Ain Shams Engineering Journal 11 (2020) 1265–1273

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Ain Shams Engineering Journal

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Engineering Physics and Mathematics

Removal sulfur components from heavy crude oil by natural clay

Mayssaa Ali Al-Bidry ⇑, Rana Abbas Azeez
Petroleum Technology Department, University of Technology, Baghdad, Iraq

a r t i c l e i n f o a b s t r a c t

Article history: Reducing the sulfur content of crude oil and its derivatives has drawn the attention of researchers around
Received 1 November 2019 the world to reduce environmental pollution. Desulfurization is a process used for the effective removal
Revised 2 March 2020 of sulfur from the heavy crude oil. In this work, the adsorption desulfurization technique was applied for
Accepted 21 March 2020
heavy crude oil Baghdad east field with 4.31% sulfur content and treated with modified Iraqi bentonite
Available online 5 May 2020
(Fe and H-bentonite) to increase effectiveness of sorbent surfaces. The modified bentonite was used in
sulfur removal experiments, the efficiency of modified bentonites was studied under different ratio of
Keywords:
oil to adsorbent (10:0.3, 10:0.6, 10:0.9, 10:1.2) and different interval times (1, 2, 3, 4 and 5 h) at a constant
Acid activation
Bentonite
temperature of 40 °C. The results showed that high yield desulfurization were achieved with Fe-bentonite
Clay adsorbent after 5 h, at 40 °C, and using oil to adsorbent ratio (10:1.2), under these optimal conditions the Fe- ben-
Desulfurization tonite was adsorbed about 81.4385% of sulfur from the crude oil, while 37.28% by H-bentonite at the
Modified bentonite same condition. In this study, energy-dispersive spectroscopy techniques, surface characterization, x-
Specific surface area ray diffraction, x-ray fluorescence spectrometer and scanning electron microscope analysis of raw and
modified bentonite were performed. The particles size distribution of H-bentonite range from
1.763 mm to 158.866 mm, while Fe-bentonite is 0.036–126.191 mm, the modification of bentonite with
Fe enhances the surface area, pore and decreasing particle size over acid treatment, which explained
the high desulfurization efficiency by Fe-bentonite.
Ó 2020 The Authors. Published by Elsevier B.V. on behalf of Faculty of Engineering, Ain Shams University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

1. Introduction needs high conditions of temperature and pressure, also could

not remove aromatic heterocyclic sulfur compounds such as thio-
The demand for crude oil as an energy source is continuously phene, benzothiophene, and dibenzothiophene [5]. An alternative
increasing driven by economic development, which prompted sci- to hydro-desulfurization process is desulfurization through solvent
entists to improve desulfurization techniques to enhance crude oil extraction, adsorption, photo-oxidation, ionic liquid [6–10].
quality and reduce sulfur components [1,2]. High sulfur compo- Adsorption is the most promising process to desulfurize using var-
nents in crude oil has undesirable influence in the refining process ious adsorbents, where an effective adsorbent has to provide an
because of erosion problems in pipelines and refining equipment, active surface, high surface area, and proper pore size distribution
also its harmful impact on the environment [3,4]. The essential [11,12]. Adsorption desulfurization is a technique based on the
characteristics of heavy crude oil are high viscosity, high density, selection of the adsorbent material and its ability to remove the
high acidity and high sulfur. One of the traditional industrial meth- sulfur organic compounds due to physical and chemical properties
ods for desulfurization is hydro-desulfurization (HDS), which is the [13]. However, a variety of adsorbents have been used for this pur-
most commonly used method in petroleum refineries for reducing pose such as activated carbon [14], Y-type zeolites [15] sewage
the sulfur content to a minimum, but HDS method is high costs, sludge [13] and bentonite [11].
The reactive adsorption is more complicate than ordinary phys-
⇑ Corresponding author. ical adsorption because it involves p complexation bonds between
E-mail address: [email protected] (M.A. Al-Bidry). sulfur compounds and the adsorbent, p complexation bonds are
Peer review under responsibility of Ain Shams University. stronger than van der waals interactions, but can be broken by
increasing temperature or decreasing pressure, thereby it is easy
to regenerate the adsorbent [15]. Several researchers illustrated
that modify of adsorbents enhancement the adsorption capacity
Production and hosting by Elsevier of organic sulfur compounds by impregnation with cations.

https://doi.org/10.1016/j.asej.2020.03.010
2090-4479/Ó 2020 The Authors. Published by Elsevier B.V. on behalf of Faculty of Engineering, Ain Shams University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1266 M.A. Al-Bidry, R.A. Azeez / Ain Shams Engineering Journal 11 (2020) 1265–1273

Therefore various metal cations were impregnated at various sup- ning electron microscope (SEM) (silicon drift detector (SDD)-X-
ports have been used as adsorbents for the desulfurization of liquid Max, oxford instruments group).
fuels [15,16]. Al hamed and Bamufleh indicated that desulfuriza-
tion of model diesel oil using granular activated carbon modified 2.2.1. Acid modification of bentonite
with ZnCl2 as adsorbent was effective in removing organic sulfur Before Trifawy bentonite (Ca-type) used for desulfurization, it
compounds [17]. Shah et al. showed that Sn impregnated on acti- was modified with acid (HCl) in order to replace calcium ions by
vated carbon increased the adsorption capacity during desulfuriza- hydrogen ions in the effective sites of sorption, also increases
tion of model diesel oil compared with untreated activated carbon adsorb capacity. In addition, increase purity of clay by remove car-
[18]. bonate impurities. The sample was dried 110 °C for 5 h before trea-
Bentonite has taken a lot of attention from researchers as a new ted with hydrochloric acid. 10 gm of dry bentonite sample was
type of adsorbent material which is characterized by low cost, high mixing with 100 ml of 0.1 N HCl for 1 h. The clay slurry was then
specific surface area, high adsorption properties, ion exchangeable washed with deionized water several times until PH = 7. The sam-
and non-toxic [19,20]. Many researchers studied the removal of ple then dried in the oven at 110 °C for 8 h.
sulfur compounds from petroleum products using modified ben-
tonite with metal oxides. Dezhi et al. studied selective adsorption 2.2.2. Fe modification of bentonite
of dimethyl sulfide and propylmercaptan from model oil using H-bentonite (modified previously), was mixed with NaOH solu-
bentonite modified by CuCl2 [21], they noticed that adsorption effi- tion (4 gm NaOH/100 ml distilled water) and stirred for 30 min fol-
ciency of modified bentonite was effective for removing dimethyl lowed by washing in distilled water several times. Then, Fe(NO3)3
sulfide and propylmercaptan. Ahmad et al. studied desulfurization solution (2 gm Fe(NO3)3/100 ml distilled water) was added slowly
of kerosene and diesel oil by modified montmorillonite clay with to a suspension of parent material with stirred for 1 h. Fe(NO3)3
different metal [22], they found that montmorillonite improved solution added slowly to prevent deposition of free hydrous ferric
with Zn impregnation. oxides [23]. After that, the sample dried in the oven at 110 °C for
Several researchers have studied the desulfurization process of 8 h.
various petroleum products using adsorption technique; however,
there is no previous investigation for removing organic sulfur com- 2.3. Desulfurization process
pounds from heavy crude oil. Therefore, this work will throw some
light to investigate the desulfurization of heavy crude oil obtained Desulfurization procedure of crude oil includes; mixing 20 ml of
from East Baghdad oil field that contains 4.31% of sulfur using heavy crude oil with bentonite at different concentrations 0.6, 0.9,
adsorption technique by using modified bentonite with cations. 1.2 and 1.5 gm in the Erlenmeyer flask. After that, the sample was
Apart of that the effect of adsorption time and the concentration mixed by ultrasonic for different time intervals 1, 2, 3, 4 and 5 h
of modified bentonite on the efficiency of adsorptive have also moreover; the water temperature in the ultrasonic device was
studied. 40 °C. The mixture gave time to settle clay and treated crude oil
was reserved for sulfur analysis.
2. Methodology
2.4. Equilibrium adsorption
Several practical steps have been used in this work to demon-
strate the desulfurization of heavy crude oil. These practical steps The percentage of sulfur removal SR% and the amount of sulfur
were accomplished sequentially, which start from the characteri- adsorbed by modified bentonite were calculated from Eq. (1) [21].
zation of crude oil and modification of bentonite with cations,
ðCo  Ceq Þ
down to adsorptive desulfurization. The flowchart of these practi- SR% ¼  100 ð1Þ
cal steps is illustrated in Fig. 1. Co
where Co and Ceq (mg/L) are the initial and the final concentrations
2.1. Characterization of the crude oil of sulfur in crude oil, respectively, and ms is the weight of modified
bentonite.
Samples of crude oil were collected from East Baghdad oil field.
A prior process to the desulfurization the oil, chemical and physical 3. Results and discussion
properties are determined using the standard procedures of ASTM
as shown in Table 1. 3.1. Characterization of the bentonite

2.2. Bentonite preparation 3.1.1. X-Ray diffraction

Raw bentonite composes from montmorillonite with gangue
Trifawy bentonite was received from Iraqi Geological Survey minerals mainly include quartz with a quantity of calcite Fig. 2.
Company (Western desert -Iraq). The sample was crushed by jaw Bentonite typically consists of montmorillonite and other addi-
crusher and dried at 110 °C for 8 h. This sample was grinded to a tional clay minerals. Montmorillonite (smectite group) has con-
particle size less than 75 mm. In this research different techniques sisted of one an octahedral alumina sheet between two
were used to characterize raw and modify bentonite which they tetrahedral silica sheets. The bonding between two silica sheets
are: X-Ray diffraction (XRD) (type X-Ray tube Cu 1.54060 A., is very weak, which allows the water and exchangeable ions to
40.0 Kv, current 30.0 m A) was used to determine the mineral com- enter between sheets [24].
position of raw bentonite. X-Ray fluorescence spectrometer (XRF)
(type SHIMADZU XRF-1800) and energy-dispersive spectroscopy 3.1.2. XRF and EDS
techniques (EDS), were used to analyse the chemical composition The XRF analysis of the raw and modified bentonite was per-
of raw and modified bentonite. Particles size distribution and sur- formed in order to know its chemical composition and the type
face area are evaluated at the surface area analyzer type Malvern of raw bentonite. Table 2 illustrate the percentage of SiO2 and
Master sizer 2000 laser diffraction instrument. The surface mor- Al2O3 in the raw bentonite is 54.55% and 16.90%, respectively.
phology of a raw and modified bentonite was examined by scan- Whereas the percentages of other oxides Fe2O3, CaO, Na2O, MgO
 M.A. Al-Bidry, R.A. Azeez / Ain Shams Engineering Journal 11 (2020) 1265–1273 1267

Fig. 1. Flowchart represents the desulfurization process of heavy crude oil.

Table 1 and K2O are 5.89%, 8.21%, 0.88% and 0.75% respectively. Moreover,
Physical and chemical properties of crude oil (East the percentage of L.O.I equal 10.20% which indicates the presence
Baghdad oil field).
of carbonate minerals. All the aforementioned elements represent
Characteristics Crude oil the major constituents of bentonite. Bentonite composed mainly of
API gravity 21.8 hydrous magnesium-calcium aluminum silicate called montmoril-
Specific gravity SG at 60°F 0.923 lonite, which is a clay mineral of the smectite group [24]. In the
Kinematic Viscosity C.st at 26.7 °C 78.731 smectite-group minerals, isomorphic substitutions in either tetra-
Sulphur content wt% 4.31
hedral or octahedral sites induce a permanent negative layer
H2S content ppm 4.36
Sediment content vol% 0.0126 charge, which is compensated by the presence of hydrated cations
Micro carbon residue wt% 9.947 in the interlayer. A wide range of cations can occupy tetrahedral,
Asphaltenes wt% 6.412 octahedral and interlayer positions. Most of the smectite uses are
Salt content ppm 21 related to reactions taking place in the interlayer space where
Water content wt% 1.60
cations such as Na, K, Ca and Mg, which balance the negative 2:1

Fig. 2. X-Ray of raw bentonite.

1268 M.A. Al-Bidry, R.A. Azeez / Ain Shams Engineering Journal 11 (2020) 1265–1273

Table 2 ment is caused by two reasons which are, the Na concentrates in

XRF analysis of raw bentonite, H- bentonite and Fe-bentonite. certain interlayers, significantly impacts on break-up and forma-
Oxides Raw-Bentonite H-Bentonite Fe-Bentonite tion of smectite particles and thus on swelling [25]. The second
wt% wt% wt% reason, the agglomerated structures of iron oxide particles, which
SiO2 54.55 53.85 51.21 have been created during the precipitation process [29]. The parti-
Al2O3 16.90 16.43 15.62 cle size distribution of H-bentonite ranges from 1.763 lm to
Fe2O3 5.89 5.88 8.99 158.866 lm, the particle size median is 20 lm, and the mean is
CaO 8.21 4.60 5.81
Na2O 0.88 1.10 6.3
43.66 lm. While Fe-bentonite is 0.036–126.191 lm, the median
MgO 2.56 2.78 2.32 is 2 lm, and the mean is 5.696 lm, which indicates that during
K2O 0.75 0.78 0.70 Fe and Na were treated the particle size decrease and surface area
L.O.I 10.20 6.43 8.00 increase significantly.

3.1.4. Scanning electron microscopy

The SEM examination was carried out to study the effect of the
layer charge, commonly hydrated and exchangeable [25]. Raw ben- cations treatment on the surface morphology of the bentonite.
tonite (Table 2) shows a high content of CaO (8.21%), also Na2O/ Fig. 5(A–F) show SEM images of raw and modified bentonite. The
CaO ratio is less than 1, which indicates it is Ca-bentonite. While surface of raw bentonite (Fig. 5A and B) appears to ragged, particle
the XRF analysis of bentonite after modified by HCl shows that size is non-uniform and porous. Fig. 5(C and D) shows that H-
chemical composition is almost the same as that of raw clay, bentonite is more aggregated, more non-uniform and more pores
except the weight percent of CaO (4.60%) and L.O.I (10.20%) which compared to raw bentonite. This result is also in accordance with
indicate high removal of carbonate minerals by acid. Also, the diva- the specific surface areas and particle size distribution of H-
lent cation (Ca+2) that occupies tetrahedral, octahedral interlayer bentonite. The reasons behind Fig. 5(C and D) are that HCl leads
positions were replaced by H+. From the aforementioned results, to leach cations and opening more micro pores; hence, more sur-
we can conclude that acid treatment has led to the conversion of faces became available for adsorption and ion exchange [24]. The
Ca-bentonite (raw) into H-bentonite, likewise, the chemical com- formation of smaller pores takes place as the impurities are
position of modified bentonite with Fe show a difference in removed and the exchangeable cations are replaced by H+ ions.
Fe2O3 8.99%, Na2O 6.3% and Ca2O 4.60%. The high content of Na These chemical reactions alter the morphology and open up the
and Fe refers to cations (almost H+) that occupy the active positions pores, thus the bentonite surface became more porous and homo-
and replaced by Fe and Na cations. According to Na2O/CaO ratio geneous [26].
above one, refer to bentonite converted to Na- type, but the high The surface of the Fe-bentonite appears to uniform compared to
value of Fe could be called Fe-Na-bentonite (will abbreviate as raw bentonite and H-bentonite (Fig. 5E and F). SEM images show
Fe-bentonite in the current study). that a combination chemical treated with Na and Fe resulted in
EDS surface map of the raw bentonite, H-bentonite and Fe- forming more uniform and less aggregate bentonite than the raw
bentonite were used to obtain information about distribution of and H-bentonite. These results are in accordance with the specific
major chemical elements and changes after modify. Fig. 3 shows surface areas and particle size. From the aforementioned results,
EDS surface map of the raw and modified bentonite that its major pre-treatment of bentonite by Na and Fe decrease particle size
chemical composition is almost the same as the raw bentonite (Ca- and enhance the surface area.
bentonite) except cations Ca, Na and Fe as mentioned above. Clay
modified with cation changes the weight present of the exchange-
able cations due to replacement and almost does not change the 3.2. Optimization of conditions
main chemical component
Sulfur removal from crude oil was studied at different time
intervals and different concentrations for two types of modified
3.1.3. Surface area and particles size distribution bentonite to find the best conditions for desulfurization.
The results of particle size distribution and surface area are
given in Fig. 4. It is clear from the figure according to technique 3.2.1. Effect of time
wet laser diffraction, the surface area of Ca-bentonite is Figs. 6 and 7 show the effect of contact time on desulfurization
0.449 m2/gm whereas H-bentonite is 0.548 m2/gm, and Fe - of heavy crude oil with different concentrations of H-bentonite and
bentonite is 26.4 m2/gm respectively. The results illustrate that Fe-bentonite at 40 °C. In the case of both clays, H-bentonite and Fe-
the surface area of bentonite increased slightly due to H- bentonite, the desulfurization slight increased with an increase in
treatment compared to the raw bentonite (Ca-bentonite), while contact time. Fig. 6 demonstrates the effect of time with different
surface area increased clear and significant after Fe treatment. concentration of H-bentonite, where sulfur weight percentage
The reason being this increase is the removal of carbonate miner- decreases from 4.1% to 3.8% at 0.3 gm, while in 0.6 gm decreases
als, replacement of exchangeable cations with hydrogen ions, and from 3.9% to 3.2%, in 0.9 gm decreases from 3.5% to 2.75% and in
leaching of Al3+, Fe3+ and Mg2+ from the octahedral and tetrahedral 1.2 gm decreases from 3.5% to 2.68% with an increase in contact
sites in the bentonite which exposes the edges of sheets [26]. Thus, time from 1 h to 5 h. Fig. 7 illustrates the effect of contact time
according to Ajemba, modification of bentonite with hydrochloric on the Fe-bentonite, it shows that sulfur weight percentage
acid enhances its surface properties and adsorption capacity [27]. decreases from 4.1% to 3.11%, 4.1% to 2.78%, 3% to 1.95% and from
Moreover, according to Uddin, the slight increase in the surface 2% to 0.8% with different quantities of Fe-bentonite (0.3, 0.6, 0.9
area of bentonite after acid-treated is due to the penetration of and 1.2 gm) and increases in contact time from 1 h to 5 h. Also,
HCl into the voids and excessive leaching of Al3+, Fe3+ and Mg2+, the highest desulfurization is achieved at 5 h, and the best type
leading to the breakdown of layered structure and close packing of modified bentonite is Fe-bentonite. So the Fe-bentonite is more
of clay particles [28]. While, the pre-treated with Fe and Na effective than H-bentonite in adsorption desulfurization. The con-
enhances the surface area of bentonite. Through this modification, clusions from this research, the process of desulfurization occurs
the bentonite becomes higher surface area and smaller particle size through adsorption and with the passage of time adsorption
compare with raw and H-bentonite. This surface area enhance- increases and completes at 5 h.
 M.A. Al-Bidry, R.A. Azeez / Ain Shams Engineering Journal 11 (2020) 1265–1273 1269

Fig. 3. EDS surface map of raw bentonite (Ca-bentonite), H-bentonite and Fe-bentonite.

Uddin, reported that the adsorption capacity increased rapidly with time and completes at 4 h [30]. Ahmad et al. using Zn impreg-
within 20 min, and there are two mechanisms that affect adsorp- nated montmorillonite clay mentioned that adsorption progresses
tion, through first 5 min of interaction the mechanism of a cation completed at 6 h time [22].
exchange occurred, but the second mechanism of sorption be tied
to the formation of inner-sphere surface complexes [24]. Majid and 3.2.2. Effect of concentration
Fakhry also studied the effect of time using Ni/y zeolite as adsor- Figs. 8 and 9 show the effect of bentonite concentration on
bent, and they noted that the process of desulfurization increases desulfurization with different contact time. Increasing quantities
1270 M.A. Al-Bidry, R.A. Azeez / Ain Shams Engineering Journal 11 (2020) 1265–1273

Fig. 4. The particle size distribution for H-bentonite and Fe-bentonite.

of H-bentonite from 0.3 to 0.6, 0.9 and 1.2 gm caused increasing that increased the adsorbent amount would lead to increased
desulfurization from 0.23% to 9.51%, 18.79% and 18.79% at contact desulfurization [32]
time 1 h. Also, From 4.87% to 9.51%, 28.07% and 30.39% at 2 h,
from 4.87% to 18.97%, 35.03% and 35.73% at 3 h, from 9.51% to 3.3. Desulfurization with modified bentonite
22.74%, 35.73% and 36.19% at 4 h, from11.83% to 25.75%, 36.19%
and 37.28% at 5 h. Likewise in the case of Fe-bentonite desulfur- Montmorillonite has a complex porous structure and high sur-
ization was increasing from 4.87% to 30.39% and 54.60% at contact face area due to small particle size, which allows being strong
time 1 h. Also, From 7.66% to 9.74%, 39.68% and 63.81% at 2 h, interactions physical or chemical with dissolved species. These
from 15.31% to 20.42%, 53.36% and 74.01% at 3 h, From 18.79% interactions are due to the high adsorbing capacity, cation
to 30.16%, 53.83% and 77.96% at 4 h, and from 27.84% to exchange and ability to hold ions, or water on the surface, etc.
33.41%, 54.76% and 81.44% at 5 h. The results showed increased These properties of montmorillonite accumulate all types of inor-
desulfurization of heavy crude oil with an increased concentra- ganic and organic molecules on their surfaces [24]. Modification
tion of modified bentonite due to greater surface area and of Ca-bentonite is required to enhance the adsorption capacity of
effective sites for sulfur compounds. Increasing concentration of montmorillonite and increase metal uptake [33]. The desulfuriza-
H-bentonite from 0.3 to 0.9 provides more absorption sites for tion efficiency from heavy crude oil by cations modified bentonite
sulfur compounds. The desulfurization ratio did not increase was displayed in Figs. 8 and 9 that illustrated the high value of
significantly at a concentration of 1.2 gm compared to 0.9 gm. sulfur removal is 37.81% with H-bentonite and 81.43% with
In the case of Fe-bentonite, desulfurization increases with increas- Fe-bentonite under optimal conditions which 1.2 gm of modified
ing concentration and the desulfurization yield is high. The bentonite, 40 °C and contact time at 5 h. Treatment of clay with
optimum removal of the sulfur component is achieved at a high hydrochloric acid improves surface area also increases the porous
concentration of 1.2 gm. and the number of acidic sites on the surface. In addition, it
Several researchers used bentonite impregnated with different enhances the properties of bentonite due to decreases particle size,
cations to remove sulfur from model oil, but they did not use but desulfurization yield is low dose not be over 40%, this may due
heavy crude oil. However, we compare our results with the other to cation exchange selectivity small non-ionic organic compound.
research to show the effect of concentration on desulfurization. These results are consistent with the interpretation Uddin,
Ali also studied the effect of the dose on sulfur removal, using explained, through acid treatment the clay minerals become
model fuel with a different amount of Na-bentonite and hydrophobic, organophilic, and this enhances the uptake of small
mentioned that sulfur removal increased by increasing the non-ionic organic compounds [24]. While, when modification of
absorption dose [31]. Ullah et al. studied desulfurization of bentonite with alkali solution and Fe(NO3)3, this modification
model oil using activated charcoal and bentonite, and indicated enhances the surface area with pore and decrease the particle size
 M.A. Al-Bidry, R.A. Azeez / Ain Shams Engineering Journal 11 (2020) 1265–1273 1271

Fig. 5. SEM images of bentonite. A and B: raw bentonite. C and D: H-bentonite. E and F: Fe-bentonite.

Fig. 6. Sulfur wt% versus time of H-bentonite. Fig. 7. Sulfur wt% versus time of Fe-bentonite.

and it is better than acid treatment, this may explain the high effi- surfaces. Layer charge may show an indirect effect also on co-
ciency of desulfurization by Fe-bentonite, also interlayer cations volume swelling; Na preferentially concentrates in certain inter-
and layer charge influence the size, stability of montmorillonite layers, significantly impacts on break-up and formation of smectite
particles thus removal effectiveness. In mixed cation-smectite sys- particles and thus on swelling and increase surface area [25]. In the
tems, layer charge significantly affects cation exchange selectivity present study, it is clear from the results that the desulfurization
and thus the relative proportions and distributions of the various yield of Fe-bentonite is superior to H-bentonite, which exhibits
cations in the interlayer and in exchange sites on external crystal high desulfurization efficiency of crude.
1272 M.A. Al-Bidry, R.A. Azeez / Ain Shams Engineering Journal 11 (2020) 1265–1273

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