these, lignin is the main constituent for als with low ash content (Yun et al., 2003). Such materials
char formation, responsible for the adsorption process (Suhas may include coconut shells, sugarcane bagasse, and hardwood
et al., 2007). On the other hand, cellulose and hemicellulose are among others. To avoid the negative influences of the unusu-
the volatile fractions removed during pyrolysis, and are asso- ally high ash content in the rice husks, leaching of rice husks
ciated with low carbon yields since a significant fraction of by a base and/or an acid is necessary, since leaching poten-
carbon is lost during pyrolysis (Viswanathan et al., 2009). This tially reduces the ash content of rice husks by as much as
in turn contributes to micropore formation (Correa Rodriguez 92–98 wt% (Hsieh et al., 2009; Liou and Wu, 2009; Yeganeh et al.,
et al., 2017). Generally, these and many other properties of rice 2006), depending on concentration of the leaching agent, pre-
husks have been reported to vary with several factors, includ- treatment ratio, soaking time, process temperature and pH
ing rice variety, geographical location, climatic variation, soil (Yalçin and Sevinç, 2001; Hsieh et al., 2009). Consequently,
chemistry, methods of cultivation and type of fertilizer used in leaching of rice husks increases the BET surface area, pore
paddy growth (Benassi et al., 2015; Deiana et al., 2008; Mansary widening and also creates a new pore structure of the result-
and Ghaly, 1997). For instance, Mansary and Ghaly (1997) stud- ing activated carbon (Liou and Wu, 2009). A study by Liou and
ied the physical and thermochemical properties of four rice Wu (2009) obtained a BET surface area of 2434 m2 g−1 for base-
husk varieties from Sierra Leone, and found that their chem- leached rice husks activated using ZnCl2 , which was higher
ical properties were significantly influenced by rice variety. than 1262 m2 g−1 resulting from ZnCl2 activation of rice husks
Olupot et al. (2016) characterized ten rice husk varieties from without base-leaching.
Uganda, and concluded that their physico- and bio-chemical Leaching of rice husks using a base such as NaOH predomi-
properties varied with rice variety. Ahiduzzaman and Islam nantly removes SiO2 when it reacts with NaOH to form sodium
(2015) carried out a thermogravimetric analysis of six rice silicate (Na2 SiO3 ) according to Eq. (1) (Liou and Wu, 2009).
husk varieties from Bangladesh, and found that their rate of
thermal degradation varied with rice husk varieties due to dif- 2NaOH(s) + SiO2 (s) → Na2 SiO3 (s) + H2 O(l) (1)
ferences in their chemical composition. Zhang et al. (2012)
determined the physical properties of rice husks from Egypt, Because the Na2 SiO3 formed is soluble in water, it is easily
Cuba and China, and found that the properties varied with removed by water-washing (Liou and Wu, 2009). On the other
country of origin, due to variations in climatic conditions, soil hand, acid-leaching of rice husks removes most of the remain-
type, methods of cultivation and type of fertilizer used. Their ing metallic impurities in the rice husks, which further avoids
study further revealed significant differences in the physical obstruction to pore development (Liou and Wu, 2009). The
properties of rice husk varieties even when paddy was sub- removal of metallic impurities in rice husks via acid-leaching
jected to similar agronomic practices. A study by Benassi et al. is due to dissolution of metals in acid, which are later removed
(2015) revealed that applying the same physicochemical treat- by rinsing the treated rice husk samples with distilled water
ments to rice husk grown in different geographic areas, results (Muniandy et al., 2014). In a study by Liou et al. (1997), about
in variations in rice husk ash crystalline structure. Additional 84% of the metallic impurities were extracted when rice husks
studies regarding the physico- and bio-chemical properties of were refluxed with 3 N HCl at 100 ◦ C for 1 h. Leaching of rice
rice husks based on geographical location of growth are high- husks may be done either before or after the activation step
lighted in Table 1. (Deiana et al., 2008). However, the leaching sequence followed
Because of the possible variations in properties of rice influences the overall quality of the resulting activated carbon
husks with rice variety, geographical location, climatic vari- from rice husks. For example, Deiana et al. (2008) found the
ation, soil chemistry, methods of cultivation and type of leaching sequence carbonization-activation-leaching more
fertilizer used in paddy growth, conditions for preparation of efficient than the sequence carbonization-leaching-activation
activated carbon cannot merely be transferred from either one from the viewpoint of specific surface area and micropore
geographical location to another or from one rice husk variety volume development. The authors further reported that the
to another. As such, preparation conditions need to be tailored former resulted in activated carbon with textural parameters
Table 1 – Overview of the physico- and bio-chemical properties of rice husk based on geographical location.

Geographical Biochemical analysis (%db) Proximate analysis (%db) Ultimate analysis (%dab) References
location
Lignin Hemicellulose Cellulose Ash VM FC C H O N S
China – – – 16.64 67.63 16.89 37.65 5.13 36.20 1.63 0.18 Liu et al. (2016)
Malaysia 26.10 21.25 42.45 11.98 74.54 12.11 – – – – – Naqvi et al. (2015)
Sierra Leone 24.95–31.41 18.10–21.35 25.89–35.50 18.20–24.60 63.00–70.20 12.40–14.50 38.70–44.50 4.70–5.51 31.50–35.20 0.40–0.51 0.014–0.025 Mansary and Ghaly (1997)
– 26.91 22.18 34.56 10.54 – – 42.43 5.82 40.63 0.58 – Liou and Wu (2009)
Uruguay – – – 17.20 – – 48.30 0.50 44.40 6.80 0.00 Deiana et al. (2008)
a
Uganda 10.58–13.47 11.39–19.97 31.03–36.54 15.87–25.56 58.78–66.37 14.77–17.75 29.98–34.48 4.46–5.59 40.48–43.36 0.36–0.63 0.005–0.041 Olupot et al. (2016)
Colombia 35.84 24.50 39.65 21.86 63.65 14.49 33.80 4.90 40.20 1.40 0.01 Marrugo et al. (2016)
Japan – – – 12.70–22.00 – – 35.2–41.2 4.6–5.4 34.8–42.1 0.4 0.6–0.7 Kumagai et al. (2009)
India – – – 16.81 64.72 18.48 – – – – – Kalderis et al. (2008a,b)
Egypt 20.00 21.00 35.00 19.00 – – – – – – – Toniazzo et al. (2013)
Bangladesh – – – 11.38 71.56 17.06 38.48 6.60 44.05 – – Hossain et al. (2017)
b
Portugal – – – 11.70–15.60 59.90–61.90 14.70–15.90 38.80–40.00 4.60–5.00 29.60–31.70 0.80–1.30 0.30 Casaca and Costa (2009)
Thailand – – – 17.90 72.80 9.30 48.90 6.20 44.10 0.80 – Wannapeera et al. (2008)
Tanzania – – – 26.20 59.20 14.60 45.60 4.50 33.40 0.19 0.02 Mhilu (2014)
Pakistan 40.16 11.14 38.35 15.22 59.04 25.74 44.13 5.01 50.40 0.39 0.07 Danish et al. (2015)
South Korea – – – 12.98 73.73 13.28 55.13 6.43 38.43 0.01 0.00 Kook et al. (2016)
India 20.30 26.70 34.80 17.89 76.84 5.26 39.45 6.49 52.98 0.83 0.25 Prakash and Sheeba (2016)
Note: VM—volatile matter; FC—fixed carbon; db—dry basis; dab—dry ash free basis.
a
Biochemical composition is expressed on dry ash free basis.
b
Implies the composition of rice husks is expressed on wet basis (wb%).
275
276
Table 2 – Composition of rice husk ash based on different geographical locations

Geographical Metallic impurities (%) Reference
location
SiO2 Al2 O3 Fe2 O3 MnO MgO CaO Na2 O K2 O TiO2 P2 O5 Others
– 98.02 0.52 0.11 0.01 0.11 0.23 0.10 0.38 0.02 0.08 0.42 Álvarez et al., Álvarez et al. (2015)
Sierra Leone 90–97 0.09–0.25 0.09–0.27 – 0.30–0.45 0.33–2.00 0.03–0.23 1.80–2.80 0.02–0.06 0.03–1.20 – Mansary and Ghaly (1997)
Louisiana 96.00 0.05 0.09 – 0.44 0.48 0.08 2.10 0.035 0.59 0.135 Mansary and Ghaly (1997)
Japan 86.80–91.50 – – – – 1.2–2.5 – 4.3–8.0 – 1.0–1.4 1.5–2.1 Kumagai et al. (2009)
India 84.76 0.36 0.28 – 0.76 0.74 0.20 2.51 – 0.62 – Kalderis et al. (2008a,b)
Brazil 94.95 0.39 0.26 0.16 0.90 0.54 0.25 0.94 0.02 0.74 – Della et al. (2002)
Spain 76.70 0.183 0.233 – 0.654 0.821 – 2.03 – 1.62 – Eliche-Quesada et al. (2017)
– 94.50 – <0.5 – 0.23 0.25 0.78 1.10 – 0.53 – Daifullah et al. (2003)
Malaysia 92.00 0.18 0.20 0.056 0.56 0.83 0.03 1.70 – 0.77 – Tan et al. (2011)
Thailand 93.59 0.54 0.82 0.19 0.15 1.45 0.01 1.94 0.07 – – Sutas et al. (2012)
Pakistan 77.31 6.77 4.64 – 1.39 3.70 1.23 2.60 – – – Kazmi et al. (2016)
Uruguay 87.20 0.15 0.16 – 0.35 0.55 1.12 3.60 – – – Rodríguez De Sensale (2010)
Iran 85.15 0.29 0.19 0.25 0.92 1.31 – 4.95 – 2.50 – Ghorbani et al. (2015)
Sri Lanka 84.14 4.08 1.15 – 0.44 0.97 1.69 1.34 – – – De Silva and Surangi (2017)
Nigeria 91.56 – 0.21 – 0.53 1.58 – 0.39 – – – Alaneme et al. (2014)
Brazil 89.51 0.13 0.05 – 0.30 – – 1.68 – – 1.38 Geraldo et al. (2017)
Tanzania 88.84 0.80 0.39 – 0.92 1.78 1.10 2.80 0.04 – – Msinjili et al. (2017)
Brazil 90.02–96.71 0.06–0.09 0.01–0.03 0.01 ND ND – 0.66–0.81 ND 0.23–0.34 – Fernandes et al. (2016)
Vietnam 95.60 – 0.24 – – 0.70 – 2.66 0.02 0.52 – Hwang and Huynh (2015)
Note: ND—not detected.

similar to when rice husks were leached prior to carboniza- C(s) + H2 O(l) → CO(g) + H2 (g), steam activation
tion. Although results obtained in literature emphasize the
(H = + 117 kJ/mol) (2)
need for silica removal to improve the quality of rice husk
derived activated carbons, leached rice husks are associated
with low carbon yields since the lignin which is the main con-
stituent for char formation is removed after base-leaching.
For example, Yeganeh et al. (2006) reported carbon yields of
44 and 51.36%, resulting from rice husks with and without C(s) + CO2 (g) → 2CO(g), activation by CO2
base-leaching respectively. The leaching process should there-
(H = + 159 kJ/mol) (3)
fore be carefully controlled not to adversely compromise the
yield and quality attributes of the rice husk derived activated
carbon.
Although, the above reactions result in activated carbon
with maximum BET surface areas that are similar, the perfor-
mance of the two oxidizers is significantly different (Álvarez
5. Activation of rice husks et al., 2015). For instance, the H2 O molecule diffuses faster into
the pores of the carbon than the CO2 molecule, due to its com-
Generally, activated carbon from rice husks has been pre-
paratively smaller size. Consequently, the reaction between
viously prepared through either physical activation (Álvarez
char and steam is faster than that with CO2 . While steam
et al., 2014; Kumagai et al., 2009; Malik, 2003) or chemical
causes widening of micropores from earlier activation stages,
activation (Isoda et al., 2014; Liou and Wu, 2009; Muniandy
activation by CO2 favors the development of new fine poros-
et al., 2014). Although a combination of these methods (physic-
ity followed by pore enlargement (Rodriguez-Reinoso et al.,
ochemical activation) has been successfully employed to
1995). A study by Álvarez et al. (2015) also reported that a
activate lignocellulosic biomass such as bamboo (Hameed
more developed microporous structure is obtained when rice
et al., 2007), its effect on rice husk still remains largely unstud-
husk char is activated using CO2 compared to steam acti-
ied. The following section includes a review of the methods
vation. CO2 is preferred as an activating agent because it is
for activation of rice husks under different preparation condi-
clean, easy to handle and the activation process can be easily
tions.
controlled at temperatures around 800 ◦ C due to its slow reac-
tion rate (Ioannidou and Zabaniotou, 2007). Pretreatment of
rice husk, pyrolysis conditions, activation temperature, acti-
5.1. Physical or thermal activation vation time, choice of activating agent, and steam/gas flow,
have significant effects on the surface area and porosity of
In physical activation, char is obtained in the first stage by activated carbon (Table 3). Similar findings were reported else-
carbonization of rice husks at temperatures (400–700 ◦ C) in an where (Serp and Machado, 2015; Tan et al., 2017). Activation
inert environment (Deiana et al., 2008; Kalderis et al., 2008a,b; of raw rice husk without leaching results in activated carbon
Malik, 2003). However, the resulting char still exhibits a very with BET surface area as low as 166–473 m2 g−1 (Hsi et al.,
small adsorption capacity since its pores remain blocked 2011; Kalderis et al., 2008a,b; Kumagai et al., 2009; Li et al.,
by tarry products evolved during carbonization. These tarry 2016; Malik, 2003). On the other hand, leaching of rice husks
products are removed in the second stage, also known as prior to activation greatly enhances the adsorptive properties
“activation process,” at high temperatures (600–1000 ◦ C) in the of rice husk activated carbon, with BET surface areas as high
presence of suitable oxidizing gases such as carbon dioxide, as 970–1600 m2 g−1 (Álvarez et al., 2015; Deiana et al., 2008;
steam, air or their mixtures (Deiana et al., 2008; Han et al., Han et al., 2014), depending on the experimental conditions.
2014; Malik, 2003). Besides the removal of tarry products, the For this reason, leaching of rice husks is a key consideration
diameter of pores created during the carbonization process in the production of activated carbon from rice husks if good
is enlarged, while at the same time, new porosity is created. adsorptive properties are to be realized.
Consequently, a well-developed and readily accessible pore
structure with a relatively larger BET surface area is formed 5.2. Chemical activation
after the activation process. However, carbon is lost during
activation, decreasing the weight of the host carbon. Similar In chemical activation of rice husks, both carbonization and
to other materials, weight loss during physical activation of activation may be performed in a single-stage process, by
rice husk char increases linearly with activation temperature employing chemical activating agents such as ZnCl2 (Isoda
and time. Activation of rice husk char using steam and carbon et al., 2014), H3 PO4 (Somasundaram et al., 2013), NaOH (Guo
dioxide are the most commonly employed activating agents et al., 2005), and KOH (Muniandy et al., 2014) at relatively
via physical activation as highlighted in Table 3. Although it low temperatures of 400–700 ◦ C (Isoda et al., 2014; Kalderis
may be possible to activate rice husk char with oxygen, the et al., 2008a,b; Liou and Wu, 2009). While the single-stage
activation process may be problematic, since excessive burn- process has often been generalized to be suited for chemical
ing of the char occurs due to the exothermic nature of the activation, the process is only efficient when activating rice
reactions, which are difficult to control. In addition, burning husks using acidic activating agents (Isoda et al., 2014; Kalderis
also occurs on the surface of the grains, causing excessive et al., 2008a,b; Liou and Wu, 2009). The single-stage process
weight loss. The product obtained is also not uniform due to is therefore not efficient when the metal alkaline hydroxides
local overheating of the char (Manocha, 2003). The endother- are employed as activating agents (Chowdhury et al., 2013).
mic reactions that occur during physical activation of rice husk This is because not enough activating agent is able to pene-
char with steam and carbon dioxide are as shown in Eqs. (2) trate inside the biomass and break down the cross-linkages
and (3) respectively (Álvarez et al., 2015). or react with the resultant carbon sufficiently to generate
278
Table 3 – Physical activation of rice husks as reported in literature.
Pre-treatment of rice husk Pyrolysis conditions Chemical agent(s) Activation conditions Optimum conditions/textural Reference
properties
Base-leached Not mentioned Steam Temperature 946 ◦ C, heating BET surface area Han et al. (2014)
rate 8 ◦ C min−1 , activation time 1004.30 m2 g−1 , Iodine

31 min adsorption capacity
970.06 mg g−1 , carbon yield
31.36%
Not leached Temperature 400 ± 10 ◦ C for 1 h Steam (50% H2 O/50% N2 ) Temperature 800 ± 10 ◦ C, BET surface area 362.3 m2 g−1 Hsi et al. (2011)
under N2 flow of 0.4 normal heating rate 3.5 ◦ C min−1 ,
litre (NL) min−1 steam flow rate 0.4 NL min−1 ,
activation time 10–240 min
No leaching Temperature 400 ◦ C for 1 h Steam Temperatures 600 ◦ C, heating BET surface area 272.5 m2 g−1 Malik (2003)
under N2 atmosphere period 1 h, steam pressure
1.5 kg cm−2
Acid-leached Temperature 500 ◦ C, N2 flow Steam Heating rate 5 K min−1 , BET surface area 1180 m2 g−1 , Deiana et al. (2008)
1.4 K min−1 , heating time 2 h temperature 850 ◦ C in N2 gas total pore volume 1.09 cm3 g−1
flowing at 300 mL min−1 , switch
to steam for 105 min
Not leached Temperature 400 ◦ C, heating CO2 Temperature 800–900 ◦ C for 1 h Temperature 850 ◦ C for 1 h, BET Kumagai et al. (2009)
period 1 h, N2 flow and at 850 ◦ C for 0.25–3 h in a surface area 325–473 m2 g−1
500 mL min−1 CO2 flow of 500 mL min−1
Acid- and base- leached Rice husk char obtained by Either steam or CO2 diluted Temperature 800 ◦ C, heating Maximum BET surface areas Álvarez et al. (2015)
flash pyrolysis at 500 ◦ C in N2 (75:25) rate 15 ◦ Cmin−1 , activation obtained using CO2 and steam
time 15–60 min. were 1514 and 1365 m2 g−1
respectively
Not leached Rice husk (100 g) purged with CO2 CO2 (purity of 99.5%) purged Maximum BET surface area of Li et al. (2016)
N2 , flow rate 35 mL min−1 , into the furnace at a flow rate 350.1 m2 g−1 , micropore surface
heating rate 20 ◦ C min−1 , of 200 mL min−1 , activation area of 279.0 m2 g−1 at a
isothermal heating 1 h temperatures 650, 750 and temperature of 850 ◦ C
850 ◦ C
Not leached RH pyrolyzed at 700 ◦ C for CO2 (4 L min−1 ) Activation temperature 700 ◦ C, BET surface area 166 m2 g−1 Kalderis et al. (2008a,b)
30 min in a N2 atmosphere activation time 30 min
Table 4 – Summary of experimental conditions for production of activated carbons from rice husk by chemical activation.
Pre-carbonization conditions Chemical agent(s) Impregnation conditions Activation conditions Optimum conditions/textural Reference
properties

RH carbonized at 400 ◦ C for 4 h H3 PO4 Impregnation ratio-2.3:1 Activation temperatures 700, Activation at 800 ◦ C, BET Somasundaram et al. (2013)
800, and 900 ◦ C, heating surface area-291.15 m2 g−1
rate-5 ◦ C min−1 , isothermal
heating period 1 h
NA H3 PO4 and ZnCl2 IR-(1–4):1. Impregnated RH set in a Activation at 400–700 ◦ C, Optimum ratio-2, Liou and Wu (2009)
sand bath at about 150 ◦ C to activation time 1 h, under N2 temperature-500 ◦ C. For H3 PO4 ,
remove excess water, and then atmosphere BET surface area 1741 m2 g−1 ,
oven-dried at 105 ◦ C for 24 h for ZnCl2 , BET surface area
2434 m2 g−1
RH carbonized at 400 ◦ C for 4 h, NaOH and ZnCl2 Ratios-3:1 and 3:2, RHC heated in Activation at 400 and 600 ◦ C, Temperature-600 ◦ C, BET Isoda et al. (2014)
under N2 (100 mL min−1 ), presence of NaOH or ZnCl2 at 60 ◦ C activation times (1 and 4 h), surface area-660 m2 g−1 for
heating rate of 5 ◦ C min−1 for 6 h, followed by drying at 100 ◦ C under N2 atmosphere NaOH, 900 m2 g−1 for ZnCl2
for 24 h (100 mL min−1 )
NA NaOH and ZnCl2 Ratio-3:1 and 3:2, RH heated in Activation at 400 and 600 ◦ C, Temperature-600 ◦ C, BET Isoda et al. (2014)
presence of NaOH or ZnCl2 at 60 ◦ C activation times (1 and 4 h), surface area-280 m2 g−1 for
for 6 h, followed by drying at 100 ◦ C under N2 atmosphere NaOH, 1240 m2 g−1 for ZnCl2
for 24 h (100 mL min−1 )
Acid-leached RH carbonized at NaOH and KOH Ratio (1–4):1 for NaOH and (1–7):1 Activation at 450, 750, 850 and Activation at 850 ◦ C, BET Muniandy et al. (2014)
400 ◦ C for 4 h for KOH. 3.0 g of RHC mixed with 950 ◦ C, heating surface area-2696 m2 g−1 for
40% (w/w) of either NaOH or KOH rate-10 ◦ C min−1 , under both N2 ratio-5 KOH: 1 RHC,
in the above ratios, stirred for atmosphere
30 min at room conditions
RH carbonized at 450 ◦ C in the NaOH and KOH Ratio-3:1 for NaOH and 4:1 for Activation at 750 ◦ C for 30, 60 Not mentioned Guo et al. (2005)
presence of N2 for 25 min KOH. RHC was heated in presence and 90 min for NaOH, while
of KOH or NaOH at 400 ◦ C for activation at 650, 700 and
0.3–1.0 h to dehydrate the 750 ◦ C for 60 and 120 min for
combination KOH
279
280
– Table 4 (Continued)
Pre-carbonization conditions Chemical agent(s) Impregnation conditions Activation conditions Optimum conditions/textural Reference
properties
RH carbonized at 400 ◦ C under NaOH Impregnation ratio-3:1. Activation temperatures BET surface area 2681 m2 g−1 , Le Van and Luong Thi (2014)
N2 flow (300 mL for 90 min) Impregnated RHC oven dried at (650–800 ◦ C), heating maximum temperature 800 ◦ C
120 ◦ C for 12 h, followed by heating rate-10 ◦ C min−1 and
at 400 ◦ C for 20 min under N2 flow maintained at the final

(300 mL min−1 ) temperature for 60 min to
activate the sample
Dried RH sample carbonized at KOH Impregnation ratio 1:0.75 Activation time of 7 min under Adsorption capacity Foo and Hameed (2011)
700 ◦ C under N2 flow microwave heating 362.60 mg g−1
NA ZnCl2 20 g of dried RH impregnated with Activation temperature-600 ◦ C 10% (w/w) ZnCl2 yielding AC Yalçin and Sevinç (2000)
200 cm3 of 0–30% (w/w) ZnCl2 , under argon gas flow with BET surface area of
heated at about 70 ◦ C. Samples (3 L min−1 , for 3 h). After this 480 m2 g−1
were oven-dried at 120 ◦ C for 24 h time, CO2 gas was passed
through the reactor
(1.5 L min−1 , for 1 h).
RH carbonized at 400 ◦ C, H3 PO4 50 g of RHC agitated with 250 g of Samples heated to activating Activating temperature-900 ◦ C, Kennedy et al. (2007)
heating rate- 10 ◦ C min−1 for 85% H3 PO4 solution. Impregnation temperatures- 700, 800 and maximum total surface area of
4 h under N2 atmosphere ratio of 4.2:1, homogeneously 900 ◦ C, under N2 flow 438.9 m2 g−1 and mesopore
mixed at 85 ◦ C for 4 h, followed by (100 mL min−1 ) at a heating surface area 224 m2 g−1
drying under vacuum at 110 ◦ C for rate-5 ◦ C min−1 , and
24 h. maintained at the final
temperature for 1 h before
cooling
NA ZnCl2 , NaOH and Impregnation ratios 0.25:1, 0.5:1, Activation temperature 400, ZnCl2 activated RH yielded AC Kalderis et al. (2008a,b)
H3 PO4 0.75:1, and 1:1. 600, 700 and 800 ◦ C, activation with maximum BET surface
time 30 and 60 min area of 750 m2 g−1 for 1:1
(ZnCl2 :rice husk) at 700 ◦ C
Dried RH carbonized at 400 ◦ C KOH and NaOH Rice husk char heated in presence Temperature 800 ◦ C for KOH For KOH, (SBET > 3000 m2 g−1 , Guo et al. (2002)
for 3 h under N2 flow of KOH (4:1) or NaOH (3:1) at and 750 ◦ C for NaOH, heating pore volume >1.9 cm3 g−1 ). For
350–400 ◦ C for 0.3 h to dehydrate for 1 h NaOH, (SBET > 2500 m2 g−1 , pore
the combination, thereafter, the volume >1.6 cm3 g−1 ) and pore
temperature raised to 650–850 ◦ C diameter 1–4 nm.
for 1 h to activate the combination
RHC—rice husk char; Impregnation ratio (IR)—ratio of weight of activating agent to weight of precursor (Namasivayam and Kadirvelu, 1997); NA—not applicable.
abundant pores. Consequently, the BET surface area of the surface area of the acid-washed activated carbon is enhanced
activated carbon from rice husks is low (Isoda et al., 2014; (Liou and Wu, 2009). The data from literature summarized in
Kalderis et al., 2008a,b). A two-stage process, where the pre- Table 5 indicate that the removal efficiency of both ash con-
cursor material is pre-carbonized in the first stage, and later tent and residual chemicals largely depends on their solubility,
chemically activated in the subsequent stage is more suited acid concentration, contact time and temperature.
when employing metal alkaline hydroxides (Guo et al., 2005;
Isoda et al., 2014; Muniandy et al., 2014). This eases the reac- 5.4. Comparison of physical and chemical activation
tion of the activating agent with the carbon by impregnating
the pre-carbonized material containing a certain amount of Physical activation is associated with lower energy require-
porosity with the chemical activating agent (Cao et al., 2006). ments due to its relatively low activating temperatures
The two-stage process involving metal alkaline hydroxides compared to chemical activation (Kumar and Jena, 2016; Liu
enhances the BET surface area of the rice husk derived acti- et al., 2014). By acting as dehydrating agents, chemical acti-
vated carbon compared to when the hydroxides are employed vating agents favor the elimination of hydrogen and oxygen
in the single stage process (Guo et al., 2005; Isoda et al., 2014; as water instead of carbon oxides (COx ) and hydrocarbons.
Le Van and Luong Thi, 2014; Muniandy et al., 2014). For exam- Consequently, the loss of volatile matter and tars is inhib-
ple, the BET surface area obtained from NaOH activation of ited, leaving behind more fixed carbon and a higher carbon
pre-carbonized rice husk was 660 m2 g−1 , which is higher than yield compared to physical activation (Kalderis et al., 2008a,b;
280 m2 g−1 obtained from NaOH activation of raw rice husk Kumar and Jena, 2016). Furthermore, the BET surface area of
(Isoda et al., 2014). Le Van and Luong Thi (2014) also obtained activated carbon due to chemical activation is higher than
activated carbon with a high BET surface area of 2681 m2 g−1 that obtained from physical activation (Kalderis et al., 2008a,b;
resulting from NaOH activation of pre-carbonized rice husk. Namasivayam and Kadirvelu, 1997; Okada et al., 2003). For
These and many other experimental data from literature are instance, under the same activation temperature, the BET sur-
summarized in Table 4. The data from literature also reveals face areas due to chemical and physical activation of rice
that pre-carbonization conditions, type of activating agent, husks were 750 and 166 m2 g−1 , respectively (Kalderis et al.,
impregnation ratio, activation temperature, heating rate, acti- 2008a,b). Notwithstanding the enhanced yield and adsorptive
vation time, and inert atmosphere influence the quality of the properties of chemically activated carbon, chemical activation
rice husk derived activated carbon. As such, these factors need is associated with problems of corrosion, need for washing of
to be carefully controlled to obtain activated carbon with the activated carbon, and inefficient recovery of residual chemi-
desired adsorption properties. cals from the activated carbon (Kumar and Jena, 2016; Prahas
et al., 2008), which may be leached in the process of treat-
5.3. Washing of activated carbon ing drinking water. As such, most activated carbon employed
in drinking water treatment are produced via physical activa-
Once rice husks have been activated via physical or chemical tion. Physical activation is also known to be less costly (Álvarez
methods, the resulting activated carbons need to be washed et al., 2015), and results in activated carbons that are harder
to further lower the ash content (Li et al., 2011; Malik, 2003), as than those prepared via chemical activation (Ahmedna et al.,
well as remove the residual chemicals in the activated carbon 2000). Fig. 1 is a schematic drawing illustrating a possible
(Cheah et al., 2016). This is possible via acid and/or water- approach to produce activated carbon from rice husks for NOM
washing of activated carbon (Guo et al., 2005; Liou and Wu, removal in drinking water treatment.
2009; Muniandy et al., 2014; Somasundaram et al., 2013). A
study by Li et al. (2011) found water-washing to effectively 5.5. Comparison of textural properties of rice husk
remove ash from rice husks activated via H3 PO4 activation. activated carbon with other source-derived activated
This is because silicon phosphate (SiP2 O7 ) formed when sili- carbon
con in rice husks reacts with H3 PO4 has good solubility in hot
water. The authors further reported ash removal efficiencies In this section, the textural properties of rice husk activated
of 38.1 and 11.2% when activated carbon were washed with carbon are compared with other source-derived activated car-
water at 20 and 100 ◦ C respectively, suggesting that temper- bons, including the commercial activated carbon. The results
ature of the washing water significantly influences the ash in Table 6 indicate that activated carbon from rice husks may
removal efficiency. As a result, BET surface areas of rice husk exhibit textural properties similar to, or even better than those
derived activated carbons were 635 and 1820 m2 g−1 , respec- exhibited by other source-derived activated carbons, including
tively. However, the residual phosphorous in the activated the commercial activated carbons. However, to achieve this,
carbon is not sufficiently removed by water-washing due to careful selection of the activation method, and control of the
its low solubility in water (Liou and Wu, 2009). For this reason, activation process conditions is much desired. More insight
when raw rice husks are base-leached, activated using H3 PO4 , into the textural properties of activated carbon prepared from
and then water-washed, the residual phosphorous in the rice rice husks, under different activation methods and activation
husk derived activated carbon is usually much higher than in process conditions can be obtained under Sections 5.1 and 5.2.
the raw rice husks (Liou, 2010). Kalderis et al. (2008a,b) reported
a 6.5% removal efficiency of the residual zinc from rice husk 5.6. Cost comparison of rice husk activated carbon
derived activated carbon when water-washed compared to with other activated carbons
a removal efficiency of 30.2% when washed with HCl. This
suggests that acid-washing is a better option to remove the As can be seen from Table 7, the cost of production of
residual metallic elements than water-washing. The removal rice husk activated carbon compares well with other source-
of the metallic impurities is due to dissolution of the met- derived activated carbons. The major items considered in
als in the acidic solution, which are later removed by rinsing analyzing the cost of production of activated carbon may
with water (Lozano-Castelló et al., 2001). Moreover, the BET include the cost of equipment, raw material (precursor), trans-
Table 5 – Washing of activated carbon to remove residual activating agents.

Raw rice husk base/acid Activating agent Washing procedure for activated carbon Reference
leached/water-washed
Raw rice husk washed with H3 PO4 Activated carbon washed with hot water to remove Somasundaram et al. (2013)
distilled water only excess phosphorus compounds until wash water
attained a pH of 7, followed by oven drying at 110 ◦ C
Raw rice husk washed with ZnCl2 Activated carbon washed by refluxing in 4 M HCl Guo et al. (2005)
distilled water only solution for 48 h, and was later washed with distilled
water until H+ was removed, then dried at 120 ◦ C
Raw rice husk washed with water NaOH and KOH Activated carbon washed with distilled water and Muniandy et al. (2014)
and also acid-leached with 1.0 M dilute 1.0 M HNO3 until the pH of the rinse became
HNO3 for 24 h neutral (pH 6.8–7.2), followed by drying at 105 ◦ C for
24 h
Raw rice husk washed with KOH Activated carbon washed with deionized water and Foo and Hameed (2011)
distilled water only 0.1 N HCl until pH of washing solution reached 6–7
Raw rice husk base-leached with H3 PO4 and ZnCl2 Activated carbon refluxed with a hot 3 M HCl Liou (2010)
0.5 M NaOH solution for 1 h to remove phosphorous and Zinc
compounds. Remaining solid was washed with
distilled water until neutralization, followed by
drying at 105 ◦ C for 24 h
Raw rice husk washed with NaOH Activated carbon neutralized by 0.1 M HCl solution, Le Van and Luong Thi (2014)
distilled water only washed several times with hot distilled water to a
constant pH (6.6–7.0), followed by drying under
vacuum at 120 ◦ C for 24 h and stored in a desiccator
Raw rice husk washed with H3 PO4 Activated carbon washed several times with hot Kennedy et al. (2007)
distilled water only water until the pH became neutral and finally with
cold water to remove the excess phosphorus
compounds. The washed sample was then dried at
110 ◦ C
Rice husk refluxed with a 1 M H3 PO4 and ZnCl2 Activated carbon refluxed with a 3 M HCl solution at Liou and Wu (2009)
NaOH solution at 100 ◦ C, 373 K for 1 h, followed by washing with hot distilled
followed by washing repeatedly water several times to remove residual chemicals,
with warm distilled water until and oven drying at 105 ◦ C for 24 h
filtrate was free from the base
Fig. 1 – Proposed schematic for the preparation, pre-treatment and physical activation of rice husks for drinking water
treatment.
portation costs, chemicals, water, gases, power consumption, could be considerably reduced (Stavropoulos and Zabaniotou,
employees’ salaries and allowances, maintenance costs, and 2009). Other factors that could influence the cost of production
environmental impact assessment (EIA) studies (Ko et al., include the properties of the precursor material, method of
2004; Selvaraju and Bakar, 2017; Suzuki et al., 2007). How- activation, and plant capacity (Choy et al., 2005; Stavropoulos
ever, the cost and availability of these items may vary with and Zabaniotou, 2009). Aside from the cost of production, the
geographical location, which in turn influences the cost of pro- selling price of activated carbon largely depends on its BET
duction. For instance, in locations where the precursor can be surface area (Song et al., 2012; Stavropoulos and Zabaniotou,
obtained at no cost, the cost of production of activated carbon 2009). Consequently, the price of rice husk activated carbon
Table 6 – Comparison of textural properties of rice husk activated carbon with other source derived activated carbon.
Precursor Activation conditions Textural properties of activated carbon Reference

Activating Activation Activation BET surface Micropore Total pore Micropore
agent temperature time (min) area (m2 g−1 ) surface area volume volume
(◦ C) (m2 g−1 ) (cm3 g−1 ) (cm3 g−1 )
Corn cob KOH 900 60 1198 – 0.672 – Guo et al. (2015)

Rice husk Steam 850 105 1180 – 1.09 – Deiana et al. (2008)
Rice husk NaOH 800 60 2681 – – – Le Van and Luong Thi (2014)
Rice husk NaOH 600 – 280 – – – Isoda et al. (2014)
Jatropha hull CO2 950 40 1207 – 0.86 0.50 Duan et al. (2011)
Sisal-derived activated carbons H3 PO4 800 180 818 – 24.50 – Raja et al. (2016)
Commercial activated carbon (YP17D) – – – 1586 – 0.80 – Lee et al. (2014a,b)
Commercial activated carbon (CXV) – – – 1488 – 1.27 – Lee et al. (2014a,b)
Jackfruit peel H3 PO4 450–550 45 907–1260 – 0.525–0.733 – Prahas et al. (2008)
Oil palm empty fruit bunch CO2 900 15 345.10 – – – Alam et al. (2009)
Sewage sludge NaOH 700 60 179 46.60 0.253 0.0085 de Andrés et al. (2013)
Commercial activated carbon (Airpel 10) – – – 1020 – – – de Andrés et al. (2013)
Jujube seeds Steam activation 700 120 1276 – 15.30 – Bae et al. (2014)
Walnut shells Steam activation 700 120 991 – 12.10 – Bae et al. (2014)
a
Chinese chestnut burs KOH 800 17 1255 – 0.6565 – Li et al. (2015)
Commercial activated carbon – – – 904 – – – Gutierrez-Segura et al. (2009)
Commercial activated carbon (3S) – – – 971 – 0.78 – Lee et al. (2014a,b)
Fox nut shell H3 PO4 700 60 2636 2042 1.53 1.32 Kumar and Jena (2016)
Dry okra waste ZnCl2 500 60 1044 – 0.778 0.049 Üner et al. (2017)
Date palm tree fronds CO2 577 30 1094 – 0.4382 – Shoaib and Al-Swaidan (2015)
Rice bran CO2 850 90 652 – 0.137 – Suzuki et al. (2007)
a
Implies the units are watts, since the activated carbon was prepared under microwave heating.
283
has been reported to range from US $ 2.08–6.30 kg−1 (Song
Stavropoulos and Zabaniotou (2009)

et al., 2012). This is considerably lower than the price of com-
mercial activated carbon (Table 7), suggesting that rice husk
activated carbon could be a possible cheap alternative to the
Selvaraju and Bakar (2017)

commercial activated carbons.
Del-Campo et al. (2015)

Del-Campo et al. (2015)
Lin and Juang (2009)
Suzuki et al. (2007)
Suzuki et al. (2007)
6. Mechanism of NOM removal by activated

Toles et al. (2000)
Toles et al. (2000)
Toles et al. (2000)
Choy et al. (2005)

Lima et al. (2008)
Song et al. (2012)
Badi et al. (2014)

Ng et al. (2003)
Ng et al. (2003)
Ng et al. (2002)
carbon
Reference
Generally, NOM adsorption by activated carbon occurs only

if the total free energy of adsorption (Gads ) is less than
zero (Newcombe and Drikas, 1997). A wide range of energies
contributing to Gads include, (i) the electrostatic contribu-
Cost of production/price (US $kg−1 )
tion (Gelec ) which may comprise both coulombic and dipole

interactions, and (ii) specific contribution (Gspec ) which com-
prises all other interactions specific to the system including
hydrophobic interactions, and van der Waals forces among
others. These contributions to Gads occur according to Eq. (4),
and may favor or oppose adsorption (Bjelopavlic et al., 1999;
Newcombe and Drikas, 1997).
1.19–16.34
3.58–3.77
1.54–1.91
2.56–2.93
2.45–2.82
0.62–1.27
Gads = Gelec + Gspec (4)

20–22
20.45
3.54
1.44
2.72
2.89
3.12
1.67
2.49
1.25
2.18
1.93
15
The three major contributions to Gelec include, (i) surface-

NOM electrostatic interactions which may favour or oppose
United States of America (USA)
adsorption. The former occurs with positively charged carbon

surface, while the latter occurs with negatively charged carbon
surface. However, attractive or repulsive interactions could
Geographical location
also occur by varying solution pH which influence the surface

Table 7 – Cost comparison of rice husk activated carbon with other source-derived activated carbon.
charge of an activated carbon, (ii) lateral electrostatic repul-

sion between adsorbed NOM molecules, opposing adsorption,
and (iii) repulsive interactions between adsorbed NOM and
Malaysia
NOM in solution, opposing adsorption. The relative contribu-

China
China
Brazil
Brazil
USA
USA
USA
USA
USA
tions of (i)–(iii) to Gelec depend on the surface concentration

–
–
–
–
–
–
( ), with surface-adsorbate interactions described in (i) usu-

ally occurring at low surface concentrations. As the charge
Activating agent
from the adsorbed NOM builds up on the carbon surface, (ii)

and (iii) become the major contributions to Gelec (Bjelopavlic
The figure indicated is for the unit market price of the commercial activated carbon.
et al., 1999; Newcombe and Drikas, 1997). Therefore, while

Steam
Steam
Steam
Steam
Steam
Steam
H3 PO4
H3 PO4
NaOH
at low surface concentrations, (ii) and (iii) may either favour

KOH
KOH
KOH
KOH
CO2
CO2
CO2
or oppose adsorption depending on the charge of the car-

–
bon surface, at high surface concentrations, adsorption will

be opposed.
Type of activated carbon
The factors influencing Gspec include, (i) pore size dis-

tribution of activated carbon and the relationship between
pore size and the size of NOM, (ii) hydrophobic interaction
between the graphitic surface of the carbon and hydropho-
Granular
Granular
Granular
Granular
Granular
Granular
Granular
Granular
Granular
Granular
Granular
Granular
Granular
bic parts of the adsorbing species, (iii) interaction between

aromatic rings on the adsorbate and carbon, and (iv) hydro-
gen bonding between functional groups on the surface and
–
–
–
–
–
those on the adsorbate. For NOM adsorption by activated car-

bon from an aqueous solution, Gspec can be expected to
Artocarpus integer fruit processing waste
be negative, implying that Gelec may be attractive or repul-

sive as long as Gelec + Gspec < 0. The mechanism of NOM
Source derived activated carbon
Commercial activated carbon
removal by activated carbon has been described in detail else-

where (Bjelopavlic et al., 1999; Newcombe, 2006; Newcombe
Bamboo scaffolding waste
Broiler litter-based carbon
and Drikas, 1997).

Acid treated rice bran
Sugar cane bagasse
7. Factors affecting NOM adsorption by

Almond shells
Almond shells
Almond shells
Red oak wood
activated carbon
Pecan shells
Pecan shells
Rice husk
Rice bran
Charcoal
Lignite
Numerous studies have been conducted to determine the

Wood
factors that influence NOM removal by activated carbon

a
(Bjelopavlic et al., 1999; Newcombe, 2006). The factors relate

to physicochemical properties of activated carbon, NOM char- tition depends on the composition and initial concentration
acteristics, competing organic species and the conditions of of the micropollutant.
the aqueous solution (Fettig, 1999; Newcombe, 1999). A greater
understanding of these factors is helpful in ensuring effec- 7.3. Solution pH and charge
tive application of the adsorbent. Each of the aforementioned
factors is briefly discussed in the sections that follow. Typically, NOM carries a negative charge at pH values (6.5–8)
encountered in drinking water treatment. This is due to the
presence of carboxylic acid and phenolic groups in the NOM
7.1. Physicochemical properties of activated carbon
structure (Li et al., 2002). The dissociation of phenolic groups
occurs at pH greater than 8, while that of carboxylic groups
Pore size distribution, surface chemistry, and mineral matter
occurs at pH greater than 4, suggesting that the negative
content are the most important characteristics of activated
charge of NOM increases with increasing pH of the solution
carbon in the adsorption of NOM (Dias et al., 2007; Iriarte-
(Maghsoodloo et al., 2011). This is in agreement with findings
Velasco et al., 2008). Micropores are susceptible to blockage
from the study of the effect of pH on humic acid sorption
by NOM with large molecular sizes, making the large portion
onto powdered activated carbon by Tavengwa et al. (2015).
of activated carbon unavailable for adsorption. For this rea-
In their study, humic acid molecules generally gained excess
son, activated carbon with large micropores (1–2 nm width)
negative surface charge as the pH was increased due to depro-
and mesopores (2–50 nm width) is suited for NOM adsorption
tonation, firstly by the carboxylic groups at pH values of 4–6,
(Velten et al., 2011; Dias et al., 2007; Cheng et al., 2005; Han
followed by the dissociation of phenolic groups at higher pH.
et al., 2014). Depending on surface properties, activated carbon
Similar findings were reported by Bjelopavlic et al. (1999),
from rice husks may possess a positive, negative or zero net
where the magnitude of the negative charge of NOM at pH
charge, which influences NOM adsorption. For instance, a pos-
7 and 9 was twice that at pH 4. With the negative charge on
itively charged carbon surface favourably adsorbs NOM at pH
NOM, an attractive electrostatic interaction occurs for a pos-
values encountered in drinking water treatment, since at this
itively charged carbon, at low surface concentrations, while
pH value, NOM carries a negative charge. On the other hand,
the repulsive NOM–surface interaction occur for negatively
the presence of mineral components such as SiO2 and P2 O5
charged carbon surfaces (Bjelopavlic et al., 1999; Fettig, 1999;
(commonly present in ash) on the carbon surface is reported
Joseph et al., 2012; Li et al., 2002). A study by Li et al. (2002)
to enhance the adsorption of NOM fractions such as humic
revealed that the adsorption capacity of activated carbon for
and fulvic acids by lowering the solution pH (Daifullah et al.,
dissolved natural organic matter remaining after precoagula-
2004). A study by Park et al. (2015) revealed that impregnation
tion was increased with decreasing water pH. However, due to
of iron oxides into powdered activated carbons results into
the amphoteric nature of activated carbons, pore surfaces can
enhanced NOM removal from water. A study by Li et al. (2002)
also be either positively charged, negatively charged or neu-
revealed that increase in Ca(II) could enhance the adsorp-
tral depending on the pH of the water being treated as well as
tion capacity of commercial humic acid. These results suggest
on the base material and activation process used to prepare
that, for rice husks with unusually high ash content, leach-
the activated carbon. While acidic activated carbons carry a
ing activities should not simply target complete removal of
negative surface charge at neutral pH, basic carbons (carbons
ash from rice husks/or activated carbon with the sole aim of
containing inorganics) carry a positive surface charge when in
increasing the BET surface area. Instead, the mineral compo-
aqueous solution. On the other hand, repulsive electrostatic
nents should be reduced to acceptable limits that enhance
forces occur if (i) activated carbon pore surfaces are negative
the adsorption capacity of rice husk derived activated carbon
(ii) adsorbed NOM renders the activated carbon pore surfaces
for NOM removal in drinking water treatment. The acceptable
negative, and (iii) adsorbed NOM molecules interact at high
limits could be established through laboratory investigations,
surface concentrations, and (iv) repulsion between adsorbed
since the nature of NOM varies widely as discussed in Sec-
negatively charged NOM and NOM in solution. These repulsive
tion 1. However, according to (Serp and Machado, 2015), the
electrostatic interactions can be minimised by decreasing the
practical limit for the level of ash content allowed in activated
pH, thus decreasing the negative charge on the NOM, and on
carbon ranges from 2 to 5 wt%.
the activated carbon (Newcombe, 1999).
7.2. NOM characteristics and competing organic 7.4. Temperature

species
The temperature may affect adsorption by altering the prop-
The relationship between NOM’s molecular size distribution erties of NOM, carbon surface, and solvent, as well as their
and activated carbon’s pore size distribution predominantly mutual interactions (Carroll, 2009). Normally physical adsorp-
influence NOM adsorption (Newcombe et al., 2002). NOM fraction, which is weak, decreases with increasing temperature,
tions of size similar to pore size of activated carbon are more probably due to increased solubility of NOM. And since sol-
likely to adsorb due to more contact points between NOM and ubility and adsorption are inversely related, the temperature
the pores (Parsons et al., 2014). On the other hand, adsorp- affects the adsorption capacity of the adsorbent for a particu-
tion of NOM with molecular size larger than the pore size lar adsorbate. In the case of chemical adsorption, adsorption
of activated carbon is hindered, since these may not be able increases within a certain temperature range, above which
to penetrate into the pores of activated carbon. Competing it decreases. This increase in adsorption is mainly due to
organic species influence NOM adsorption by competing for increase in the number of adsorption sites created by break-
adsorption sites (Ding et al., 2008). In drinking water treating some of the internal bonds near the edge of the active
ment, micropollutants are the competing organic species surface sites of the adsorbents (Panda et al., 2009). A study
which are about 3–6 orders of magnitude smaller than the by Schreiber et al. (2005) revealed that NOM in its dissolved
NOM concentration (Newcombe, 2006). The degree of compe- form is preferentially adsorbed onto granular activated carbon
at higher water temperatures. Summers and Roberts (1988) 9. NOM adsorption by rice husk activated
also reported an increase in adsorption of humic substances carbon
with increasing temperatures (1–41 ◦ C). However, from a ther-
modynamic point of view, a decrease in NOM adsorption Because coagulation may only remove a finite fraction of NOM
with increasing temperature would be expected since adsorp- in drinking water, activated carbon is often employed to sup-
tion is an exothermic process (Schreiber et al., 2005). The plement coagulation through increased NOM removal, thereby
increase in adsorption of NOM with increasing temperature lowering the forming potential of DBPs (El-demerdash et al.,
could be explained by entropic effects in which NOM forms 2015; Najm et al., 1998). Generally, two types of activated car-
larger aggregates at lower temperatures, but disintegrates into bon can be employed for NOM removal from water namely;
smaller molecules at higher temperatures. As a result, the rel- powdered activated carbon (PAC) and granular activated car-
atively smaller molecules of NOM have increased access to the bon (GAC) (Newcombe, 2006; Parsons et al., 2014). Although
internal surface area of granular activated carbon, and vice the performance of these types of activated carbon for NOM
versa. removal in drinking water treatment has been well docu-
mented (Bhatnagar and Sillanpää, 2017; Humbert et al., 2008;
Newcombe et al., 2002; Velten et al., 2011), majority of the stud-
ies mainly focus on the application of commercial activated
7.5. Contact time carbons rather than the low cost activated carbon derived
from agricultural residues like rice husks. The sections that
In physical adsorption, majority of the adsorbate species are follow highlight the useful applications of the powdered and
adsorbed on the adsorbent surface within a short contact time, granular forms of activated carbon from rice husks for NOM
while in chemical adsorption, a longer contact time is required removal from water. Where possible, a comparison with com-
to attain equilibrium (Xu et al., 2013). Uptake of adsorbate mercial activated carbons and other low cost adsorbents has
species is fast in the initial stages of the contact period, and been made.
thereafter, the adsorption rate lowers near the equilibrium
(Mall et al., 2006; Nandi et al., 2009). For instance, time-
dependent experiments conducted in the range of 5–120 min 9.1. Powdered activated carbon
at 37 ◦ C by Tavengwa et al. (2015), indicated that sorption with
powdered activated carbon was fast in the initial stages, with Powdered activated carbon typically consists of particle size
a maximum value attained after 30 min. In another study by ranging from 10–100 ␮m in diameter (Newcombe, 2006). This
Humbert et al. (2008), using a combination of powdered acti- type of activated carbon is not well developed since char-
vated carbon and ion exchange resin, DOC content and UV254 acteristics such as density, hardness and abrasion index
absorbance decreased progressively as a function of time and are typically low. The cost of producing PAC is normally
reached a minimum value after 30 min contact time. The fast kept to a minimum since it is usually discarded after use
uptake in the initial stage may be attributed to the large num- (Parsons et al., 2014). PAC is most often employed to remove
ber of vacant active surface sites available for adsorption. The NOM in drinking water that causes odor and tastes (Carrière
molecules of the NOM fractions will bind to all the active sites et al., 2009), but is ineffective in removing DBP precursors
until they are fully occupied. Thus, with time, fewer active (Carrière et al., 2009). PAC can be applied at various stages of
sites remain available for adsorption leading to a reduction in water treatment, including before coagulation, during chemi-
the amount of NOM adsorbed by activated carbon. cal addition, or during the settling stage prior to sand filtration
(Newcombe, 2006). However, its use presents some practical
problems because of the requirement to separate PAC from the
water after use (Gupta et al., 2009). According to Newcombe
8. NOM removal using raw and pyrolyzed (2006), PAC applied either before or during coagulation can be
rice husks removed from water during the coagulation process, while PAC
applied during the settling stage prior to sand filtration can
Even in its raw form, rice husk without activation has been be removed through filtration. However, studies have revealed
reported to remove 98.24% of humic acid from aquatic solution that application of PAC before coagulation results into more
(Nsaifabbas and Abbas, 2014). On the contrary, preliminary enhanced NOM removal than when PAC and coagulation are
tests conducted by Imyim and Prapalimrungsi (2010) showed applied simultaneously (Duan et al., 2003; Tomaszewska et al.,
that rice husk in its raw form has no ability to adsorb humic 2004). This also reduces the dosage of the coagulant when
acids, thus the need for activation. Rice husk merely treated NOM concentration is reduced by PAC adsorption. On the other
with NaOH and citric acid without carbonization was also hand, application of PAC after coagulation (or during the set-
reported to remove 60–70% of humic substances from peat tling stage prior to sand filtration) results in increased turbidity
swamp runoff (Lee et al., 2014a,b). The residual rice husk since PAC is not incorporated into the flocs. PAC can also be
loaded with the humic substances could then be employed as applied solely without coagulation, though NOM removal effi-
a soil conditioner (Lee et al., 2014a,b). Pyrolyzed rice husk has ciencies are as low as 4–75% (Uyak et al., 2007). Generally, a
also been successfully employed to reduce color and turbid- combined application of chemical coagulation with PAC may
ity by 97.64% and 98.98% respectively (Emanuelle et al., 2016). be a more cost effective alternative than chemical coagulation
With such interesting and promising results, NOM removal alone for meeting the requirements of Stage 1 of the disinfec-
efficiency could even be enhanced if the pyrolyzed rice husks tants/DBP rule (Najm et al., 1998).
are further activated under controlled conditions. However, From the review of literature, it was found that very few
more studies are needed, especially to optimize process con- adsorption studies have been conducted concerning NOM
ditions for NOM removal from drinking water using the raw removal using powdered activated carbon derived from rice
and pyrolyzed rice husks. husks. Among these include studies by El-demerdash et al.
Table 8 – Summary of NOM removal efficiencies by rice husk activated carbon, as compared to commercial activated
carbons, and other low cost adsorbents.
Adsorbent NOM/NOM fraction/DBP Removal efficiency (%) Reference
PAC from rice husks NOM 9.7–76.10 El-demerdash et al. (2015)

Commercial PAC only NOM 71.20 Joseph et al. (2012)
PAC from rice husks Trihalomethane 12–58.8 El-demerdash et al. (2015)
Alum + commercial PAC NOM 19–92.0 Joseph et al. (2012)
FeCl3 + commercial PAC NOM 2.5–84.0 Joseph et al. (2012)
Coconut palm PAC DOC 77.00 Ribau Teixeira et al. (2017)
Bituminous coal-based GAC THMFP >85.00 Iriarte-Velasco et al. (2008)
Commercial activated carbon TOC 42–45.00 Luukkonen et al. (2014)
Commercial activated carbon DOC 58–68.00 Luukkonen et al. (2014)
Rice husk activated carbon COD 70.00 Kalderis et al. (2008a,b)
Note: THMFP is trihalomethane formation potential.
(2015) who studied the removal of NOM and THM using pow- available treatment technology for removal of DBP precursors
dered activated carbon from rice husks. In their findings, NOM from water for meeting the Stage 2 D/DBP rule (Najm et al.,
removal ranged from 9.7 to 76.1%, while THM removal ranged 1998). Similar to PAC, GAC is not suitable for sole application in
from 12.0 to 58.8% depending on the dose of activated carbon drinking water treatment, since its sorption capacity is rapidly
in mg L−1 . Kalderis et al. (2008a) investigated the adsorption reduced by pore blockage caused by the large molecules of
of humic acids on PAC derived from rice husks. A maximum humic substances (Ødegaard et al., 2010). For this reason,
loading of 11.59 mg of humic acid per gram of activated carbon GAC adsorption is more effective for DBP precursor control in
was achieved. The authors attributed the low maximum load- waters containing a larger percentage of low molecular weight
ing to the microporosity and the low Fe2 O3 and CaO content NOM (Velten et al., 2011). To achieve this possibility, NOM
of the rice husk activated carbon. This is in agreement with adsorption by GAC is best applied as a post-treatment pro-
findings by Daifullah et al. (2004), who reported that rice husk cess when other processes such as coagulation have removed
activated carbons with more mesoporosity were found to have humic substances to quantities sufficiently small to arrive at
adsorption capacity of humic acid 20% larger than those with sites in the finer pores. For example, GAC can be employed
less mesoporosity. It has also been reported that the presence as a filter medium in which either some or all of the filter
of acidic oxides such as SiO2 and P2 O5 (commonly present media in a granular media is replaced with GAC. On the other
in ash) on the carbon surface enhances the adsorption of hand, GAC can be employed as a post-filtration medium prior
humic acids by lowering the solution pH (Daifullah et al., 2004). to disinfection.
Diamadopoulos et al. (1992) found the ash-free activated car- In post-filtration applications, backwashing of GAC is usu-
bons to have low adsorption capacities for fulvic acids. In their ally not necessary due to the fact that the GAC receives water
study, activated carbon with a surface area of over 1000 m2 g−1 , of the highest quality, and therefore its sole objective is to
had a significantly lower adsorption capacity for fulvic acid remove the DBP precursors. Backwashing is necessary if exces-
compared to activated carbon with high ash content and sive biological growth occurs, and this is a common practice
surface area less than 300 m2 g−1 . The authors attribute the when GAC is employed as a filtration media. In this option,
increase in adsorption capacity of fulvic acids with increase NOM removal occurs via adsorption of soluble NOM, physi-
in ash content of activated carbon due to the ability of the ful- cal filtration of particulate NOM, and through biodegradation
vic acid to interact with metal oxides and metal ions, which of biodegradable NOM when an active biofilm forms onto
constitute a significant fraction of the ash. These findings sug- GAC particles. Over time, the two latter mechanisms lead to
gest that the presence of ash in the rice husk activated carbon progressive clogging of GAC filters, resulting in a head-loss
can have significant influence on NOM removal from water. build-up and deterioration in the quality of filtered water. It is
Table 8 highlights previous studies regarding NOM removal for these reasons that GAC filters require periodic backwash-
efficiencies by rice husk derived activated carbon, in compar- ing to ensure their long-term performance. However, in order
ison with commercial activated carbons, and other low cost to withstand abrasion and attrition during the backwash-
adsorbents. ing process, the GAC should possess sufficient mechanical
From the data indicated in Table 8, NOM removal efficien- strength. To achieve this, the production of GAC from soft, low
cies by rice husk derived activated carbon compare well with density agricultural residues such as rice husks necessitates
those resulting from the application of commercial activated the use of a suitable binder such as coal tar, cane molasses,
carbon. Rice husk derived activated carbon could therefore corn syrup and beet molasses among others to produce a hard,
serve as a potential alternative to the costly commercial acti- higher density briquette or pellet before carbonization and
vated carbon. However, there is still need to subject both the activation (Pendyal, 1999). The procedure must be performed
rice husk derived activated carbon and commercial activated in this order, otherwise the binders would block the entire
carbon to quite similar water conditions to obtain a better pore network (Menéndez-Díaz and Martín-Gullón, 2006). The
comparison between the two adsorbents. binder ensures that the low density material remains intact
as granules even after carbonization and activation (Qureshi
9.2. Granular activated carbon et al., 2008). While the char characteristics before activation
are predominately due to the binder, the characteristics of
Granular activated carbon typically consists of particle sizes the GACs are exactly those of the base material (Pendyal,
ranging between 0.4 and 2.5 mm (Newcombe, 2006). Adsorp- 1999). About 60-80% of DOM can be removed by GAC (Owen
tion by GAC has been designated by US EPA (1998) as the best et al., 1995). The preformed THMs can also be removed by
passing the treated, chlorinated water through a GAC filter, activated carbons was performed can be accessed from the
though this may not be economically feasible at full-scale, respective original articles.
due to the frequent need for regeneration of GACs. How-
ever, for rice husk derived activated carbon, regeneration is 10. Future prospects
not necessary, thanks to the reasonably low production costs
(Ahmaruzzaman and Gupta, 2011).
The data from the literature reviewed reaffirms the consensus
reached to date, that conventional water treatment methods
9.3. Adsorption isotherms do not completely remove NOM from water, posing numer-
ous problems in water treatment. To improve NOM removal
Adsorption is normally described using isotherms, which are from water, conventional water treatment methods can be
plots of the equilibrium relationship between the amount of employed in combination with other methods such as adsorp-
organic compound left in solution and the amount of com- tion, membrane separation, ion exchange, and advanced
pound that is on the surface of the adsorbent. At equilibrium, oxidation processes. Out of these, NOM removal by adsorption
the amount of adsorbate on the adsorbent at equilibrium using activated carbon is most preferred. However, commer-
(mg/g), qe , can be calculated using the balance Eq. (5). cial activated carbons are expensive, limiting their widespread
large scale application in water treatment, especially by the
qe = V (Co − Ce ) /m (5) developing world. The production of activated carbon from
the abundantly available rice husks for drinking water treat-
ment is therefore the future for developing countries, where
where; V is the volume of solution (L), Co and Ce are the
over 96% of the rice husks is generated globally. Interestingly,
initial and equilibrium concentrations of the adsorbate in
the adsorptive properties of rice husk derived activated carbon
mg/L respectively, and m is the mass of adsorbent used (g).
are comparable, and in some instances higher than those of
Various isotherms exist that describe the equilibrium char-
commercial activated carbons depending on the properties of
acteristics of adsorption including Freundlich, Langmuir, BET,
rice husks, pretreatment, activation method and process con-
and Redlich–Peterson (R–P), etc. However, Freundlich and
ditions. However, the preparation of rice husk activated carbon
Langmuir isotherms are the most commonly used in water
needs to be carried out in an eco-friendly manner to avoid any
treatment. The linearized forms of the Langmuir and Fre-
environmental hazards that could possibly arise due to poor
undlich isotherms are given in Eqs. (6) and (7), respectively.
disposal of the residual chemicals and the spent rice husk
These can be employed to indicate the adsorption capacity of
activated carbon. Since most studies do not address these
carbon for humic substances (Duan et al., 2003).
concerns, then future studies could prioritize finding sustain-
able ways of disposing of the generated waste. In our view,
1 1 1
= + (6) the residual chemicals could be recycled and reused for either
qe qo bqo Ce
leaching or activating rice husks. Consequently, this makes
the production of activated carbon from rice husks even more
1
log qe = log Kf + log Ce (7) economically viable. On the other hand, the spent rice husk
n
activated carbon, particularly the granular form could be pul-
verized, and reused as low cost adsorbents for micro-pollutant
where qe is the quantity of humic substance adsorbed per unit
adsorption from a secondary treated wastewater effluent (Hu
weight of carbon (mg/g) at equilibrium; Ce the equilibrium
et al., 2015). Alternatively, the spent rice husk activated carbon
concentration of humic substance in solution (mg/l); b the
could be densified to make fuel briquettes for meeting energy
constant characterizing strength of humic substance–carbon
needs.
bond (l/mg); qo adsorptive capacity (mg/g); Kf a Freundlich
Generally, the data reported in this review article regard-
affinity parameter for a hetero-disperse system (l/g); and n
ing NOM removal from water by rice husk activated carbon is
is the adsorptive intensity related to the magnitude of the
very promising, with the adsorption capacities being compa-
adsorption driving force and to the distribution of the energy
rable to those of commercial activated carbons and other low
sites on the adsorbent. Table 9 is a summary of Freundlich
cost adsorbents. However, few studies have been conducted
and Langmuir parameters for adsorption of humic substances
regarding application of rice husk derived activated carbon
on rice husk activated carbon, selected commercial activated
for NOM removal from water. Consequently, future studies
carbons and other low cost adsorbents as reported by various
could focus on optimizing conditions for NOM removal from
researchers.
water using rice husk derived activated carbon. Majority of the
The data from literature summarized in Table 9 is very
results are also laboratory scale based, suggesting the need
interesting and promising, since adsorptive capacities of rice
for pilot-plant scale studies to test the rice husk activated
husk derived activated carbon for NOM are comparable to
carbon at actual field conditions. Lastly, studies focusing on
those of commercial activated carbons, and other low cost
the techno-economic evaluation of the production processes
adsorbents. However, majority of the studies focus on the
and application of low cost adsorbents for NOM removal from
removal of humic, as compared to fulvic acids. It is also
water remain to be explored.
worth noting that the adsorptive capacities of activated carbon
reported in Table 9 are specific to the conditions under which
the experiments were conducted. This is of importance since 11. Conclusions
the adsorption capacities of activated carbon vary depending
on the material characteristics, experimental conditions, and An overall review has been made regarding production and
also the extent of chemical modifications (Qureshi et al., 2008). potential application of rice husk activated carbon for NOM
For this reason, detailed information regarding the experi- removal from water. Properties of rice husks, pretreatment,
mental conditions for which NOM adsorption by the respective extent of activation, and activation method influence the
Table 9 – Langmuir and Freundlich adsorption model coefficients for rice husk activated carbon in comparison with other
adsorbents.
Activated carbon/adsorbent Freundlich parameters Reference
Kf 1/n R2
HA FA DOC HA FA DOC HA FA DOC
Rice husk activated carbon 4.9496 – – 0.1619 – – – – – Kalderis et al. (2008a)

Rice husk activated carbon 32.3000 – – 0.0880 – – 0.9960 – – Daifullah et al. (2004)
Commercial GAC 1.0910 – – 1.2510 – – 0.9800 – – Maghsoodloo et al. (2011)
Commercial GAC 25.9000 9.000 – 0.4050 0.649 – 0.9150 0.984 – Fan et al. (2007)
Chitosan hydrogel beads – 1.390 – – 0.586 – – 0.994 – Wang et al. (2008)
Commercial PAC 10.9000 – – 1.4493 – – 0.9589 – – Tavengwa et al. (2015)
Coconut palm PAC – – 16.07 – – 0.4926 – – 0.7880 Ribau Teixeira et al. (2017)
Coconut shell-based GAC – – 1.67 – – 2.3810 – – 0.9999 Iriarte-Velasco et al. (2008)
Bituminous coal-based GAC – – 5.85 – – 0.6289 – – 0.9996 Iriarte-Velasco et al. (2008)
Lignite coal-based GAC Graf et al. (2014)
Bituminous coal-based GAC – – 1.68 – – 1.4925 – – 0.8510 Graf et al. (2014)
Modified natural zeolite 33.3000 – – 3.3223 – – 0.9640 – – Zhan et al. (2010)
Activated sludge 2.13 × 10−6 – – 4.5455 – – 0.9787 – – Jonglertjunya and
Lertchutimakul (2012)
Fly ash 5.7200 – – 0.1470 – – 0.989 – – Wang and Zhu (2007)
Unburned carbon 9.9300 – – 0.4520 – – 0.9420 – – Wang and Zhu (2007)
Chitin 3.1900 – – 0.5128 – – – – – Wan Ngah and Musa (1998)
Chitosan 17.9300 – – 0.1458 – – – – – Wan Ngah and Musa (1998)
Graphite 0.9300 – – 0.6510 – – 0.9490 – – Hartono et al. (2009)
Graphite oxide 21.4900 – – 0.4900 – – 0.9720 – – Hartono et al. (2009)
Adsorbent/activated carbon Langmuir parameters Reference

−1 −1 −1 2
b (mg L ) qo (mg g ) R
HA FA DOC HA FA DOC HA FA DOC
Rice husk activated carbon 0.0005 – – 11.59 – – – – – Kalderis et al. (2008a)

Commercial GAC 0.0148 – – – – – 0.9900 – – Maghsoodloo et al. (2011)
Commercial GAC 0.014 0.016 – – – – 0.9630 0.9720 – Fan et al. (2007)
Commercial PAC 0.0049 – – 30.40 – – 0.9479 – – Tavengwa et al. (2015)
Commercial activated carbon – – – 97.40 – – 0.9556 – – Rauthula and Srivastava (2011)
Coconut palm PAC – – 0.489 – – 51.81 – – 0.9360 Ribau Teixeira et al. (2017)
Coconut shell-based GAC – – 0.53 – – 2.21 – – 0.9803 Iriarte-Velasco et al. (2008)
Bituminous coal-based GAC – – 0.27 – – 27.60 – – 0.9983 Iriarte-Velasco et al. (2008)
Modified natural zeolite 0.3600 – – 92.00 – – 0.9940 – – Zhan et al. (2010)
Rice husk ash 0.1800 – – 2.70 – – 0.9558 – – Imyim and Prapalimrungsi
(2010)
Functionalized rice husk ash 1.8800 – – 8.20 – – 0.9988 – – Imyim and Prapalimrungsi
(RHA-NH2 ) (2010)
Activated sludge 0.0300 – – 1.03 – – 0.9142 – – Jonglertjunya and
Lertchutimakul (2012)
Fly ash 0.2990 – – 10.70 – – 0.9950 – – Wang and Zhu (2007)
Unburned carbon 0.0655 – – 71.80 – – 0.9370 – – Wang and Zhu (2007)
Chitin 72.9000 – – 27.30 – – – – – Wan Ngah and Musa (1998)
Chitosan 2720.7000 – – 28.88 – – – – – Wan Ngah and Musa (1998)
Graphite 0.0343 – – 16.50 – – 0.9560 – – Hartono et al. (2009)
Graphite oxide 0.0516 – – 190.30 – – 0.9870 – – Hartono et al. (2009)
Note: (1) HA is humic acid, (2) FA is fulvic acid, (3) DOC is dissolved organic carbon; (4) RHA is rice husk ash.
adsorption properties of rice husk activated carbon. The data husk activated carbon in relation to NOM removal from water
from literature emphasize the need for ash removal from rice compares well with commercial activated carbon, and other
husks prior to activation to improve the adsorptive proper- low cost adsorbents. Rice husk derived activated carbon could
ties of rice husk activated carbon. However, the adsorption therefore serve as a potential alternative to the costly commer-
capacity of carbon is not merely related to its surface area, cial activated carbon. Of the two possible forms of activated
porosity, surface chemistry and mineral matter content, but carbon from rice husks, powdered activated carbon is more
also on the accessibility of NOM to the carbon’s inner surface. suited to remove NOM that causes taste and color problems,
For this reason, NOM is well adsorbed in mesopores (2–50 nm while granular activated carbon is more suited to remove DBP
width) and micropores (1–2 nm width). The data from liter- precursors (low and intermediate molecular size NOM) that
ature also revealed that the adsorption performance of rice are poorly removed via coagulation. Despite rice husk acti-
vated carbon having good prospects for NOM removal from between rice husk ash grown in different regions for
water, the information is still very limited to this effect. More stabilizing fly ash from a solid waste incinerator. J. Environ.
research is therefore needed to investigate the adsorption per- Manag. 159, 128–134,
http://dx.doi.org/10.1016/j.jenvman.2015.05.015.
formance of rice husk activated carbon for NOM removal from
Betancur, M., Martínez, J.D., Murillo, R., 2009. Production of
water. activated carbon by waste tire thermochemical degradation
with CO2 . J. Hazard. Mater. 168 (2–3), 882–887,
Conflicts of interest http://dx.doi.org/10.1016/j.jhazmat.2009.02.167.
Bhatnagar, A., Sillanpää, M., 2017. Removal of natural organic
matter (NOM) and its constituents from water by
There is no conflict of interest among the authors.
adsorption—a review. Chemosphere 166, 497–510,
http://dx.doi.org/10.1016/j.chemosphere.2016.09.098.
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Bjelopavlic, M., Newcombe, G., Hayes, R., 1999. Adsorption of
for African Researchers in the Engineering Sciences (Grant
NOM onto activated carbon: effect of surface charge, ionic
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Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

Production and performance of activated carbon

E. Menya a,b,∗ , P.W. Olupot a , H. Storz c , M. Lubwama a , Y. Kiros d

Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296

Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296

Note: ND—not detected.

Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296

Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296

Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296

Table 5 – Washing of activated carbon to remove residual activating agents.

Chemical Engineering Research and Design 1 2 9 ( 2 0 1 8 ) 271–296

Corn cob KOH 900 60 1198 – 0.672 – Guo et al. (2015)

has been reported to range from US $ 2.08–6.30 kg−1 (Song

Stavropoulos and Zabaniotou (2009)

Selvaraju and Bakar (2017)

Del-Campo et al. (2015)

6. Mechanism of NOM removal by activated

Choy et al. (2005)

Badi et al. (2014)

Generally, NOM adsorption by activated carbon occurs only

tion (Gelec ) which may comprise both coulombic and dipole

Gads = Gelec + Gspec (4)

The three major contributions to Gelec include, (i) surface-

adsorption. The former occurs with positively charged carbon

also occur by varying solution pH which inﬂuence the surface

charge of an activated carbon, (ii) lateral electrostatic repul-

NOM in solution, opposing adsorption. The relative contribu-

tions of (i)–(iii) to Gelec depend on the surface concentration

( ), with surface-adsorbate interactions described in (i) usu-

from the adsorbed NOM builds up on the carbon surface, (ii)

et al., 1999; Newcombe and Drikas, 1997). Therefore, while

at low surface concentrations, (ii) and (iii) may either favour

or oppose adsorption depending on the charge of the car-

bon surface, at high surface concentrations, adsorption will

The factors inﬂuencing Gspec include, (i) pore size dis-

bic parts of the adsorbing species, (iii) interaction between

those on the adsorbate. For NOM adsorption by activated car-

be negative, implying that Gelec may be attractive or repul-

Commercial activated carbon

Commercial activated carbon

Commercial activated carbon

removal by activated carbon has been described in detail else-

and Drikas, 1997).

Sugar cane bagasse

7. Factors affecting NOM adsorption by

Red oak wood

Numerous studies have been conducted to determine the

factors that inﬂuence NOM removal by activated carbon

(Bjelopavlic et al., 1999; Newcombe, 2006). The factors relate

7.2. NOM characteristics and competing organic 7.4. Temperature

PAC from rice husks NOM 9.7–76.10 El-demerdash et al. (2015)

Note: THMFP is trihalomethane formation potential.

HA FA DOC HA FA DOC HA FA DOC

Rice husk activated carbon 4.9496 – – 0.1619 – – – – – Kalderis et al. (2008a)

Adsorbent/activated carbon Langmuir parameters Reference

HA FA DOC HA FA DOC HA FA DOC