ABSTRACT

The effect of three process parameters (adsorbent dosage, time and pH) was examined on rate of
adsorption of lead metal ions on modified groundnut shell using design expert software (Response
Surface Methodology) so as to determine the optimal rate. Modified activated carbon from
groundnut shell was obtained via carbonation and activation process using 1M concentration of
HN03. Characterization of the modified activated absorbent was also carried out to determine its
moisture contents, bulk density and surface area. Batch adsorption study was carried out at
different levels of the varying process parameters as specified by Box-Behnken model design and
the capacity of the adsorbent (groundnut shell) being able to adsorb the adsorbate (lead metallic
ions) was determined using atomic absorption spectrophotometer (AAS) to measure the
concentration of the solution after adsorption process. Characterization study showed that
activated groundnut shell had 7.25% moisture content, 0.43g/cm3 bulk density and 980m2/g
surface area. Analysis of variance indicated that the proposed quadratic model successfully
interpreted the experimental data with coefficients of determination of R 2lead=0.9768. Numerical
optimization applying desirability function setting goal at target criterion, was used to identify the
optimum conditions of the three chosen variables for lead ion removal and it was found to be
adsorbent dosage of 0.94g, contact time of 115.36minutes and pH of 5.42 giving a desirability of
0.933 and percentage adsorption capacity of 99.8002%. The effect of the process parameter
chosen showed that the interaction between high contact time and adsorbent dosage showed
increase in percentage adsorption rate. Also the interaction of high contact time and increased pH
showed increase in percentage adsorption rate. So in general adsorption rate of lead metal ion on
modified groundnut shell is favored by increased contact time, adsorbent dosage and pH.
INTRODUCTION

https://control.com/textbook/control-valves/split-ranging/

Environmental issues due to globalization and rapid industrialization are becoming more and
more nuisance for human being. Heavy metals such as lead present in wastewater and industrial
effluent is a major concern of environmental pollution. Pollution problems of industrial
wastewater is becoming serious in the world. Consequently, the treatment of polluted industrial
wastewater remain a topic of global concern since wastewater collected from municipalities,
communities and industries must ultimately be returned to receiving waters or to the land.
Moreover, contamination of ground water is today a major concern in the management of water
resources (Weber et al., 1991). Contaminants such as pesticides (El-Geundi et al., 2005), heavy
metals (Adesola et al, 2006) and organic substances (Khouider et al., 2004) are characterized by
a wide variety of processes occurring in the soil including diffusion: mechanical dispersion,
chemical reaction, decay, adsorption and biodegradation. The presence of copper, zinc, lead,
iron, nickel and others metals, has a potentially damaging effect on human physiology and other
biological systems when the tolerance levels are exceeded. Many methods of treatment for
industrial wastewater have been reported in literature (Periasany and Namasivayam, 1995;
Dimitrova and Mehandgiev, 1998). Amongst these methods are ultrafiltration, precipitation, ion
exchange and adsorption. For low concentrations of metal ions in wastewater, the adsorption
process is recommended for their removal. The process of adsorption implies the presence of an
“adsorbent” solid that binds molecules by physical attractive forces, ion exchange, and chemical
binding.

This research focuses on industrial waste water produced in industries evolving or utilizing lead
as either raw material or finished products. Lead's toxicity has been a reason why lead was or is
being phased out for some uses. If ingested or inhaled, lead and its compounds are poisonous to
animals and humans. Lead is a neurotoxin which accumulates in soft tissues and bones,
damaging the nervous system and causing brain disorders. Excessive lead also causes blood
disorders in mammals. With this adverse effect the need of removing or adsorbing lead from
waste water is necessary so as to save life (promoting healthy living) and ensure better eco
system. Also when adsorbing lead from waste water cost of adsorption should be minimal and
studying most adsorption processes such as ion exchange, chemical precipitation, coagulation
and flocculation, membrane filtration ultra-filtration are quite expensive processes this calls for
the use of low cost adsorbent such activated carbon which can be obtained from waste such as
groundnut shell, rice husk, coconut shell, etc.

Adsorption is operative in most physical, biological, and chemical systems, and is widely used in
industrial applications such as activated charcoal, synthetic resins and water purification. Growth
in the industrial sector in the last few decades has led to a number of environmental related
issues. Extensive use of metals, chemicals, natural and artificial materials in manufacturing
sector with ineffective treatment of effluent has led to generation of various levels of toxic heavy
metals such as Lead, Copper, Zinc, Iron, Nickel, Arsenic, Cobalt, Mercury, Cadmium,
Chromium etc., into the environment [Jaime, et.al, 2010].
In this study lead has been chosen because of its environmental importance related to its well
known toxicity (Hepple, 1972) and intensive use in industries such as storage-battery
manufacture, printing, pigment manufacturing, petrochemicals, fuel combustion and photographic
materials (Carson et al., 1986). Assimilation in the human body of relatively small amounts of
lead over a long period of time can lead to malfunctioning of certain organs and chronic toxicity
(Khurshid and Qureshi, 1984).
Findings of this study will help reduce the industrial waste water pollution with lead ions to be
minimal thereby enhancing and allowing a comfortable ecosystem, it will also help the industries
producing pollutant to optimize cost of lead adsorption since low cost adsorbent (ground nut
shell) is used. Lead pollution in water has been increasing progressively in Nigeria. This gives
rise to concern in health problems and wellbeing of man and animals. Therefore it is of great
relevance to develop a new method for its removal from water. This study may generate useful
information for the utilization of native agricultural by-products for the removal of Pb 2+ from
wastewater. Groundnut wastes, as agricultural byproducts from groundnut, oil or peanut
producing industries, could be heavy metal adsorbents which could be selective for some metal
ions. In this study the capabilities of groundnut shell wastes for lead ion adsorption was tested.
The effect of pH, contact stime and adsorbent dose, on the rate of removal of lead was
investigated.
MATERIALS AND METHODS.

Adsorbent preparation

The groundnut shells used for this research were bought from one of the famous markets in Benin
City called Uselu market.
The groundnut shells were ripped off to remove dusts and washed with water to remove adhered
particles before sun drying for 8 hours for easy carbonation. The dried samples were weighed on
an electrical balance in the Chemical Engineering Laboratory at University of Benin. 1M
concentration of Nitric acid was used as activating agents. The ratio used for the activation was
1:4 by weight; 1g of groundnut shells with 4g of activating agent. The measured groundnut shell
was placed in the muffle furnace at 500oC for 1 hour, after which the carbonated groundnut shell
was sieved to attain 0.425mm before activation. The activation was done by soaking the sieved
carbonated groundnut shell in the solution of nitric acid following the above ratio for 24 hours for
activation purposes. Then the activated groundnut shells were removed from the solution and
washed to neutral pH with distilled before placing it in the oven for 2 hours, at 105 0C (Samuel et
al.,) then it was left to cool in a desiccator. After cooling, the modified groundnut shell was
placed in an air-tight container ready for use.
Adsorbate preparation.
The salt used for the preparation of the aqueous solution was analytical grade Lead (II) nitrate.
Other chemicals used were sodium hydroxide and trioxonitrate (V) acid. All reagents were of
analytical grade. Stock solution of 1000 mg/l of lead (ii) nitrate (Pb(NO 3)2) was prepared by
dissolving reagent grade Pb(NO3)2 in an appropriate amount of distilled water. From this stock
solution a working solution of 100mg/l was prepared which was used for the batch adsorption
process.
Batch Adsorption Study
The batch adsorption experiments were carried out on the removal of lead ion from aqueous
solution to study the effect of some specific process parameter.
 In the kinetic experiments, the parametric effects of adsorbent dosage, contact time, and pH were
investigated for the adsorption onto groundnut shell. 100mg/l of concentration of lead solution
(Ci) with pH range of 2 to 6 was transferred into a conical flask with a range of amount of
adsorbent dosage (0.2g to 1g). Each solution was agitated at 250rpm in an orbital shaker at a room
temperature and contacted for a period of 10minutes to 120minutes. At the end of each contact
time, the solution was filtered using Whatmann No. 1 filter paper and the residual concentrations
were analyzed. The pH of the solution was adjusted using tri-oxo nitrate v acid and sodium
hydroxide.
The concentrations of the metal ion in the filtrate were analyzed using the atomic adsorption
spectrophotometer (AAS). Batch adsorption experiments were carried out at room temperature
by shaking a series of beakers containing the desired dose of adsorbent in a known concentration
of lead solution. Samples of lead solutions were withdrawn at different intervals, filtered and the
filtrate was analyzed for the trace of heavy metal content.
The design of this experiment was done using Box-Behnken Design method of response surface
analysis which specifically made each effect to require only three (3) levels given in table 1.0.
Table 3.0 EXPERIMENTAL BOX-BEHNKEN DESIGN WITHOUT RESPONSES
STD RUN BLOCK FACTOR 1 FACTOR 2 FACTOR 3 RESPONSE 1
A:ADSORBENT B: CONTACT C: pH % REMOVAL
DOSAGE(grams) TIME (%)
(minutes)
16 1 Block1 0.6 65.0 4.0
4 2 Block1 0.6 120.0 6.0
9 3 Block1 0.2 10.0 4.0
2 4 Block1 0.6 10.0 6.0
11 5 Block1 1 10.0 4.0
15 6 Block1 0.6 65.0 4.0
14 7 Block1 0.6 65.0 4.0
17 8 Block1 0.6 65.0 4.0
1 9 Block1 0.6 10.0 2.0
8 10 Block1 1.0 65.0 6.0
7 11 Block1 1.0 65.0 2.0
12 12 Block1 1.0 120.0 4.0
13 13 Block1 0.6 65.0 4.0
10 14 Block1 0.2 120.0 4.0
6 15 Block1 0.2 65.0 6.0
5 16 Block1 0.2 65.0 2.0
3 17 Block1 0.6 120.0 2.0
100ml of 100mg/L of lead solution was used for the adsorption studies at the various conditions
stated on the table.
Investigations over different tests such as sequential model sum of squares, lack of fit tests,
model summary statistics helps in selecting the best model for describing the relationship
between the response and other influencing independent variable.
For this study, the independent variables were coded as A, B, and C. Thus, the equation can be
represented as equation (3.1):
Y= β0 + βiA + βiC + βiC + βiiA2 +βiiB2 + βiiC2 + βijAB + βijAC + βijBC (3.1)
The removal efficiency of Pb ion was defined as:
Ci−Cf
Re (%) = × 100 (3.2)
Ci
Where;
Re (%) was the ratio of difference in metal concentration before and after adsorption.
Ci was the concentration of heavy metals ions before adsorption (mg/L)
Cf as the concentration of heavy metals ions after adsorption (mg/L)
The amount of ach metal ion adsorbed at time t, (qt) was calculated using the formula (Badmus et
al., 2007):
Ci−Cf
qt = × V (3.3)
M
Where;
V was the volume (L) of the aqueous solution used for adsorption.
M was the mass (g) of the adsorbent used.

4.0 RESULTS AND DISCUSSIONS

Table 4.0: PHYSIOCHEMICAL CHARACTERISTICS OF ADSORBENT

PARAMETER VALUE UNIT

Moisture content 7.25 %
Bulk density 0.43 g/cm3
Surface area 980 m2/g

4.1 BOX-BEHNKEN STATISTICAL ANALYSIS

The Box-Behnken responses were analyzed and the results for adsorption study of lead metal ions
is presented in table 4.1
TABLE 4.1 EXPERIMENTAL BOX-BENHKEN DESIGN WITH RESPONSES
STD RUN BLOCK FACTOR 1 FACTOR 2 FACTOR RESPONSE 1
A:ADSORBENT B: CONTACT 3 % Removal
DOSAGE(grams) TIME C: Ph (%)
(minutes)
16 1 Block1 0.6 65.0 4.0 90.00
4 2 Block1 0.6 120.0 6.0 99.10
9 3 Block1 0.2 10.0 4.0 98.00
2 4 Block1 0.6 10.0 6.0 98.80
11 5 Block1 1 10.0 4.0 96.65
15 6 Block1 0.6 65.0 4.0 91.50
14 7 Block1 0.6 65.0 4.0 92.00
17 8 Block1 0.6 65.0 4.0 92.50
1 9 Block1 0.6 10.0 2.0 97.75
8 10 Block1 1.0 65.0 6.0 99.80
7 11 Block1 1.0 65.0 2.0 98.40
12 12 Block1 1.0 120.0 4.0 99.02
13 13 Block1 0.6 65.0 4.0 92.30
10 14 Block1 0.2 120.0 4.0 96.79
6 15 Block1 0.2 65.0 6.0 99.00
5 16 Block1 0.2 65.0 2.0 98.80
3 17 Block1 0.6 120.0 2.0 98.90

4.2 REGRESSION MODEL EQUATION FOR LEAD ION CONCENTRATION

A system or process with several variables is likely to be influenced by several external as well
as internal parameters and low order interactions. Investigations on linear, cubic, two factor
interaction and quadratic model were done to select the statistically significant model for
determining the relationship between the response and input (independent variables). From the
 sequential model sum of squares, it can be seen that p value is less than 0.0001 and F value
(94.84) for quadratic model. From table 4.3 Lack of fit test for quadratic model was found to be
insignificant which indicate that the model fits the experiment and its p value was 0.9961.
From the model summary statistics (Table 4.2), it can be predicted that the quadratic model had
maximum predicted and adjusted R2 value. From the above results, it had been concluded that
quadratic model provides an excellent relationship between the response and the independent
variables.
TABLE 4.2: Model Summary for Lead Metal Response
Std. Adjusted Predicted
R- R-
Source Dev. R-Squared Squared Squared PRESS
Linear 3.65 0.0118 -0.2162 -0.4201 248.77
2FI 4.12 0.0332 -0.5469 -1.2719 397.98
Quadratic 0.76 0.9768 0.9469 0.9592 7.14 Suggested
Cubic 1.00 0.9771 0.9084 N/A N/A Aliased

The relationship between the adsorption efficiency and the three chosen factors is shown in
Eq.4.1
Y lead =120.04394−27.43494 A−0.13092 B−8.28381 C+0.040682 AB+ 0.37500 AC−1.93182 X 10−3 BC +19.7421
(4.1)
From equation, it can be said that none of the factors, adsorbent dosage, A, Contact time, B, and
P H, C have positive impact on the lead metal adsorption whereas the interaction between
adsorbent dosage, A and Contact time, B, adsorbent dosage, A and pH, C contact time, B and pH,
C, have an overall positive effect on the adsorption but the interaction between contact time, B,
and pH, C, have a negative impact on the adsorption concentration.
4.3 ANALYSIS OF VARIANCE (ANOVA)
Analysis of variance (ANOVA) was used to check the adequacy of the model for the responses in
the experimentation. It subdivides the total variation of the results in two sources of variation, the
model and the experimental error, showing whether the variation from the model is significant
when compared to the variation due to residual error (Segurola et al., 1996). Fisher’s F-test value,
which is the ratio between the mean square of the model and the residual error, performs this
comparison (Kasiri et al., 2013; Khataee et al., 2010).
4.3.1 (ANOVA) FOR RESPONSE SURFACE QUADRATIC MODEL OF LEAD.
Table 4.3: (Analysis Of Variance for Lead Metal)
Sources Sum of Degree of Mean F value P value
squares freedom square prob>F
Model 171.11 9 19.01 32.73 <0.0001 significant
A- 0.2 1 0.20 0.35 0.5714
Adsorbent
dosage
B- contact 0.85 1 0.85 1.47 0.2653
time
C- pH 1.02 1 1.02 1.75 0.2277
AB 3.20 1 3.20 5.52 0.0512
AC 0.36 1 0.36 0.62 0.4570
BC 0.18 1 0.18 0.31 0.5945
A2 42.01 1 42.01 72.32 <0.0001
B2 32.92 1 32.92 56.67 0.0001
C2 73.61 1 73.61 126.71 <0.0001
Residual 4.07 7 0.58
Lack of fit 0.0055 3 0.018 0.018 0.9961 Not significant
Pure Error 4.01 4 1.00
Cor Total 175.18 16

Table 4.4: Statistical Information on Box-Behnken Design for Lead.

Std Dev. 0.76 R-Squared 0.9768
Mean 96.43 Adj R- Squared 0.9469
C.V% 0.79 Pred. R- Squared 0.9592
PRESS 7.14 Adequate precision 13.952

The coefficient of Variance (CV) is the ratio of standard error of estimation to the mean value and
considered reproducible once it is not greater than 10%. In my study, CV obtained was 0.79%.
Adequate precision value measures signal to noise ratio. A ratio greater than 4 is desirable. The
obtained ratio from my research was 13.952 which indicate and adequate signal.

4.4 ESTIMATION OF QUANTITATIVE EFFECTS OF THE FACTORS

4.4.1 INTERACTION BETWEEN ADSORBENT DOSAGE AND CONTACT TIME.
 Figure 4.1a: surface plot of the predicted percent adsorption capacity as a function of
adsorbent dosage and contact time with pH fixed at 4.
From the fig 4.1a above, it was observed that as both contact time and adsorbent dosage increases,
lead ion concentration decreases leading to percent increase in adsorption capacity. This can be
traced back to effect of time on rate of adsorption since increasing time of contact between the
adsorbent and the adsorbate increases the rate of adsorption it implies that the active site are well
filled with lead ion if contacted for long, this result is line with the obtained result that reported by
Lo et al., (2012).. Also adsorbent dosage increase, increases the rate of adsorption in the sense
that when there is enough adsorbent dosage, the actives site increases leading to large surface area
and adsorption rate increases as well because there is enough space for the adsorbate to bind.
4.4.2 INTERACTION BETWEEN pH and TIME
Fig. 4.1b: surface plot of the predicted percent adsorption capacity as a function of contact
time and pH with adsorbent dosage fixed at 0.6g.
From the above fig 4.1b, it can be deduced that as both contact time and pH increases,
adsorption capacity increases from 97.75% to 99.1%. This value is obtained from table 4.1
indicating low pH (2) and low time (10minutes) corresponding to 97.75% to higher pH (6) at
increased time (120minutes) corresponding to 99.1%. This is reasonable because research has
shown that increased pH increases the rate of adsorption for metal since metals are protons with
positive ions they tend not to be adsorbed when the solution is acidic with low pH since like
charges repels each other but easily absorbed in basic solution with high pH. Also Increase in
contact time from 10minutes to 120 minutes led to an increase in percentage adsorption capacity
from 96.65% to 99.1%. PH increment led to increase in percentage adsorption capacity from
97.75% to 99.10%. Therefore it can be concluded that the interaction between both factors have
an overall positive effects on lead ion adsorption process.

4.4.3 INTERACTION BETWEEN ADSORBENT DOSAGE AND pH

Fig 4.1c: surface plot of the predicted percentage adsorption capacity as a function of
adsorbent dosage and pH with contact time fixed at 65minutes.
From figure 4.1c it is observed that as both adsorbent dosage and pH increase, percentage
adsorption capacity increases from 98.8 %to 99.8% these corresponds to lower pH and adsorbent
dosage value(2,0.2g respectively) to a higher pH and adsorbent value (6,1g respectively) as shown
in table 4.1. An increase in adsorbent dosage (0.2-1) gram resulted to an increase in percentage
adsorption capacity from 96.79% to 99.80%. Also an increase in pH from (2-6) resulted into an
increase in percentage adsorption capacity from 97.75% to 99.1%. Therefore it can be concluded
that the interaction between adsorbent dosage and pH has an overall positive effect in the
adsorption process of lead ion.

CONCLUSIONS

The present study shows that groundnut shell can be used as an adsorbent in removing lead from
aqueous solutions. The adsorption of lead onto groundnut shell depends on, contact time, pH and
adsorbent dose. However, it is suggested to study more parameter such as particle size, initial
concentration of lead ions and temperature in order to determine optimum condition for which
this factors affect the rate of adsorption of lead onto groundnut shell. Furthermore, the statistical
methodology, Box-Behnken Response Surface Design was demonstrated to be effective and
reliable in finding the optimal conditions for the adsorption of lead metal ion onto modified
groundnut shell. The results showed that the adsorption conditions have significant effects on the
removal of lead metals.
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