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ARTICLE ANALYSIS
Application of Langmuir Isotherm on Adsorption
to Monitor the Uptake of oil using Abura
Sawdust in Seawater medium
Ikenyiri PN, Abowei FMN, Ukpaka CP, Amadi SA
Department of Chemical/Petrochemical Engineering, Rivers State University Port Harcourt
Corresponding author:
Department of Chemical/Petrochemical Engineering,
Rivers State University Port Harcourt,
Email: [email protected]
Article History
Received: 24 October 2018
Accepted: 13 December 2018
Published: January 2019
Citation
Ikenyiri PN, Abowei FMN, Ukpaka CP, Amadi SA. Application of Langmuir Isotherm on Adsorption to Monitor the Uptake of oil using
Abura Sawdust in Seawater medium. Science & Technology, 2019, 5, 30-37
Publication License
This work is licensed under a Creative Commons Attribution 4.0 International License.
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Article is recommended to print as color digital version in recycled paper.
ABSTRACT
This research was conducted to examine the significance of the application of Langmuir isotherm on the rate of adsorption to
monitor, predict and simulate the uptake of soil using Abura wood sawdust in sea water medium. The Langmuir isotherm concepts
were adopted to determine the amount of the crude oil absorbed and the influence of the absorbent. The result obtained revealed
that increase in reduction in crude oil was observed with increase in reduction in crude oil was observed with increase in dosage of
the Abura word sawdust and the possible elements identified in terms of character are 𝐶𝑎 𝑘, 𝑠, 𝑝, 𝑆𝑖, 𝑆𝑏, 𝑆𝑛, 𝐶𝑟, 𝑍𝑛, 𝑃𝑏, 𝑀𝑜, 𝑁𝑏, 𝑒𝑡𝑐.As
well as the morphology of the Abura wood sawdust species well described in this paper. The effect of time on the concentration of
ANALYSIS VOL. 5, 2019
ISSN 2394–3750
EISSN
2394–3769
SCIENCE TECHNOLOGY
&
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ARTICLE ANALYSIS
the Langmuir parameter were evaluated as the result obtained also revealed decrease with increase in weight of adsorbent used and
increase with increase in time. Finally, the research work demonstrates the significance of the Langmuir isotherm concept of
monitoring, predicting and simulating the rate of crude oil adsorption using Abura wood sawdust in seawater medium.
Key words Application, Langmuir isotherm, adsorption, monitor, crude oil, abura sawdust, seawater medium
1. INTRODUCTION
It is of great importance to explore the capability of natural adsorbent (sawdust) for the adsorption process in clean - up operations
of oil spilled environment. A better understanding of the mechanism of adsorption of crude oil on this adsorbent (sawdust
materials) will require investigation into the particle size of the adsorbent and the critical factors that affect its rate of adsorption in
terms of adsorbent characteristics (adsorption capacity) will be valuable in ascertaining the suitability or otherwise of these materials
for oil spill cleanup. It will also involve the determination of the physical and chemical properties of the sawdust. These will entail
carrying out experimental works to determine the rate of adsorption.
This work shall explore different kinds of locally available adsorbents and examine the challenges associated with their use for
this process. The study will include examining their characteristics, evaluating their effectiveness and feasibility for application as
remediation materials. Suggestions will be made based on findings from experimental results and appropriate adsorption models
will be developed.
Crude oil is made up of hydrocarbons and other compounds. The physical and chemical properties of petroleum oil change
progressively, which means these physico-chemical changes facilitate oil disintegration in aquatic environment [1, 15]. This
disintegration process is referred to as weathering, which includes spreading, evaporation, dissolution, oxidation, biodegradation,
sedimentation, dispersion, agglomeration, adsorption into suspended materials, etc. To some extent the speed with which
weathering showcases depends on the location where petroleum was released, that is, water surface or subsurface [2]. Spilled oil has
an unpleasant taste and smell, and results in environmental nuisance, generally destroys birds and life in the sea [3]. Consequently,
diverse processes have been created to take away oil from contaminated areas by use of man- made device/materials such as:
booms, dispersers and skimmers, oil water separator or the use of assorted kinds of sorbent material [4].Although the main
constraint of the use of these techniques is their expense and not achieving complete uptake of contaminant via adsorption [5]. Oil
sorbent materials can be separated into three major classes: organic synthetic products (polyethylene, polypropylene etc), inorganic
mineral products (sand, clay, volcanic ash etc) and natural organic vegetable products (sawdust, hay, peat etc) [6]. A certain number
of studies indicate that sawdust sorbents have ability for high oil sorption capacity and low water uptake when compared to
materials which can be used for this purpose. And as a result sawdust sorbents could be a considerable material for oil recovery on
water surface. Previous studies have shown that mechanical recovery is the transfer of oil from the spilled area to some storage
materials in form of oil sorbents or skimmers in a short while [7]. Recent evaluations by several studies show that porous and
natural adsorbent material have been used to conduct investigation into crude oil spill cleanup using different natural, synthetic
and mineral sorbents [8, 16]. Some of these materials, which may be oleophilic, hydrophobic and floatable on water can showcase
selective absorption of hydrocarbons [9]. Frequently used sorbents are sawdust sorbents made of woody materials [10]. They exhibit
good olephilic, hydrophobic and biodegradability features [11]. A biodegradable material with exceptional adsorption attributes
would be beneficial in this aspect. A number of investigations have been made on natural sorbents for use in oil-spill cleanup, for
example, cotton [12], these material could be splendid oil sorbent due to their hydrophobic and oliophilic character. Baltrenas &
Vaisis, [13] also explored the thermal alteration influence on sorption qualities of bio-sorbents. Cellulosic sorbent that has been
chemically treated such as Sugarcane bagasse was esterified with acetic anhydride using N-bromosuccinimide as a catalyst under
placid conditions [14].
2. MATERIALS AND METHODS
Experiment on salt water
Firstly, 100ml of the salt water sample was measured into a beaker then 5ml of the crude oil was measured and poured into the
beaker with the salt water to contaminate it. Thereafter, the wood sawdust sample was introduced into the mixture to effect
remediation.
The initial concentration Co (mg/l) of the contaminated water was taken with a UV Spectrophotometer before applying the
adsorbent (sawdust).
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Thereafter, this was repeated for each sample of the four wood sawdust samples selected using the already weighed wood
sawdust samples 10g, 20g, 30g, 40g, 50g of each at time interval of 1hr, 2hrs and 3hrs respectively. This was done for each of the
wood sample. After the batch adsorption processes the oil/ water filtered sample was sent to a spectrophotometer to determine the
final oil concentration Ce(mg/l) of the contaminated oil/saltwater mixture.
Computational Procedure
The amount of the crude oil adsorbed and percentage of removal of crude oil by the adsorbent were calculated by applying the two
equation below:
% removal =
Where q is the amount of crude oil adsorbed by the sorbent (mg/g) Co is the initial crude oil concentration put in contact with the
adsorbent (mg/l) Ce is the final concentration (mg/l) after the batch adsorption procedure, V is the volume of aqueous solution (L)
that the sum of volume of crude oil and water in the plastic container (L) put in content with the adsorbent and M is the mass (g) of
the adsorbent.
Application of Langmuir Adsorption Isotherm Equation
Langmuir Adsorption Isotherm Equation was employed to evaluate the adsorption process;
qe =(Co − Ce)V
M
Where qe= Oil Adsorption Capacity in mg/g
Co = Initial concentration In mg/L (69.25mg/L)
Ce = Final Concentration In mg/L
V= Volume of crude oil solution in L (100ml)
M= mass of Adsorbent in gram
Figure 1 Experimental Set Up for the Batch Adsorption Process
Vxm
CCq eo
100x
C
CeC
o
o
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Figure 2 Energy Dispersive X-ray Fluorescence (EDXRF) Equipment
Figure 3 Scanning electronic microscope(SEM)
3. RESULTS AND DISCUSSION
Adsorption test was also carried out on seawater to monitor the uptake of oil using sawdust; the Langmuir isotherm was also
applied to evaluate the level of adsorption.
The plot of 𝐶𝑒
𝑞𝑒 versus 𝐶𝑒 are presented thus:
(a)
y = 8.7252x - 146.34R² = 0.9994
0
20
40
60
80
100
120
140
160
28 29 30 31 32 33
Ce
/qe
(g/
L)
Ce(mg/L)
10g ABURA
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(b)
(c)
(d)
y = 17x - 258.72R² = 0.8824
136
138
140
142
144
146
148
150
152
154
23.2 23.4 23.6 23.8 24 24.2 24.4
Ce
/qe
(g/
L)
Ce (mg/L)
20g ABURA
y = 50.05x - 953.48R² = 0.7527
0
50
100
150
200
250
21.8 22 22.2 22.4 22.6 22.8 23 23.2 23.4 23.6
Ce
/qe
(g/
L)
Ce (mg/L)
30g ABURA
y = 11.112x - 0.0137R² = 1
210
215
220
225
230
235
240
19 19.5 20 20.5 21 21.5
Ce
/qe
(g/
L)
Ce (mg/L)
40g ABURA
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(e)
Figure 4(a), (b), (c), (d), (e): A plot of Langmuir Isotherm Ce/qe versus for Abura
Figure 4(a),(b),(c),(d) and (e) illustrates the relationship between the Langmuir isotherm functional parameter of Ce/qe and the
Ce value of the various wood sawdust sample species. The equation of line for 10g of Abura is given as y = 8.7252-146.34 with the
square root of the best fit given as R2=0.9994 for Figure 4(a).Considering Figure 4 (b),it is shown that the equation of the line is
given as y = 1.7x-2.58.72 with the square root of the best fit as R2=0.8824(20g of Abura used for the analysis).For 30g of Abura we
have the equation of the line as y=50.5x- 953.48 with the square of the best fit R 2=0.7527.For 40g of Abura specie we have the
equation of the line as y=11.112x-0.0137 with the square root of the best fit R2=1,whereas for 50g of Abura it is seen that the
equation of the line is given as y=325x-8E-11 with the square root of the best fit given as R2=1.The variation in the Langmuir
isotherm functional parameter of Ce/qe can be attributed to the variation in the concentration of Ce. The results obtained revealed
that the rate of adsorption is more effective with increase in concentration of the wood sawdust dosage.
Based on the evaluation made using Langmuir adsorption isotherm and the adsorption of crude oil using selected wood sawdust
the R 2 value was significant which depicts that mahogany has high sorption capacity. Mahogany sample could be recommended for
remediation process.
Table 1 Abura Adsorption Experiment with seawater
LANGMUIR PAREMETERS
(mg/g)
Weight of Adsorbent Used(M)
(grams)
Conc.(mg/l)/Time
1Hr 2Hrs 3Hrs
𝑞𝑒 10 0.39 0.39 0.43
20 0.24 0.24 0.24
30 0.16 0.16 0.17
40 0.13 0.13 0.13
50 0.11 0.11 0.11
𝐶𝑒 10 32.2 32.0 28.4
20 23.8 24.2 23.4
30 23.4 22.3 22.0
40 19.4 21.2 19.8
50 18.9 18.4 17.9
𝐶𝑒
𝑞𝑒
10 82.56 82.05 66.05
20 99.17 100.83 97.5
30 146.25 139.38 129.41
40 149.23 163.08 152.31
50 171.82 167.27 162.73
y = 12.5x - 8E-11R² = 1
222
224
226
228
230
232
234
236
238
17.8 18 18.2 18.4 18.6 18.8 19
Ce
/qe
(g/
L)
Ce (mg/L)
50g ABURA
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Characterization of Abura Sample using XRF and EDXRF
For the Abura sample, the quantity of the elements present in terms of intensity and energy content is low but present in traces. The
same elements found in the other samples are also seen in Abura sample. Majorly, Ca, K, S, P. Si, Sb, Sn, Cr, Zn, Pb, etc are seen in
small quantities and traces too. The rest of the elements are having zero intensity versus energy content values. Quantitatively, the
EDXRF test profile described the presence of the elements, Mo, Nb, Ca, K, Z, which were prevalent than Si, S, Rb, Pb, Zn, Cu, and P
whereas the rest had zero content. Figure 4.19 presents the intensity versus the energy in XRF and EDXRF analyzer and the following
elements were identified.
Energy (0)
Figure 5 Plot of Intensity (c/s) against Energy (0) for Abura before Contamination
Figure 6(a) SEM pictures –Morphology of the raw wood sawdust before contamination with Crude oil
Figure 6(b) SEM pictures –Morphology of the raw wood sawdust contaminated with Crude oil
4. CONCLUSION
The following conclusion was drawn from the research work, such as;
1. The Abura wood sawdust is a good adsorbent, which can be used in bioadsorption processes.
2. It is observed that the presence of the microorganism made it possible for increase in the rate of degradation of crude oil as well
as increases the rate of adsorption in the process.
3. The Langmuir isotherm concept is a mechanism adapted to monitory, predict and simulate the rate of adsorption of the Abura
wood sawdust in terms of its functional parameters of 𝑔𝑒𝐶𝑎 and 𝐶𝑎/𝑔𝑒 ration of the process.
4. The relationship of the intensity and the energy in XF and EDXRF was considered to identify the possible elements process.
Intensity (c/s)
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5. The morphology of the raw Abura wood sawdust and the mixture of crude oil and the Abura wood sawdust were shown in this
research wood and shape nature well defined.
RREEFFEERREENNCCEE
1. Adebajo, M. O. & Forest, R.L., (2004). Infrared and C MADS
nuclear magnetic resonance spectroscopic study of
acetylation of Cotton; Spectrochim. Acta. A, 60 (1), 449-453.
2. Angelova D.I. Uzunov,S. Uzunova, A. Gigova. (2011). Kinetics
of oil and oil products adsorption by carbonized rice husks.
Chemical Engineering journal Elsevier, 172:306-311.
3. Atlas, R.M & Bartha R. (1972). Degradation and
mineralization of petroleum in seawater: limitation by
nitrogen and phosphorus. Biotechnol. Bioeng. 14:309-318.
4. Ayoob S, Gupta AK. (2008). Insights into isotherm making in
the sorptive removal of fluoride from drinking water. Journal
of hazard material 152,3, 976-85
5. Baltrenas, P. & Vaisis V. (2005). Experimental investigation of
thermal modification influence on sorption qualities of
biosorbents, J. Environ.Eng. Landscape Management, 13(1),3-
8
6. Banerjee S.S., Joshi,M.V., & Jayaram, R.V (2006). Treatment of
oil spill by sorption technique using fatty acid grafted
sawdust. Chemosphere, 64, 6 1026-1031.
7. Cojocaru, C; Macoveanu, M, & Cretescu I. (2011). Peat-based
sorbents for the removal of oil spills from water surface
:Application of artificial neural network modeling, colloids
and surfaces Aphysiochem Eng. Asp, 384(1-3),675-684
8. Deschamps, G., Caruel, H., Borredon, M. E., Bonnin, C., &
Vignoles, C.; (2003). Oil Removal from Water by Selective
Sorption on Hydrophobic Cotton Fibres. 1. Study of Sorption
Properties and Comparison with other Cotton Fiber-Based
Sorbents., Environ. Sci Tech., 37 (5), 1013-1015.
9. Dulman V. & Cucu-man S. M. (2009). Sorption of some
textile dyes by beech wood sawdust. Journal of Hazardous
materials, 162:1457-1464
10. Edyta, W.J., Jan, H., Piotr, P., (2003). Investigation of Olephilic
Nature of Straw Sorbent Conditioned in Water., Spill Sci.
Tech. B., 8 (5-6), 561-564.
11. Garg, V. K., Moirangthem, A., Kumar, R. & Gupta, R. (2004).
Basic Dye (Methylene Blue) Removal from Simulated
Wastewater by Adsorption Using Indian Rosewood Sawdust:
Timer Industry Waste. Dyes Pigents, 63 (3), 243-250.
12. Horisawa, S.M. Sunagawa, Y., Tamai, Y. Matsuoka, T. Miura,
M. & Terazawa. (1999). Biodegradation of non-
lignocellulosic substance II: Physical and Chemical properties
of sawdust before and after use as artificial soil. Journal of
wood science. 45(6): 492-497
13. Ikenyiri P. N. & Ukpaka C.P. (2014). Mathematical model to
monitor the inhibiting effect of pH on the adsorption of
crude oil in bioremediation. Scholars research library,
Archives of Applied science research, 6(6), 100-110
14. Ikenyiri P. N. & Ukpaka C.P. (2016) Overview on the effect of
particle size on the performance of wood based adsorbent.
Journal of Chemical Engineering and process Technology.
7(5), 230-239.
15. Gnanasangeetha D, Sarala Thambavani D. Construe of Five
Green Adsorbent for Water Remediation with One Chemical
Adsorbent. Discovery, 2016, 52(252), 2433-2441
16. Rajeshwar Man Shrestha. Adsorption Isotherms and Kinetics
Studies of Ni(II) Adsorption from Aqueous Solution onto
Activated Carbon Prepared from Lapsi Seed Stone. Indian
Journal of Engineering, 2018, 15, 291-298
