2. T.

Schuster: Analiza metod prognozowania produktywnoci gazowej wysypisk odpadw komunal-

nych i opracowanie programu najlepiej odpowiadajcego krajowym warunkom klimatycznym oraz
sposobem skadowania odpadw, praca statutowa IGNiG, 1999.
3. Untersuchungen zur Optimierung des Zusammenwirkens von Technologien zur dezentralen
Energieerzeugung mit Brenngasen aus Erneuerbaren Energietrgern, 2006.
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640
Deep Desulfurization of Fuel by Liquid-Liquid Extraction
using Ionic Liquids
Likhanova N.V., R. Martnez-Palou, D. Guzmn-Lucero, Flores-Oropeza E.A.
(Instituto Mexicano del Petrleo)

. ,

( 90%). , 17
.
The alternative process for desulfurization of fuels by liquid-liquid extraction at ambient
pressure and room temperature condition is present in this work. In one step operation, the sul-
fur-containing compounds in the different fuels were extracted into ionic liquids with high ef -
ficiency (more than 90%). In this work, 17 ionic liquids were synthesized with the object of
evaluating the effect of different molecular arrays of these compounds on their efficiency for
removing sulfur from fuels.
Introduction
The gasoline production in accordance with the new environmental norms of the European
Union in 2005 was established to diminish the quantity of sulfur in gasoline and Diesel at lev-
els lower than 50 parts for million (ppm). For example, in Germany one proposed to reduce the
quantity of sulfur in gasoline and Diesel in 2005 up to 10 ppm. In the case of the US, the norm
related to the the maximum content of sulfur in gasoline is limited to a maximum of 80 ppm
and to an average of 30 ppm. Mexican oils (PEMEX Refinery) attending his commitment to
produce and distribute gasoline that meet the environmental legislations under international
standards, this quality fitting his parameters of production of gasoline, establishing as a norm
to reach a content of maximum sulfur between 15 and 30 ppm for the year 20082010.
The classic method used today in the refineries for the desulfurization of hydrocarbons of
the oil is the catalytic hydrodesulfurization with high pressures and temperatures (process of
HDS). Nevertheless, this process is very costly, it needs drastic conditions of operation as well
as the use of noble metal catalysts that poison themselves relatively rapidly [1]. HDS is an effi-
cient process for the reduction of sulfur aliphatic compounds, but it is slightly effective in the
reduction of sulfur compounds, aromatic, especially in case of heavy Mexican oils that have a
very high sulfur content which are difficult to process.
Some countries for the solution of this problem develop new technological lines, [2]
between that they are: the adsorption of sulfur compounds on solid adsorbents as the process
IRVAD [3] from the Black & Veatch Pritchard Inc.; the process S Zorb [4] from Phillips
Petroleum and the process of Haldor Topsoe [5] by the liquid liquid extraction with organic
common solvents; and the oxidative desulphurization with different agents of oxidizers. Recently,
the extraction of the sulfur compounds by ionic liquids has performed interest for the scientific
international community.
The ionic liquids (ILs) are known more than 30 years, but its application in different industrial
process initiated in last 10 years [6,7]. They are applied as solvents and catalysts in reactions of alky-
lation [8], polymerization [9], Diels-Alder [10], in electrochemistry processes [11], but his most
interesting use is like a solvent for the extraction of CO
2
, aromatic and sulfur compounds from the
mixtures of hydrocarbons. Recently, novel processes for removing sulfur from refinery streams have
been studied [12, 13], including the use of ionic liquids (ILs) as extract [14-19].
In this paper, we investigate the process for deep desulphurization of different fuels using model
diesel (MD), naphtha from catalytic cracking process (CN) and natural gasoline (NG), research makes
use of a liquid-liquids extraction using ionic liquids at ambient pressure and room temperature.
Experimental Sections
1. Materials and equipments
General. All reagents (Aldrich) were used without previous purification, except
1-methy limidazole and pyridine which were vacuum distilled from CaH
2
prior to use.
FT-IR spectra were registered on a Nicolet FT-IR 5DX FT spectrometer as KBr discs.
Specific rotation was measured in a Perkin Elmer 241 polarimeter. H NMR (300 MHz) and
C NMR (75.4 MHz) spectra were obtained with Jeol Eclipse-300 equipment using TMS as
internal standard and using the solvent specified in each case at room temperature.
2. Sampling
The model diesel was prepared by adding of equivalents parts of thiophene and benzothio-
phene into mixture hexane/heptane (1:1) with total sulfur contents of 500 ppm.
Naphtha from catalytic cracking process with 1600 ppm sulfur contents were obtained from
the Pemex Refinery, Tula, Mexico. The natural gasoline with 210 ppm sulfur contents was
obtained from The Gas Processing Center Morelos in Coatzacoalco, Veracruz, Mexico.
3. Extraction Desulfurization of the Model Diesel, Naphtha from catalytic cracking
process or Natural gasoline
All the desulfurization experiments were conducted in a 100-ml glass vial. The ionic liquid
was added into correspondent fuel at room temperature. The mass ratios of ionic liquids to fuel
were 1:10. The obtained biphasic mixture was then stirred for 15 min. Then the mixtures were
left in rest during 30 minutes and the fuel was decanted carefully.
4. Analysis of Sulfur Content in Fuel
Total sulfur was determinated in an Antex 9000S equipment, employing the standard proce-
dure ASTM-D 5453-05: Standard Test Method for Determination of Total Sulfur in Light
Hydrocarbons, Motor Fuels and Oils by Ultraviolet Fluorescence. The concentration of indi -
vidual sulfur compounds were analyzed by gas chromatography using an atomic emmisor
detector (GC-AED) Hewlett-Packard 6890 equipped with AED G2350A) in accordance with a
previously described procedure [20].
5. ILs Synthesis and Characterization
Ionic liquids (2 [21]; 1, 4, 9, 11, 13, 15, 17 [22-23]; 7, 12 [24]; 3, 5, 16 [25]; 6 [15]; 8, 10
[26]; 14 [27]) were synthesized according with a previously described procedure and the puri-
ty and composition was confirmed by NMR spectra.
, ,
641
a
Molar ratio between LI containing halogen as anion/MX
n
on methatesis reaction.
Result and Discussion
ILs Screening
In this work,17 ILs were synthesized with the object of evaluated the effect of different
structural aspects of these compounds in their efficiency for removing sulfur from fuels.
In previous reports [14-19] the ILs containing chloroaluminate anion showed promising
results for desulfurization of model gasoline and diesel oil, thus we prepared a series of IL con-
taining metal transition in their anion for study their efficiency in desulfurization of fuels. In
addition, other anions, both inorganics and organics were synthesized for screening this aspect.
In other sense, heterocyclic cations based on imidazolium, pyridonium, were evaluated.
In Table 1 the content of the total sulfur after the liquid-liquid extraction experiments are
described.
Table 1
Sulfur removal from fuels sample by liquid-liquid extraction employing ILs.
a
, ,
642
Entries
Ionic Liquid Total sulfur removed (%)
Cation Anion
a
MD CN NG
1 MIMB
+

FeCl
4
(1:1.5)
95 50 93
2 MIMB
+
PF
6

8 <1 12
3 MIMB
+

CF
3
SO
3
11 <1 15
4 DMIMB
+

FeCl
4
(1:1.5)
97 48 95
5 PyO
+
Cl

25 3 28
6 PyO
+

Cu
2
Cl
3
(1:1.5)
18 <1 20
7 PyO
+

AlCl
4
(1:1.3)
40 5 46
8 PyO
+

SnCl
5
(1:1.3)
25 3 30
9 PyO
+

FeCl
4
(1:1.3)
59 28 69
10 PyO
+

SnCl
4
(1:1.3)
1 <1 2
11 MIMO
+

FeBrCl
3
(1:1.5)
90 39 95
12 MIMO
+

AlCl
4
(1:1.5)
93 46 97
13 MIMO
+

FeCl
4
(1:1.5)
99 53 99
14 DAIM
+

FeBrCl
3
(1:1.5)
93 45 95
15 BIMBn
+

FeCl
4
(1:1.5)
99 56 99
16 BIMBn
+

CH
3
COO
40 18 53
17 PyHOH
+

FeCl
4
(1:1.5)
30 10 35
It is evident from Table 1, that the aluminates and ferrates type anions showed an excellent
performace for deep desulfurization of fuels, as was observed by other research group using
model diesels and naphtha from catalytic cracking process where mercaptants and sulfides are
virtually non existent [14, 19], however, presumably the same mechanism of extractions for sul-
fur compounds take place.
Considering that the reactivity between the sulfur organic molecules, mercaptanes and thio-
phenes, and a halogen methalate based ionic liquid with an excess of the pristine metallic salt,
is through the direct interaction of the sulfur atom with the metallic center, it is possible that a
donation-retrodonation Dewar-Chatt-Duncanson-like (1953)[28] mechanism occurs. Another
interesting observation for halogenferrate and aluminate based IL, is that the performance of
these compounds for desulfuration of fuels is highly depend on the ratio of LI containing halo-
gen as anion/MX
n
on methatesis reaction. A ratio > 1:1 is referred to as an acidic IL. It is well
known that these acidic ILs contains MX
4

and M
2
X
7

as principal anionic constituents [29, 30].
The enhanced ability of acidic IL could be related with the enables of the cations to be coor-
dinated with the sulfur atom in this case.
From Table 1 we concluded the following observations:
LI containing chloroaluminate and chloroferrate as anion are good extracting phase for
desulfuration of fuels.
The extracting phase efficiency decreased considerably when anions containing other
chlorometalates (i.e. Sn, Zn, Cu ) are used.
Anion composition play more important role than cation in the efficiency of IL as sulfur
compounds extracting.
With the same anion, imidazolium cations are the best counterpart for increasing the effi-
ciency of sulfur removing. The presence of methyl substituents in position 2, do not affect the
efficiency to removed sulfur compounds.
Acetate anion showed remarkable desulfurization ability for fuels. It anion is less efficient
than ferrates and aluminates, however, to a different of these last, IL containing acetates can be
recycled and reused without lost their performance significantly, at last in three extractive
cycles. Additionally this organic anion is halogen-free, moisture-insensitive, and air and tem-
perature stable.
Conclusions
ILs contains imidazolium cation and halogenaluminate and ferrate anions showed remark-
able efficience to remove sulfur compounds from fuels sample, however this compounds are air
and moisture sensitive ILs containing acetate as anion are a good alternative as desulfurization
agent because its shows high capacity to removed sulfur compounds and due to their stability
to air, temperature and moisture, this halogen free ILs can be easily regenerated and recycled.
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644
Desfluorination of Alkylated Gasoline using Ionic Liquids
Olivares-Xometl O., Garcia-Chavez L., Martnez-Palou R., Likhanova N.V.
(Benemerita Universidad Autnoma de Puebla, Universidad Autnoma de Guanajuato,
Instituto Mexicano del Petrleo)

, -
. ,
.
,
.
HF .
Hydrogen fluoride is a common catalytic reagent for alkyling of gasoline; however handling
is difficult due to its toxicity and corrosive properties. For this reason, it is very important to