Zeolites for adsorptive desulfurization from fuels

Submitted by: Ahmed Khames Rija

Supervised by: Dr.Arezoo Sodagar
2022
Introduction
In tyears, removal of aliphatic and aromatic sulfur compounds from liquid fuels
(gasoline, jet fuel, diesel fuel), gaseous he recent fuels (natural gas, reformates and
syngas) and liquid petroleum gas (LPG) has received considerable attention by both the
scientific community and the petroleum refineries. Table 1 shows some of structure of
aliphatic and aromatic sulfur compounds in fuel. Combustion of sulfur compounds in
fuels leads to SOx emissions, which causes important health problems and are
precursors of the acid rain. Furthermore, sulfur concludes catalysts deactivation in the
downstream refining processes, corrosion problems in pipelines, pumps, and refining
equipments. Total sulfur in crude oil can vary between 0.05 and 6 wt% depending on the
type and source of crude oil [1]. The sulfur concentrations in transport fuels such as
gasoline and diesel according to the environmental regulations should be lower than 10
ppm [2]. There are several approaches such as adsorptive desulfurization [3], extractive
desulfurization [4], bio-desulfurization (BDS) [5], hydrodesulfurization (HDS),
Oxidative desulfurization (ODS) and precipitative desulfurization to reduce sulfur
content in fuels. These technologies are outlined in Fig. 1.
Among these methods used for desulfurization, hydrodesulfurization (HDS) is efficient in the removal of most
aliphatic sulfur compounds such as mercaptanes, sulfides and disulfides from fuels. Nevertheless, it is not
efficient in the removal of aromatic refractory sulfur compounds such as thiophene derivatives. H2S generated
in some thiophene compounds reaction is a major inhibitor for HDS [7,8]. In addition, it requires high
temperature, pressure and high dosage of catalyst before achieving the desired objectivewhich is uneconomical
[6]. Theadsorption process has become a promising approach in the ultra-deep desulfurization, because it is
easily available, environmentally friendly, economical method and being able to decrease content of sulfur to b1
ppm [9]. Current area of studies in adsorptive desulfurization focuses on the development of a novel and
adequate adsorbentwhich has high adsorptive capacity,high selectivity and can be easily regenerated [3]. Awide
varietyofadsorbent such as carbon-based sorbents [10],metal adsorbents (reduced metals, metal oxides and
metal sulfides) [11–15], silica-based sorbents [16–18], metal-organic frameworks (MOFs) [19,20] and zeolites
have been reported. Advantages of the Carbon-based sorbents such as activated carbons are that, sources for
preparation of them arewide and the production cost is relatively cheaper for removal of sulfur compounds.
However, lack of low thermal and mechanical stability are disadvantages of thesematerials [21]. Ordered
mesoporous carbons (CMKx) are another group of Carbon-based sorbents which are typically biocompatible
and quite chemically stable under nonoxidizing conditions and exhibits mechanical stability but the
hydrophobic and inert nature of mesoporous carbons can be unfavorable for adsorptive desulfurization
applications [22]. One of drawbacks ofmetal adsorbents is that they are used with expensive components (metal
or support) in significant quantities. Further, regeneration of them for subsequent runs is relatively more
difficult and also adsorption capacity of them is lower than that of zeolite based adsorbents [23,24]. MOF
adsorbents have good adsorption selectivity and capacity for adsorptive desulfurization. In 2008, Matzger et al.
reported adsorptive desulfurization by the MOFs HKUST-1 (also known as Cu- BTC), UMCM-150, MOF-5,
MOF-505, and MOF-177 [25]. In their report, the adsorption capacities were 0.38 mmol/g of BT using MOF-5
and 0.45 and 0.19 mmol/g of DBT and DMDBT
respectively, using UMCM-150. These amounts were higher than those obtained previously by Na-Y zeolite.
This observation was due to the MOFs offer the higher surface areand pore volume than zeolites adsorbents.
However, high cost of organic precursors for preparation of these adsorbents and thermal/hydrothermal
instability makes them difficult to be used in industry. Recent progressions in adsorptive desulfurization with
metal-organic frameworks (MOFs) are thoroughly discussed by Ahmed and Jhung [26]. Aiming at selection of
adequate adsorbent which can have a high selectivity, high adsorption capacity, regenerability and safe
operations, zeolites are effective for removal of sulfur compounds [27]. There are N200 unique zeolite
frameworks and naturally occurring zeolites which have different shapes (channels, cages, cavities, etc.) and
sizes [28]. Applications of zeolites are numerous. Zeolites can be used not only as adsorbents, but also as
catalyst, separation media, catalyst support and animal feeding. These applications depend on the presence of
suitable active centers, size, and geometry of cavities inside the zeolite. Various outstanding reviews on different
application of zeolites such as removal of H2S [29], upgrading of bioethanol to fuels [30], benzene removal
from gasoline [31] pyrolysis of biomass [32] anaerobic digestion processes [33] removal of volatile organic
compounds [34], wastewater treatment [35] crop protection [36] and aquaculture industry [37], have been
published. However, there is no review report on adsorptive desulfurization of zeolites from fuels. The aim of
this review is to describe the recent progress in adsorptive desulfurization of fuel by using some of natural
zeolites such as Clinoptilolite and some of synthesic zeolites, including FAU (X and Y), LTA, ZSM-5 and Beta
with respect to increasing demand for producing sulfur free fuels. In the first part of the study, the possible
mechanisms of adsorptive desulfurization by zeolites have been reviewed. In the second part of the study, the
use of zeolites in adsorptive desulfurization and in the last part, thermal and solvent regeneration of zeolites in
adsorptive desulfurization process have been discussed in details.
Mechanisms of absorptive desulfurization
Investigation of the interaction between sulfur compounds and zeolites are necessary to guide the
design and preparation of suitable adsorbent for adsorptive desulfurization. Van der Waal's forces,
chemical affinity and electrostatic attraction are responsible for adsorption. Adsorptive
desulfurization is based on physisorption or chemisorption process of organosulfur compounds on
adsorbents [38]. There are various forms of adsorptive desulfurization include reactive adsorption,
polar adsorption, selective adsorption, integrated adsorption and π- complexation. Among these
forms of adsorptive desulfurization, π- complexation and selective adsorption are widely used for
adsorptive desulfurization by zeolites. In addition, reactive adsorption by zeolites has been reported
in few studies. Tawfik et al. studied full details of these forms adsorptive desulfurization [3].
2.1. π-Complexation mechanism

Zeolites loadedwith different metal ions such as Fe2+, K+, Ag+, Cu+, Ni2+, and Zn2+ or Pd2+ cause π-
complexation (chemical complexation) between metal ions and sulfur compounds. The metal ions form σ-bonds
with free s-orbitals and the d-orbitals will back-donate electron density to the antibonding π-orbitals in the
sulfur containing ring of thiophenes. Bonds formed due to this interaction, are stronger and yet easily broken by
alternating the temperature or pressure which enhances the capacity and selectivity to sulfur compounds [10]. π-
Complexation yields better results compared to the normal van der Waals interactions occurring in adsorption
studies [3]. It should be pointed out that although zeolites ion exchanged with metal ions increase the selectivity
and adsorption capacity of sulfur compounds, but the loaded metal ions are washed away during the procedure
of adsorption-desorption desulfurization. Therefore, the stability of zeolites ion exchanged with metal ions is
reduced [39]. Many studies have been done on the π-complexation by zeolites. In the following, the zeolites
used in π-complexation form have been mentioned.
2.2. Selective adsorption

Selective adsorption form removes sulfur compounds from fuels, which constitute only b1% of the fuels. For
selective adsorption mechanism, adsorbents need to be effective, selective and appropriate for sulfur removal.
Nickel based sorbents and air regenerable metal oxide based sorbents are the most common adsorbent materials
used in this process [3]. Ce4+ ion, with the valence electronic configuration 4f05d06s0, has high positive charge
and polarizability. Sulfur compounds are adsorbed over zeolites ion exchanged with Ce4+ by a direct S–
adsorbent (S\\M) interaction.
Use of zeolites in adsorptive desulfurization
Until now, about fifty natural zeolites are known. Commercially significant natural zeolites include mordenite
(MOR), chabazite (CHA), and clinoptilolite (HEU) [42]. Among them, Clinoptilolite is the most studied of all
zeolites and it is considered as adsorbent for deep desulfurizationIn this regard, Mahmoudi and Falamaki used
Ni2+ ion exchanged dealuminated clinoptilolite for removal of some sulfur compounds such as thiophene (T),
benzothiophene (BT), dibenzothiophene (DBT) and isopropyl mercaptan (IPM). Oxalic acid was used as
dealumination reagent. Si/Al molar ratio of raw clinoptilolite was 5.65. After dealumination and the ion-
exchange process with Ni2+, deep desulfurization with zeolite powder (raw, dealuminated or dealuminated/ion-
exchanged or solely ion-exchanged) was performed. The Powders were exposed at 300 °C in an electrical
furnace for 2 h. Then cooling was performed at 100 °C and immediately isolated in 50 cm3 glass bottles. The
adsorption process was performed by shaking at 20 °C for 1.5 h. The adsorption capacity of the optimum zeolite
(0.3 oxalic acid molarity and dealumination treatment time of 120 min) for IMP, T, BT and DBT were 10.10,
6.33, 3.60 and 2.70 mg s/g.
Regeneration of zeolites
4.1. Thermal regeneration During the thermal regeneration process, some side products are formedwhich cause
regeneration of adsorbent are not easily. Especially at higher temperatures, these products will undergo further
reactions and will lead to coke formation. For example, mercaptans are oxidized to sulfides, disulfides and/or
polysulfides. These newly formed sulfur compounds are then adsorbed more strongly onto the synthetic
faujasite, due to their highermolecularweight, thereby reducing the adsorbent capacity of the faujasite. Hawes et
al. [75] reported novel desorption process for removal of sulfur compounds, including mercaptans, sulfides,
disulfides, thiophenes and thiophanes from liquid and gas feed streams with synthetic 13X adsorbents. The
process is characterized as a dedicated way to regenerate the adsorbent to avoid decomposition and coking of
the adsorbed sulfur compounds. Degradation of the mercaptans takes place above 200 °C. Degradation of the
mercaptans can be reduced remarkably, if temperature increase is done stepwise with a halt step at different
levels. In one successful experiment, the temperature was increased in steps of 10 °C at a time and the
temperature was left unchanged for 30 min before it was increased by another 10 °C. Using this approach, no
exothermic reaction could be observed, indicating that no degradation of the mercaptans took place.
Thermal regenerationwas used successfully for regeneration of Ag-Y after sulfur removal at air-calcination at
450 °C for 6 h and a full regeneration of used Ag-Y was achieved. Air-calcination of used Ag-Y at temperatures
b 350 °C causes incomplete decomposition of the adsorbed sulfur species, resulting in declined adsorption
performance [49]. Yi et al. [61] regenerated the Dimethyl disulfide absorbed on Cu(I)–Y zeolite in air at 450 °C
for 4 h and then switched into N2 atmosphere for 4 h at the same temperature in the fixed bed. After three times
of cyclic regeneration, desulfurization property of the adsorbent was recovered to 66.7%. The Dimethyl
disulfide absorbed on Cu(I)–Y zeolite fully was burned at 450 °C in air, nevertheless, cuprous ions were
oxidated to cupric ions. In the N2 regeneration, the sulfur onto the adsorbent was not removed completely and
the regeneration effect was unsatisfactory. Moreover, results of the Pyridine-FTIR spectra and XRD of the
regenerated Cu(I)–Y zeolites showed the Lewis acid sites and crystal structure were destroyed in the
regeneration process and so the desulfurization performance of Dimethyl disulfide onto the Cu(I)–Y zeolite was
affected. Tian et al. [27] performed regeneration of used Ce/beta-40 at 450 °C, first under dried nitrogen flow
for 2 h, and then in a muffle for 4 h. The XRD analysis and FT-IR of the regenerated Ce/beta-40 indicated that
the zeolite structure was not affected by the thermal treatment. The sulfur removal of themodel fuel containing
DBT and toluene over fresh and regenerated Ce/beta-40 indicated that the sulfur removal decreases from 39.2%
over fresh Ce/beta-40 to 31.3% and 30.4% after the first and second regeneration, respectively. That is, ca. 80%
of the sulfur removal of the fresh adsorbent can be recovered by thermal treatment, which is ascribed to the
open 3D channels and better thermal stability of beta zeolite- based adsorbent [27]. Bakhtiari et al. [76]
performed the regeneration process for situation AgX-zeolite that had been situated by sulfur compounds in air
at 210 °C for 1 h. Regenerated AgX-zeolite adsorbent was used five times.
4.2. Solvent regeneration
For solvent elution method options, the solvents used undergo some type of interaction with the spent sorbent,
and these interactions have effect on the adsorption of the organosulfur compounds during the second
adsorption cycle. The solvent regeneration is applied to the adsorbate that is weakly bound to the surface of the
sorbents. On the other hand, this is used for the interactions with adsorption energy typically 5100 kJ/mol.
Regeneration by solvent is an environmentally kind method because it avoids the emissions of SOx and H2S
generated by thermal regeneration. In other caseswhere solvent regeneration of the spent adsorbent was
recommended a large solvent inventory along with suitable solvent recovery and recycle system has to be
considered which will add to the complexity of the overall process. Solvent regeneration is suitable for certain
applications for those involving heat sensitivematerials [77]. Lin et al. [59] used ethanol as desorption agent at
certain temperature until the sulfur concentration in the washing solvent became unchangeable. The outgoing
solvent fractions were collected from the fixed bed in order to estimate the amount of solvent required. The
sulfur concentration in the initial fractions was over 2000 mg/L. The results indicate thatmost of the sulfur
compoundswere recovered using 20 g of the solvent per gram of adsorbent.Washing solvent desorption process
is presented in Fig. 6. In another study, Shan et al. [53] regenerated the saturated CuCeY with thiophene in a
static bath of solvent containing a mixture of 30 wt% toluene and 70 wt% isooctane for 4 h, followed by
reactivation in nitrogen at 450 °C for 4 h. Desorption was about 90% of the initial one. Also, helium atmosphere
was used for regeneration of the consumed adsorbent. Results showed that helium exhibited a similar
performance as that regenerated in nitrogen.
Conclusion
Recently, zeolites have been developed for deep adsorptive desulfurization of fuel, which shows a high selectivity,
high adsorption capacity, regenerability and safe operations. Therefore, this review has focused on the recent studies
on adsorptive desulfurization of fuel by zeolites. Deep adsorptive desulfurization are strongly dependent on
adsorption methods of the sulfur compounds on the zeolites, the charge of metal cations, texture properties of the
zeolite, number of active sites on the framework of zeolite, acid properties of the zeolites, Si/Al ratio and the pore
size of the zeolites. X and Y zeolites have been widely studied for adsorption of sulfur compounds, due to their
tuneable selectivity regarding polar molecules. Zeolites showed good sulfur loading capacity, good regenerability
and stable structure for removal of sulfur compounds. Nevertheless, some of zeolites such as LTA zeolites fail when
using as adsorbent for adsorption of sulfur compounds. This is due to the presence of pores with molecular size
typically below 1 nm, cease steric limitations to the diffusion of bulky molecules. Also, ZSM-5 zeolites are not
suitable for removing sulfur derivatives fromhydrocarbons duo to oligomerization of thiophenic compounds on
these zeolites, which is unfavorable for easy regeneration purposes. Modification of HZSM-5 with alkali or alkaline-
earth metals cations can be decreased the number of strong Brønsted acid sites and diminish oligomerization of
thiophenic compounds on these zeolites. These adsorbents for adsorptive desulfurization were rarely reported.
Zeolites loaded with different metal ions such as Fe2+, K+, Ag+, Cu+, Ni2+, and Zn2+ or Pd2+ conclude π-
complexation between metal ions and the sulfur compounds and have shown good adsorption performance for most
of refractory sulfur compounds. However, because of steric effect of the DBTs with one or two alkyl groups it is
very difficult to remove these sulfur compounds. One of the most successful strategies for improving accessibility is
the case of hierarchical zeolites. The presence of a bimodal pore size distribution, formed by both micropores and
mesopores improve mass transfer properties of micropores zeolites materials, which can be have advantageous for
interactingwith bulkymolecules. However, hierarchical zeolites have not been studied for adsorptive desulfurization
so much with respect to the limitation of zeolites in adsorption of bulky sulfur compounds.
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