JKAU: Eng. Sci., Vol 17 No. 2, pp: 75 - 100 (2006A.D. /1427 A.H.

Activated Carbon from Dates' Stone by ZnCl2 Activation

Yahia A. Alhamed

Department of Chemical and Materials Engineering, Faculty of

Engineering, King Abdulaziz University, Jeddah, Saudi Arabia
[email protected]

Abstract. A study of the effect of preparation conditions on the yield

and quality of activated carbon (AC) produced from dates’ stones
was made using zinc chloride as an activator. The optimum
conditions for AC production was evaluated based on the
determination of various adsorption parameters of methylene blue
(MB) and phenol. Using MB as an adsorbate it was found that the
optimum ratio of activator to dates’ stones (R) is 2. The maximum
unit capacity for MB was 148 mg/g at carbonization time (Ct) = 1
hour and carbonization temperature (CT) = 600 OC and the
corresponding yield was 32%. Milder conditions (Ct = 0.5 hr and CT
= 500OC) produced AC with maximum adsorption capacity of 286.3
mg/g with a yield of 31%.
Using phenol as an adsorbate it was found that the optimum
value of R = 0.5. The maximum unit capacity for phenol was 19
mg/g at Ct = 3 hours and CT = 600 OC and AC yield of 47.3%. On
the other hand milder conditions (Ct = 0.5 hr and CT = 500OC) were
required to produce AC with maximum capacity for phenol removal
of 75.0 mg/g and AC yield of 64.6%.
Keywords: Activated carbon, phenol adsorption, activation, dates’
stones, dates’ pits

1. Introduction
Activated carbon (AC) is an amorphous form of carbon that is
specially treated to produce a highly developed internal pore structure
and a large surface area, thus, producing reasonably cheap and excellent
adsorbent [1-3]. There is a multitude of industrial applications of AC
including decolorization, purification and deodorization of vegetable oils
and fats, sugar refining and other food industries. Pollution control and

75
 76
Yahia A. Alhamed

wastewater treatment are growing areas of use to combat environmental

pollution [1-4].

Two distinct methods are described in the literature for production of

AC, namely, chemical activation (activation with mineral salts) and physical
activation (activation using oxidizing agents such as steam or CO2). In
chemical activation, the precursor is impregnated with an activating agent
such as zinc chloride or phosphoric acid followed by carbonization in an
inert atmosphere at temperatures ranging from 400 to 800 OC. This is
followed by a leaching process to remove the activator [1,5-6]. Chemical
activation is carried out if the raw material is wood or peat. Possible
advantages of chemical activation over physical activation include: higher
yield, simplicity (no need of the previous carbonization of raw material),
lower temperature of activation and good development of the porous
structure [7].

Although the characteristics of the produced AC depend to some

extent on the precursor used, the most influential factors are those related
to preparation conditions, namely, the impregnation ratio (R),
carbonization time (Ct) and, carbonization temperature (CT). R, that is,
the weight ratio of the activator to the dry precursor seems to influence
the porosity of the resulting products. The activation agent seems to
influence the chemistry of pyrolytic processes (acting as a dehydrating
agent) so that the formation of tar is restricted to a minimum and the
pyrolysis temperature is lowered. This in turn seems to promote the
development of a porous structure [1-3,7]. Usually micropores predominate
at low values of R whereas at higher values wide micropores and
mesopores predominate [8-9]. The speed and extent of the pyrolysis
reaction taking place will depend primarily on the temperature and time
of carbonization respectively. These three factors are interrelated in a
complex manner and play a crucial rule in determining the characteristics
of the final product [1-3, 8-9]. Many investigators [6, 19-20] found that zinc
chloride is the best amongst other activators studied.

In the past few years there has been a wide realization of the
importance of agricultural waste as a cheap and renewable source of raw
materials for AC production. Studies about the production of AC from
agricultural wastes included dates stones [10-13], corncob [14-16], coconuts
shells [6, 17-18], nuts shells and stones [19-33], oil palm stones and shells [34-41],
apple pulp [8-9], chickpea husks [42], rice straw, lignin [43-47] and palm tree
77
Activated Carbon from Dates' Stone by ZnCl2 Activation

branches [5]. On the other hand there were few studies in the literature
about production of AC from Dates’ stones (DS) [10-13]. Gergis et al. [10]
used phosphoric acid as an activator and carbonization time of two hours
only. Best-developed porosity was at 700 OC. Banat et al. [11] found that
raw date pits are better than activated ones for MB removal. Table 1
summarizes the optimum conditions reported in recent literature for
production of activated carbon from dates’ stones. We can notice from
Table 1 that almost all studies were made using H3PO4 as an activator.
Also different parameters are used to assess the quality of the produced
AC (e.g. phenol number, iodine number, maximum capacity…… etc.).
The optimum conditions reported varied widely depending on the method
of evaluation where optimum CT varied between 500 to 800 OC and R
from 0.4 to 2 depending on the assessment method used and the
activator.

Table 1. Summary of optimum conditions reported in recent literature for production of

activated carbon from dates stones.

Optimum conditions
Evaluated Maximum
Activator Ct CT R PS Comments Ref.
Parameter Value
O
(h) ( C) (mm)

H3PO4 (qm)MB 240 mg/g 2 700 1.2

Only Ct = 2
H3PO4 kMB 100 mg/g 2 700 1.2 hr was
investigated
10
H3PO4 IN 528 mg/g 2 500 1.68 (see Tables 5
and 6 in this
reference).
H3PO4 PhN 166 mg/g 700 1.2
2
Used
H3PO4 IN 495 mg/g 1 800 0.4 0.6 12
fluidized bed
Raw dates
pits are better
None (qm)MB 80.3 mg/g NA NA NA 11
than activated
ones

ZnCl2 PMBR 99% 0.5 600 2 13

(qm)MB = maximum capacity as estimated from Langmuir isotherm, kMB = Unit capacity estimated using
Freundlich equation, IN = Iodine number, PhN = Phenol number, and PMBR = percentage methylene blue
removal. PS = particle size.
 78
Yahia A. Alhamed

The previous discussion clearly shows the need for further

investigation about the production of AC from dates’ stones to bring
about more understanding of the effect of preparation conditions on the
quality of the produced AC and the influence of the assessment method
in the determination of the optimum conditions.
Also large quantities of dates’ stones which can be obtained from
more than 830,000 metric tons of dates produced annually in Saudi
Arabia [48] justify the use of dates’ stones as a raw material production of
AC. Knowing that dates' stone account for about 10% of fruit weight [12]
it can be easily shown that about 83,000 metric tons of dates' stones are
available annually. A reasonable fraction of this quantity can be
reclaimed easily from dates’ processing plants and can be used for
production of AC.
Therefore, the objective of this study is to explore the effect of
preparation conditions on the yield and quality of AC produced from
dates’ stones. Zinc chloride will be used in this study since little
attention has been paid for this activator in literature. The optimum
conditions for AC production will be evaluated based on the
determination of various adsorption parameters (e.g. unit capacity,
maximum capacity, and percentage removal) using methylene blue and
phenol as adsorbate.

2. Experimental Procedures
2.1 Preparation of Activated Carbon
The characteristics of the activated carbon (AC) can be
manipulated by controlling three major variables viz. carbonization
temperature (CT), weight ratio of activator to dates’ stones (R) and,
carbonization time (Ct). The range of variables investigated in this study
were; CT = 500, 600, and 700 OC, Ct = 0.5, 1, 1.5, 2 and 3 h and R = 0.5,
1.0, 1.5 and 2.0.
Production of activated carbon involves the following steps:
pretreatment of the dates' stones, impregnation of the dates’ stones with
the activator, carbonization of the impregnated stones and finally the
removal of activator. Further details are given below.
79
Activated Carbon from Dates' Stone by ZnCl2 Activation

2.1.1 Pretreatment of the Dates’ Stones

Dates’ stones were obtained from a dates’ packaging factory in
Almadinah Almonaorah, Saudi Arabia. Received dates’ stones were first
washed thoroughly with water to remove all foreign materials, mud and
sticky sweet remnants of dates, then, they were spread in one layer over
plastic sheets and left to dry in doors. Washed-clean whole dates’ stones
were then dried in a drying oven at 110 OC to facilitate crushing and
grinding. A disk mill was used for grinding.
2.1.2 Impregnation
The required amount of ZnCl2 (necessary of the desired ratio of
ZnCl2 to dates’ stones) was dissolved in 25 ml of distilled water. The
zinc chloride solution was then added to 25 g of the crushed dates’ stones
and then mixed thoroughly. The mixture was left overnight before
carbonization.
2.1.3 Carbonization
The impregnated dates’ stones were then loaded into cylindrical
stainless steel reactor (3.8 cm ID x 13 cm long). The reactor was sealed
at one end. The other end had a removable cover with 2 mm hole at the
center to allow for the escape of the pyrolysis vapors and gases. The
required numbers of reactors were placed in a muffle furnace and heating
started by adjusting the furnace temperature to the desired value. The
furnace took about 2 to 2.3 hours to reach the desired temperature (the
average heating rate was 5 OC/min.). The carbonization times was
measured from the moment the furnace reached the desired temperature
(not from the start of heating). At prescribed times a sample of each ratio
was withdrawn from the furnace and allowed to cool. The activated
carbon was then extracted from the reactor and kept in a carefully labeled
and tightly closed plastic bottles.
2.1.4 Washing
The next step is the removal of the activator from the carbonization
products by through washing. To do this, first the pyrolysis products
were grinded into fine powder and the required volume of dilute HCl (3
wt.%) was added to it such that the liquid to solid ratio (LSR) is 10 ml/g.
The mixture was then left overnight at room temperature in a conical
flask. Next morning supernatant liquid was decanted in a filter paper
followed by three successive washings and decantation using distilled
 80
Yahia A. Alhamed

water. In the third washing, the whole carbon was transferred to the filter
paper and washing using distilled water was continued on the filter paper
till free of chloride ion as indicated by silver nitrate test. Finally the
carbon was dried at 110oC for 2 h and kept in tightly closed plastic
bottles and carefully labeled.
2.2. Adsorption Measurements
2.2.1 Percentage Removal of Methylene Blue (PMBR) and
Phenol (PPhR)
Rapid screening for assessing the quality of the obtained AC was
accomplished using single bottle uptake of MB or phenol from its
aqueous solution [10]. For phenol, 0.15 g of AC powder was added to 25
ml of aqueous phenol solution (250 mg/l) in 100 ml Erlenmeyer flask
provided with glass stoppers. In case of MB, 0.1 g of AC powder was
added to 25 ml of 1200 mg/l MB solution. In each case the mixture was
allowed to equilibrate at room temperature for at least 20 hours under
continuous shaking. Clear liquid samples (free of carbon particles) were
obtained for analysis by centrifugation. The residual concentration of MB
or phenol was then determined using UV/V a spectrophotometer
(Geneysis 10 UV/V).

The percentage of MB removal (PMBR) was calculated using the

formula:

PMBR = ([(CMB)0 - (CMB)e ]/(CMB0))x 100 (1)

Where:

(CMB)0 and (CMB)e = Initial and equilibrium concentrations of

MB, in mg/l, respectively.

Similarly, the percentage phenol removal (PPhR) was calculated

using the formula:

PPhR = [(CPh)0 - (CPh)e ] /(CPh)0)x 100 (2)

Where:

(CPh)0 and (CPh)e = initial and equilibrium concentrations of

phenol in mg/l, respectively.
81
Activated Carbon from Dates' Stone by ZnCl2 Activation

2.2.2 Adsorption Isotherms for MB and Phenol

Adsorption data for MB and phenol were collected by equilibrating
different weights of AC powder ranging from 0.05 to 0.5 g with 25 ml of
an aqueous solution of the adsorbate (1200 mg/l for MB and 250 mg/l for
phenol) in 100 ml Erlenmeyer flask provided with glass stoppers.
Adsorption tests were made at room temperature under continuous
shaking. Preliminary tests have shown that most of the adsorption takes
place in the first few hours. All samples were allowed to equilibrate for at
least 20 hours. Sample of the supernatant liquid was then withdrawn for
analysis using hypodermic syringe fitted with 2 µm sintered-steel filter.
The residual concentrations of MB and phenol were determined using a
Genysis10 UV/V spectrophotometer which was previously calibrated for
each adsorbate.

The adsorption data for phenol and MB were fitted to a Freundlich

isotherm described by the equation:

qe = k Ce1/n (3)

Where:

Ce = equilibrium concentration of the sorbet in mg/l

qe = the amount adsorbed in mg per gram of AC.

k = the so-called unit capacity factor,

and n is an empirical parameter that represents the heterogeneity of

the site energies [49] or the affinity of the adsorbate to the carbon surface
[50]
.

The adsorption data were also fitted to a Langmuir isotherm given

by the equation:

qe = qm (KL Ce/(1 + KL Ce)) (4)

Where:
qm = the maximum adsorption capacity or monolayer coverage in
mg/g
KL = the adsorption equilibrium constant in l/mg [51].
 82
Yahia A. Alhamed

Equations 3 and 4 were fitted using nonlinear regression and the

values of the constants (k , n, qm and KL) were evaluated and used for
comparing the performance of different AC samples.

3. Results and Discussion

3.1 Characterization of Dates’ Stones
Important physical properties of dates’ stones used such as bulk
density, moisture content, and particle size distribution of grounded
dates’ stones are presented in Table 2.

Table 2. Some physical properties of dates’ stone.

Characteristic Value Units Remarks

Bulk density 0.954 g/ml For a particle size cut

– 2 mm/+1 mm,
Moisture content 10.3 Weight % Based on drying at
110 OC for 2 hours
Volume of water needed to 100 ml H2O per ml/g determined in this
achieve incipient wetness. 100 g dates stones study
Particle size distribution:
Weight %
-2 mm/ +1 mm 65.5
(mesh size: -10/+18)
-1 mm/ + 0.5 mm 25.3
(Mesh size: -8/+35)
-0.5 mm (mesh size: -35) 9.2

3.2 Thermogravimetric Analysis of Dates’ Stone

Thermogravimetric analysis (TG) was performed to bring about
more understanding of the pyrolysis of dates’ stones (DS) and to
elucidate the influence of activator on the pyrolysis process. TG and
DTG data were obtained in a flow of nitrogen at a heating rate of 10
O
C/min. after an isothermal period at 110 OC to allow for the removal of
moisture. Figure 1 shows DTG curves for dates’ stones (solid line) and
83
Activated Carbon from Dates' Stone by ZnCl2 Activation

for dates stones loaded with 50 wt.% ZnCl2 (dotted line). As can be seen
from this figure there is only one prominent peak with a maximum at
300OC for dates’ stones without activator. Decomposition starts at about
250OC and continues to about 400OC. This peak has a shoulder that
extends from 400 OC to higher temperatures. These two peaks are
attributed to cellulose and lignin decomposition in the temperature range
from 250 to 350 OC and 250 to 500 OC, respectively [52-54]. For dates’
stones loaded with activator, two major peaks are observed in the DTG
curve. The first peak starts at about 100 OC and ends around 300 OC with
a maximum at 180OC. This peak is corresponding to the first peak
observed at 300OC for DS without activator but shifted to a lower
temperature . Thus it is clear that the presence of ZnCl2 caused a great
reduction in the decomposition and/or dehydration temperature of the
cellulose structure of DS. The second major peak observed in the
temperature range from 500 to 700 OC is due to the evaporation of zinc
chloride (the melting and boiling points of ZnCl2 are 318 and 732 OC
respectively) [55].

3.3 Yield of Activated Carbon

The yield is defined as the ratio of final weight of the obtained AC
after washing and drying to the weight of dried dates stones initially
used. Figure 2 shows the % yield of AC obtained as function of R for
different values of Ct and CT. For Ct = 0.5 h, the yield depended strongly
on CT where a maximum yield of 68.8% was obtained at CT = 500OC
and R = 1.0. Similar effect of R was also observed at CT = 600 and 700
O
C but the yield was substantially lower and decreased with temperature.
For Ct = 1.0 h the yield again depended strongly on CT where a
maximum yield of 68.1% was obtained at CT = 500OC and R = 0.5
Similar behavior was also observed at CT = 600 and 700 OC but the yield
was substantially lower and decreased with temperature. For Ct greater
than 1.0 h, the effect of temperature on AC yield was less pronounced
than observed at lower Ct values with maximum yield at R = 0.5
followed by a gradual and slow decrease with increasing R. A similar
behavior was reported by Aik and Yang [56] for activated carbon prepared
from pistachio-nuts shell using zinc chloride activation where a
maximum yield of about 41% was observed at R = 0.25 to 0.33 with CT=
500 OC and Ct = 2 h. They also reported a gradual decrease in yield with
increase in R.
 84
Yahia A. Alhamed

0.9
300
0.8
None
0.7
ZnCl2

0.6
-dW/dT
0.5

0.4
180

0.3
560

0.2

0.1

0
0 100 200 300 400 500 600 700 800
O
Temperature ( C)

Fig. 1: Comparison of DTG curves for date's stones with and

Fig. 1. Comparison O stones with and without Zn Cl .
withoutofZn
DTG. Heating
2
O
curves for
ratedate's
= 10 C/min. Sample dried for 2 2
HeadingClratebefore
hours = 10 temperature
C/min. Sample
ramping.dried for 2 h before temperature
ramping.
85
Activated Carbon from Dates' Stone by ZnCl2 Activation

68.8 Ct = 0.5 hr
60

% Yield
40
500C 600 C 700 C
20
0.0 0.5 1.0 1.5 2.0

68.1 Ct = 1.0 hr
60
% Yield

40
500C 600 C 700 C
20
0.0 0.5 1.0 1.5 2.0

Ct = 1.5 hr
60 54.6
% Yield

40
500C 600 C 700 C
20
0.0 0.5 1.0 1.5 2.0

500C 600 C 700 C Ct = 2.0 hr

60 53.6
% Yield

40

20
0.0 0.5 1.0 1.5 2.0

500C 600 C 700 C Ct = 3.0 hr

60 47.3
% Yield

40

20
0.0 0.5 1.0 1.5 2.0
R
Fig. 2R: for
Fig. 2. Yield verses Yield
ACversus R for AC
produced produced
at various at various temperature and
carbonization
carbonization temperatures
carbonization times (Ct). and carbonization times (Ct).
 86
Yahia A. Alhamed

3.4 Effect of Activation Parameters on Percentage Removal

Figure 3 shows the effect of R on PMBR and PPhR for AC
produced at different carbonization temperatures (CT = 500OC, 600OC
and 700OC) and carbonization times (Ct = 0.5, 1.0, 1.5, 2.0 and 3 hr).
Maximum value of MBR removal is indicated in each chart. The charts
in left hand side of Fig. 3 for PMBR show that for all carbonization
temperature there is a gradual increase in PMBR with R. The maximum
value of PMBR was obtained at R = 2 and for Ct and CT values used.
This maximum value however varied within a narrow range from 87.3 to
89.8. Carbonization temperatures between 500 to 600 OC give AC with
higher PMBR. Based on the PMBR, the optimum conditions are Ct = 1
hr, R = 2 and CT 500 to 600 OC.
It can be seen from the phenol removal charts in Fig. 3 that there is
a considerable removal of phenol even with AC produced without
activator (R = 0) compared with what was observed with MB removal.
The highest value of PPhR (52%), however was obtained at Ct = 1.5 and
CT = 600OC. The effect of R on PPhR depended on the CT and Ct. For a
given CT and for intermediate values of Ct (1, 1.5 and 2.0 hr), the PPhR
did not change significantly with R above R =0.5, while for Ct = 0.5
hour, a gradual increase of PPhR with R was observed at Ct = 500OC. A
maximum PPhR value of 94.3% was obtained at R = 0.5 and CT = 700
O
C when for this Ct value was 0.5 hr. On the other hand a large Ct of 3
hours resulted in a gradual decrease of PPhR with R. A maximum value
of 97.1% at R = 0.5 and CT = 700 OC was obtained for the Ct value of 3h.
Depending on the Ct, the maximum value of PPhR varied within a
narrow range from 94 to 97% and mostly occurred at R = 0.5 Based on
the PPhR, the optimum conditions that produce AC with the highest
PPhR (97.1%) are Ct = 3 hr, R = 0.5 and CT 700OC.

3.5 Effect of Activation Parameters on Unit Capacity

Another parameter upon which a comparison between the
performance of different AC can be made is the unit capacity kMB and kPh
of the Freundlich isotherm for methylene blue and phenol, respectively.
Such comparison is depicted in Fig. 4 where the effect of R on kMB and kPh
87
Activated Carbon from Dates' Stone by ZnCl2 Activation

100 100
80 80

PMBR
60 60

PPhR
40 40 MAX =
MAX =
20 (Ct = 0.5) 94.3
89.0 20 (Ct = 0.5)
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

100 100

80 80
60 60
PMBR

PPhR
40 MAX = 40
(Ct = 1.0 hr) MAX = 95.7
20 89.8 20
(Ct = 1.0 hr)
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

100 100
80 80
60 60
PMBR

PPhR
40 40
MAX =
(Ct = 1.5 hr) MAX = (Ct = 1.5 hr))
20 87.7 20
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

100 100
80 80
60 60
PMBR

PPhR

40 MAX = 40 MAX =
20 87.7 (Ct = 2.0 hr) (Ct = 2.0 hr)
20 96.6
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

100 100
80 80
60 60
PMBR

PPhR

40 40
MAX = MAX +=
(Ct = 3.0 hr) 20 (Ct = 3.0 hr)
20 87.3 97.12
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0
R R

Fig. 3. Effect of R on PMBR and PPhR for AC produced at various carbonization

temperatures (CT = 500OC (squares), 600OC (triangles) and 700OC (circles)) and
carbonization times (Ct = 0.5, 1.0 , 1.5, 2.0 and 3 hr).
 88
Yahia A. Alhamed

for AC produced at different carbonization temperatures (CT = 500OC

(squares), 600OC (triangles) and 700OC (circles)) and carbonization times
(Ct = 0.5, 1.0, 1.5, 2.0 and 3 h) is shown. In each chart in figure 4 the
maximum value kMB and kPh is indicated on the chart.

For MB adsorption, it can be seen from the charts in the left hand
side of Fig. 4 that regardless of the carbonization temperature there is a
gradual increase in kMB with increasing R above R = 0.5 with stronger
effect of R at 500 OC at short Ct. The maximum value of kMB varied
between 136 to 148 mg/g depending on Ct and mostly occurred at R = 2
and CT = 600 to 700 OC. Based on kMB, the optimum conditions are Ct =
1 h, R = 2 and CT = 600 OC, which are similar conditions to those
obtained based on maximum PMBR.

The effect of R on the unit capacity for phenol adsorption (kPh) is

shown in the charts on the right hand side of Fig. 4. The effect of R on
kPh depended on both CT and Ct values, where for a given Ct, high CT
resulted in higher values of kPh. For Ct values less than 2 hours, R did not
show a significant effect on kPh for most values of CT. On the other hand,
for Ct = 2 and 3 hours, kPh decreased gradually with R with maximum
occurring at R = 0.5, also, higher values of kPh were obtained at higher
CT. The maximum values of kPh varied between 12 and 19 mg/g
depending on preparation conditions. Based on the values of kPh, the
optimum condition for production of AC are R = 0.5, CT = 700 OC and
Ct = 3 hours.

3.6 Effect of Activation Parameters on Maximum Capacity

A third parameter used to compare AC produced at different
conditions is the maximum capacity (qm) of Langmuir isotherm, Equation
4. The effect of R on the maximum capacity of MB, (qm)MB and phenol
(qm)Ph are depicted in Fig. 5 for AC produced at different carbonization
temperatures (CT = 500OC (squares), 600OC (triangles) and 700OC
(circles)) and carbonization times (Ct = 0.5, 1.0, 1.5, 2.0 and 3 hr). In
each chart in Fig. 5 the maximum values of (qm)MB and (qm)Ph are
indicated.
89
Activated Carbon from Dates' Stone by ZnCl2 Activation

200 MAX = (Ct = 0.5 hr) 20 MAX = (Ct = 0.5 hr))

141 14.8
150 15

kMB (mg/g)

kPh (mg/g)
100 10

50 5
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

200 MAX (Ct = 1.0 hr) 20 MAX = 12 (Ct = 1.0 hr)

=148
150 15
kMB (mg/g)

kPh (mg/g)
100 10

50 5

0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

200 MAX = 20 MAX =

(Ct = 1.5 hr) (Ct = 1.5 hr)
136 13.7
150 15
kMB (mg/g)

kPh (mg/g)
100 10

50 5

0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

200 MAX = 20 MAX =

(Ct = 2.0 hr) (Ct = 2.0 hr)
143 17.0
150 15
kMB (mg/g)

kPh (mg/g)

100 10

50 5

0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

200 MAX = 20 MAX = (Ct = 3 hr)

(Ct = 3.0 ).
140 19.0
15
kMB (mg/g)

kPh (mg/g)

100 10

5
0
0
0.0 0.5 1.0 1.5 2.0
0.0 0.5 1.0 1.5 2.0
R
R

Fig. 4. Effect of R on kMB and kPh for AC produced at various carbonization temperatures
(CT = 500 OC (squares), 600OC (triangles) and 700 OC (circles)) and carbonization
times (Ct = 0.5, 1.0, 1.5, 2.0 and 3 hr).
 90
Yahia A. Alhamed

300 MAX = 100 MAX = (Ct = 0.5 hr)

286.3 75.0
80

(qm)MB (mg/g)

(qm)Ph (mg/g)
200
60

100 40
(Ct = 0.5 hr)
20
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

300 MAX 100 (Ct =1.0 hr)

MAX
=280.7 80 =63.80
(qm)MB (mg/g)

(qm)Ph (mg/g)
200 60
(Ct =1.0 hr)
40
100
20

0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

300 MAX 100 MAX =

=280.8 68.0 (Ct = 1.5 hr)
80
(qm)MB (mg/g)

(qm)Ph (mg/g)
200
(Ct = 1.5 hr) 60

100 40
20
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

300 MAX = (Ct = 2.0 hr) 100 MAX = (Ct = 2.0 hr)
123.1 65.0
80
(qm)MB (mg/g)

200
(qm)Ph (mg/g)

60

100 40
20
0 0
0.0 0.5 1.0 1.5 2.0 0.0 0.5 1.0 1.5 2.0

300 100 MAX

MAX = (Ct = 3.0 hr)
107.1 (Ct = 3.0 hr) =73.15
80
(qm)MB (mg/g)

200
(qm)Ph (mg/g)

60

100 40
20
0 0
0.0 0.5 R 1.0 1.5 2.0 0.0 0.5 R 1.0 1.5 2.0

Fig. 5. Effect of R on (qm)MB and (qm)Ph for AC produced at different carbonization

temperatures (CT = 500 OC (squares), 600OC (triangles) and 700 OC (circles)) and
carbonization times (Ct = 0.5, 1.0 , 1.5, 2.0 and 3 hr).
91
Activated Carbon from Dates' Stone by ZnCl2 Activation

For MB adsorption, it can be seen from the charts on the left hand
side of figure 5 that depending on preparation conditions (qm)MB varied
widely from as low as 38 to 286 mg/g. For Ct less than 2 hours there is a
gradual increase in (qm)MB with increasing R. Strong effect of R is
observed at CT = 500 OC and short Ct. The maximum values of (qm)MB
varied between 286.3 and 280.1 mg/g in this range of Ct with the highest
value (286.3 mg/g) occurring at Ct = 0.5 hours, R = 2 and CT = 500 OC.
A sudden decrease in (qm)MB occurred at Ct = 2 and 3 with maximum
value of (qm)MB of only 123 mg/g. Therefore, the optimum conditions for
the production of AC based on (qm)MB are Ct = 0.5 h, R = 2 and CT = 500
O
C.
As can be seen from the charts on the right hand side of Fig. 5, the
effect of R on (qm)Ph depended on the CT and Ct with a common
observation that for a given Ct, always high CT resulted in a slightly
higher values of (qm)Ph. For all AC produced, (qm)Ph varied within a
narrow range from 43.7 to 75 mg/g with the highest value obtained for
AC prepared at Ct = 0.5 h, R = 0.5 and CT = 500OC as optimum
conditions.
Table 3 shows a summary of optimum conditions for production of
AC based on the evaluation of different adsorption parameters. As can be
seen from this table, assessment of the AC based on MB adsorption
indicates a relatively high R value of 2 is essentially to produce AC with
good capacity for MB removal. Due to the relatively large size MB
molecule, it is usually adsorbed in mesopores which are formed when
high ratios of ZnCl2 are used [8-9].
Table 3. Summary of optimum conditions for production of AC based on the evaluation of
different adsorption parameters.
Optimum conditions Yield
Maximum
O
Adsorbate Parameter Value CT ( C) Ct (h) R (%)
Methylene 32
Blue PMBR 89.8% 600 1.0 2

(MB) kMB 148 mg/g 600 1.0 2 32

(qm)MB 286.3 mg/g 500 0.5 2 31

Phenol (Ph) PPhR 97.1% 700 3 0.5 47.3

kPh 19 mg/g 700 3 0.5 47.3
(qm)Ph 75 mg/g 500 0.5 0.5 64.6
 92
Yahia A. Alhamed

On the other hand, the opposite is observed when the AC is

assessed using parameters obtained based on phenol adsorption. Again,
these phenomena can be explained in terms of the optimum pore size for
the adsorption process for a given surface chemistry not forgetting the
effects related to the surface chemistry of the AC and the pH of the
adsorption medium. Since phenol can be adsorbed in micropores due to
its small size and since micropores predominate at low values of R [8-9],
therefore, it is expected that low R is essential to produce AC with higher
capacity for phenol removal.

3.7 Comparison with Literature

The AC produced in this study using ZnCl2 as activator performed
better than that produced using H3PO4 as activator reported in the
literature. For example, Girgis and El-Hendawy [10] reported a maximum
value of kMB as 100 mg /g (see Table 1) compared to 148 mg/g obtained
in this study. Also the maximum adsorption capacity reported by them
for MB ((qm)MB)) was 240 mg/g compared to 286 mg/g obtained in this
study. The adsorption capacity obtained in this study is above the lower
recommended value for carbon adsorbents (200 mg MB/g AC) [10]. The
yield obtained at optimum conditions varied between 31 to 64.6%
depending on the assessment method (see Table 4) where the lower yield
is associated with high values of R. On the other, hand the yield reported
by Girgis and El-Hendawy [10] was between 38 to 43 using H3PO4. This
is consistent with the findings of other investigators [12] who reported that
H3PO4 gives lower yield than ZnCl2. Therefore it can be concluded that
ZnCl2 is a better activator based on the yield of the AC and its ability for
removal of MB and phenol. However, AC production should be
optimized based on its final use.

4. Conclusions

In this study it was shown that the choice of the optimum

conditions for production of AC depend on the method of assessment.
The conclusions made from the optimization of preparation conditions
for AC production based on the determination of various adsorption
parameters for methylene blue (MB) and phenol are as follows:
93
Activated Carbon from Dates' Stone by ZnCl2 Activation

• Using MB as an adsorbate it was found that an optimum ratio of

activator to dates’ stones (R) of 2 is always necessary.
• The maximum unit capacity for MB was 148 mg/g at
carbonization time (Ct) = 1 hour and carbonization temperature (CT) =
600 OC and the corresponding yield was 32%. Milder conditions (Ct =
0.5 h and CT = 500OC) were required to produce AC with maximum
capacity of 286.3 mg/g with a yield of 31%.
• Using phenol as an adsorbate it was found that the optimum value
of R = 0.5 is always necessary.
• The maximum unit capacity for phenol was 19 mg/g at Ct = 3
hours and CT = 600 OC and the corresponding AC yield was 47.3%.
• On other hand, milder conditions (Ct = 0.5 h and CT = 500OC)
were required to produce AC with maximum capacity for phenol removal
of 75.0 mg/g and AC yield of 64.6%.

Acknowledgement
This work was sponsored by KAU, Jeddah, Saudi Arabia under
grant No. 109/422.

Notations
AC = activated carbon
Ct = carbonization time (h).
CT = carbonization temperature (OC)
Ce = equilibrium concentration of the sorbet in mg/l

(CMB)0 = Initial concentration of MB

(CMB)e = equilibrium concentration of MB

(CPh)0 = initial concentration of phenol.

(CPh)e = equilibrium concentrations of phenol respectively.

IN = Iodine number,
k = the so-called unit capacity factor in Freundlich equation

KL = the adsorption equilibrium constant in l/mg.

 94
Yahia A. Alhamed
kMB = Unit capacity for MB estimated using Freundlich equation.
MB = methylene blue.
n = empirical parameter in Freundlich equation.

PhN = Phenol number.

PMBR = percentage methylene blue removal.
PPhR = percentage phenol removal.

(qm)MB = maximum capacity for MB estimated from Langmuir isotherm,

qe = the amount adsorbed in mg per gram of AC in Freundlich or Langmuie equation.

qm = the maximum adsorption capacity or monolayer coverage in mg/g

R = ratio of zinc chloride to dry dates’ stones

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99
Activated Carbon from Dates' Stone by ZnCl2 Activation

         



  

 
 

 

        
    
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