Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

Potential of used Camellia sinensis leaves as

precursor for activated carbon preparation by
chemical activation with H3 PO4 ; optimization
using response surface methodology

Tahira Mahmood a,∗ , Rahmat Ali a , Abdul Naeem a ,

Muhammad Hamayun b , Madeeha Aslam a
a National Center of Excellence in Physical Chemistry, University of Peshawar, Peshawar 25120, Pakistan
b Department of Chemistry, University of Gujrat, Gujrat, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: In this study, an attempt was made to produce a low cost activated carbon (AC) from a
Received 20 January 2017 cheap precursor material, used tea leaves (UTLs) by chemical activation with H3 PO4 . The
Received in revised form 21 April operating variables of the preparation process were optimized by central composite design
2017 (CCD), a subset of response surface methodology (RSM). The conditions optimized were acti-
Accepted 24 April 2017 vation temperature, chemical impregnation ratio (IR) and activation time with % age yield,
Available online 3 May 2017 iodine (I2 ) and methylene blue (MB) number as the targeted responses. The optimization
was carried out to maximize yield, I2 and MB number values. The optimal preparation con-
Keywords: ditions were determined as: activation temperature of 600 ◦ C, IR of 1.30 and activation time of
Activated carbon 130 min, under which a carbon yield 33.55%, I2 and MB uptake of 1051 mg g−1 and 321 mg g−1
Used tea respectively, could be achieved. The surface properties of optimized AC were characterized
CCD by various physio-chemical techniques including scanning electron microscope imaging
Optimization (SEM), FTIR analysis, surface area and X-rays diffraction analysis, Boehm’s titration, point of
Yield zero charge (pHPZC ) and proximate-ultimate analysis. The results showed that the surface
Iodine number of AC was highly porous with many channels and cracks and has acidic nature, have large
amount of acidic functional groups and low ash content.
© 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Activated carbons are the most effective and versatile adsorbents that
have been used widely in many applications such as industrial purifi-
cation, chemical recovery operations, air purification, removal of color,
odor, and taste from water/wastewater, as catalyst and catalyst sup-
port and separation of metals (Bansal et al., 1988; Soylak and Elci,
2000; Edwards et al., 2013). Besides, being used as an adsorbent and
catalyst support, the activated carbon due to their large surface area
and good conductivity, are also used in super capacitors (Yang et al.,
2014). The large scale applications of activated carbons are related to
their high active surface area, well-developed pore structure, variety of
surface functional groups, high degree of surface reactivity and good
mechanical strength. However, due to high production costs, activated
carbon tend to be more expensive which limits its large-scale appli-
cation. Therefore, the production of activated carbon from renewable
and cheaper precursors such as agricultural byproducts and wastes has
attracted the interest of researchers all over the world (Diasa et al., 2007;
Gundogdu et al., 2013). The properties of activated carbons depend on
the precursor material, type of activating agent, preparation conditions
and method of preparation.
Activated carbon can be prepared from a variety of raw materi-
als with high carbon content and low inorganic contents. There are
huge amount of low-cost solid raw materials in hand which contain

∗
Corresponding author.
E-mail addresses: tahiramahmood@uop.edu.pk, tahiramah@yahoo.com (T. Mahmood).
http://dx.doi.org/10.1016/j.psep.2017.04.024
0957-5820/© 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563
sufficient amount of carbon in their structure, can be used for the
production of AC. Various agricultural byproducts such as cotton stalk
(Deng et al., 2010), coconut shell (Yang et al., 2010), tobacco stems (Li
et al., 2008), lotus stalks (Huang et al., 2011), peanut shell (AL-Othman
et al., 2012), carrot residue (Naushad et al., 2016), orange peel (Koseoglu
and Akmil-Basar, 2015), tea industry wastes (Gundogdu et al., 2012),
mixed wastes (Habila et al., 2015) etc. have been used as suitable precur-
sor for activated carbon production. Tea is one of the most important
agricultural products in the world which is obtained by drying and pro-
cessing the leaves of the plant known as Camellia sinensis (Mokgalaka
et al., 2004). Tea is a popular beverage which is consumed by most of
the people in the world. During the preparation of a tea beverage or
the manufacturing of instant tea and bottled tea drinks, tea leaves are
contacted with hot water. After extraction a solid residue, called UTLs,
is produced which are discarded as worthless materials that create dis-
posal problems. Moreover, these UTLs mainly contain 3.5–7.0% of the
inorganic substances and 93.00–96.50% of organic substances. Hence,
the utilization of such abundantly available solid waste for value added
products is highly desirable (Akar et al., 2013; Peng et al., 2013). More-
over, conversion of this waste into activated carbon would increase its
economic value, help reduce the cost of waste disposal, and provide a
potentially inexpensive raw material for commercial activated carbon.
Activation of precursor can be carried out either through physical
or chemical activation method. In chemical activation, the precursor
material is impregnated with activating agents such as KOH, ZnCl2 ,
H3 PO4 , K2 CO3 etc., the impregnated material is then subjected to heat
treatment in an inert atmosphere at different temperatures (Wang
et al., 2011), while physical activation involves the carbonization of the
raw materials under inert atmosphere followed by the activation of the
resulting char at high temperature in the presence of carbon dioxide
or steam (Klijanienko et al., 2008). As chemical activation takes place
at temperature lower than that used in physical activation. Therefore,
chemical activation is preferred over physical activation as it results in
the production of activated carbons with well-developed porosity and
high yields and low energy cost (Molina-Sabio and Rodriguez-Reinoso,
2004; Sundaryanto et al., 2006).
Different activating agents have different effects on the properties
of the final product. Activated carbons obtained by chemical activa-
tion with ZnCl2 had large surface area, microporosity and high yield
(Molina-Sabio and Rodriguez-Reinoso, 2004; Williams and Reed, 2006).
Similarly, KOH develops large microporosity with lower yield than those
activated with H3 PO4 and ZnCl2 ·H3 PO4 is widely used as an activating
agent in the preparation of activated carbons from biomass precursor
as it offers some advantages such as non-polluting and non-corrosive
nature compared to ZnCl2, KOH, NaOH and ease of elimination by
extraction with water (AL-Othman et al., 2013; Suarez-Garcia et al.,
2002a). Moreover, the activated carbons prepared by chemical activa-
tion with zinc chloride cannot be used in food and pharmaceutical
industries as it may contaminate the product (Srinivasakannan and
Bakar, 2004).
The production of activated carbons with high yield, large surface
area and suitable pore size depend upon the production conditions. The
balancing of the production conditions is a difficult task for producers
as there are more operating variables and resultant characteristics that
need to be considered. The production conditions must be properly
balanced in order to obtain activated carbons with desirable proper-
ties. The main factors of the preparation method that influence the
properties of activated carbons are chemical IR, activation tempera-
ture and activation time (Ioannidou and Zabaniotou, 2007; Izquierdo
et al., 2011). The best operating conditions for the production of acti-
vated carbon can be evaluated by the use of a sufficient experimental
design. Response surface methodology (RSM) is a very valuable tool to
study simultaneously the interactions of two or more variables. RSM
is a set of statistical and mathematical techniques used for designing
experiment, response surface modeling through regression, evaluat-
ing the effects of several factors and searching optimum conditions
for desirable responses and reducing number of experiments (Danish
et al., 2014). Recently RSM has been used for the optimization of acti-
vated carbons prepared from different precursor materials such as
moso bamboo (Huang et al., 2015) date stone biomass (Danish et al.,
549
2014), palm shell (Arami-Niya et al., 2012), jatropha hull (Duan et al.,
2011), bamboo waste (Ahmad and Hameed, 2010), tamarind wood (Sahu
et al., 2010) and mangosteen peel (Ahmad and Alrozi, 2010).
According to the compilation of information carried out in this
study, it has been found that many studies have reported the produc-
tion of activated carbon from used tea leaves treated with phosphoric
acid, but very limited work has been done on optimization of activated
carbon prepared from H3 PO4 activation of UTLs using RSM approach.
I2 and MB numbers can be used as the two key parameters to properly
measure the adsorption capacity of micropore and mesopore struc-
tures of the prepared ACs. I2 can be also approximately equivalent to the
inner surface area (m2 g−1 ) of the carbon particles (Chen et al., 2013). In
this context, the present work aims to evaluate the optimum conditions
for the production of UTLs based activated carbon by H3 PO4 activa-
tion with desired adsorption performance. A central composite design
(CCD) was selected to evaluate the effects of major process variables
based on carbon yield, I2 and MB adsorption values as responses.
2. Materials and methods
2.1. Material
UTLs used as the precursor material for the production of acti-
vated carbon, were collected from a local tea making shop
in Swat, Pakistan. The precursor materials were first washed
thoroughly with hot water until the filtrate became clear and
then dried in an oven at 80 ◦ C for 48 h. The dried samples were
sieved to particle size range of 0.125–1 mm. The raw UTLs were
characterized by various physicochemical techniques such as,
proximate-ultimate analysis and TGA analysis to check its
advantages for AC production. Thermo gravimetric analysis
(TGA) of raw UTLs was carried out on a thermal analyzer (STA
625) to study the mass loss with respect to temperature. All
the thermal analysis were made by heating the sample from
30 ◦ C to 1000 ◦ C at a constant heating rate (10 ◦ C min−1 ) under
nitrogen flow (flow rate 150 ml min−1 ) using alumina crucible
with a pin hole.
All the chemicals/reagents used in this work were of analyt-
ical grade. H3 PO4 (85%) was purchased from Merck, Germany
while NaOH, HCl, NaCl, I2 , sodium thiosulfate (Na2 S2 O3 ·5H2 O),
potassium iodide (KI) and MB (C16 H18 ClN3 S) (85%) were pur-
chased from Scharlau, Spain. All working solutions were
prepared in deionized water.
2.2. Preparation of activated carbons
Twenty grams of dried precursor (UTLs) was mixed with
50 wt% H3 PO4 solution at different H3 PO4 /precursor IR (0.60-2).
The mixture was allowed to soak for 24 h at room tempera-
ture and then dried in an oven at 105 ◦ C for 6 h. The resulting
impregnated material was loaded in the reactor and heated
from room temperature to 200 ◦ C for 30 min and then to the
final desired temperature (400–800 ◦ C) in a horizontal tube fur-
nace (Lindberg/Blue-M, Model, TF 55030-Cm romm-1, USA) at
a heating rate of 10 ◦ C min−1 for predetermined time intervals
(60–180 min) under nitrogen flow (flow rate, 100 mL min−1 ).
The products obtained were cooled to room temperature
inside the furnace in the presence of nitrogen flow and then
washed repeatedly with double-distilled water in a soxhlet
extractor at 100 ◦ C until the pH of the rinse water was neu-
tral and finally dried at 110 ◦ C for 24 h. The resulting activated
carbons were cooled in desiccators, sieved to desired particle
size (170–200 mesh) and stored in airtight bottles for further
study.
550 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563
2.3. Design of experiments
The various parameters used for the production of UTLs based
activated carbon were studied with a standard response sur-
face methodology design known as central composite design
(CCD). The CCD method was selected as experimental design
which is suitable for fitting a quadratic surface with a min-
imum number of experiments. It also helps to optimize the
effective process parameters as well as to analyze the inter-
action between these parameters (Azargohar and Dalai, 2005;
Salman, 2014). CCD consists of three operations namely, 2n
factorial runs, 2n axial runs and nC center runs. The inde-
pendent variables studied were activation temperature (X1),
activation time (X2) and impregnation ratio (X3). These three
variables with their respective ranges were selected based on
the literature and preliminary studies.
In this study, the 23 full factorial CCD design for the three
variables was employed that consists of 8 factorial points, 6
axial points and 6 replicates at the center which gives a total
of 20 experiments as calculated from Eq. (1).
N = 2n + 2n + nc
where N is the total number of experimental runs and n is the
number of independent variables.
The independent variables were coded as +1 and −1 which
represent the eight factorial points at their low and high levels
respectively. The six axial points were located at (±˛, 0, 0),
(0, ±˛, 0), (0, 0, ±˛). The six replicates located at the center
(0, 0, 0) were run to examine the experimental error and the
reproducibility of the data. Where ˛ is the distance of axial
point from center which makes the design rotatable and had
value fixed at 1.68. This value of rotatability ˛, which depends
on the number of parameters in the experiment, was obtained
from the following equation (Ahmad and Alrozi, 2010).
∝= NP 1/4
The ranges and levels of the coded variables and their
corresponding values explored, are given in Table 1. The
responses considered in this study were AC yield (Y1 ), I2 (Y2 )
and MB (Y3 ) adsorption values. Each response was used to
develop an empirical model that correlated the response to
the preparation variables using a second-degree polynomial
equation as expressed by Eq. (3) (Montgomery, 2002).
 n 2

n  
n−1 
n used.
Y = bo + bi Xi + bii Xi + bij Xi Xj
i=1 i=1 i=1 j=i+1
where Y is the predicted response, bo the constant coefficient,
bi the linear term coefficients, bij the interaction coefficients,
bii the quadratic coefficients, Xi , Xj are the coded values of
the AC preparation variables and n is number of variables.
The experimental sequence was randomized to minimize the
effects of the uncontrolled factors (Arami-Niya et al., 2012).
2.4. Model fitting and statistical analysis
Design expert software (version 7.0.0, Stat-Ease, Inc., Min-
neapolis, USA) (Montgomery, 2002) was used for statistical
analysis of experimental data to fit the empirical mathemat-
ical model and evaluate the subsequent regression analysis,
analysis of variance (ANOVA) and 3D plots of response sur-
faces. Response surface and contour plots were produced from
the models to examine the relationship between the experi-
mental variables and responses. R squared coefficient were
used for estimating the fitting quality of the selected poly-
nomial models. The optimum values of the process variables
were obtained from the response surface. The significance
and adequacy of process parameters was further investigated
by using probability value (prob > F), F-value (Fisher variation
ratio) and adequate precision (AP) (Garba et al., 2014).
2.5. Activated carbon yield
The experimental AC yield was calculated using the following
equation:
Wc
Yield % = × 100 (4)
Wo
where Wc is the dry weight of the prepared AC (g) and Wo
(1) is the dry weight of the impregnated raw materials (g) before
activation.
2.6. Iodine number
It is a simple and commonly used technique for the rapid
assessment of activated carbons quality. I2 is usually used as
a probe molecule for evaluating the adsorption capacity of AC
and gives information about microporous structure lower than
I nm, rather than the total surface area (Gundogdu et al., 2013).
The I2 number values expected for good quality AC are equal
to or higher than 900 mg g−1 . It has also been reported that
the typical I2 number range is 500–1200 mg g1 which is equiva-
lent to the surface area between 900 and 1100 m2 g−1 (Ozdemir
(2) et al., 2014). The I2 number (mg g−1 ) for the final AC product
was determined according to ASTM D4607-94 (ASTM, 1999).
About 0.10 g of AC was taken in 250 ml dry Erlenmeyer flask,
and were fully wetted by boiling for 30 s with 10 ml of diluted
HCl (5 wt. %) and subsequently cooled. Then 100 ml of I2 solu-
tion (0.1 N) was added to the mixture and shaken for 30 min.
The resulting solution was filtered and 50 ml of the filtrate was
titrated with sodium thiosulfate solution (0.1 N) using starch
as indicator. The remaining concentration of I2 in the solution
was calculated from the total volume of sodium thiosulfate
(3)
2.7. Methylene blue number
This is a measure of mesoporosity (2–5 nm) in activated
carbon. MB is used as model molecule for evaluating the
adsorption capacity of AC to adsorb the solutes of molecu-
lar size larger than 1.50 nm (Deng et al., 2009). It is defined as
the maximum amount of dye adsorbed on 1.00 g of adsorbent.
For determination of MB adsorption values, a known amount
(0.05 g) of prepared AC samples was added to 40 ml of MB solu-
tion (10–500 mg L−1 ) and agitated in isothermal shaker (SHEL
LAB, WS 17-2, USA) at 150 rpm at 30 ◦ C for 12 h. The remain-
ing concentration of MB in the filtrates was determined by
UV–vis spectrophotometer (UV-160A Shimadzu Japan), at the
wavelength of maximum absorbance of 664 nm (Raposo et al.,
2009). The amount of MB adsorbed per unit weight of adsor-
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563
Table 1 – Independent variables and their coded levels for the central composite design.
Variables Code Units
◦
Activation temperature X1 ( C)
Activation time X2 (min)
Impregnation ratio X3
bent, qeq (mg g−1 ) from each solution was calculated by the
following equation:
(Co − Ce )
qeq = ×V (5)
M
where C0 and Ce are the initial and equilibrium concentrations
(mg L−1 ) of MB solution, respectively, V (L) is the volume of MB
solution and M (g) is the mass of adsorbent.
2.8. Surface and chemical characterization
Textural properties of optimal AC were estimated by N2
adsorption at 77 K, using Quanta Chrome NOVA 2200e surface
area and pore size analyzer. The SBET was determined by the
Brunauer, Emmett, and Teller (BET) method using the adsorp-
tion isotherms (Gregg and Sing, 1982). The total pore volume
was calculated from the amount of nitrogen adsorbed at P/Po
0.95, by applying Barrett–Joiner–Halenda (BJH) method (Barrett
et al., 1951). Dubinin–Radushkevich (DR) equation (Dubinin,
1975) was used for the measurement of micropore volume and
micropore surface area while the mesopore volume was cal-
culated by subtracting the micropore volume from the total
pore volume (Reinoso et al., 1995).
The surface morphology of precursor material and opti-
mized AC was observed by a scanning electron microscope
(JEOL-JSM-5910, Japan). The functional groups present on the
surface of AC were determined by Fourier Transform Infrared
(FTIR) spectrometer (FTIR-2000, PerkinElmer) by recording the
spectra in range of 4000–400 cm−1 using KBr pellets. The pel-
lets were prepared by mixing AC with KBr crystals and pressed
into pellets. X-rays diffraction analysis was carried out to
observe the crystal structure of optimized AC by using JEOL X-
ray diffractometer (model JDX-3532), equipped with a Cu–K␣
radiations source, with wavelength of 1.54 Å at a step size of
0.04/0.50 s of 2 angle, operated at a voltage of 40 kV and of
30 mA current in the scan range of 10–80◦ . The proximate
analysis of the precursor material and AC was carried out
according to the ASTM D1762-84 (ASTM, 1984)to obtain infor-
mation about the content of moisture, ash, volatile matter and
fixed carbon. All analysis was performed in three replicates.
Ultimate analysis was performed by pyrolyzing the samples
in the elemental analyzer (LECO CHNS-932, St. Joseph, USA).
The point of zero charge (pHPZC ) of AC was determined by the
so-called drift method (Benadjemia et al., 2011). The pH value
was determined by shaking 0.20 g of AC with 40 ml of boiling
double-distilled water, followed by measuring pH of filtrate
(Gundogdu et al., 2013) with a pH meter (Neo Met, pH 250 L,
Korea).
The acidic and basic functional groups on the surface of
AC were determined quantitatively by the Boehm’s titration
method (Boehm, 2002). The oxygen groups on the surface
have different acidities which can be neutralized by bases
of different strength. The number of acidic sites of the AC
were determined from the amount of Na2 CO3 , NaHCO3 and
NaOH reacted with AC. This was based on the assumption that
551
Coded variable levels
−˛ −1 0 +1 +˛
263.64 400 600 800 936.36
19.09 60 120 180 220.91
0.12 0.60 1.30 2 2.48
NaOH neutralizes carboxylic, lactonic and phenolic groups,
while Na2 CO3 neutralizes carboxylic and lactonic groups and
NaHCO3 neutralizes carboxylic groups only. Whereas, the total
content of basic group was determined by titration with HCl.
3. Results and discussion
3.1. Development of regression model equation
To correlate the activated carbon preparation variables and
responses central composite design was used. The complete
design matrix together with the experimental results obtained
for the three responses is given in Table 2. Based on the
sequential model sum of squares, the highest order polynomi-
als were used for selecting the models. Quadratic model was
selected for all the three responses under study, as suggested
by the software. To fit the response function of AC yield, I2 and
MB adsorption values, regression analysis was carried out. The
final empirical models for % yield (Y1 ), I2 number (Y2 ) and MB
(Y3 ) adsorption values in terms of coded factors after exclud-
ing insignificant terms are given in Eqs. (6)–(8), respectively:
Y1 = 27.80 − 7.18x1 + 9.79x3 + 0.56x1 x3
−1.73x1 x3 − 0.76x12 − 4.26x32 (6)
Y2 = 892.34 + 104.41x1 + 250.69x3 − 30.27x1 x2 + 29.64x2 x3
−126.16x12 − 46.75x22 − 99.12x32 (7)
Y3 = 216.32 + 33.84x1 + 153.21x3 + 9.13x1 x3 − 23.95x12
−12.31x22 − 55.03x32 (8)
where X1, X2 and X3 are the coded values of the preparation
variables, activation temperature, activation time and impreg-
nation ratio (IR), respectively. In Eq. (6)–(8) the positive signs
in front of the terms show synergistic effects, whereas the
negative signs show antagonistic effects. The coefficient of
the responses for the model was determined by RSM method
using multiple regression analysis. The fitness of model equa-
tion was estimated using the correlation coefficient, R2 and
standard deviation (SD) (Table 3). The correlation coefficient
(R2 = 0.98) for Eq. (6), (R2 = 0.99) for Eq. (7) and (R2 = 0.99) for
Eq. (8) were found to be higher than 0.80, indicating that only
1.50%, 0.40% and 0.20% of the total variation for yield, I2 and
MB adsorption values respectively, cannot be explained by the
model. For a model to mark good fit, R2 must be minimum of
0.80 (Bashir et al., 2010).
The closeness of R2 values to unity and smaller SD
show good capability of the developed quadratic models and
demonstrate good agreement between the calculated and
 552
Table 2 – Experimental design matrix and response results using CCD for preparation of AC from UTLs.

Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563

Run Temperature (◦ C) X1 Time (min) X2 Impregnation ratio X3 Responses
−1
Yield (Y1) % I2 (Y2) (mg g ) MB (Y3) (mg g−1 )

Coded Actual Coded Actual Coded Actual Experimental Predicted Experimental Predicted Experimental Predicted

1 0 600 1.68 220.91 0 1.30 32.03 32.44 990.30 973.15 295.80 293.92
2 1 800 1 180 1 2 17.20 18.92 955.70 965.27 320.80 324.42
3 1 800 1 180 −1 0.60 24.56 23.33 914.40 924.12 297.30 294.44
4 −1 400 −1 60 −1 0.60 42.24 40.46 690.60 683.66 213.90 211.39
5 0 600 0 120 1.68 2.48 27.66 25.88 920.20 904.40 262.70 257.82
6 0 600 0 120 0 1.30 33.30 33.33 1050.10 1050.72 322.30 322.49
7 0 600 0 120 0 1.30 33.23 33.33 1050.20 1050.72 322.10 322.49
8 −1 400 −1 60 1 2 40.11 40.28 629.90 622.81 205.80 209.77
9 −1 400 1 180 −1 0.60 39.32 38.65 773.70 767.71 212.90 214.34
10 0 600 0 120 0 1.30 33.27 33.33 1051.30 1050.72 322.20 322.49
11 0 600 0 120 0 1.30 33.89 33.33 1050.40 1050.72 322.60 322.49
12 −1 400 1 180 1 2 39.62 39.07 772.20 789.87 216.90 218.76
13 0 600 0 120 −1.68 0.12 27.05 28.91 908.90 921.00 230.60 233.92
14 1 800 −1 60 1 2 18.27 18.88 910.70 919.32 312.80 312.43
15 0 600 −1.68 19.09 0 1.30 34.26 33.94 850.40 863.83 281.10 281.41
16 1 800 −1 60 −1 0.60 22.41 22.90 976.20 961.16 289.30 288.55
17 0 600 0 120 0 1.30 33.09 33.33 1050.80 1050.72 322.80 322.49
18 −1.68 263.64 0 120 0 1.30 45.99 47.05 500.80 503.46 180.20 177.90
19 0 600 0 120 0 1.30 33.21 33.33 1050.90 1050.72 322.70 322.49
20 1.68 936.36 0 120 0 1.30 16.31 15.34 890.70 884.32 330.90 331.63
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563 553

Table 3 – R2 , SD, AP and CV values of the model equations for AC yield, I2 and MB adsorption values.
Response R-squared Adj. R-squared Pred R-squared SD AP CV (%)

AC yield 0.98 0.97 0.88 1.40 31.92 4.48

I2 number 0.99 0.99 0.97 13.61 56.87 1.51
MB number 0.99 0.99 0.98 3.07 70.82 1.10

Table 4 – ANOVA results of the response surface quadratic model for AC yield.
Source Sum of squares Degree of freedom Mean square F-value p-Value prob > F Comment

Model 1310.37 9 145.60 73.77 <0.0001 Significant

X1 102.33 1 102.33 51.85 <0.0001
X2 0.14 1 0.14 0.07 0.7983
X3 45.91 1 45.91 23.26 0.0007
X1 X2 2.52 1 2.52 1.28 0.2849
X1 X3 11.69 1 11.69 5.92 0.0352
X2 X3 0.08 1 0.08 0.04 0.8464
X1 2 8.22 1 8.22 4.17 0.0685
X2 2 0.04 1 0.04 0.02 0.8949
X3 2 63.26 1 63.26 32.06 0.0002
Residual 19.74 10 1.97
Lack of fit 19.34 5 3.87 48.33 0.0003 Significant
Pure error 0.40 5 0.08
Cor total 1330.40 19

Table 5 – ANOVA results of the response surface quadratic model for I2 adsorption.
Source Sum of squares Degree of freedom Mean square F-value p-Value prob > F Comment

Model 4.631E + 005 9 51,457.86 277.83 <0.0001 Significant

X1 21,613.39 1 21,613.39 116.69 <0.0001
X2 72.17 1 72.17 0.39 0.5465
X3 30,091.95 1 30,091.95 162.47 <0.0001
X1 X2 7332.60 1 7332.60 39.59 <0.0001
X1 X3 180.50 1 180.50 0.97 0.3468
X2 X3 3444.50 1 3444.50 18.60 0.0015
X1 2 2.29E + 005 1 2.29E + 005 1238.15 <0.0001
X2 2 31,491.12 1 31,491.12 170.02 <0.0001
X3 2 34,249.61 1 34,249.61 184.92 <0.0001
Residual 1852.15 10 185.22
Lack of fit 1851.08 5 370.22 1732.68 <0.0001 Significant
Pure error 1.07 5 0.21
Cor total 4.65E + 005 19

Table 6 – ANOVA results of the response surface quadratic model for MB adsorption capacity.
Source Sum of squares Degree of freedom Mean square F-value p-Value prob > F comment

Model 4734.46 9 5303.83 562.90 <0.0001 significant

X1 2270.50 1 2270.50 240.97 <0.0001
X2 1.65 1 1.65 0.18 0.6844
X3 11,239.37 1 11,239.37 1192.85 <0.0001
X1 X2 4.35 1 4.35 0.46 0.5122
X1 X3 326.40 1 326.40 34.64 0.0002
X2 X3 18.30 1 18.30 1.94 0.1936
X1 2 8261.98 1 8261.98 876.85 <0.0001
X2 2 2184.86 1 2184.86 231.88 <0.0001
X3 2 10,556.35 1 10,556.35 1120.36 <0.0001
Residual 94.22 10 9.42
Lack of fit 93.81 5 18.76 226.04 <0.0001 Significant
Pure error 0.41 5 0.08
Cor total 47,828.69 19

observed results within the experimental range (Regti et al.,
2017). This is also clear from the plots of predicted versus
experimental AC yield, I2 and MB adsorption values as shown
by Fig. 1(a)–(c) respectively. These plots show the excellent
capability of the model to fit the experimental results.
3.2. Statistical analysis
The analysis of variance (ANOVA) was used to determine the
significance of the model and to find the relationship between
variables and responses. The ANOVA for the quadratic models
for AC yield, I2 and MB uptake is shown in Tables 4, 5 and 6,
respectively. The F-value and value of Prob > F were used to
554 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563

find regression coefficients, standard error and significance

of each coefficient. The ANOVA for the response surface
quadratic model for yield (Y1) is listed in Table 4, where the
model F-value of 73.77 and Prob > F less than 0.0001 confirm
that the model is significant. Usually, the value of “Prob > F” is
less than 0.05, the model terms are significant and when the
values are greater than 0.10, will indicate that the model terms
are not significant. In this case, activation temperature (X1 ),
IR (X3 ), interaction and quadratic parameters X1 X3 , X1 2 and
X3 2 were significant model terms. Insignificant model terms,
such as X2 , X1 X2 , X2 X3 and X2 2 , has limited influence on the
response and were excluded from the study to improve the
model. ANOVA results for the quadratic model for I2 number
(Y2 ) (Table 5), showed a model F-value of 277.83 and Prob > F
less than 0.0001 implied that the model was significant. In this
study, X1 , X3 , X1 X2 , X2 X3 , X1 2 , X2 2 , X3 2 were significant model
terms while X1 and X1 X2 were insignificant and were excluded
from the study. Similarly, the ANOVA for the quadratic model
for MB adsorption capacity (Y3 ) is shown in Table 6. In this case
the significant model terms to the response are, X1 , X3 , X1 X3 ,
X1 2 , X2 2 , X3 2 and the insignificant were X1 X2, X2 X3 with model
F-value of 562.90 and Prob > F less than 0.0001, proved that the
model is suitable to predict the MB adsorption capacity with
in the range of the variable studied.
The AP ratio of the models were found to be 31.92, 56.86
and 70.82 for AC yield, I2 and MB number respectively. AP is
an adequate signal for the model, having value greater than 4
are desirable, which confirm that the predicted models can be
used to navigate the space defined by the CCD (Bashir et al.,
2010). The coefficient of variance (CV) which shows the repro-
ducibility of a model, is determined as the percent ratio of
the standard error of the estimate to the mean value of the
observed response. A model can be considered reproducible
if its CV is less than 10% (Alslaibi et al., 2013). The CV values
(Table 3) obtained for AC yield, I2 and MB number were smaller
than 10% indicating that the models are reproducible. The sta-
tistical analysis showed that these models accurately predict
the AC yield, I2 and MB adsorption values within the range of
variables studied.

3.3. Effects of preparation variables

The RSM plots of the regression model analysis has been

greatly recommended for graphical interpretation of the inter-
actions between different experimental variables (Danish
et al., 2014). Three dimensional (3D) response surface plots
can be used to understand the major interactions of pro-
cess variables within the experimental design. It can help in
the assessment of experimental factors such as activation
temperature, IR and activation time on selected responses.
Therefore, to explore the effect of experimental factors on the
responses, 3D response surface curves and contour plots were
generated for the statistically significant models (Eqs. (6)–(8))
using Design- Expert software.

Fig. 1 – Correlation between predicted and actual values of
response for (a) AC yield, (b) I2 and (c) MB adsorption
capacity.
3.3.1. Effect on AC yield
Experimental observations showed that the preparation vari-
ables have great effect on AC yield (Y1 ). Based on F-values
given in Table 4, activation temperature (X1 ) and IR (X3 ) with
highest F-value of 51.85 and 23.26 respectively, had substantial
effect on the carbon yield (Y1 ) while activation time (X2 ) was
infective (F-value 0.069). Moreover, the interaction between
activation temperature and IR (X1 X3 ), activation temperature
and activation time (X1 X2 ) had significant effect on AC yield
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563 555

Fig. 2 – Three-dimensional response surface and contour plots for combined effects on yield of UTLs based AC: (a) effect of
activation temperature and activation time, IR = 1.3 and (b) effect of activation temperature and IR, t = 120 min.

with larger F-value of 5.92 and 1.28 respectively, whereas the
interaction between activation time and IR (X2 X3 ) had smaller
effect (F-value 0.04) on AC yield. The quadratic function of
activation temperature and IR had also significant effects.
Fig. 2(a) and (b) shows the three-dimensional (3D) response
surface plots of the interaction effects of preparation variables
on AC yield. Fig. 2(a) shows the combined effect of activation
temperature and activation time on yield by keeping IR fixed
at zero level (IR = 1.3), whereas Fig. 2(b) show the combined
effect of activation temperature and IR on yield with activation
time being fixed at zero level (t = 120 min). It can be observed
from these figures that at lower activation temperature, the
yield is not significantly influenced by increasing activation
time and IR due to inadequate energy required for the reac-
tion between the precursor and activating agent. As can be
seen in Fig. 2(a), the interaction effect of activation tempera-
ture and activation time does not significantly influence AC
yield. An increase in activation temperature increase the car-
bon burn off and thereby reducing the carbon yield. At higher
temperature the volatile matter were rapidly released from
precursor material by accelerating the rate of dehydration and
elimination reactions which cause an increase in the weight
loss, leads to a decrease in AC yield (Salman, 2014). Fig. 2(b)
shows significant interaction between activation temperature
and IR. It can be seen from this figure that at low activation
temperature, the AC yield increases with increasing H3 PO4 IR,
556 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563
while at high activation temperature and high IR the yield was
lower than the average condition. The highest yield was found
at optimum H3 PO4 IR within the range studied and at low acti-
vation temperature. Similar results were also reported by other
worker (Danish et al., 2014) for AC obtained from H3 PO4 activa-
tion of date stone that with the rise of impregnation, the yield
increases at a lower activation temperature and decreases at
higher activation temperature.
3.3.2. Effect on iodine adsorption values
The AVOVA for I2 adsorption experiments on the prepared
ACs (Table 5) shows that the activation temperature (X1 )
and IR (X3 ) had considerable effect on I2 adsorption capac-
ity, whereas activation time (X2 ) was ineffective based on its
p-value of 0.5465 which is greater than 0.05. The interac-
tion effects between the X1 X2 and X2 X3 are significant, with
higher F-values of 39.59 and 18.60 respectively. Furthermore,
the quadratic effects of all the three variables (X1, X2 and X3)
were also significant and have higher F-values. Fig. 3(a–c) show
the three dimensional response surface plots of the quadratic
model, demonstrating the effects of activation temperature,
IR and activation time on I2 adsorption value (Y2 ).
It can be seen from the 3D responses surfaces and the con-
tour plots that maximum I2 uptake can be achieved within the
design space (Tang et al., 2011). Fig. 3(a) shows the combined
effect of activation temperature and activation time on the
I2 number at an IR ratio of 1.30. It is evident from Fig. 3(a),
the I2 number increases continuously with increase in the
activation temperature and activation time and reaches the
highest value of about 1051 mg g−1 at activation temperature
of 600 ◦ C and then goes on decreasing with further increase
in activation temperature beyond 600 ◦ C. A possible explana-
tion for this effect is that at 600 ◦ C temperature an increase in
activation time may increase the extent of precursor- H3 PO4
reaction, thereby facilitating the development of the pore
structure and resulting in the formation of a large number of
active sites. While elevated temperature (above 600 ◦ C) caused
some of the pores to enlarge or even collapse which leads to
the reduction in I2 adsorption value of AC.
Fig. 3(b) shows the 3D response surface and contour plot
of the combined effect of IR and activation temperature on
the I2 number with activation time being fixed at zero level
(t = 120 min). It can be revealed from the plot that both the
variables have great effect on I2 uptake of ACs. Maximum I2
number of about 1051 mg g−1 was obtained at IR of about 1.30
and activation temperature of 600 ◦ C. Further increase in IR
and activation temperature results in considerable decrease
in I2 uptake which confirms that both variables combiningly
affect the I2 number. Fig. 3(c) shows the combined effect of
IR and activation time on I2 number with activation tempera-
ture being fixed at zero level (T = 600 ◦ C). As can be seen, that
the I2 uptake increases with the increase in IR and activation
time and reaches the maximum value of 1051 mg g−1 near the
highest values of both the variables. This may be due to the
fact that with increased activation time, more pores and active
sites develop on the AC surface due to the release of more
volatile matters.
3.3.3. Effect on MB adsorption values
RSM was employed to explore the effects of the three variables
(activation temperature (X1 ), activation time (X2 ) and IR (X3 ))
on MB adsorption capacity (Y3 ). The ANOVA results (Table 6)
shows that activation temperature and IR highly influencing
the adsorption of MB. IR with the highest F-value of 1192.85
imposing the greatest effect, while activation time with low-
est F-value of 0.18 has no significant effect on MB adsorption
capacity. Similarly the quadratic effects of activation tempera-
ture, activation time and IR was also high while the interaction
effect between X1 X3 was moderate. The response surface 3D
graphs which demonstrates the effect of preparation variables
on MB adsorption capacity (Y3 ) was shown in Fig. 4(a–c).
The interaction effect of activation temperature (X1 ) and
activation time (X2 ) on the adsorption capacity of MB at con-
stant IR (IR = 1.30) was shown in Fig. 4(a). It can be seen that the
MB uptake of AC increased with the increasing of activation
temperature and activation time until reaches the maximum
value of about 331 mg g−1 . At higher activation time, further
increase in activation temperature beyond the optimum limit
would cause the decreasing of MB adsorption value. This may
be due to the fact that at higher temperature the mesopores
were converted to macropores which are not effective for
MB adsorption, as explained by Theydan and Ahmed for the
preparation of activated carbon from date stones (Theydan
and Ahmed, 2012). Therefore, the highest adsorption of MB
can be achieved by keeping the activation temperature around
730 ◦ C.
Fig. 4(b) represents the combined effect of IR and activation
temperature on MB uptake of AC by keeping the activation
time at zero level (t = 120 min). It can be observed that the
IR and activation temperature had significant effect on MB
adsorption value of AC. By increasing IR and activation tem-
perature up to the optimum point would increase the active
sites and pore volume of AC that would leads to an increase
in the MB adsorption capacity. Maximum MB adsorption of
about 331 mg g−1 was obtained at IR of about 1.30 and acti-
vation temperature of 730 ◦ C. The three-dimension response
surface which shows the combined effect of IR and activa-
tion time on MB uptake at constant activation temperature
(T = 600 ◦ C) is shown in Fig. 4(c). This figure shows that at
low IR and activation time, MB has low adsorption capacity
(about 180.20 mg g−1 ). This may be due to the insufficient reac-
tion between the precursor material and H3 PO4 that results
in imperfect pore development and low surface area. The
increase in IR and activation time improves the MB adsorption
capacity of AC. However, MB adsorption was found to decrease
at too higher ratio of H3 PO4 . Adding activating agents to the
precursor promotes the weight loss which may increase the
average pore width and thereby decreasing the MB adsorption
capacity of AC.
3.4. Process optimization
It is highly desired to prepare AC with good yield and high
adsorption capacity. This study aims to find the optimum
conditions at which AC should have high I2 number (which
is equivalent to surface area in m2 g−1 ), high MB adsorption
values and good yield by using RSM method. However, the
interest region of variables is different for I2 number, MB
adsorption and AC yield; therefore, it is difficult to optimize
all responses under the same process variables. In order to
compromise among AC yield, I2 and MB adsorption values,
the function of desirability was applied by using Design expert
software version 7.0.0 (Stat-Ease, Inc., Minneapolis, USA). In
this optimization analysis, the operational variables (activa-
tion temperature, IR and activation time) were selected to be
“within the range” while the target criteria was set as “max-
imum” to achieve AC with highest values for all the three
responses (Garba and Rahim, 2014). The experimental con-
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563 557

Fig. 3 – Three-dimensional response surface and contour plots for combined effects on the iodine adsorption value: (a)
effect of activation temperature and activation time, IR = 1.3, (b) effect of activation temperature and IR, t = 120 min and (c)
effect of activation time and IR, T = 600 ◦ C.

ditions with highest desirability were selected to be verified. ity value of 0.82 shows that probable function may represent
To obtain the optimal value for each variable and response, the experimental model and desired conditions. The optimum
numerical optimization was selected. The desirability ramp conditions calculated for the preparation of AC were found
for numerical optimization is shown in Fig. 5. The desirabil- to be an activation temperature of 600 ◦ C, activation time of
558 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563

Fig. 4 – Three-dimensional response surface and contour plots for combined effects on the MB adsorption value: (a) effect of
activation temperature and activation time, IR = 1.3, (b) effect of activation temperature and IR, t = 120 min and (c) effect of
activation time and IR, T = 600 ◦ C.

130 min, and IR of 1.30 with predicting values for AC yield of was 1047 mg g−1 , 318 mg g−1 and 30%, respectively. It is evi-
33.55%, I2 number of 1051 mg g−1 and MB adsorption values dent from the table that the experimental values obtained for
of 321 mg g−1 as given in Table 7. Whereas, the experimen- AC yield; I2 and MB number were in good agreement with the
tal value for I2 number, MB adsorption values and AC yield values predicted from the regression models, with relatively
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563 559

Fig. 5 – Desirability ramp for numerical optimization of UTLs based AC yield, I2 and MB adsorption values.

Table 7 – Model validation of UTLs based AC, preparation variable and responses by RSM.
X1 : temp. X2: X3: IR Yield % (Y1 ) Error I2 (Y2 ) (mg g−1 ) Error MB (Y3 ) (mg g−1 ) Error Desirability
(◦ C) time(min) (%) (%) (%)
Predicted Experimental Predicted Experimental Predicted Experimental

600 130 1.30 33.55 31 2.55 1051 1047 4.00 321 318 3.00 0.82

is also evident from the exothermic DTA peaks observed in

this temperature range. Very little weight loss was observed
above 555 ◦ C and at nearly 600 ◦ C the breakdown of lignocel-
lulosic material was terminated and no further weight loss
was observed. This shows that the basic structure of carbon
has been formed at about this temperature. Therefore, this
temperature can be considered as the lowest activation tem-
perature for AC production from UTLs.

3.6. Characterization of the optimized UTLs AC

3.6.1. Textural analysis and surface morphology

Fig. 6 – TG/DTA curves of raw UTLs.
small percentage error between the experimental and pre-
dicted values which indicate the accuracy of the optimization
process. This result agrees with the work done by (Chen et al.,
2013).
3.5. Thermal analysis of raw materials
To investigate the thermal behavior of the raw UTLs during
activation steps, TG/DTA analysis was carried out as shown
by Fig. 6. Initially the TG curve shows a weight loss of 10.25%
in the temperature range of 37–200 ◦ C which is due to the dehy-
dration of raw material. This value is larger than the moisture
content (8.24%) of raw UTLs as determined by proximate anal-
ysis which shows that some light gases like CO2 and CO and
volatile components may also be released in this temperature
range. The major weight loss (76.37%) was observed in the
temperature range of 200–555 ◦ C which is due to the thermal
decomposition of cellulose, hemicelluloses and lignin which
The specific surface area (SBET ) and pore size distribution of
AC prepared under optimum conditions was determined from
N2 adsorption isotherms and the values obtained are listed in
Table 9. As can be seen from this table, the optimal AC con-
tains both mesopores and micropores. The SBET and the total
pore volume were found to be 1136.24 m2 g−1 and 0.86 cm3 g−1 ,
respectively. The micropore volume measured by using DR
equation was found to be 0.47 cm3 g−1 and mesopore volume
was found to be 0.39 cm3 g−1 . These results show that a sig-
nificant amount of microporosity (54.65%) and mesoporosity
(45.35%) were formed in the AC prepared under optimal con-
ditions.
The scanning electron microscope (SEM) images of the raw
UTLs and AC prepared under optimized conditions are shown
in Fig. 7(a) and (b) respectively. It can be seen from these
images that the external surface of raw UTLs is rough with
very few small pores and some occasional cracks, whereas the
surface of optimized AC is full of cavities and pores of different
sizes and shapes that have been developed during the chem-
ical activation and heat treatment process. These cavities
and pores may have been arisen from the evaporation of the
H3 PO4 during activation process, leaving the spaces previously
560 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563

Table 8 – Proximate-ultimate analysis of raw UTLs and AC prepared under optimum conditions.
Sample Proximate analysis (dry basis, wt %) Ultimate analysis (dry basis, wt %)

Moisture Volatile Ash Fixed carbon Carbon Hydrogen Nitrogen Oxygen

Raw waste tea 8.24 76.13 2.06 13.57 49.84 5.80 0.57 43.79
AC 4.15 7.11 10.13 78.61 81.51 1.10 1.15 16.24

Fig. 7 – Scanning electron micrograph of (a) raw UTLs and (b) AC prepared under optimum conditions.

occupied by H3 PO4 . This well-developed porous structure was

responsible for high MB and iodine uptake which made the
prepared AC to be a good adsorbent for adsorption of vari-
ous organic pollutants from solutions (Junior et al., 2014). This
highly porous structure makes AC suitable for adsorption of
large number of pollutants from aqueous solutions.

3.6.2. Proximate and ultimate analysis

The proximate-ultimate analysis of UTLs and AC prepared
under optimum conditions were determined by ASTM tech-
niques, and the results obtained are shown in Table 8. It is
evident from this table that the AC has greater amount of fixed
carbon and low volatile matter content than the raw UTLs.
After activation steps, the volatile content of AC was reduced
by 69.02%, the fixed carbon content was increased by 65.04%
and the ash content was increased by 8.07%. This behavior
was due to the release of volatile matter from the precursor
during thermal treatment. The optimized AC possessed a low
ash content (10.13%) which make it a high-quality adsorbent
for adsorption of organic pollutants from aqueous systems
(Saygıli et al., 2015). The elemental analysis also revealed that
the carbon content of AC increased from 49.84% to 81.51%
while the amounts of hydrogen and oxygen was decreased
from 5.80% to 1.10% and 43.79% to 16.24% respectively. This
may be due to the fact that H3 PO4 activation of UTLs extract
hydrogen and oxygen away from the precursor. These results
are in good agreement with the results obtained for activated
carbon prepared from H3 PO4 activation of palm shell (Arami-
Niya et al., 2012).
3.6.3. Surface chemistry
To observe the functional groups present on the surface of
raw used tea and AC prepared under optimum conditions,
Fourier-transform infrared (FTIR) analysis was carried out and
the spectra obtained were shown in Fig. 8. It can be seen
from the figure that the surface chemistry of AC was differ-
ent from the raw UTLs. Some peaks were of low intensity or
even disappeared in the prepared AC relative to the raw UTLs
Fig. 8 – FT-IR spectra of (a) raw UTLs and (b) AC prepared
under optimum conditions.
after carbonization and activation processes. This is due to
the destruction of some intermolecular bonding as a result of
thermal degradation effect during the activation process.
The peaks at about 3437 cm−1 correspond to O H stretch-
ing vibrations of the hydroxyl functional groups including
hydrogen bonding, was of low intensity in AC. This reduction
in the peak intensity correspond to the reduction in hydrogen
bonding which may be due to the reaction between H3 PO4 (acts
as a dehydrating agent) and precursor (Suarez-Garcia et al.,
2002b). The peaks detected at band width of 2902–2939 cm−1
were assigned to C H stretching vibration of alkanes and alkyl
groups, was more obvious in raw UTLs than AC, which shows
that a large amount of hydrogen has been removed during
activation process. The reduction in hydrogen and oxygen
content of AC is also evident from ultimate analysis, where
the hydrogen and oxygen contents decreased to 81.03% and
62.91% respectively. The band at around 2336 cm−1 corre-
sponds to C C vibrations in alkyne and methylene groups.
The peak at about 1734 cm−1 correspond to C O stretching
 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563
Table 9 – Textural properties, surface functional groups, pHpzc and pH values of the AC prepared under optimum
conditions.
Acidic functional groups (mmol g−1 )
Carboxylic groups Lactonic groups Phenolic groups
1.27 0.59 1.25
Textural properties
Surface area Micropore surface Micropore volume
(SBET ), (m2 g−1 ) area (DR), (m2 g−1 ) (DR), (cm3 g−1 )
1136.24 688.73 0.47
Fig. 9 – X-rays diffraction pattern of AC prepared under
optimum conditions.
vibration of carbonyls, disappeared in the AC which shows
that many aliphatic and aromatic bonds have been broken
as a result of chemical activation and eliminated much of
the volatile matter (Hesas et al., 2013; Yagmur et al., 2008).
As can be seen from Table 8, the volatile matter content
of AC decreased by 90.66%. The band occurring at around
1616–1644 cm−1 correspond to aromatic ring or C C stretch-
ing vibration which shows the aromatization of the precursor
(Shi et al., 2010). The band at about 1530 cm−1 and 1300 cm−1
were attributed to bond vibrations of an aromatic species and
C O axial deformation (Silverstein et al., 2014). After activa-
tion with phosphoric acid a band at about 1062 cm−1 appear
in the FTIR spectrum of AC which correspond to (P O C)
stretching vibration of aliphatic phosphates groups. The peaks
around 1320 and 1240 cm−1 show the presence of C N stretch-
ing in aromatic tertiary amines. The peak around 1055 cm−1
indicates the presence of C O stretching in primary alcohol.
The peaks around 914 and 756–697 cm−1 indicate C H out-of-
plane bending in an aromatic ring.
3.6.4. X-rays diffraction (XRD) analysis
The X-rays diffractogram of AC prepared under optimal con-
ditions is shown in Fig. 9. It can be seen from the figure
that a broad peak was observed due to the reflections from
the planes. The presence of the broad peak in the XRD pat-
tern shows the amorphous nature of the sample, which is a
valuable property for highly porous material (Barpanda et al.,
2011). The wide diffraction pattern at angle 2 of about 25◦
are assigned to (002) plane are related to graphite like reflec-
tion, shows the occurrence of some graphitic like ordering in
molecular planes (González and Pliego-Cuervo, 2013).
561
Total acidic groups Basic groups (mmol g−1 ) pHPZC pH
3.11 0.13 4.60 4.11
Mesopore Total pore volume Fraction, % Fraction, %
volume (cm3 g−1 ) (BJH), (cm3 g−1 ) (micropore) (mesopore)
0.39 0.86 54.65 45.35
3.6.5. Boehm’s titration
Oxygen surface functional groups are important characteris-
tics of the activated carbons as they determine the surface of
adsorbent materials. The amounts of acidic and basic groups
present on the surface of AC obtained from Boehm’s titra-
tion method are given in Table 9. Boehm’s titration results
show that the surface of AC is rich in acidic groups with small
amount of basic groups (0.13 mmol g−1 ). The amounts of acidic
groups measured were 1.27, 0.59 and 1.25 mmol g−1 for car-
boxylic, lactonic and phenolic groups, respectively. The acidic
groups may be derived from the reaction between H3 PO4 and
precursor material during activation process. Similar results
have been reported for the H3 PO4 activated carbons prepared
from lignocellulosic materials (Altenor et al., 2009; Liu et al.,
2010).
3.6.6. Point of zero charge
The pHPZC value is another characteristic which shows the
acidic and basic properties of adsorbents beyond a definite pH
value. It represents the pH value at the point where net charge
on the surface of adsorbent is zero. Below pHPZC , adsorbent has
positive surface charge, while it is negative above pHPZC . The
pHPZC and pH values (Table 9) of the optimized AC fall in the
acidic region which shows that the acidic groups are dominant
on the surface (Gundogdu et al., 2013).
4. Conclusion
Process optimization of UTLs based AC was successfully
conducted by CCD of RSM. The effect of three preparation
variables (activation temperature, IR and activation time)
investigated by analysis of variance (ANOVA), showed that
activation temperature and IR had the most significant effect
on AC yield, I2 and MB uptakes. The optimum activation con-
ditions for the production of AC with good yield, high I2 and
MB number values has been identified to be an activation tem-
perature of 600 ◦ C, IR 1.3 and activation time of 130 min.It was
observed that the experimental values for AC yield, I2 and MB
adsorption were in good agreement with model predicted val-
ues with relatively small error. The closeness of R2 values to
unity and smaller SD show good capability of the developed
quadratic models and demonstrate good agreement between
the calculated and observed results within the experimental
range. The optimized AC possessed a well-developed porous
structure with cracks and channels and have high carbon
(81.51%) and low ash content (10.13%). The X-rays diffraction
analysis shows the amorphous nature of the sample which
is a valuable property for highly porous material. The BET
surface area and pore size analysis confirmed that the AC pre-
pared under optimum conditions was highly porous with SBET
of 1136.24 m2 g−1 and total pore volume of 0.86 cm3 g−1 and
562 Process Safety and Environmental Protection 1 0 9 ( 2 0 1 7 ) 548–563
the fraction of micopores was 45.35% and that of mesopores
was 54.65%. The Boehm’s titration results and pHPZC measure-
ment showed the presence of a large amount of acidic groups
on the surface of AC which makes it suitable and a high-
quality adsorbent for the adsorption of organic pollutants in
which acidic groups are desired. Furthermore, the AC pre-
pared under optimum conditions had a good yield with high I2
(1051 mg g−1 ) and MB (321 mg g−1 ) number values which shows
sufficient amount of micopores and mesopores, revealed that
UTLs could be recommended as an effective, promising and
cheap precursor for the production of AC.
Acknowledgment
Authors are gratified to acknowledge the help and support
provided by the National Center of Excellence in Physi-
cal Chemistry, University of Peshawar, Peshawar. Khyber
Pukhtunkhwa, Pakistan for completing the research project.
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