3.1.

Removal of heavy metals from aqueous solution by using

low cost rice husk in batch and continuous fluidized
experiments

Adsorbate Material :

Heavy metals was chosen in this study because of its long recognized as eco-toxicological
hazardous substances, and their chronic toxicities and accumulation abilities in living
organisms have been of great interest for many years (Z. B. Yonebayashi et al., 1999). The
heavy metals were tested in the present study are cadmium (Cd), lead (Pb) and chromium
(Cr).

Adsorbent material :

Rice husk was crushed, sieved and stored in plastic bags by size. Then, husks were
thoroughly washed at several times with distilled water to remove impurities and dried by
exposure to the sun light for 12hr. The dried husks were stored in desiccators until used (S. Y.
Mohammed et al., 2012). Physical properties of rice husk are reported in Table 4.

Preparation of the stock solution :

Synthetic stock solutions of cadmium, and lead were prepared using their nitrate salts,
Cd(NO3)2.4H2O, Pb(NO3)2.2H2O respectively, in distilled water. The stock solution of Cr(VI)
was prepared using potassium dichromate (K2Cr2O7). All working solutions were prepared by
diluting the stock solutions with distilled water to the desired concentration of 25 mg/l. The
experiment was done with synthetic solutions pH of 6 (S. Y. Mohammed et al., 2012) .
Adsorption experiments were carried out at temperature of 25±5 Co .

3.1.1. Experimental procedure for Batch experiments :

The batch sorption experiment conducted by varying the mass of adsorbent. The experiments
were carried out in 250 ml Erlenmeyer flasks and the total volume of the reaction mixture
was kept at 100 ml. The pH of solution was maintained at a desired value by adding NaOH or
HCl. Portions of the solution with 25 mg/l initial concentration was placed in 5 bottles,
containing accurately rice husk ranging in weight (0.25, 0.5, 1, 2, and 3) g with the particle
size of (0.6-1.2) mm. Then the bottles placed on a shaker and agitated at 150 rpm
continuously for 3 hours. At this point the concentration is in equilibrium. The flasks were
withdrawn and the reaction mixtures were filtered through (Wattman 42) filters to remove
any suspended adsorbent. All batch experiments were conducted at constant temperature (25
± 5 ºC). Initial and final concentrations of metals were determined by atomic absorption
spectrophotometer (AAS). The percentage of removal of heavy metals adsorption by the
adsorbents was computed by using the following equation:

Cₒ−Ce
%Adsorption =
Cₒ
ₓ 100 ………………(1)

The results are given in Table 5 to 7. The adsorbed amount is then calculated by the
following equation:

V (C ₒ−Ce)
qe = ………………….. (2)
W

where Cₒ and Ce are the initial and equilibrium concentrations of each metal (mg/l) in the
solution. V is the volume of the solution (L) and W is the mass of dry adsorbent used (gm).

3.1.2. Column Experiments :

Continuous flow adsorption studies were conducted in glass column made of Pyrex glass tube
of (0.8m) height and (0.05m) inner diameter, a layer of glass beads was placed in the bottom
of the column to ensure a uniform distribution of influent through the bed and the adsorbent
bed was placed above it. The influent solution was introduced to the column through a fine
stainless steel screens, fixed at the bottom of the column.

Estimation of the minimum fluidization velocity:

Minimum fluidized velocity in continuous experiments can be determined theoretically and

experimentally. The calculation of theoretical value of minimum fluidized velocity can be
obtained by using Equation (5). The minimum fluidized velocity is equal to 1.3525 ×10 -3
m/sec which corresponds to a minimum flow rate = 9.5604 l/hr. Experimentally, minimum
fluidized velocity can be determined by visual observation as the lower velocity that lifts the
particles and making them suspended. The experimental minimum fluidized velocity was
approximately equal to the theoretical velocity. The minimum flow rate used in continuous
experiments was equal to 9.6 l/hr. Different flow rates of higher than the minimum were used
to increase the mixing and to show its effect on the removal efficiency of Cd (II).
3.2. Removal of heavy metals from acidic synthetic wastewater
by using pressmud-rice husk mixtures

Preparation of Pressmud :

Pressmud was collected from a sugar mill, Malaysian Sugar Manufacturing (MSM) . The
pressmud was air-dried at a shady place outdoor for one week. Then, it was sieved through
500μm sieve to remove large and coarse pebbles. The pressmud was later dried in the oven at
60ºC for 24 hours to remove moisture until the weight is constant and stored in air-tied bottle.

Preparation of Rice husk :

Raw rice husk was obtained from a local rice mill. The rice husk was washed and soaked in
distilled water for 3 days. It was washed with distilled water until it was odorless. The
washing process was continued until the water was colorless, air-dried at room temperature
and then dried in the oven at 105ºC for 24 hours to remove moisture until the weight was
constant. The dried rice husk was grounded and sieved to desired particle sizes in the range of
125 - 250μm (Nhapi, I., et al., 2011)and then stored in air-tied bottles.

Preparation of acidic synthetic wastewater :

Metal solutions (chromium, iron, lead, manganese, nickel and zinc) of 1000mg/L in nitric
acid from Fisher Scientific, UK were purchased. Each metal solution was diluted with
deionized water to obtain similar initial concentrations of acidic synthetic wastewater
containing each type of heavy metal at below 10mg/L and later confirmed with ICP Optical
Emission Spectrometer Model Varian 715-ES. The pH of the synthetic wastewater was
measured using HACH sensION+ PH3 pH meter before and after the experiment.

Initial concentration of heavy metals in acidic synthetic wastewater :

Several heavy metals were chosen in this study. These heavy metals were usually
encountered in leachates from landfills. In this study, the initial concentrations of heavy
metals for Cr, Fe, Mn, Ni, Pb and Zn with their concentrations were 2.07 mg/L, 2.28 mg/L,
2.13 mg/L, 2.18 mg/L, 2.12 mg/L and 2.17 mg/L respectively determined by using ICP-OES.

Initial pH of acidic synthetic wastewater :

The synthetic wastewater was prepared with metal solutions of 1000mg/L in nitric acid from
Fisher Scientific resulting the prepared synthetic wastewater to be acidic. The initial pH
values of the acidic synthetic wastewater were low at between 1.04 and 1.45. The higher the
initial concentration of heavy metals, the lower the pH value of the synthetic wastewater. The
process of heavy metals removal seemed to occur in acidic condition.

Batch equilibrium test :

A 5±0.02 g adsorbent of pressmud-rice husk mixture at different ratio was weighed and
poured into 250mL conical flasks respectively. The adsorbent was designated as

i) pressmud alone (RH 0);

ii) pressmud 80% while rice husk 20% (RH 20);
iii) pressmud 60% while rice husk 40% (RH 40);
iv) pressmud 40% while rice husk 60% (RH 60);
v) pressmud 20% while rice husk 80% (RH 80) and
vi) rice husk alone (RH 100).

The adsorbent were equilibrated with 100 ml of the prepared acidic synthetic wastewater
containing heavy metals (Cr, Fe, Mn, Ni, Pb and Zn) in 250mL conical flasks. The conical
flasks were agitated using horizontal shaker at a speed of 180 rpm for 24 hours at room
temperature (Annadurai et al., 2002; Gupta et al., 2012).

After reaching the equilibrium, the sorbent-solution was centrifuged at 4000 rpm for 20
minutes to separate the liquid and solid form. The supernatant was filtered with No.601
Whatman filter paper and collected in small plastic bottles. The samples were preserved to a
pH < 2 with ultrapure HNO3 according to U.S. EPA Method 2007 (USEPA, 1994). The
samples were stored at 4oC in refrigerator before analysed by ICP-OES Model Varian 715-
ES. The concentration of heavy metals left in the solution was used to calculate the amounts
of heavy metals absorbed by the pressmud-rice husk mixtures.

The percentage removal of heavy metals from the initial solution concentration Co, was
calculated from the following equation.

Percentage removal = (Co – Ce) / Co × 100

Where , Co = initial concentration of heavy metals in the solution (mg/L)

Ce = concentration of heavy metals left in the solution (mg/L)

Results and discussion :
Adsorption isotherm :

Adsorption equilibrium data of Cd(II) was fitted to the Langmiur and Freundlich isotherm
models. These isotherms are expressed by the following equations:

qmax KGe
qe = 1+ KGe
……………… (3)

qe = KFCe 1/n …………………. (4)

where qe is the amount of adsorbate adsorbed per unit mass of adsorbent at equilibrium
(mg/g), Ce: The equilibrium concentration in the solution (mg/l), qmax: The maximum
adsorption capacity, K is the adsorption equilibrium constant (rate of adsorption), KF is
roughly an indicator of the adsorption capacity of the adsorbent which can be defined as the
adsorption or distribution coefficient (mg/g (l/mg) 1/n) and 1/n is the adsorption intensity or
surface heterogeneity. The experimental data was also correlated by both linearized Langmuir
and Freundlich equations (Eq. (3) and Eq. (4)). For Cd(II) the Langmuir and Freundlich
isotherm constant are summarized in Table 8 for rice husk.

It is clear from Fig. 1 to Fig. 3 and Table 8 that:

i) The present results show that the low cost adsorbent rice husk is considerably
efficient for the removal of Cd(II) from its solution.
ii) The value for the maximum adsorption capacity of rice husk with cadmium (5.54)
mg/g.
iii) The maximum removal efficiency of Cd(II) was achieved at high mass of adsorbent,
while the maximum uptake was achieved at low mass of adsorbent.
iv) In order to assess the different isotherms and their ability to correlate with
experimental results, the coefficient of determination (R 2 ) was employed to ascertain
the fit of each isotherm with experimental data. From Table 8, the coefficient of
determination values were higher for Freundlich than for Langmuir. This indicates
that the Freundlich isotherm is clearly the better fitting isotherm to the experimental
data with a high correlation coefficient of 0.9934. The equilibrium isotherm for the
removal of Cd(II) was of a favourable type 1/n < 1.
4.1.2. Result of Column Experiment :
Effect of initial concentration :

The effects of initial concentration are illustrated in Fig. 4. It is clear that the time required
reaching saturation decreases with the increasing of the inlet solute concentration. In the case
of low initial solute concentration, the diffusion rate will take a longer time to reach
saturation. It is also clear that when the influent concentration increases, the adsorption
capacity increases. This is due to a high concentration difference between the bulk solution
and the concentration of the solute on the solid phase. This will increase the rate of mass
transfer of solute to attach a free site(s) on the solid phase of the rice husk. The driving force
for adsorption is the concentrations difference between the solute on the adsorbent and in the
solution. If the initial concentration is high, the saturation of the bed is faster and the slope of
the breakthrough curve is higher.

Effect of Adsorbent Bed Height :

Fig. 5 shows the effects of bed height on removal efficiency. It is obvious that when the bed
height increases, the time to reach breakpoint increases. The increasing of bed height will
provide an extra surface area for the adsorption process. This shows that at a low bed height
the effluent adsorbate concentration ratio increases more rapidly than for a higher bed height.
Furthermore, in a low bed height, the bed is saturated in less time. A lower bed height
corresponds to lesser amount of adsorbent and weak capacity for the bed to adsorb adsorbate
from solution. When the flow rate kept constant, the increasing of the bed height will increase
the contact time of the solute in the bed, and these improve the solute removal efficiency.

Effect of the solution flow rate :

When the flow rate increases the breakthrough curves become steeper. At a high flow rate,
the adsorbate solution leaves the column before the complete equilibrium occurs due to the
reduction in the contact time as shown clearly in Fig. 6. The increasing of flow rate will cause
a reduction in thickness of the surface film which considered the resistance for the mass
transfer. As a result of that the increasing in flow rate will increases the mass transfer rate.
The increasing of flow rate leads to an additional disturbances (mixing) which makes the
penetration and the passage of the adsorbate molecules through the particles and occupy a
site(s) on the adsorbent easier.

Comparing the results :

Two different adsorbents, namely commercial activated carbon and rice husk were used
fluidized bed experiments to evaluate the adsorption performance of the rice husk as
compared to commercial activated carbon as can be seen from Fig. 7 and Fig. 8.

In fact, the commercial activated carbon has higher surface area, adsorption capacity, and
higher porosity than any other adsorbent. The comparison was made with activated carbon
which showed that high removal efficiencies were achieved. This can be attributed to the fact
that the commercial activated carbon has higher adsorption capacity than rice husk.
Difference in sorption of heavy metals by sorbent materials depends probably on the affinity
of metal ions for active groups on the substrate (Jabbar H. Al-Baidhani and Simaa T. Al-
Salihy et al., 2016)