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APPLICATION OF CARBON NANOTUBES

TO REMOVE LEAD FROM AQUEOUS SOLUTION

Kabbashi A. N1,2, Isam Y. Qudsieh2, Salawudeen Taofeeq Olalekan 2, and Muataz. Ali. A3
1,2*
International Islamic University Malaysia, Kulliyyah Engineering, Department of Biotechnology
Engineering, Bioenvironmental Engineering Research Unit (BERU), Jalan Gombak P. O. Box 10,
50728 Kuala Lumpur Malaysia
2
International Islamic University Malaysia, Kulliyyah Engineering, Department of Biotechnology
Engineering, Nanoscience and Nanotechnology Research Group, Jalan Gombak P. O. Box 10,
50728 Kuala Lumpur Malaysia, IIUM
3
King Fahd University for Petroleum and Minerals, Faculty of Engineering, Dept of Chemical Engineering,
Saudi arabia
Tel: +60-3-61964524, Fax: +60-3-61964442, E-mail: [email protected]

Abstract: The removal of Pb (II) ions from aqueous solution using Carbon Nanotubes
(CNT) as the adsorbent is reported in this project. The effects of pH, CNT dosage,
contact time and agitation speed were studied at 25° C. Batch mode adsorption study has
revealed that the removal of Pb (II) ions was maximum (85% removal) at pH 5, and
achieved 83% removal at 40 mg/L of CNTs. The uptake of Pb was very rapid, and
equilibrium was attained within 40 minutes. The homogeneous suspension can be
attained at mild agitation (50 rpm). In kinetic modeling, it was found that the overall
adsorption process was best described by pseudo second-order kinetics. Adsorption
Isothermal Model (Langmuir and Freundlich) were tested, and it was found that the
former had a better fitting with the data in which it obtained high adsorption capacity
(102.4 mg/g). The adsorption continuously increased in the pH range of 3 to 5, beyond
which the adsorption could not be carried out due to the precipitation of metal. This study
was also supported by characterization of CNTs and EDX analysis using FESEM. The
characterization suggested that at acidic condition (pH 5), the surfaces of CNTs are more
aligned and well-integrated compared to CNTs at different pHs. The data obtained from
the batch mode adsorption experiment were fitted into the MINITAB Statistical Software
for the development of optimization equation. The interactions of each factor were
considered during this analysis, and the result indicates that the highest removal (96.03%)
of Pb can be attained at pH 5, with 40 mg/L CNTs dosage at 50 rpm. The amount of Pb
adsorbed onto the CNTs (pH 5) increased rapidly for the first 40 minutes and
subsequently, the adsorption rate reaches equilibrium after 80 min of contact time.
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INTRODUCTION
Nanotechnology is one of the latest advancement in material science and

engineering. Nanotechnology refers broadly to using materials and structures with

nanoscale dimensions, usually ranging from 1 to 100 nanometers (nm) (Masciangioli and

Zhang, 2003). Heavy metals, which most are toxic and harmful to human being as well as

the fauna and flora, are enriched in wastewater. Lead, arsenic, fluoride, cadmium,

chromium and nitrates among the metal ion pollutants contained in the untreated water

which threaten water supplies in many regions (Li et al., 2002). The existence of these

heavy metals in wastewater treatment are mainly comes from discharge of battery

manufacturing, painting, dying photography, electroplating and other industries (Li et al.,

2006). Long term drinking water containing all these elements can cause many chronic or

acute diseases. Various technologies are currently employed in industry to deal with

heavy metals such as chemical precipitation, reverse osmosis (Ahalya et al., 2007) and

adsorption or ion exchange (Lu et al., 2007). In wastewater treatment, nanomaterials

especially CNTs have been developed in remediation and end-of-pipe treatment

technologies. Various reports have stated the use of CNTs for treatment and remediation

of pollutants in the environment (Masciangioli and Zhang, 2003).

Sources and Toxicity of Lead

Most lead pollutes drinking water through corrosion of lead-containing pipes and

plumbing fixtures, especially copper pipes with lead soldered joints. These pipes and

fixtures can be in the house or in the drinking water pipelines. Lead in wastewater comes

mainly from the discharge of battery manufacturing, printing, dying and other industries

(Li et al., 2002). Other major sources of lead in the environment include lead-based paint,
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household dust and food containers (http://www.safe-drinking-water.com). Lead has been

found to be acute toxic to human beings when present in high amounts in water. It

accumulates in human body and will be retained throughout human blood stream

(http://www.nebguide.com). Studies have shown that young children, infants and pregnant

women are particularly susceptible to unsafe lead levels. For adults, increased levels of lead

have been linked to high blood pressure and damaged hearing. Drinking, eating, inhaling

even at low level of lead can cause other serious health effects.

Experimental Details

The production of carbon nanotubes were conducted in two horizontal tubular reactors,

using CVD technique. The horizontal reactors are a ceramic tube of 50 mm in diameter

and 1200 mm in length and heated by silicon carbide heating element. The ferosine

( C10 H 10 Fe ) catalyst of 100 mg was be fixed at the first reaction chamber at 150 C for 10

minutes while the second reaction chamber was be used for the reaction with H2O2 and

growth processes at 800 C for 30 minutes. Two types of gases used in this system were

hydrogen as a reacting gas and the argon for flushing the air from the system, and both of

them will be controlled by a flow meter (Muataz, 2005). The morphology of filamentous

carbon grown was observed by field emission scanning microscopy, FESEM (JEOL

JSM-6700F). The diameter of the carbon nanotubes was range of 16 - 19 nm and the

surface of the adsorbents has been observed.

Characterization of CNTs

The morphology of filamentous carbon grown was observed using Field Emission
Scanning Electron Microscopy (FESEM). Firstly, the carbon holder used to place the
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adsorbents was cleaned using Acetone to remove the impurities that exists on the surface
of the holder. After that, the surface of the carbon holder was coated with Carbon Coating
to stick the adsorbents on its surface.

Preparation of Lead Stock Solution

5 mg/L. Laboratory glass wares that were used in this project were rinsed with 2%

of Nitric Acid to remove all the impurities on the glassware and to prevent further

adsorption of lead on the wall of the glassware. The stock solution was prepared by

pipetting 20mL of lead from lead standard solution of concentration, 1000 mg/L into

Schott Bottle (5 L). Distilled water was added till the mark of the Schott Bottle and mix

thoroughly using magnetic stirrer. The stock solution was divided into three different

working solutions for pH adjustment (pH 3, pH 5 and pH 7). Initially, buffer solutions

were added to the three working solutions to maintain constant pH during fixation.This is

followed by the adjustment of pH using 1.0 M Nitric Acid or 1.0 M NaOH. Finally, the

initial concentration of each working solution with three different pHs was analyzed

using Atomic Absorption Spectroscopy (AAS).

Batch Mode Adsorption Experiment

Experiments were conducted at approximately 25 oC to study the effect of initial solution

pH, CNTs dosage, contact time and agitation speed on the adsorption of Pb (II) ions.
Each experiment was conducted in volumetric flask and the initial and final concentration
of Pb (II) was analyzed using AAS at wavelengths of 283.3 nm for lead. The detection
limit of 0.05 mg/L was used while air and acetylene mixture was used as the oxidant. The
final concentration of each study was tabulated in order to determine the percentage
removal of Pb (II) by CNTs. The run orders for complete batch mode adsorption
experiment were determined using Matrix analysis (Levine, 2001).
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RESULTS AND DISCUSSIONS

Characterization of Carbon Nanotubes before Batch Mode Adsorption Study

The adsorbents images before the adsorption experiments have been characterized

using Field Emission Scanning Electron Microscopy (FESEM, JEOL JSM-6700F).

Characterization of Carbon Nanotubes after Batch Mode Adsorption Study

The adsorbent which have been used in the adsorption studies are shown in Figure 1 for

CNTs at pH 3, pH 5 and pH 7 respectively.

(a) (b)

(c) (d)
Figure 1: FESEM representative images of CNTs after the adsorption experiment
at pH 3 with different magnifications

The structures of CNTs at pH 3 were not aligned and it formed knotted layer of

CNTs. In comparison with the effect on the removal of Pb (II), it was observed that the
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percentage removal by CNTs at pH 3 (2.64%) was very poor compared to other CNTs at

pH 5 (84.78%) and pH 7 (20.88%) respectively.

(a) (b)

Figure 2: FESEM representative images of CNTs after the adsorption experiment at pH

5 with different magnifications

Based from Figure 2, it was observed that the structures of CNTs at pH 5 are

well-integrated and the layers of the tube walls can be discerned clearly. It was also

observed that, the CNTs have more surface area and this can be proven by the higher

percentage removal at pH 5 (84.78%). Figure 3 shows the images of CNTs after batch

mode experiment at pH 7. It was observed that there are many large white crystal

structures on the surface of CNTs. It was reported by Li et al., 2002 that as the pH of the

lead aqueous solution exceeds pH 7, precipitation that occurred between Pb (II) and OH-

will cause lower percentage removal of Pb (II). Thus, the formation of precipitate has

caused the decreases in the percentage removal of Pb (II).

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(a) (b)
Figure 3: FESEM images of CNTs after the adsorption experiment at pH 7 with different
magnifications
Effect of acidity (pH) on the uptake of lead

The pH of the aqueous solution is an important variable which controls the

adsorption of the metal at the solid-water interfaces. Hence, the influence of pH on the

adsorption of Pb (II) ions CNTs was examined in the pH range of 3 to 7. Figure 4 shows

the influence of acidity on the uptake of lead and the percentage uptake of Pb (II) at

different pH values. It can be observed that the percentage removal increases from pH 3

to pH 5 and started to decrease as it exceeds pH 5.

100
84.78
80
% removal

60

40

20 2.64
20.88
0
3 4 5 6 7
pH

Figure 4: Effect of pH on the uptake of lead

[Conditions: Contact time (20 min), Adsorbent (20 mg/L), pH (3, 5 and 7)]

Previous study has stated that the adsorption of Pb (II) increases with an increase

in pH of the solution from 3 to 7 (Li et al., 2002). This is because the adsorption

capability of CNTs is mainly determined by the functional groups introduced by

oxidation. Oxidation of CNTs with oxidized acid can introduce many functional groups
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such as hydroxyl, carbonyl and carboxyl on the surface of CNTs (Li et al., 2002). Thus,

the attachment of these functional groups on CNTs’ surface enhances the lead adsorption.

It was observed that there are many formations of white crystal structures on the surface

of CNTs. This white crystal structure in this image was analyzed as Pb (II) ions, in which

this explanation was supported by Energy Dispersive X-Ray (EDX) analysis in Figure 5.

Figure 5 (a) and (b) shows the presence of Pb (II) ions peak which has been obtained

from the EDX analysis. From the figure also, it was observed that CNTs at pH 5 obtained

the highest peak when compared with CNTs at pH 3 and 7, respectively.

003 13000
15000 12000
4400
13500 11000
4000
10000 C
12000 3600 C
C 9000
3200
10500 8000
2800
Counts

9000 2400 7000

Counts
Counts

7500 2000 6000

1600 Pb 5000
6000 1200 Pb
Pb
4000
4500 800 Pb
Pb 3000 Pb
400
3000 Pb Pb Pb 2000 Pb Pb Pb
0
1500 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 1000
0 keV 0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 20 µm
keV 20 µm
20 µm keV

(a) pH 3 (b) pH 5 (c) pH 7

Figure 5: Energy Dispersive X-Ray Analysis of CNTs for, (a) pH 3, (b) pH 5, and
(c) pH 7

Table 1, has shown that pH 5 obtained the highest percentage of Pb distribution. Thus,

from this analysis, it was verified that Pb (II) ions have been adsorbed on the surface of

CNTs and the maximum adsorption can be achieved at pH 5 with 84.78%e removal.

Table 1: Quantitative analysis using EDX for different pH values

pH Distribution of Pb(%)
3 0.45
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5 10.91
7 1.74

Effect of agitation speed on the uptake of lead

Experimental results for the effect of agitation speed (50, 100, 150 rpm) are

presented in Figure 6. It was observed that the percentage removal of lead is decreasing

as the speed increases. The removal of lead using Carbon Nanotubes reaches 37.76 % at

50 rpm while at 150 rpm, only 3.49% of Pb (II) ions were removed from the solution.

100

80
% removal

60
37.76
40

20 8.01 3.49
0
50 100 150
Agitation speed (rpm)

Figure 6: Effect of agitation speed on the uptake of lead

[Conditions: Contact time (120 min), Adsorbent (40 mg/L), Agitation speed (50, 100 and 150)]

Effect of CNTs dosage on the uptake of lead

The effect of CNTs dosage was examined using two different dosages (5 mg and

10 mg). This effect is shown in Figure 7. It was observed that, the highest percentage

removal (82.54%) occurred at higher dosage (10 mg).

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5 mg 1 0 mg
100
8 2 .5 4
80
% r em ov a l

60
3 9 .6 5
40

20

0
20 40 60 80 100 120
C onta ct tim e (m in)

Figure 7: Effect of dosage on the uptake of lead

[Conditions: Adsorbent (20 and 40 mg/L), Contact time (20 -120 min)]
The dosage can be related to the availability of the adsorption site for lead

adsorption (Inglezakias et al., 2007). This is due to the fact that maximum CNTs dosage

provides more adsorption site for the attachment of lead ions and this accessibility greatly

enhanced the adsorption of lead. EDX analysis was conducted to verify the effect of

dosage (5 mg and 10 mg) on the removal of Pb (II) ions from aqueous solution as in

Figure 10 (a) and (b) which shows the presence of Pb (II) ions peak.

Table 2: Quantitative analysis using EDX for different dosage of CNTs

CNTs dosage Distribution of Pb (%)
5 1.74
10 15.90

It was observed that higher dosage of CNTs obtained a higher peak than lower

dosage of CNTs. From Table 2, it was also observed that higher dosage of CNTs

obtained higher percentage distribution (15.90%) compared to lower dosage of CNTs.

Thus, it was verified that Pb (II) ions have been adsorbed on the surface of CNTs and the

maximum adsorption can be achieved at higher dosage of CNTs (10 mg).

Effect of contact time on the uptake of lead

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The contact time is a variable which depends on the pH of the solution, agitation

speed and CNTs dosage. It is important to establish the time dependency of such systems

for various pollutant removal processes (Augustine et al., 2007). In this study, the

equilibrium time was measured from 20 minutes to 120 minutes and the effect of contact

time is determined by plotting the percentage uptake of Pb (II) against contact time as

shown in Figure 8. It was observed that the removal rate was very fast for the first 40

minutes, but it gradually becomes slower with time until it reached a maximum in 80

minutes. It was also observed that the percentage uptake of Pb (II) became saturated from

time 80 min to 120 minutes. Based from preliminary studies, it was reported by Li et al.,

(2002) that at pH 5, the time required for the maximum removal of lead from water is 40

minutes. It may be concluded that metal binding sites became constant as contact time

increases from 40 to 120 minutes.

100

95
% removal

90

85

80
20 40 60 80 100 120
Contact time (min)

Figure 8: Effect of contact time on the uptake of lead

[Conditions: Adsorbent (40 mg/L), pH 5, Contact time (20 to 120 min)]

Modeling for the removal of lead using CNTs

The regression analysis for CNTs has been done by analyzing both primary

variable and also the four factors interaction variables. Box 1 was constructed to illustrate
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the output obtained from MINITAB Statistical Software. The regression equation

comprising all the explanatory variables for CNTs analysis was constructed as follows:

% Removal of Pb = 528 - 72.7 *A - 5.07* B + 18.5* C - 2.24* D + 0.722 *A*B

- 4.00* A*C + 0.385* A*D - 0.419* B*C + 0.0294* B*D
+ 0.0581*C*D + 0.0843*A*B*C - 0.00603* A*B*D
By referring to the MINITAB Output Box 1, the t-values and the corresponding

significant p-values give the evidence of a slope and the significance of the explanatory

variables to the response variables. While the R2 value gives the information of the

variation in the Y variable that is explained by the variations in the independent factors.

The adjusted R2 takes into account the factors that can contribute to the inflating the

results.

Box 1: Regression analysis for Carbon Nanotubes

The regression equation is

% Removal of Pb = 528 - 72.7 A - 5.07 B + 18.5 C - 2.24 D

+ 0.722 AB - 4.00 AC + 0.385 AD - 0.419 BC
+ 0.0294 BD + 0.0581 CD + 0.0843 ABC
- 0.00603 ABD

Predictor Coef SE Coef T P

Constant 528.49 83.02 6.37 0.000
A -72.74 13.57 -5.36 0.000
B -5.068 1.044 -4.85 0.000
C 18.512 7.667 2.41 0.026
D -2.2405 0.9583 -2.34 0.030
AB 0.7216 0.1717 4.20 0.000
AC -3.995 1.245 -3.21 0.005
AD 0.3854 0.1557 2.48 0.023
BC -0.41927 0.09582 -4.38 0.000
BD 0.02935 0.01198 2.45 0.024
CD 0.05813 0.01969 2.95 0.008
ABC 0.08425 0.01575 5.35 0.000
ABD -0.006029 0.001969 -3.06 0.006

S = 5.569 R-Sq = 98.3% R-Sq(adj) = 97.2%

PRESS = 1671.67 R-Sq(pred) = 95.09%

Analysis of Variance

Source DF SS MS F P
Regression 12 33484.7 2790.4 89.96 0.000
Residual Error 19 589.3 31.0
Total 31 34074.0
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The notations are as follows:

A: pH; B: Agitation speed; C: CNTs dosage; D: Contact time

From the t-table with α-value of 0.05 and degree of freedom equal to 31, the critical value

of "t" was determined. The t-critical that was obtained from the table is 1.696. It was

observed that all the t-values are greater than t-critical and the p-values are closed to zero.

Thus, all the parameters are said to be significance to the response variable. The

coefficient of determination, R2 that was obtained from this study is 0.983 which means

98.93% of the variation in adsorption capacity can be explained by the pH, CNTs dosage,

and agitation speed and contact time. It was also noted that the adjusted R2 obtained from

this study is 97.2% of the variation in the adsorption capacity. It can be concluded from

this study that the most influential factors that contribute to the highest percentage

removal of lead are pH, CNTs dosage and agitation speed in which the interactions of

these factors contribute to the highest t-value and lowest p-value.

Optimum Conditions for the Removal of Pb (II) Using CNTs

The highest predictive percentage removal is 96.03%. The parameters that contribute to

these optimal conditions are pH 5, 10 mg dosage of CNTs in 250 mL Pb (II) solution,

agitation speed at 50 rpm and contact time of 80 minutes. Thus, it can be concluded that

in order to obtain the best percentage removal, the optimized value for the removal of Pb

(II) should be at pH 5 with adsorbent dosage of 10 mg in 250 mL solution and it requires

80 minutes for complete adsorption between the adsorbent and the adsorbate.
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CONCLUSION
Carbon Nanotubes was found to be efficient for the adsorption of Pb (II) in
aqueous solution. The characterization of Pb (II) uptake showed that the lead binding is
dependent on initial pH, agitation speed, amount of dosage, and occurs within 40
minutes. Study of the effects of operational parameters such as pH, CNTs dosage,
agitation speed and contact time produced different optimum conditions. Percentage
uptake increased with an increased in pH from pH 3 to 5 and decrease as it exceeds pH 5.
The optimum pH found in this study is pH 5 in which it gave 85% removal of Pb (II) ions
from aqueous solution. The percentage uptake decreased with an increase in agitation
speed from 50 to 150 rpm, in which 50 rpm gave 37.76% removal. The percent removal
of Pb (II) was observed to be optimal for higher dosage of CNTs, in which 10 mg (40
mg/L) contribute to 82.54% removal of Pb (II) ions.

Acknowledgments: The authors are grateful to the KOE and Department of

Biotechnology Engineering, IIUM for supporting and providing the laboratory facilities.

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