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A Comparative Studies on the Adsorption of Phenol Polluted Waste Water
A Comparative Studies on the Adsorption of Phenol Polluted Waste Water
A Comparative Studies on the Adsorption of Phenol Polluted Waste Water
1
Dr. ADERIBIGBE FATAI ALADE
Email: aderibigbe.fa@unilorin.edu.ng,
2
ENGR. TANIMOLA HAMED OLUWATOBI
Email: tanimolatobi@yahoo.com
3
SAKA HARVIS BAMIDELE
Email: sakaharvis@gmail.com
4
AWOYEMI OPEYEMI EMMANUEL
Email: eemmakulate@gmail.com
5
Owolabi John Bolaji
Email: officialengrowolabi@gmail.com
Lekki phase II underground water is an important water source that needs treatment before
drinking. Heavy metal (lead) and Organic Compound (phenol) have been detected to be above
the standard required limit. The chemical 3M H 2SO4, was employed to treat the powder in the
mass ratio 1:1 each. The treated powder was then carbonized at 250 ℃, 300 ℃ and 350 ℃. Also,
raw Luffa Cylindrica powder was carbonized at 250℃, 300℃ and 350 ℃. These two samples
were then employed to reduce the targeted pollutants in Lekki phase II underground water. At
optimum condition which is: agitation rate of 200 rpm, dosage of adsorbent of 200 mg, contact
time of 30 mins, and temperature of 30℃ , it was observed that the adsorbent (LC-AC - H 2SO4
at 300 ℃) reduces the initial concentration of phenol (120.50 mg/L) and lead (0.96 mg/L) in
water to 77.87 mg/L and 0.52 mg/L, respectively. Result showed that for adsorption isotherm
both phenol and lead adsorption followed Freundlich adsorption Isotherm. Hence, this
comparative study has developed an adsorbent with high efficiency using Luffa Cylindrica (LC)
which could treat Lekki Phase II underground water effectively.
1.0 INTRODUCTION
The most important and essential solvent of the universe and ecosystem is water with
molecular formula of H2O. Water has a bent structure and has the ability to dissolve all other
substances because of its high polarity (Adak and Pal, 2009). The major sources of water
supplied to the community are assumed to be pollutant free and safe for consumption. In
some areas of the world especially, Nigeria, activities from rapid modern industrialization,
domestic and agricultural activities, environmental and global changes are polluting our
environment. Hence, water need to be free from major pollutants as the quality of water play
a major role to protecting human health, aquatic animals and wildlife in general (Mohd et al.,
2009)
2
At low concentrations heavy metals like lead, phenol, cadmium, nickel, chromium etc. are
hazardous to the environment (Karunarathne and Amarasinghe, 2013). In water, lead
contamination occurs via glass industries, petroleum refining, battery manufacture, textile
dyeing, ceramics industries and mining operation, while household drinking water can be
contaminated with lead through the corrosion and leaching of lead pipes. Lead is poisonous
and it accumulates mainly in bones, brains, kidney and muscles which may results to the
development of cancer. The permissible level of lead in drinking water and surface water
intended for drinking as set by EU, EPA and WHO are 0.01, 0.05 and 0.01 mg L –1,
respectively. Hence, an extremely low concentration of lead in water is imperative.
Furthermore, major toxic and stable compounds such as phenol and its derivatives have been
found to contaminate the waste water of heavy industries such as the industries which
produces resin, plastics, explosives, steel, and leather. It is important to know that the phenol
and its compounds so found in waste water forms complex compounds such chlorophenol
which are classified as priority and major pollutant due to some properties such as high
toxicity, the change in taste, carcinogenicity, foul smell, low biodegradability.
Phenol at a very low level in water tends to be extremely harmful and makes it unsafe to
drink (Bazrafshan et al., 2016, Yousef et al., 2011, Biglari et al., 2013).
The environmental protection agency of the United States has listed phenolic compounds
as of major priority pollutants with a discharge limit to every water bodies in the United States to
< 1mg/l in treated industrial effluent for human protection. Moreover, in accordance with the
world health organization (W.H.O), it is recommended that a limit of 0.001mg/l for the
concentration of phenol in drinking water may be acceptable.
Lead and phenol are contaminants in water that are removed by various techniques
which includes chemical oxidation or reduction, filtration, adsorption, ion exchange,
electrochemical treatment, membrane filtration and reverse osmosis. However, most of these
methods have considerable disadvantages including incomplete and inefficient metal removal,
high capital, operational cost and the disposal of residual metal sludge which are not suitable
for small scale industries. However, of the various methods, adsorption with the aid of
activated carbon has proven to be cheaper and sustainable.
3
This comparative studies examines the capacity of an activated carbon derived from a
Luffa cylindrica produced in the laboratory to adsorb lead and phenol from Lekki
underground water solution. The influence of temperature, stirring rate, pH, contact time,
quantity of activated carbon, and concentration of lead and phenol on the adsorption process
was investigated.
Moisture 6.66
4
Ash 5.23
To improve the surface properties of the raw powder, 3M H 2SO4 was employed to treat the
powder in the mass ratio 1:1. The slurry formed was dried at 105 for 6 hours in an oven. After
6 hours, sufficient water was added to the mixture to remove the excess chemical. The washing
process with distilled water was repeated 3-4 times until pH becomes 7 (neutral). The treated
powder was then carbonized at 250 , 300 and 350 . The raw powder was also carbonized
but not chemically treated at 250 , 300 and 350 .
5
were executed for all the 15 samples of adsorbent and 45 runs performed. Also, the adsorption
capacity and percentage removal of both phenol and lead were also calculated using Equation
1 and 2 respectively.
(1)
where 𝑞𝑒 is the equilibrium adsorption capacity (mg/g), V is the volume of the solution
(L) ,Co is the initial concentration (mg/l), Ce is the equilibrium concentration (mg/l), M is the
weight of the carbon powder (g), The percentage removal is given by the expression below
(2)
6
Langmuir adsorption model describes quantitatively the formation of a monolayer adsorbate
on the outer surface of the adsorbent, and after that no further adsorption takes place. It assumes that
there is no interaction between the molecules adsorbed on neighboring sites and that the intermolecular
forces decrease rapidly with distance and consequently help to predict the existence of monolayer
coverage of the adsorbate on the outer surface of adsorbent. The Langmuir Adsorption Isotherm is as
revealed in Equation 5
(5)
Langmuir adsorption parameters were determined by transforming the Langmuir equation (5) into linear
form.
(6)
where: 𝐶𝑒= the equilibrium concentration of adsorbate (mg L -1); 𝑞𝑒= the amount of metal adsorbed per
gram of the adsorbent at equilibrium (mg/g); 𝑄𝑜 = maximum monolayer coverage capacity (mg/g); 𝐾𝐿
= Langmuir isotherm constant (L/mg).
The values of 𝑞𝑚𝑎𝑥 and 𝐾𝐿 were computed from the slope and intercept of the Langmuir plot versus
(Langmuir, 1918). The essential features of the Langmuir isotherm may be expressed in terms of
equilibrium parameter RL as shown in Equation 6, which is a dimensionless constant referred to as
separation factor or equilibrium parameter RL (Chakravarti et al., 1974).
(7)
Where: 𝐶 𝑜= initial concentration 𝐾𝐿 = the constant related to the energy of adsorption
(Langmuir Constant). RL value indicates the adsorption nature to be either un-favorable if R L >1, linear if
𝑅L =1, favorable if 0 < 𝑅L < 1 and irreversible if 𝑅L = 0. The 𝑅L is greater than 0 but less than 1 indicating
that Langmuir isotherm is favorable.
2.4.2 Freundlich Adsorption Isotherm
Freundlich adsorption isotherm is used to describe the adsorption characteristics for a
heterogeneous surface. These data usually fit the empirical equation proposed by Freundlich. The
Freundlich model as shown in Equation 8 is an empirical equation based on adsorption on
heterogeneous surface or surface supporting sites of varied affinities. It is presumed that the stronger
binding sites are occupied first and that the binding strength decreases with the increasing degree of
site occupation.
(8)
7
where Kf = Freundlich isotherm constant (mg/g), n = adsorption intensity 𝐶𝑒 = the equilibrium
concentration of adsorbate (mg/L), 𝑞𝑒 = = the amount of metal adsorbed per gram of the adsorbent at
function of the strength of adsorption in the adsorption process (Voudrias et al., 2002). The smaller
the greater the expected heterogeneity. This expression reduces to a linear adsorption isotherm when
= 1. If n lies between one and ten, this indicates a favorable sorption process (Goldberg et al., 2005).
8
300 165.74 0.60
350 94.20 0.54
Table 3: Adsorption of Experiment for Condition 2: Agitation rate of 250 rpm, dosage of adsorbent
of 300 mg, contact time of 45 mins, and temperature of 40℃
9
Table 4: Adsorption of Experiment for Condition 3: Agitation rate of 300 rpm, dosage of adsorbent
of 400mg, contact time of 45 mins, and temperature of 50℃
10
Figure 2a shows the EDX Analysis of the adsorbent with the presence of some elements and their
compositions as shown in Table 5a. It revealed the presence of carbon atoms at 26.71 wt%, Sulphur at
16.77wt %, Oxygen at 14.36 wt % and other elements. The above two listed elements (Sulphur and
Oxygen) suggests that the LC-AC contains some amount of H2SO4 on activation. Furthermore, Figure 2b
showed the EDX Analysis of the adsorbent with the presence elements and their compositions as shown
in Table 5b. It revealed that there has been a change in the chemical compositions of the elements in the
adsorbent. For example, carbon and oxygen decreases from 26.71 wt% and 14.36 wt % to 17.89 wt %
and 11.63 wt % respectively. This indicates that the adsorbents still retained it active site even after its
usage while sulphur increased from 16.77wt % to 17.54 wt %. It also suggests that the LC-AC still
contains some amount of H2SO4.
Figure 1: SEM Image of (a) LC-AC- H2SO4 at 300 before (b) LC-AC- H2SO4 at 300 After
Figure 2: EDX Analysis of (a) LC-AC- H2SO4 at 300 before (b) LC-AC- H2SO4 at 300 After
Table 5a: Elemental composition of LC-AC- H2SO4 at 300 (before)
Element C S O Si Ca Cl P Ag Nb N Y Mg Al Na Ti Fe
11
Wt. conc 26.7 16.77 14.36 4.01 2.18 4.49 0.99 5.86 4.97 0.86 4.63 2.52 2.47 2.27 0.001 2.19
%
Element K C S O Si Ca Cl P Ag Nb N Y Mg Al Na Ti Fe
Wt. conc 20.37 17.87 17.54 11.63 6.15 4.74 4.23 3.94 3.22 2.72 1.85 1.81 1.71 1.21 0.67 0.35 0.001
%
12
Figure 3: FTIR Analysis of (a) LC-AC- H2SO4 at 300 before (b) LC-AC- H2SO4 at 300 After
3.2.3 XRD Analysis for LC-AC- H2SO4
Presented in Figure 4a is the XRD analysis of the adsorbent produced without chemical
treatment. The value of 2θ angles displayed between 10° - 70° peaks are ascribed to graphite. The peak
values at 28.18°, 29.16°, 30.91°, 32.67°, 36.88° and 68.02° revealed the presence of graphite, misenite
(K8H6(SO4)7, Kircherite [Na5ca2k]Si6Al6O24(SO4)2.33H2O, Hanksite (Na22 K(SO4)9(CO3)2Cl, Marialite
(Na4Al3Si9O24Cl), Mascagnite (NH4)2SO4 respectively. Therefore, the presence of these compounds
confirmed that the adsorbent is highly active and have been properly activated by sulphuric acid. Hence,
could be used as an adsorbent. To further confirm the presence of the crystal particles after adsorption
process, XRD analysis was carried out as presented in Figure 4b. The value of 2θ angles displayed
between 10° - 70° peaks are ascribed. The peak values at 28.18°, 29.16°, 30.91°, 32.67°, 36.88° and
68.02° suggesting the presences of graphite, misenite (K8H6(SO4)7, Kircherite
[Na5ca2k]Si6Al6O24(SO4)2.33H2O, Hanksite (Na22K(SO4)9(CO3)2Cl, Marialite (Na4Al3Si9O24Cl),
Mascagnite (NH4)2SO4 have shown slight deviation. The peaks values 22.11°, 26.18°, 27.07°, 43.0°,
50.33° and 60.19° reveals the appearance of hexagonal shaped crystal structures such as Marialite
(Na4Al3Si9O24Cl), Bubnovaite K2Na8Ca(SO4)6 and Potassian in the adsorbent.
13
Figure 4: XRD Analysis of (a) LC-AC- H2SO4 at 300 ℃ before (b) LC-AC- H2SO4 at 300 ℃ After
3.2.4 Thermo graphic Analysis of the Adsorbent (LC-AC- H2SO4 at 300 ℃)
Thermal stability of the adsorbent was investigated using thermo-gravimetric analysis (TGA) and
differential thermal analysis (DTA) curves as shown in Figure 5. The TGA curve shows a weight
reduction of 80% (w/w) at a high temperature of between 300 and 450 oC which can be ascribed the
removal of impurities and water from adsorbent. The DTA profile showed a significant endothermic peak
between 200 and 600°C, which is also related to the removal of water and impurities. Stability tends to
occur between 450oC to 887 oC.
14
Figure 5: The TGA-DTA Analysis of Adsorbent
3.2.5 BET Analysis for LC-AC- H2SO4 (Before and After)
The surface area analysis was performed using the multi-point Brunauer-Emmett-Teller plot
method while the pore size and volume were performed by the Barrett-Joyner-Halenda method. The
surface areas for LC-AC- H2SO4 were found to be 495.3 m2/g and 239.1 m2/g before and after use
respectively, this indicates that the adsorbent has a large surface area that could allow for properly
adsorption of contaminants. However, the surface area tends to reduce drastically. This may be due to the
rapid adsorption of the lead, phenol and other untargeted molecules on the surface of the adsorbent. Table
6 shows the BET analysis of the adsorbent both before and after. Also, the pore volume area and pore size
was found to be 0.2769 cc/g and 2.093 nm before use and 0.1219 cc/g and 2.138 nm after use
respectively. A decrease in the pore volume could be an indication that the contaminants tends to adhere
to the surface wall of the pores of the adsorbent. The pore size distribution above 2 nm indicates that the
particles of the adsorbents are nano sized.
15
300℃(before use)
LC-AC- H2SO4 at 239.1 0.1219 2.138
300℃ (After use)
Table 9. Langmuir’s isotherm showed a correlation coefficient (R-squared) of 0.8805 for phenol and
0.439 for lead. This result indicates that for the phenol adsorption process followed Langmuir adsorption
Isotherm. Also, for the Langmuir isotherm the obtained for both phenol and lead showed that the
adsorption process was favorable. Freundlich Adsorption Isotherm showed a correlation coefficient (R-
squared) of 0.8801 for phenol and 0.7173 for lead. This result indicates that the lead adsorption process
followed Freundlich Adsorption Isotherm when compared with that of the Langmuir isotherm.
Furthermore, a value less than 1 obtained for 1/n in phenol adsorption indicates a normal Freundlich
Adsorption Isotherm while a value greater than 1 obtained for lead adsorption indicates a cooperative
adsorption process (Angin, 2014). Also, for Freundlich adsorption Isotherm the value of the obtained
is an indication adsorption capacity. A high gives a higher adsorption capacity. Hence, it could be
stated that for Freundlich isotherms, both phenol and lead was properly adsorbed.
40
35
y = 0.8434x - 60.426 Phenol
30 R² = 0.8805
25
Ce/qe
20
15
10
5
0
70 80 90 100 110 120
Ce (mg/l)
16
50
45
40 y = 33.6x - 6.907
35 R² = 0.4393
30
Ce/qe
25
20 Pb
15
10
5
0
0.5 0.6 0.7 0.8 0.9 1
Ce (mg/L)
1.2
y = -4.4245x + 9.4157
1 R² = 0.8801
0.8
Log qt
0.6
Phenol
0.4
0.2
0
1.85 1.9 1.95 2 2.05 2.1
Log Ce
17
0
-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
-0.2
-0.4
Log qt
-0.6
Pb
-1.2
Log Ce
𝑅2 0.8800 0.7173
4.0 CONCLUSION
This comparative research study employed Luffa Cylindrica (LC-AC) and LCAC - H2SO4 as
adsorbents to treat Lekki phase II underground water by removing phenol and lead in an adsorption
process. It could be concluded that out of the three categories of adsorption conditions, category 1 (the
Agitation rate of 200 rpm, dosage of adsorbent of 200mg, contact time of 30 mins, and temperature of
30℃ ) gave the best percentage removal of the pollutants under preliminary study. And that the highest
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percentage removal of phenol and Lead were found to be 77.87 mg/L and 0.52 mg/L, respectively which
are below the standard regulatory body (Standard of Organization of Nigeria). Hence, the treated Luffa
Cylindrica could significantly reduce the level of phenol and lead in Lekki phase II underground water.
Reference
Adak, A and Pal, A. (2009). Removal kinetics and mechanism for phenol uptake by surfactant-modified
Alumina, Desalination and Water Treatment, 6, 1–3, 269–275
Bazrafshan E, Biglari H and Mahvi A.H (2012). Phenol removal by electrocoagulation process from
aqueous solutions. Journal of Fresenius Environmental Bulletin, 21, (2), 364-371.
Biglari H, Bazrafshan E (2013). Performance evaluation of electrochemical process using iron and
aluminum electrodes in phenol removal from synthetic aqueous environment.
Chakravarti, T. W. (1974). Pore and Solid Diffusion Models for fixed bed adsorbers. Journal for
American Institute of Chemical Engineering, 20, 228-238.
Mohd, A. T., Din, B. H., and Ahmad, A. L.(2009). Batch adsorption of phenol onto physiochemical-
activated coconut shell, Journal of Hazardous Materials, 161, 2-3, 1522–1529.
Karunarathne, H.D. S. S and Amarasinghe, B.M.W. P. K (2013). Fixed bed adsorption column studies
for the removal of aqueous phenol from activated carbon prepared from sugarcane bagasse,
Energy Procedia, 34, 83-90
Yousef, R.I., El-Eswed, B and Al-Muhtaseb A. H. (2011). Adsorption characteristics of natural
zeolites as solid adsorbents for phenol removal from aqueous solutions: Kinetics, mechanism,
and thermodynamics studies. Chem Eng J, 171, (3), 1143-1149.
Voudrias, E., Fytianos, F., & Bozan, E. (2002). Sorption Description isotherms of Dyes from aqueous
solutions and Waste Waters with Different Sorbent materials. The International Journal of
Global Nest, 4(1), 75-83.
Zohre A. S. (2010, March). Experimental study of methylene blue adsroption from aquesod solutions
onto carbon nano tubes. International Journal of Water Resources and Environmental
Engineering, 2, 016-028.
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