Nativa, Sinop, v. 9, n. 2, p. 215-221, mar./abr. 2021.

Pesquisas Agrárias e Ambientais

DOI: https://doi.org/10.31413/nativa.v9i2.11387 ISSN: 2318-7670

Use of activated charcoal as bio-adsorbent for treament of residual waters: a review

Lucélio Mendes FERREIRA1*, Rafael Rodolfo de MELO2

1Federal University of Paraíba, Center of Human, Social, and Agricultural Sciences, Bananeiras, PB, Brazil.

2Federal Rural University of the Semi-Arid Region, Center of Agricultural Sciences, Mossoró, RN, Brazil.

*E-mail: rrmelo2@yahoo.com.br

(Orcid: 0000-0001-7536-9433; 0000-0001-6846-2496)

Received on 11/02/2021; Accepted on 02/06/2021; Published on 06/06/2021.

ABSTRACT: Adsorption is gaining attention by becoming one of the most used technologies for the removal

of contaminants from water. Adsorption with activated charcoal (AC) is an efficient method for treatment of

effluents; the main advantage of AC production is the use of residues that would be inappropriate discarded.

The objective of this work was to gather and organize the information available about the potential of using

activated charcoal as a bio-adsorbent. Researches were conducted on scientific articles about the production of

activated charcoal with adsorption characteristics for the removal of contaminants from residual waters. The

efficiency of this technique is dependent on different parameters that affect the adsorption process, such as:

pH of the solution, dye initial concentration, contact time, adsorbent amount, and temperature. The articles

studied showed that the bio-adsorbent characteristics of charcoals are promising for the removal of pollutants

from residual waters. The isotherm adsorption models developed by Langmuir, Freundlich, and Brunauer,

Emmett, and Teller (BET) are often used to evaluate the adsorption capacity of activated charcoals.

Keywords: industrial effluents; contaminants; environmental management.

Emprego do carvão ativado como bioadsorvente para o tratamento

de águas residuais: uma revisão

RESUMO: A adsorção vem ganhando destaque com uma das tecnologias mais empregadas na remoção de

contaminantes em águas. No tratamento de efluentes, a adsorção com carvão ativado (CA) apresenta-se como

um método eficiente. A principal vantagem da produção de CA é o aproveitamento de resíduos que seriam

descartados de forma inadequada. O objetivo desta pesquisa é organizar algumas informações disponíveis com

relação ao potencial do carvão ativado como bioadsorvente. Foram realizadas pesquisas em periódicos sobre

produção de carvão ativado com características adsortivas na remoção de contaminantes em águas residuais. A

eficácia dessa técnica sob diferentes parâmetros influencia no processo de adsorção, tais como: pH da solução,

concentração inicial do corante, tempo de contato, quantidade do adsorvente e temperatura. Em todos os

artigos estudados, as características dos carvões como bioadsorventes se mostraram promissores no processo

para remoção de poluentes em águas residuais. Conclui-se que os modelos de isotermas de adsorção

desenvolvidos por Langmuir, Freundlich e BET são frequentemente utilizados para avaliar a capacidade de

adsorção dos carvões ativados.

Palavras-chave: efluentes industriais; contaminantes; gestão ambiental.

1. INTRODUCTION

The conservation of natural resources has become an

important concern, mainly due to the neglect of humans who

irresponsibly pollute and contaminate springs and change

natural environments. The contamination of a water course

is not always easily detected, since most contaminants present

no visually identifiable evidences. Color is a parameter that

raises attention due to the visual impact, and facilitates the

identification of contamination.

Adsorption is gaining attention by becoming one of the

most used technologies for the removal of contaminants

from waters. It is a physical-chemical phenomenon based on

the bound of components in gas or liquid phase to the

surface of a material in solid phase. The components that

connect to this surface are called adsorbates, and the material

in solid phase that withhold them is called adsorbent.

The capacity of activated charcoal to remove different

compounds in contaminated waters increased the interest

and demand for this product. Its adsorption provides some

advantages over classic methods of treatment of effluents,

such as: low generation of residues, efficiency in the removal

of substances, simple operation, easy recovery of metals, and

the possibility of reuse the adsorbent.

Thus, the present study intended to highlight the

potential of using activated charcoal with adsorption

characteristics for the treatment of residual waters, through a

literature review.

2. LITERATURE REVIEW

2.1. Activated charcoal

The first use of activated charcoal in the industrial sector

occurred in the England, in 1794, as a discoloration agent in

the sugar industry. This event marked the beginning of

studies about activated charcoal on liquid phases. The first

large-scale application on gas phases occurred in the mid XIX

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216

century (1854); the mayor of London ordered the

implementation of charcoal filters in all ventilation systems

of sewers to remove unpleasant odors. In 1872, gas masks

with charcoal filters were used in chemical industries to

prevent inhalation of mercury vapors (BANDOSZ, 2006).

Theoretically, activated charcoal can be produced from

any carbonaceous material. However, some characteristics,

such as high fixed carbon content and low mineral content,

should be considered in the choice of a precursor material.

Products of plant origin are among the most interesting raw

materials to obtain activated charcoal, mainly, lignocellulosic

ones, which present cellulose, hemicellulose, lignin, and

inorganic components as their main chemical components.

Several agricultural wastes, including wood, plants, coconut

shells, sugarcane bagasse, and fruit seeds, are among the

products of plant origin that also present good properties for

charcoal production (BOUCHELTA et al., 2008).

Activated charcoal is the name given to a group of

charcoals that are characterized by having carbonaceous

material of porous structure that presents a small quantity of

heteroatoms bound to carbon atoms, mainly oxygen, and an

internal surface that makes it capable of adsorbing molecules

in liquid or gaseous phase (GORGULHO et al., 2008).

Commercial charcoals present a high surface area, high

porosity, and variable surface chemical characteristics

(presence of different functional groups, mainly oxygenated)

with high reactivity degree. Variations in temperature and

activation time affect the formation of chemical groups in the

charcoal surface. The surface area, volume of pores, basicity,

and adsorption capacity increase as the temperature and

activation time are increased. However, it decreases charcoal

yield and the mechanical resistance index (BORGES et al.,

2016).

Charcoal can be activated by chemical or physical

processes by using different compounds that, in general,

increase the charcoal surface area through reactions

throughout the material surface (MOHAN; PITTMAN JR,

2006).

The chemical activation consists of the impregnation of

activator agents, such as phosphoric acid (H3PO4), to the

material before carbonization. These agents provide the

formation of cross connections, making the material less

prone to volatilization when heated to high temperatures

(Figure 1). The physical activation consists of reactions of

charcoal with water or CO2 vapors, or a mixture of these two

gases after carbonization.

The most used chemical activators are: KOH (potassium

hydroxide), K2CO3 (potassium carbonate), NaOH (sodium

hydroxide), NaCO3 (sodium carbonate), MgCl2 (magnesium

chloride), H3PO4 (phosphoric acid), AlCl3 (aluminum

chloride), and ZnCl2 (zinc chloride).

KOH is very selective in the activation process, causing

more localized reactions on the precursor and is more

effective for materials with ordered structure. The use of

H3PO4 as activator provides high surface areas to charcoals

and causes physical and chemical modifications by

penetrating the structures and partially dissolving the

biomasses (WANG et al., 2010). Charcoals activated with

sodium acetate present pronounced formation of

micropores; moreover, their characteristics vary according to

size, volume, and distribution of pores and presence of

different functional groups in the charcoal surface

(UTRILLA et al., 2011).

Activated charcoal are more porous than common

charcoal (Figure 2).

Figure 1. Representation of the chemical activation process. Source: Adapted from Pereira, 2010.

Figura 1. Esquema demonstrativo de como ocorre à ativação química. Fonte: Adaptado de Pereira, 2010.

Figure 2. Representation of the porosity of common and activated charcoals. Source: Adapted from Souza, 2018.

Figura 2. Porosidade do carvão comum e ativado. Fonte: Adaptado de Souza, 2018.

2.2. Characteristics of charcoal pores

Pore size distribution depends on the charcoal material

type and activation method used. Considering the adsorption

properties, the International Union of Pure & Applied

Chemistry (IUPAC) established a classification according to

the material form and dimensions. Regarding the form, pores

can be classified as open or closed; open pores are the holes

in the external surface, represented by the letters B, C, D, and

F in Figure 3. Pores that allow the flow of fluids are classified

as transport pores, which may present branches (cage type)

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217

that do not contribute to the transport. Closed pores are

those consisted of an isolated hole. The charcoal porosity is

dependent on the different sizes and forms of the pores,

including their depth. This is an important aspect to evaluate

the performance of activated charcoals (ZDRAVKOV et al.,

2007).

All activated charcoals contain micro, meso, and

macropores in their structures, with a considerably variation

in relative proportion between them depending on the

precursor and manufacturing process used. According to the

IUPAC, charcoal pores are classified by their form and

dimensions (Table 1).

Different parameters can be used to describe the

adsorption capacity of activated charcoals (AC). This capacity

can be evaluated using different compounds, such as iodine,

methylene blue, and molasses, to measure their porosity

(Figure 4) (DI BERNARDO; DANTAS, 2005).

The iodine number describes the microporosity

expressed as quantity of iodine (weight) adsorbed by a given

AC under specific conditions, usually related to adsorption

(DABROWSKI et al., 2005).

Figure 3. Representation of the different pore types: (a) closed, (b)

bottleneck, (c) cylindrical, (d) tapered, (e) interconnected, (f)

irregular, and (g) surface rugosity. Source: Adapted from Gimenez

et al., 2014.

Figura 3. Representação dos diferentes tipos de poro: (a) fechado,

(b) gargalo, (c) cilíndrico, (d) cônico, (e) interconectado, (f) irregular,

e (g) rugosidade da superfície. Fonte: Adaptado de Gimenez et al.,

2014.

Table 1. Classification of pores according to their diameter and function.

Tabela 1. Classificação dos poros de acordo com o diâmetro e função.

Tipo

pores

Dimensions

Characteristics

rimary

micropores

Smaller

than

0.8

Contribute the most to a surface area that has high capacity to adsorb small

molecules, such as gases and common solvents.

econdary

micropores

etween

0.8

and

0.2

Mesopor

etween

0.2

and

50 nm

mportant

for

the

adsorption

large

molecules

such

dyes

and

make

most

the charcoal surface area impregnated with chemical products.

Macropor

Larger

than

50 nm

ommonly

without

importance

for

adsorption

, but

serve

transport

pathway

for gas molecules.

Fonte: IUPAC.

Figure 4. Adsorption of activated carbon. Source: Adapted from Agnicarbon.

Figura 4. Adsorção do carvão ativado. Fonte: Adaptado de Agnicarbon.

Methylene blue indicates the mesoporosity expressed as

quantity of methylene blue (weight) adsorbed by a given AC

under specific conditions. The methylene blue index

indicates the capacity of AC to adsorb molecules with similar

dimensions to methylene blue and is related to the surface

area of pores larger than 1.5 nm (DI BERNARDO;

DANTAS, 2005).

The number of molasses indicates the macroporosity; it

is a discoloration index related to the capacity of AC to

adsorb molecules of large molar masses. This discoloration

index is measured in relation to a molasse solution and is

expressed in percentage of discoloration relative to a standard

carbon (DI BERNARDO; DANTAS, 2005).

2.3. Isotherms

The adsorption capacity of a material can be

quantitatively evaluated by the isotherms, which show the

balance between the fluid phase concentration and the

accumulated adsorbate concentration in adsorbent particles,

under hot conditions. Thus, isotherms can be represented by

mathematical expressions that correlate the amount adsorbed

to the pressure or concentration in a specific temperature.

The shape of these isotherms is related to the porosity of the

solid adsorbent (LOPES et al., 2002).

Adsorption isotherms in liquid phase are represented by

curves of solute concentration in solid phase as a function of

the solute concentration in fluid phase in a specific

temperature. Isotherms are the most convenient factor to

determine the adsorption balance and the theoretical

treatment. Therefore, isotherms are the first experimental

information used to choose the most appropriate charcoal

for a specific application.

The aspect of isotherms is the first experimental tool to

determine the type of interaction between the adsorbate and

adsorbent, which can be classified in five classes, as proposed

by Brunauer, Emmett, and Teller (BET). Adsorption

isotherms are curves built by using equilibrium data (qe =

adsorption capacity in equilibrium; Ce = equilibrium

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concentration of the solute in liquid phase) at constant

temperature. Isotherms are useful and important by

providing estimates of the thermodynamic parameters of the

process.

The types of isotherms (Figure 5) are related to the type

of pores involved. Isotherms type I are associated to

micropore adsorptions; isotherms type II are related to

adsorption in non-porous systems; isotherms type IV denote

desorption not coinciding with adsorption, resulting in

presence of a fine capillarity; isotherms type VI denote a

gradual adsorption of a multilayer and are related to

adsorptions in non-porous and uniform surfaces; and

isotherms type III and V are related to weak interactions in

systems that present macro and mesopores.

Figure 5. Main isotherm types. Source: Adapted from IUPAC.

Figura 5. Principais tipos de isotermas. Fonte: Adaptado da IUPAC.

Adsorption isotherms enable the determination of

parameters related to the balance of the process, such as

constant of adsorption and maximum amount of adsorbate

that the material can retain in the adsorbent surface.

Isotherms present several forms, providing important

information on the adsorption mechanisms and the nature of

forces between the adsorbent and the solute.

Researches commonly evaluate the capacity of activated

charcoals to retain organic compounds through adsorption

isotherms in the liquid phase, relative pressure (P/P0), and

amount of gas adsorbed.

Several mathematical models describe the correlation

between the amount adsorbed per unit of weight of

adsorbent and the adsorbate concentration in water. The

most used models are Langmuir, Freundlich, and Brunauer-

Emmett-Teller (BET), due to their potential to predict the

maximum adsorption capacity of solids and describe the

dynamics of the experimental data.

2.4. Langmuir isotherm

The first theoretical equation correlating the amount of

gas adsorbed to the equilibrium pressure was proposed by

Langmuir. The Langmuir isotherm is a characteristic of

microporous solids that have relatively small external

surfaces. The interpretation of the different adsorption

models is carried out by considering the binding energy. The

equation predicts the adsorption capacity of a saturated

monolayer under high concentrations of solute (KUMAR;

SIVANESAN, 2006).

The Langmuir model estimates the adsorption capacity of

charcoals and the type of adsorbate-adsorbent interactions

(Equation 1). In this model, the attraction between the

adsorbate and adsorbent surfaces is mainly based on

electrostatic or Van Der Waals forces, and occurs in

monolayers.

Q=  . .

( .) (01)

where: Qe is the amount adsorbed in the equilibrium, expressed as

mg g-1; qmáx is the maximum sorption capacity, expressed as mg g-1;

KL is the sorption energy constant, expressed as L mg-1; and Ce _e

is the concentration of ions in equilibrium, expressed as mg L-1.

2.5. Freundlich isotherm

The Freundlich isotherm does not clearly indicates a

physical interpretation of real phenomena. However, this

empirical correlation presents a general characteristic and

usually shows good results for modeling adsorption

processes in liquid or gas phase (WAWRZKIEWICZ et al.,

2015). It considers that the adsorption occurs in a

heterogeneous surface and is based on the existence of a

structure in several layers, predicting an exponential

distribution of several adsorption sites with different

energies, and that the adsorption energy decreases because of

the adsorption; therefore, the Freundlich equation can be

applied to non-uniform surfaces.

The Freundlich model (Equation 2) provides a

representation of adsorption equilibrium of only one solute.

The equation of this model indicates that the adsorption

energy decreases logarithmically as the surface become

covered by the solute, which differentiates it from the

Langmuir equation.

Q= k . C

/ (02)

where: Qe is the amount adsorbed in the equilibrium, expressed as

mg g-1); KF is the sorption capacity (mg g-1) (L mg-1) 1/n; Ce is the

adsorbate concentration in equilibrium, expressed as mg L-1; KF and

1/n are Freundlich empirical parameters, which depend on several

experimental factors and are related to the adsorbent adsorption

capacity and the adsorption intensity, respectively; the exponent 1/n

indicates whether the isotherm is favorable; 1/n values within the

interval 0.1 < 1/n < 1 denote favorable sorption conditions: the

closer the 1/n value is to 1, the most favorable is the process.

2.6. Brunauer-Emmett-Teller (BET) equation

In 1938, Brunauer, Emmett, and Teller proposed a theory

for the adsorption phenomenon considering the same

adsorption mechanisms of the Langmuir theory. However,

they introduced some hypotheses, which admit the possibility

that the layer has the capacity to produce adsorption sites,

generating the deposition of one layer on the other.

The BET equation was developed to correlate the values

obtained from adsorption isotherms to specific areas

(Equation 3).

𝑄=   

( ) [  ( ) /] (03)

where: Qe and qm have the same meaning presented in the Langmuir

model, i.e., the amount adsorbed per unit of weight of the solvent

(mg g-1) and maximum adsorption capacity (mg g-1); b is the

saturation in all layers; Ce is the concentration of equilibrium in the

fluid; Cs is the concentration of solute in the saturation of all layers.

The constants of Langmuir and BET with negative values

Ferreira & Melo

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219

present no physical sense, since they do not fit to the

hypotheses considered in the model studied.

2.7. Methylene blue

The chemical structures of dyes present several complex

organic molecules and aromatic molecular structures, making

them more stable and resistant to degradation. There are

more than 1,000 commercial dyes available, which usually

have synthetic origin and complex aromatic molecular

structures, making them more stable and resistant to

biodegradation (WAWRZKIEWICZ et al., 2015).

Methylene blue is a water-soluble cationic dye used to

compose models in oxidation reactions by presenting

adsorption within visible wavelengths (λmáx = 665 nm), high

solubility, and similar properties to textile dyes. This material

has been used to compose models for organic contaminants,

oxidation reactions, and for the characterization of

adsorbents regarding capacity to adsorb large molecules.

AC has excellent adsorption properties due to its high

surface area and porous structure, and is the most used

adsorbent for the removal of dyes. However, its high cost has

promoted a search for cheaper adsorbent materials that do

not require many previous treatments, such as natural

materials, agricultural and industrial residues, and domestic

residues, including fruit residues.

Several low-cost adsorbent materials, and effective and

relatively easy techniques for the treatment of residual waters,

have been studied, such as sisal fiber (DIZBAY-ONAT;

VAIDYA; LUNGUC, 2017), fabric residues (NOWROUZI

et al., 2017), solid residues with lignin (HAO et al., 2017),

sunflower seed bran (MORALI; DEMIRAL; ŞENSÖZ,

2018), acrylic fiber residues (NAEEM et al., 2018), coffee

residues (POBLETE et al., 2017), fruit processing residues

(SELVARAJU; ABUBAKAR, 2017), and residues of Nigella

sativa L. (ABDEL-GHANI

et al., 2017).

2.8. Adsorption tests of activated charcoal

Several methods have been studied and used to treat

different types of effluents to meet the emerging standards

and legislations for environmental protection. The

technologies used include adsorption because it is an

efficient, highly selective, and economically viable process.

Adsorption is one of the most used technique for the

removal of contaminants from water. It is a physical-

chemical phenomenon based on the bound of components

in gas or liquid phase to the surface of a material in solid

phase. The components that connect to this surface are called

adsorbates; the material, in solid phase, that withhold them is

called adsorbent. Desorption is the removal of molecules

from sites of the surface, which is an interesting subject for

the regeneration of adsorbents.

This technique provides significant advantages, including

low cost and availability, profitability, easy operation, and

efficiency when compared to the conventional methods. The

efficiency of the adsorption process can be affected mainly

by the size of the surface area and amount (weight) of the

adsorbent. Low-cost adsorbents have presenting promising

benefits for commercial purposes and for the development

of adsorption processes. This denotes a need for deeper

studies with tests of treatments of industrial effluents using

these materials (BAZRAFSHAN et al., 2016).

The adsorption technique with the use of activated

charcoals is economically viable and presents simple

application for the removal of contaminants. The advantages

of activated charcoals over other conventional treatments

are: the low need for area (approximately 25% to 50% of the

area needed for a biological system); higher operational

flexibility; and lower sensitivity to daytime variations (AMIN,

2008).

Activated charcoal is one of the most used adsorbents for

the removal of contaminants from liquid mediums because

of its high capacity to capture molecules by chemical

interactions, and its high removal rates due to its large specific

surface area. The application of this material to effluent

treatments is related to decreases in organic material, mainly

regarding species that alter the color of contaminated

mediums.

The pH of the liquid phase is an important variable for

the control of the adsorption process because it affects the

nature of the charge on the surface of the adsorbent and the

adsorbate speciation. Thus, the efficiency of the process is

strongly affected by the pH of the medium; when the pH is

below the zero-point-charge pH of the adsorbent, the surface

is positively charged, enabling electrostatic interactions

between the surface and the free fluoride (VALENÇA et al.,

2017).

Dye adsorption processes are dependent on pH and ionic

effects. Jung et al. (2016) found maximum adsorption

capacities for activated charcoals produced from calcium

alginate/spent-coffee-grounds (CA-SCG), with pH values of

3.0 and 11.0 for 665.9 and 986.8 mg g-1 at 30 °C, respectively.

The tests showed that CA-SCG have potential for reuse,

presenting removal efficiencies higher than 80%, even after

seven consecutive cycles.

The effect of pH may vary according to the biomaterial,

type of dye, and charcoal granulometry and activation used.

Some studies on the removal of methylene blue were carried

out by Azharul Islam et al. (2017), confirming its efficiency.

Costa; Furmanski; Dominguini (2015) evaluated the

production of activated charcoal from nut shells, and physical

and chemical activations, and found that the material

produced has potential to remove methylene blue from liquid

solution and that the treatment with ZnCl2 increases the

adsorption capacity from 68 to 104 mg g-1. They also point

out that the Langmuir isotherm model presents good

correlation and adjustment to the results under the

conditions evaluated.

Activated charcoal is one of the most studied adsorbents

used for treatment of residual waters and removal of phenolic

compounds (BAZRAFSHAN et al., 2016). Zarei et al. (2013)

evaluated the efficiency of activated charcoal from Moringa

peregrina peels for the removal of phenol from liquid solutions

and found that it is a low-cost adsorbent that presents high

performance for removal of phenol from liquid solutions.

Borges et al. (2016) used wood residues (Eremanthus sp.)

to produce activated charcoals in briquette form (AC-B),

using a physical activation process and different temperatures

and activation times, and found good adsorption of phenol

(73%) and methylene blue (23%) at concentrations of 1,000

mg L-1, using tests in batches. They also found that the

isotherms of the best AC-B showed maximum adsorption

capacities of 16.1 mg g-1 (methylene blue) and 98.20 mg g-1

(phenol).

Leite et al. (2017) produced activated charcoal from

Casuarina equisetifolia cones and found satisfactory adsorption

capacity at the environment temperature, reaching 52.3 mg g-

1 within 10 minutes of contact using 1.0 g of activated

charcoal disperse in 500 mL of an oily synthetic effluent.

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220

They present similar results to those found for commercial

activated charcoals, and the adsorption capacity of the

activated charcoal produced was higher than that obtained

with the commercial product under the same operational

conditions.

3. CONCLUSIONS

The articles studied showed that the bio-adsorbent

characteristics of charcoals are promising for the removal of

pollutants from residual waters. The isotherm adsorption

models developed by Langmuir, Freundlich, and Brunauer,

Emmett, and Teller (BET) are often used to evaluate the

adsorption capacity of activated charcoals. The literature

review showed that several studies systematically detail the

adsorption and removal of residues using activated charcoal.

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