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Adsorption Process of Sulfur Removal from Diesel Oil Using Sorbent Materials

Article · January 2013

DOI: 10.7763/JOCET.2013.V1.16

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 Journal of Clean Energy Technologies, Vol. 1, No. 1, January 2013

Adsorption Process of Sulfur Removal from Diesel Oil

Using Sorbent Materials
Isam A. H. Al Zubaidy, Fatma Bin Tarsh, Noora Naif Darwish, Balsam Sweidan Sana Abdul Majeed,
Aysha Al Sharafi, and Lamis Abu Chacra

desulfurization of gasoline. The adsorption involves C-S

Abstract—The removal of organo-sulfur compounds (ORS) bond cleavage as evidenced by the formation of ethyl
from diesel fuel is an important aspect of all countries to benzene from benzothiophene in the absence of hydrogen
reduce air pollution by reducing the emission of toxic gases gas [5].
such as sulfur oxides and other polluted materials. One of the
This work will focus on the adsorption desulfurization
easily and fast method to remove sulfur from diesel oil is the
adsorption desulfurization process. Adsorption-desulfurization process of local diesel oil using activated carbon.
process of diesel fuel was proposed and examined. Local diesel
fuel of 410 ppm sulfur content was treated with commercial
activated carbon and carbonized date palm kernel powder at II. EXPERIMENTAL WORK
room temperature in batch work. The contact time were
examined and chosen. The addition of activated carbon caused A. Materials
reduction in sulfur content by more than 54% of the original Diesel oil was collected locally from one petrol station in
sulfur content value while carbonized date palm kernel powder Sharjah/ UAE. The main physical properties of the diesel oil
without any activation process showed lower performance
toward sulfur recovery. This high reduction will definitely are shown in Table I. The heavy metals presents in diesel oil
improve the emission quality and reduce the harmful effect of are shown in Table II.
the combustion process of diesel fuel to the environment.
TABLE I: PHYSICAL PROPERTIES OF DIESEL FUEL
Index Terms—Activated carbon, adsorption process, Properties Method Diesel oil
desulfurization process, diesel oil. Specific gravity, 15/15 oC ASTM D 1298 0.8426
API gravity ASTM D 1298 36.43
Water content, vol% ASTM D 96 Nil
I. INTRODUCTION
Ash content, wt% ASTM D 582 0.0247
Increasing concerns on the air quality regulation have
Aniline point, oC ASTM D 611 78
urged the petroleum refining industry to produce cleaner
Diesel index ASTM D 611 62.8
products by removing heteroatoms containing molecules
from their major products, diesel and gasoline [1]. Cetane index Ref. 6 53.9
Although extensive efforts have been made to decrease the Calorific value, joule/g ASTM D 240 46,000
sulfur contents of diesel oil, the regulation on the fuel Flash point, oC ASTM D 93 85
quality is going to be tightened faster than expected. Fruit Sulfur content, µg/g ASTM D 7220-06 410
kernel activated charcoal in batch process was used for
desulfurization process [2]. The results revealed the
potential for adsorbent as a low cost adsorbent and have a TABLE II: HEAVY METALS IN DIESEL OIL
higher capacity for sulfur at gas oil concentrations than in Metal Units Diesel Oil Treated diesel oil
kerosene. Naphtha desulfurization by adsorption was Aluminum(Al) ppm < 9.1 10.6
studied [3]. They found that 13X zeolite have the highest Iron(Fe) ppm < 1.2 1.2
capacity for sulfur at low concentration range and activated Lead(Pb) ppm < 1.0 0.1
carbon at higher concentration range. The hydro- Barium(Ba) ppm < 3.0 0
desulfurized straight run gas oil having less than 50 ppm Calcium (Ca) ppm 1.3 10.4
sulfur was adsorptivity treated with activated carbon fiber to Chlorine (Cl) ppm 25.7 28.1
attain the ultra-low sulfur gas oil having less than 10 ppm
Chromium(Cr) ppm < 1.0 < 1.0
sulfur [1]. Deep desulphurization of diesel fuel was studied
Copper(Cu) ppm 1.7 0.3
[4]. The hydro-desulfurized straight run gas oil with 50 ppm
Manganese(Mn) ppm < 1.0 < 1.0
sulfur was treated with activated carbon fiber to a low sulfur
content of less than 10 ppm. The adsorptive Molybdenum(Mo) ppm < 0.7 0
desulphurization of gasoline over nickel based adsorbent, Nickel(Ni) ppm < 1.0 0
showed high capacity and selectivity for the adsorptive Phosphorous(P) ppm 6.3 7.5
Silicon(Si) ppm 16.2 41.1
Manuscript received December 4, 2012; revised January 8, 2013. Potassium (K) ppm < 2.2 < 2.2
Isam A.H. Al Zubaidy, Fatma Bin Tarsh, Noora Naif Darwish, Balsam Vanadium(V) ppm < 1.0 < 1.0
Sweidan, Sana Abdul Majeed, Aysha Al Sharafi, and Lamis AbuChacra are
with Chemical Engineering Department/ College of Engineering, American Zinc(Zn) ppm < 1.0 0.1
University of Sharjah/ UAE (email: [email protected]).

DOI: 10.7763/JOCET.2013.V1.16 66
 Journal of Clean Energy Technologies, Vol. 1, No. 1, January 2013

The physical properties showed sulfur content of 410 III. RESULT AND DISCUSSION
ppm and high value of diesel index and cetane index. The high value of cetane index indicates that this type of
Commercial activated carbon (NORIT, product number diesel has good ignition quality and contain high amount of
C3445, Sigma Aldrich) was used. The Norit particles, (size paraffin’s. Cetane index of 53.9 indicates that this type of
100 and 400-mesh (37 to 149 micron)), were used after diesel has a short delay time that allows more time for the
heating at 105 oC for two hours prior using. Helium with fuel combustion process to be completed. Hence, higher
very high purity was also used for sulfur measurements. speed diesel engines operate more effectively with higher
Date palm kernels were collected, washed with tap water, cetane index fuels. This will result in a smoother running
distilled water to be free from dirt and allows drying in an and better performing engine with more power and fewer
oven at 100 oC for 24 hours, grinded and sieved. Fractions harmful emissions. The contact time was fixed as two hours
of maximum size of 710 micrometer and lower were as shown in Fig. 1.
collected and kept in close jar. The amount of commercial activated carbon was varied
B. Thermally Activated between 0-10%. The sulfur content was plotted vs. amount
Date palm kernel powder was placed in steel tube with of commercial activated carbon as shown in Fig. 2. The
small hole at the top for the ventilation of the gases curve showed continuous decrease of sulfur content.
produced during carbonization and heated in a muffle
furnace. The tubes were heated to 650 oC and maintained at 450

Amount of sulfur, µg/g

the selected temperature for 3 hrs. It is allowed to cool and 400
then grinded using mortar. The powder was sieved using 350
sieve shaker to collect particles of an average size of 710 300
250
micrometer and lower. The sample was kept in close jar.
200
The sample was allow to heat to 105 oC for 1 hr prior using
150
for any test.
100
C. Method 50
0
Diesel oil was mixed with 5 % by mass commercial 0 5 10
activated carbon for 1-5 hrs using flask shaker at a rate of % by mass comercial of activated carbon
500 oscillations /min at room temperature. The resulting
Fig. 2. Amount of commercial activated carbon as
solution was filtered to separate the solid adsorbent material adsorbent with sulfur content at room temperature and
from filtrate. The filtrate was analyzed for sulfur content. contact time of two hours
This step is to choose the proper contact time that gives
highest sulfur removal. The sulfur content was plotted with The sulfur breakthrough curve (Fig. 3) showed that the
time (Fig. 1) and it was found that the shaking for two hours sulfur recovery was 12.68% by adding 1% sorbent material
is enough to get reasonable sulfur removal. and this removal was increased to about 38.78% by adding
5% sorbent material and further increase to 54.98% by
increasing the activated carbon to 10% of the diesel oil
450
400
quantity. This represents a very important improvement in
350
physical properties and emitted gases to the atmosphere.
sulfur content, µg/g

300 This means that the sulfur dioxide emitted to the atmosphere
250 was reduced to the half. Further work is ongoing to use
200 active carbon from different local biomass materials base as
150 well as to make this process as an environmentally friendly
100 process.
50
0 60
0 1 2 3
Time, hr 50
% sulfur removal

Fig. 1. amount of sulfur wirh contact time using 40

commercial activated carbon 30

0-10% by mass of commercial activated carbon were 20

mixed with diesel oil for two hours with continuous mixing 10
and then subjected to filtration process. The filtrate was 0
analyzed for sulfur content. The sulfur content and metal 0 2 4 6 8 10 12
content was measured using Spectro iQ ii X-ray by mass commercial activated carbon
fluorescence analyzer tool which works according to
Fig. 3. Sulfur breakthrough curve with amount of
IP532/05 and ASTM D 7220-06. adsorbent
Samples of diesel oil and treated oil were analyzed for
other physical properties. All physical properties were The treated oil with 5% activated carbon was analyzed
conducted according to ASTM standard methods. for metal content as shown in Table II.

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 Journal of Clean Energy Technologies, Vol. 1, No. 1, January 2013

Carbonized material from date palm kernel was also used amount of sulfur dioxide emitted to the atmosphere.
but without activation for desulfurization process of diesel
fuel as shown in Fig. 4. ACKNOWLEDGMENT
The authors would like to thank the American University
500 of Sharjah/UAE for providing the equipment to perform this
work.
amount of sulfur, µg/g

450
REFERENCES
400
[1] S. Yosuke, S. Kazuom, C. Ki-Hyouk, K. Yozo, and M. Isao., “Two-
step adsorption process for deep desulphurization of diesel oil,” Fuel,
350 vol. 84, issues 7-8, pp. 903-910, 2005.
[2] M. H. R. Gamil and M. M. Nasser, “Desulphurization of Um Al Nar
300 refinery straight run kerosene and gas oil using pal fruit kernel
activated charcoal: a locally made adsorbent,” Adsorption science and
250 technology, vol. 15, no. 4, pp. 311-321, 1997.
0 2 4 6 8 [3] S. H. Abu baker Salem, “Naphtha desulphurization by adsorption,”
Ind. Eng. Chem. Res, vol. 33, pp. 336-340, 1994.
% by mass carbonized date palm kernel powder [4] Y. Toida, “Adsorption desulphurization agent for desulphurizing
petroleum fraction and desulphurization method using the same,”
USA Patent, 20050173297, 2005.
Fig. 4. Adsorption desulfurization process using [5] X. L. Ma, M. Sprague, and C. Song, “Deep desulphurization of
carbonized date palm kernel powder gasoline by selective adsorption over Nickel-based adsorbent for fuel
cell application,” Ind. Eng. Chem. Res, vol. 44, no. 15, pp. 5768-5775,
2005.
[6] W. J. Pierre, T. Pierre, and F. J. Pierre, “Petroleum products, Refining,
It was found that this material was able to reduce sulfur Petroleum,” Institut fran̨cais du pétrole publications, vol. 1, 1995.
content by 34.15% with the addition of 6% by mass sorbent
material. This value is lower than sulfur removal using
activated carbon. Isam Al Zubaidy earned BSc in Chemical
Engineering from Baghdad University/ Iraq in 1976
and MSc in Chemical and Petroleum Processing
Engineering from Herriot- Watt University,
IV. CONCLUSION Scotland-UK 1981 with thesis titled “Kinetic
studies of the Desulfurization of thiophene in the
The desulfurization of diesel oil by adsorption process presence of desulfurized gas-oil over a cobalt-
using activated carbon showed a reduction in the amount of molybdate catalyst”. He worked with Institute of
sulfur by more than half of the original amount of sulfur. Technology and College of Engineering in
Baghdad/ Iraq from 1977-1998 as assistant professor. He worked as
The sulfur content was reduced from 410 ppm to 251 ppm technical manager in waste oil recycling in UAE for the period 1999-2000.
using 5% adsorbent material and further reduction and up to He joined the American University of Sharjah/UAE since 2000. His areas
184.6 ppm using 10% sorbent material. This will definitely of research interest is the waste oil recycling, oil spill to soil and water, oil
reduce the environmental impact of using diesel fuel in sludge treatment, desulfurization process of oil products, and corrosion. He
is the author of more than 35 published papers and many textbooks and
buses and other heavy duty machineries by reducing the handouts for chemical engineering students.

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