ST 15267
ST 15267
ST 15267
(2015) 12:28472856
DOI 10.1007/s13762-014-0654-4
ORIGINAL PAPER
Received: 25 January 2014 / Revised: 6 May 2014 / Accepted: 12 July 2014 / Published online: 25 July 2014
Islamic Azad University (IAU) 2014
Introduction
Desulfurization of diesel fuel is gaining worldwide interest
among the researchers. This is due to stern regulations and
fuel specifications adopted in many countries for checking
environmental pollution caused by automobile exhaust
gases (Zhao et al. 2010). The regulations projected that the
upper limit of sulfur concentration in diesel can be reduced
from 500 to 15 mg L-1 in USA, 5010 mg L-1 in EU,
3010 mg L-1 in Korea (Park et al. 2008), and
350 mg L-1 in India. Low-sulfur fuel finds its application
in fuel cell system. Fuel cell is one of the most potential
and suitable energy conversion devices for generating
electricity for both mobile vehicles and stationary power
plants including residential applications (Song 2002). In
hydrocarbon-based fuel cell system, the catalysts used such
as reforming catalysts and watergasshift catalysts are
poisoned by the H2S produced. For automotive and military use, diesel is the ideal fuel as it has high energy
density, readily available, and safe for transportation and
storage. But the commercial diesel fuel usually contains
certain refractory sulfur compounds (Sarda et al. 2012) viz.
benzothiophene (BT), dibenzothiophene (DBT), and 4,6dimethyldibenzothiophene (DMDBT), which causes environmental pollution. In an internal combustion engine,
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Material development
The adsorbent used in this study was prepared by chemical
impregnation of coconut coir waste using H3PO4. The
waste was first cleansed with distilled water to get rid of
dirt and dried in a hot air oven at 383 K for 5 h. This is
followed by H3PO4 impregnation at 373 K for 1 h in a hot
plate. The treated waste is then carbonized at 873 K for 1 h
in a muffle furnace under nitrogen atmosphere. Finally, the
carbonized product is washed with distilled water until the
pH of the washings reached *7. It is evident that lingocellulosic materials are preferred for chemical activation
(Jagtoyen and Derbyshire 1993), particularly with H3PO4,
and as the precursor has cellulosic component; H3PO4 has
been selected for the impregnation. The idea of activation
is to augment the adsorption efficiency in addition to carbonizing the coconut coir waste. The adsorbent thus produced was kept in an oven at 383 K for 6 h to get rid of any
moisture trapped within the adsorbent pores. The adsorbent
was finely ground for use in adsorption and stored in desiccator till further use. The adsorbent thus developed is
referred to as chemically impregnated coconut coir waste
and henceforth abbreviated as CICCW.
The percentage of carbon yield of the adsorbent was
calculated by the following equation:
Carbon yield (%
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nHCl
VB
B VB HCLVHCl NaOHVNaOH
nB
Va
VB
Va
where nCSF refers to the moles of carbon surface functionalities on the surface of the carbon that reacts with the
base during the mixing step; [B] and VB are the concentration and volume of the reaction base; Va is the volume of
the aliquots taken from VB; [HCl] and VHCl are the concentration and volume of the acid added to the aliquot.
Adsorption assay
The experiments were carried out in a batch system by
shaking 20 mL feed diesel (sulfur concentration
2,050 mg L-1) with pre-weighed (0.21.2 g) dried amount
of adsorbent in 100 mL Erlenmeyer flask (with stopper)
under controlled parameters of adsorption to study the
effect of adsorbent dose, temperature, contact time, and
adsorption isotherm. The samples were withdrawn at preset
Co Ce
100
Co
qe ab a
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Ultimate analysis or
microanalysis (wt% dry
ash-free basis)
Moisture
20.76
Carbon
Volatile matter
Ash
21.78
3.59
Hydrogen
Nitrogen
3.28
0.98
Fixed carbon
53.87
Sulfur
0.00
Functional groups
55.53
nCSF
(mmol g-1)
1.160
Lactonic
0.057
Phenolic
0.403
b) Basic groups
1.620
1,207.93
BET
1,254.67
BJH
Adsorption cumulative
848.05
Desorption cumulative
1,071.67
1.02
3.24
BJH adsorption
BJH desorption
4.45
3.89
53.63
33.35
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(Bhattacharya and Venkobachar 1984) (qe vs. t1/2) is generally used to depict whether the adsorption process is
controlled by an intra-particle diffusion model (Allen et al.
1989). A straight line of the plot reveals the intra-particle
diffusion behavior of adsorption. Nevertheless, the data in
the present study do not exhibit a linear plot over the whole
range of time, demonstrating that more than one step is
controlling the adsorption process. The plot of qe versus t1/2
(Fig. 6) for sulfur adsorption from feed diesel onto CICCW
at T = 293 K reveals that the adsorption of sulfur onto
CICCW is controlled by external mass transfer followed by
intra-particle diffusion. It can be inferred from Weber
Morris plot of CICCW that at the start of the adsorption
process the diffusion of sulfur molecules from the solution
to the external surface of the adsorbent is the fastest, which
can be ascribed to the fast utilization of readily available
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1/2
where t
is the time for the half adsorption; ro is
the diameter of the adsorbent particles, i.e., 33.354 9
10-4 cm; and D is the pore diffusion constant, cm2 s-1.
The value of the pore diffusion coefficient of sulfur was
found 6.18 9 10-11 cm2 s-1, indicating pore diffusion is
not significant. To have knowledge of the mode of
diffusion, the transport number was calculated from Eq. 9
(Ahmed et al. 2014)
log Qt =Q1 log k n log t
Adsorption isotherm
Adsorption isotherm is imperative for the illustration of the
interaction of the active sites of the adsorbent with the
adsorbate and is significant in adsorbent optimization. The
experimental data in this study are correlated with Langmuir and Freundlich isotherm models. An important step in
isotherm modeling is to analysis and fit the isotherm data to
different isotherm models to well depict the adsorption
process. The linear regression analysis of Freundlich
adsorption parameters shows a significantly high R2 value
(0.977) representing a good fit to the model. However, the
linear regression coefficient value shows that the Langmuir
isotherm fits the experimental data, but Langmuir isotherm
is derived with the assumption that the surface of the
adsorbent is homogeneous, which contradicts with the
highly heterogeneous surface of CICCW as shown in
DG DH TDS
10
11
DH DS
RT
R
12
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Duration (h)/
amount (ml)
Unit cost
(USD)
Power
rating
(KWh)
Price
(USD)
Cost of drying at
oven
0.0664
1.5
0.498
Cost of
impregnation at
hot plate
Cost of activation
at furnace
0.0664
1.2
0.079
0.0664
2.5
0.166
Cost of final
drying at oven
0.0664
1.5
0.597
500
0.0168
8.4
Cost of H3PO4
used
Net cost
Overhead cost
(10 % of net
cost)
Total cost
9.74
0.974
10.714
Conclusion
The present study demonstrates that chemically impregnated coconut coir waste (CICCW) can be effectively used
for the desulfurization of feed diesel. Extensive characterization of the adsorbent revealed that it has most of the
desirable qualities of a good low-cost adsorbent. An optimum adsorbent dose of 1 g and optimum temperature of
293 K show maximum adsorption. Equilibrium between the
feed diesel and the adsorbent almost attains in 3 h. Multistage diffusion model explains the process of adsorption.
External mass transfer controls the adsorption of sulfur at
initial phase followed by intra-particle diffusion. The
mechanism of adsorption of sulfur onto CICCW follows a
Fickian mechanism of diffusion. Freundlich model best fits
the experimental data (R2 = 0.9907), signifying heterogeneous adsorption and multilayer coverage of the adsorbate
(sulfur) on the surface of CICCW. Thermodynamic data
revealed the exothermic nature of the adsorption process,
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