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Kinetic studies and evaluation of nanoporous carbon for desulfurization of fuels

coupled with GC- SCD detection method

Conference Paper · September 2013

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 Kinetic studies and evaluation of nanoporous carbon for
desulfurization of fuels coupled with GC- SCD detection
method
Khalid R. Alhooshani, Abdullah A. Al Swat; Tawfik A. Saleh, Mohammad N.
Siddiqui
Department of Chemistry
King Fahd University of Petroleum & Minerals
Dhahran 31261,
Saudi Arabia
* Previous literature reports the desulfurization activity by
E-mail: hooshani@kfupm.edu.sa
Introduction
Due to its elevated presence in crude oil and its potential to cause
undesired ecological reactions, it is imperative to develop a feasible
means by which sulfur can be extracted. For example, sulfur
compounds left in fuels often lead to the emission of sulfur oxide
gases which react with water in the atmosphere to form sulfates and
acid rain which then in turn damages buildings, destroys automotive
paint finishes, acidifies soil, and water bodies, contributes to
formation of atmospheric particulates, which ultimately leads to
water pollution, global warming, loss of forests, and various other
ecosystems. Additionally, several corrosion problems in pipelines,
pumping, and refining equipment may occur as a result of sulfur-
contents emission. Sulfur emissions also cause deleterious effects on
humans, such as respiratory illnesses, aggravated heart disease, or
induced trigger asthma.
In many countries worldwide, environmental regulations have
been introduced as an attempt to reduce the sulfur content of diesel
fuel to ultra-low levels (10 ppm) with the ultimate goal of lowering
harmful exhaust emissions and improving air quality. As a result of
the aforementioned environmental regulations, there have been
several reports successfully minimizing sulfur content in
transportation fuels to <10 ppm. For instance, of the various
desulfurization techniques, hydrodesulfurization (HDS), oxidative
desulfurization, bio-desulfurization, and adsorptive desulfurization
are being investigated for their ability to produce clean fuels. One of
the current industrial methods for removal of sulfur from fuels is
hydrodesulfurization (HDS), for reducing of organic-sulfur in
gasoline, diesel and other intermediate distillates where various
catalysts are used. This process removes many sulfur compounds
such as thiols, sulfides, disulfides and some thiophene derivatives;
however, the HDS method less efficient at the removal of
dibenzothiophene derivatives due to the steric hindrance on the sulfur
atom, such as 4,6-dimethyldibenzothiophene (4,6-DMDBT), which
are present in diesel fuel with sulfur concentrations in the order 400
ppm. Some suggestions such as the use of more active catalysts,
longer residence times, and higher temperatures and pressures have
been reported for improving the effectiveness of HDS for producing
low sulfur product. Therefore, to meet the demands of producing
ultra-clean fuels with sulfur content lower than 15 ppm via HDS,
both capital investment and operational costs would increase due to
more severe operating conditions and this would result in HDS being
an extremely costly option for desulfurization. Consequently, it is
imperative that advanced technologies be developed for
desulfurization at ambient temperature and pressure. Currently, the
most common HDS alternative method used to achieve ultra-clean
fuels is adsorptive desulfurization (AD) where steric hindrance is not
present for adsorption by π-complexation, and is thus the approach
taken in this study.
Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels 2013, 58(2), 588
Because of its low-energy consumption, ambient operation
temperature and atmospheric pressure in the absence of pressurized
hydrogen, and ability to provide regeneration of the spent adsorbent,
adsorption via porous materials is considered to be a promising
approach for removing sulfur compounds.
A variety of adsorbents such as ion-exchanged zeolites,
supported metals, metal oxides, activated carbons, ionic liquids and
other commercial adsorbents have been reported for the use of AD
under ambient conditions. Activated carbon is one of the most
important adsorbents dominating the commercial use of adsorption
due to its porous structure with high surface area, pore volume, and
efficiency [1-7].
activated carbon retrieved from various materials including wood,
coal, dates’ stones, polymer, cloth, and coconut-shell, but it is also
readily available as a commercial product.
We report here a simple procedure for desulfurization of model
fuel oil by adsorption on activated carbon. Very significant results
have been obtained.
Experimental
Preparation of Activated Carbon
Activated carbon was prepared from waste rubber tires via
carbonization, chemical treatment and steam activation as discussed
in detailed previously [8-10]. The waste rubber tires were cleaned,
thoroughly washed with deionized water, and then dried in an oven at
120 ◦C for 4 h. For carbonization, the dried material was then heated
to approximately 500 ◦C for 6 h. This was followed by treatment with
hydrogen peroxide solution for one day to oxidize adhering organic
impurities. The material was washed with deionized water and dried
in vacuum oven. The dried material was activated to 900 ◦C for 2 h.
Then it was removed from the furnace and cooled in a desiccator.
The material was then treated with 4M nitric acid solution to remove
the ash content and was then washed with deionized water. The
product was finally dried in an oven at 120 ◦C for one day.
Results and Discussion
The initial results revealed the effectiveness of prepared activated
carbon in removing sulfur compounds from model fuel oil.
Characterization of Adsorbents
After the synthesis of the adsorbents, the characterization has been
performed by the means of different techniques. The characterization
of the surface chemistry of the adsorbents and the surface
morphology were performed using scanning electron microscope
(SEM), X-ray diffraction spectroscopy (XRD) and Fourier Transform
Infrared spectroscopy (FT-IR).
Adsorption studies
The adsorption of DBT, BT and Thiophene from model fuel onto
the derived sorbents was performed using both batch and fix bed
modes. This will be discussed in the following sections.

Figure 1: High resolution field emission scanning electron
microscopy (FESEM ) image of the Activated carbon
Figure 2: FTIR of the used activated carbon
Figure 3: Gas chromatogram of desulfurized sample
Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels 2013, 58(2), 589
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Figure 3: Adsorption of sulfur compounds on Activated Carbon
The activated carbon adsorbent provided an excellent activity.
This modified metal oxides afforded approximately 80-90% of sulfur
from model fuels. These adsorbent and a very strong potential to be
used for the deep desulfurization of gasoline and diesel fuels.
Conclusions
In summary we have evaluate carbon as adsorbent for the
removal of sulfur from model fuels. We believe, the adsorbents will
find useful applications in petroleum industry because of its
operational simplicity and high efficiency.
Acknowledgement
The financial support provided by King Abdulaziz City for
Science and Technology (KACST), Riyadh, Saudi Arabia through
Project No. DRP-4-25 and facility support provided by the King
Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia for
this work are gratefully acknowledged.
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