Fuel 216 (2018) 142–152

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Fuel
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Full Length Article

Catalyst used in fluid catalytic cracking (FCC) unit as a support of NiMoP T

catalyst for light cycle oil hydroprocessing
⁎
Roberto Palos, Alazne Gutiérrez , José M. Arandes, Javier Bilbao
Department of Chemical Engineering, University of the Basque Country UPV/EHU, PO Box 644, 48080 Bilbao, Spain

G RA P H I C A L AB S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: The behavior of the NiMoP catalysts prepared by means of impregnation of different supports (MCM-41, SBA-15,
LCO catalyst used in FCC unit) has been studied, using them in the hydroprocessing of Light Cycle Oil (LCO) with the
Hydroprocessing aim of maximizing the sulfur removal and reduce polyaromatics content; so the hydroprocessed LCO can be
Hydrodesulfurization hydrocracked in another unit with metal noble catalysts.
Hydrodearomatization
Catalysts have been characterized through several techniques: N2 adsorption–desorption, elemental analysis
FCC catalyst
Deactivation
(ICP-AES), X-ray diffraction (XRD), acidity measurement by temperature programmed desorption (TPD) of tert-
butylamine, temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), UV–Vis spec-
troscopy, transmission electron microscopy (TEM), and temperature programmed oxidation (TPO) (spent cat-
alysts). The hydroprocessing runs have been carried out in a fixed bed reactor working in trickle bed regime at
320–400 °C; 80 bar; H2:LCO ratio, 1000 mLNH2 mL−1 LCO; space time, 0.2 h, and time on stream (TOS), 8 h.
The catalyst NiMoP/HY-Al2O3 (spent FCC catalyst) stands out due to its high hydrodesulfurization activity
attributable to the ease of impregnation of metals over FCC catalyst and the accessibility of the components of
the LCO to the hierarchical porous structure. Its activity for reducing polyaromatics compounds of LCO is also
remarkable, without diminishing the diesel fraction content by overcracking. Besides, the deposition of coke
over this catalyst is scarce, since the retention of the high molecular weight molecules of LCO in its porous
structure is minimized.

1. Introduction the increasingly strict policies about fuel composition [1]. In this sce-
nario, refineries have to steadily adapt their units for the processing, in
The petroleum industry has to meet the growing demand of fuels the medium and long term, of the non-conventional crudes (heavy-oil,
solving the inherent difficulties of the lower quality of the crude and of extra-heavy oil, oil sands). Besides, the incorporation of new feeds

⁎
Corresponding author.
E-mail address: [email protected] (A. Gutiérrez).

https://doi.org/10.1016/j.fuel.2017.11.148
Received 26 June 2017; Received in revised form 27 October 2017; Accepted 29 November 2017
Available online 08 December 2017
0016-2361/ © 2017 Elsevier Ltd. All rights reserved.
R. Palos et al. Fuel 216 (2018) 142–152

derived from biomass (bio-refinery) [2–4] and residua from consumer 2. Experimental
society, such as plastics and tires (waste-refinery) [5–7] is being studied
with the aim of obtaining fuels and raw materials for the petrochemical 2.1. Catalysts preparation
industry (such as olefins and BTX aromatics).
Currently, a technological effort in industrial development is being For LCO hydroprocessing three NiMoP catalysts have been used
done to intensify the valorization of petroleum, by means of the with the same nominal content of Ni, Mo and P, of 3, 8 and 1 wt%,
adaptation (revamping) of the units to co-feed refinery secondary respectively. Three different acidic materials, with different porous
streams. Due to its high capacity and versatility, the catalytic cracking structure, have been used as support. Discarded FCC catalyst (referred
units (FCC) are receiving great attention for the co-feeding of non-usual as HY-Al2O3 from now on), being its composition: 53.79 wt% alumina,
streams [2,4,8,9]. Nevertheless, within the scheme of a conventional 13.8 wt% zeolite, 4 wt% metals (Cu, Ni, V, Fe, Na, REO) and binder, has
refinery, best prospects are focused in the usage of hydroprocessing been removed from the catalytic cracking unit of the Petronor S.A.
units [10], even though this process shows several limitations, such as refinery (Somorrostro, Biscay, Spain) and prior to its usage as support,
the high deactivation of the catalyst [11]. it has been regenerated for about 12 h in oxidizing atmosphere at
Among the refinery streams that potentially can be valorized, the 550 °C, in order to remove the residual coke. MCM-41 mesoporous
light cycle oil (LCO) awakens great interest as its conversion into fuels support has been synthesized from a sodium silicate solution using
has a high economic incidence. The LCO is produced in FCC units with a CnH2n+1N(CH3)3Br as surfactant [26]. The SBA-15 silicate has been
high yield (15–20%) but its composition, with high content of aro- prepared from triblock amphiphilic copolymers (polyethylene and
matics (75–90 wt%), sulfur (0.2–1.5 wt%) and low cetane number (CN polypropylene oxides) in acidic medium, with the aim of producing
15-25), limit its inclusion into refinery diesel pool [12]. The LCO can be highly ordered bidimensional mesophases of hexagonal silica [27].
valorized both via cracking [13,14] and hydroprocessing [15–18], The incorporation of Ni, Mo and P has been carried out by means of
being the latest the most effective and versatile route to achieve the consecutive wet impregnations with aqueous solutions (water solution
sulfur (hydrodesulfurization) and aromatics (hydrodearomatization) ratio, 20:1) of H3PO4, then (NH4)6Mo7O2·4H2O and, finally, Ni
content values demanded for gasoline and diesel pools. Although noble (NO3)·6H2O, being the following stages: (i) stabilization via stirring for
metal catalysts are very active not only for the hydrodesulfurization 24 h; (ii) drying with air at 110 °C during 12 h, and; (iii) calcination at
reactions, but also for the ring opening reactions implied in the LCO 500 °C in N2 atmosphere during 2 h. Afterwards, catalysts have been
hydrocracking, they suffer from a fast deactivation caused by sulfur tableted and sieved (150–300 µm). Phosphorus has been incorporated
poisoning and coke deposition [19,20]. Consequently, the most ap- due to following benefits: (i) metal-support interaction decrease; (ii)
propriate strategy for LCO and another residual streams valorization ease Ni and Mo metals impregnation on the support; (iii) inhibition the
(REVAHS, REsidua VAlorization by means of Hydrogen Surplus) con- formation of inactive NiAl2O4 species; (iv) act as a second promoter;
sists on the hydrotreating of LCO in two stages [21] i) hydroprocessing and (v) improve the formation of type (II) Ni–Mo–S structures [28].
which is generally considered as the process to perform hydrogenation
and hydrogenolysis reactions; i.e. the removal of C=C and C–X bonds 2.2. Catalysts characterization
(where X=C, S, N, metals…), using low cost catalysts based on tran-
sition metals (Co, Ni, Mo, W) [15,16]; and; ii) hydrocracking, using The surface properties of the catalysts have been determined from
more severe conditions and noble metal based catalysts with acidic the N2 adsorption-desorption isotherms obtained with Micromeritics
supports, which are able to achieve high dearomatization yields by ASAP 2010 equipment. The specific surfaces of the samples have been
means of ring opening [22]. These catalysts show a moderate deacti- determined according to BET procedure using the data in the relative
vation when are used in the hydrocracking of the hydroprocessed pressure range of 0.05 to 0.2. Average pore sizes have been calculated
streams obtained in the first stage (low content of sulfur and polyaro- by means of BJH method.
matics) [23]. The acidity has been determined by temperature programmed des-
In this work, the influence of the support in the first stage of the orption (TPD) of tert-butylamine (t-BA) adsorbed at 100 °C, using a
REVAHS process for LCO valorization has been studied. For this pur- thermogravimetric-calorimetric analyzer Setaram DSC coupled in line
pose, three NiMoP catalysts prepared with different acidic supports to a mass spectrometer Balzers Quadstar 422, for the monitoring of the
have been used. MCM-41 and SBA-15 are mesoporous silica, with un- formed butenes as a result of t-BA cracking [29].
imodal and bimodal structures, respectively; and hexagonal and round The amount of coke deposited on the spent catalysts has been de-
porous shapes, respectively; having the MCM-41 support a higher termined by temperature programmed oxidation (TPO), by means of air
acidity. The usage of discarded FCC catalyst as a support is a promising combustion in a TA Instruments TGA Q5000 IR thermogravimetric
strategy due to its porous structure designed for easing the access of apparatus, coupled in line to a mass spectrometer Balzers Quadstar 422
high molecular weight molecules, such as those present in LCO [24], to monitor the CO2 formed in the coke combustion [30]. Previous to the
since the catalyst particles are prepared with a combination of HY combustion, an initial sweeping with N2 was carried out to quantify the
zeolite and a meso and macroporous matrix aluminas (HY-Al2O3) [25]. content of the retained compounds in the porous structure (possible
Furthermore, as the spent FCC catalyst is a residue highly available in coke precursors). In this stage, once the sample was stabilized at 100 °C,
refineries, if it is used in the first stage of the REVAHS process for LCO the temperature was raised up to 450 °C with a heating rate of
valorization, its lifespan will be extended. 5 °C min−1 under a N2 flow of 50 mL min−1. Temperature was held for
The main objective of the first stage of the REVAHS process for LCO 30 min and then the sample was cooled down again to 100 °C. After-
is achieving the maximum conversion of the sulfur compounds (hy- wards, the gas was switched to air (50 mL min−1) and stabilized for
drodesulfurization) with a remarkable removal of the polyaromatics 5 min. Then, to carry out the coke combustion, the sample was heated
(hydrodearomatization), but without significantly diminishing the following a ramp of 5 °C min−1 up to 550 °C, holding that temperature
boiling point range of its components. For this purpose, the spent FCC for 2 h with the aim of obtaining complete coke combustion. Finally,
(HY-Al2O3) catalyst is a suitable support, since it has a limited acidity, the sample was cooled down to room temperature.
as a consequence of the severe dealumination suffered in the con- Coke content (Cc, wt%) is defined from the mass of spent catalyst
secutive reaction-regeneration cycles, providing to it a low activity for (m0) and the mass of remaining catalyst after coke is burned (mcat):
the cracking of the aliphatic chains of LCO.
m 0−m cat
Cc = ·100
m cat (1)

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Table 1 Table 3
LCO properties. Sulfur compounds content in LCO.

Density (kg L−1) 0.887 Compound Concentration (ppm)

Simulated distillation
IBP–FBP (°C) 95.7–438.0 Total sulfur 10,212
T50–T95 (°C) 288.6–381.3 BT 344
Elemental analysis (wt%) M1BT 1414
C 89.56 M2BT 2204
H 9.37 M3BT 2641
S 1.01 DBT 280
N 0.67 M1DBT 1093
M2DBT 1255
M3DBT 981
The description of other characterization techniques: elemental
analysis (ICP-AES), X ray diffraction (XRD), temperature programmed
time, 0.2 h, and time on stream (TOS), 8 h. Previous to the reaction, the
reduction (TPR), X ray photoelectron spectroscopy (XPS), UV–Vis
catalyst has been sulfided in-situ with 50 mL min−1 of H2S:H2 (10 vol%)
spectroscopy and transmission electron microscopy (TEM), can be
mixture flow, at 400 °C during 4 h. With the aim of favoring plug flow
found in the supplementary material.
and avoiding temperature gradients in the catalyst bed, the catalyst has
been mixed with silicon carbide according to the protocol described by
2.3. Light Cycle Oil (LCO) Van Herk et al. [33]. As a reaction progress measurement it has been
determined LCO hydrodesulfurization conversion as follows:
The LCO (properties shown in Table 1) has been supplied by Pet-
ronor S.A. (Somorrostro, Biscay, Spain), and it corresponds to a product Sfeed−S prod
XHDS = ·100
fraction of the FCC unit. The density has been determined according to Sfeed (2)
the ASTM D 4052 standard. On the other hand, the simulated distilla-
tion curve has been obtained according to the ASTM D 2887 standard, where Sfeed and Sproduct are the sulfur content of the feed and liquid
using a gas chromatograph (Agilent Technologies 6890) equipped with product, respectively.
a FID detector. C–H–N content has been measured in LECO TruSpec
CHN Macrom equipment. The sulfur content has been measured with a 3. Results and discussion
specific module (TruSpec S) using an IR detector with high SO2 sensi-
bility. 3.1. Properties of the catalysts
LCO composition (Table 2) has been determined by means of bidi-
mensional gas chromatography (GC × GC) in an Agilent 7890A, The composition and surface properties of the studied catalysts are
equipped with a FID detector and coupled in line to a mass spectro- shown in Table 4, obtained from ICP-AES analyses and N2 adsorption-
meter (Agilent 5975C inert XL MSD), which has two capillary columns desorption isotherms (Fig. 2a), respectively. The three catalysts have
connected by means of a flow modulator. As it can be seen, LCO is metal contents close to nominal loading, with contents around 8 wt% of
mainly composed by aromatics (62.10 wt%) although its paraffin and the main metal (Mo) and with contents around 3 and 1 wt% of the
isoparaffin concentration is significantly high (34.25 wt%). promoters, Ni and P, respectively. However, due to the different porous
Sulfur compounds quantification and identification in the LCO structure of the supports, the catalysts have noticeably different su-
(Table 3) has been carried out with a gas chromatograph (Agilent perficial properties. The isotherms of NiMoP/MCM-41 and NiMoP/SBA-
Technologies 7890) equipped with FID and PFPD detectors. It can be 15 catalysts are type IV, with type H1 cycles of hysteresis characteristic
seen that the results obtained for total sulfur are in concordance with of mesoporous materials with one-dimensional cylindrical channels
those obtained in the elemental analysis (1.01 wt% in Table 1). The [34], that is well established for the MCM-41 [35,36] and SBA-15
identified sulfur compounds are the common ones found in LCO and [37,38] materials. In the Fig. 2b it is observed that NiMoP/MCM-41
correspond to two different families: i) reactive compounds in hydro- catalyst has a unimodal pore distribution with a maximum at 3.5 nm,
desulfurization (benzotiophene (BT) and its derivatives (MXBT)), and ii) whereas NiMoP/SBA-15 catalyst presents a bimodal distribution with
refractory compounds (dibenzotiophene (DBT) and its derivatives maxima at 3.7 and 5.5 nm corresponding to two hysteresis cycles in the
(MXDBT)). adsorption-desorption isotherms of the Fig. 2a. NiMoP/HY-Al2O3 cat-
alyst has an apparent unimodal frame, with a maximum at 3.8 nm that
2.4. Catalytic testing can be attributed to the high dilution of HY zeolite, which is embedded
in a meso and macroporous matrix of Al2O3 and SiO2-Al2O3. The
The runs have been carried out in an automatic equipment (Fig. 1) structure of the matrix has been studied by means of Hg porosimetry in
provided with a fixed bed reactor working with continuous feeding of an Autopore 9220 II equipment of Micromeritics (Fig. 2c), observing
LCO, in trickle-bed regime. The equipment has been described in detail that it has macropores in the 0.02–0.3 μm range. Due to the existence of
in previous works [31,32]. The operation conditions have been the this matrix, the porous structure of the HY-Al2O3 catalyst, with a
following: 320–400 °C; 80 bar; H2:LCO ratio, 1000 mLNH2 mL−1
LCO; space
macropore volume of 0.69 cm3 g−1, is different to that of MCM-41 and
SBA-15 mesoporous supports, which do not have macropores. Due to
Table 2 mesoporous contribution, NiMoP/MCM-41 catalyst has the biggest
LCO composition. specific surface (477 m2 g−1) and the NiMoP/HY-Al2O3 catalyst the
lowest (89 m2 g−1).
Composition (wt%)
The crystalline nature of the supports has been studied by XRD
Paraffins and isoparaffins (P + iP) 34.25 (Fig. 3a), and it can be seen that the diffractograms of NiMoP/MCM-41
Naphthenes (N) 3.65 and NiMoP/SBA-15 catalysts show a wide signal between 15 and 35°
Aromatics 62.10 corresponding to the amorphous SiO2 [39]. Besides, for the NiMoP/
1 ring aromatics (A1) 31.10
SBA-15 catalyst, two diffraction peaks are obtained corresponding to
2 ring aromatics (A2) 25.50
3 ring aromatics (A3) 5.50 the formation of orthorhombic crystals of MoO3, perceptible also in the
NiMoP/HY-Al2O3 catalyst. This MoO3 formation is attributable to the

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Fig. 1. Scheme of experimental reaction equipment.

Table 4 disordered structure of NiMoP/MCM-41 [42]. The NiMoP/SBA-15

Properties of the fresh catalysts. catalyst shows a characteristic diffractogram of this material, with a
hexagonal p6mm type mesopore arrangement, with a unique peak at
Catalyst HY-Al2O3 MCM-41 SBA-15
0.95° corresponding to (1 0 0) plane. Due to the high metallic content of
Ni (wt%)a 3.04 2.21 2.40 the catalyst (∼12 wt%), the diffraction signals corresponding to (1 1 0)
Mo (wt%)a 7.34 8.09 8.50 and (2 0 0) planes, which are typical of this material [43], are im-
P (wt%)a 0.89 0.63 0.74
perceptible.
SBET (m2 g−1)b 89 477 309
VP/P0=0,2Ads (cm3 g−1)b 24 137 88
The results of tert-butylamine (t-BA) TPD in Fig. 4, where peaks at
VP/P0=0,5Ads (cm3 g−1)b 27 183 117 temperatures below 200 °C are not found, indicate that these catalysts
VP/P0=0,5Des (cm3 g−1)b 28 196 121 have medium acidic strength [29,44], which can be attributed to the
Mesopore volume (cm3 g−1)b 0.083* 0.40 0.55 passivation of the strong acidic sites in the support by the deposition of
Macropore volume (cm3 g−1)c 0.29 – –
the metals [45]. The NiMoP/HY-Al2O3 catalyst shows a slightly higher
Average pore diameter (nm)b 26.6* 5.8 11.3
Total acidity (mmolt-BA g−1)d 0.132 0.860 0.471 acidic strength than the other two catalysts, as it cracks the t-BA at
H2 uptake (10−3 mL g−1)e 17.1 13.0 3.1 243 °C, instead of 250 °C. On the other hand, the total acidity of the
catalysts (determined by means of the integration of the area under the
Characterization technique used: aICP-AES, bN2 adsorption-desorption, cHg porosimetry, curves of the Fig. 4) follows the trend: NiMoP/MCM-41 > NiMoP/
d
t-BA TPD, eH2 chemisorption
*
SBA-15 > NiMoP/HY-Al2O3 with values being 0.860, 0.471 and
Without considering the macropores of the matrix.
0.132 mmolt-BA g−1, respectively.
The TPR profiles are depicted in Fig. 5. For NiMoP/MCM-41, cata-
high Mo concentration in the catalyst surface, due to the heterogeneous
lyst a peak at 370 °C can be seen, which is shifted for NiMoP/SBA-15
impregnation of the support [40]. In the NiMoP/HY-Al2O3 catalyst, the
and NiMoP/HY-Al2O3 catalysts until 375 and 390 °C, respectively. This
characteristic peaks of Y zeolite can be seen, with a low intensity as a
peak is commonly related to the partial reduction of the molybdate
consequence of both the low zeolite content (13.8 wt%) and the con-
species (e.g. Mo6+ → Mo4+), and the shift towards higher tempera-
secutive steaming cycles that it has been subjected to in the industrial
tures is attributed to a stronger metal–support interaction. The reduc-
unit. Moreover, the deposition of the metallic phase also contributes to
tions of the Ni2+ to Ni0 and Mo6+ to Mo4+ species take place at higher
the low intensity [41].
temperatures, at around 440 °C with a well defined peak for the NiMoP/
Fig. 3b shows low-angle XRD patterns obtained for the catalysts. It
HY-Al2O3 catalyst, and with a shoulder for the other two catalysts. At
can be seen that NiMoP/HY-Al2O3 catalyst has no signal. On the con-
temperatures around 550 °C the reduction of the Mo4+ species to Mo0
trary, the other catalysts show characteristic diffraction peaks of the
takes place [46], which is clearer observed for the NiMoP/HY-Al2O3
supports. So, for the NiMoP/MCM-41, catalyst a very well defined peak
and NiMoP/MCM-41 catalysts. Moreover, the intensity of the peaks
can be seen at 2.88° corresponding to the (1 0 0) plane, as well as other
follows the trend: NiMoP/HY-Al2O3 > NiMoP/MCM-41 > NiMoP/
less pronounced peaks between 3.5 and 4.0°, corresponding to (1 1 0)
SBA-15, which is in concordance with the H2 uptake results obtained in
and (2 0 0) planes, which is in agreement with the crystalline
the chemisorption analyses (Table 4).

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R. Palos et al. Fuel 216 (2018) 142–152

Fig. 3. Wide (a) and low (b) angle XRD patterns of the fresh catalysts.

Fig. 2. N2 adsorption-desorption isotherms of the fresh catalysts (a), mesopore size dis-
tribution (b), and macropore size distribution of the NiMoP/HY-Al2O3 catalyst (c).

The XPS spectra corresponding to Mo and to Ni are depicted in

Fig. 6a and b, respectively, whereas, the atomic contents of the ele-
ments have been displayed in Table 5. It should be noted that the
spectra corresponding to orbitals 1s of O and 2p of Si have been iden-
tified in all the catalysts but the one corresponding to the orbital 2p of P
has only been found in NiMoP/HY-Al2O3 catalyst. For the Mo (Fig. 6a)
two well defined peaks are obtained, at 232.2 and 235.6 eV, which can
be assigned to binding energies corresponding to 3d5/2 and 3d3/2 or-
bitals, respectively, of the Mo in its highest oxidation state (IV) [39]. Ni
shows two peaks, the first one with a binding energy of 856.4 corre-
sponds to 2p3/2 orbital, while the second one, at 862.2 eV is a satellite
peak of the previous one [47]. Analyzing the results of the elemental
composition of the catalysts (Table 5), remarkable differences can be
seen. NiMoP/SBA-15 catalyst has the lowest metal concentration, due
to the poor dispersion of the metallic phases, as it has been determined
Fig. 4. tert-Butylamine TPD patterns of the fresh catalysts.
with XRD analysis (Fig. 3). The greatest metal content corresponds to
the NiMoP/HY-Al2O3 catalyst, which is also, the one with the greatest
metallic dispersion and H2 chemisorption capacity (Fig. 5). polimolybdate species in octahedral coordination, respectively, and
UV–Vis spectra (Fig. 7) provide information about the coordination these two species have a second absorption band at 220 nm [40,48].
and aggregation states of the oxidized Ni and Mo species. The absorp- Although the three catalysts show tetrahedral and octahedral Mo spe-
tion band in the 200–400 nm range corresponds to the O2− → Mo6+ cies, the relative presence of these species is different. In this way,
ligand-to-metal charge transfer transition. The bands in the ranges of NiMoP/MCM-41 and NiMoP/SBA-15 catalysts have more octahedral
260–280 and 300–320 nm are related to the tetrahedral Mo species and species and NiMoP/HY-Al2O3 catalyst has a similar quantity of both Mo

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R. Palos et al. Fuel 216 (2018) 142–152

observed as well as Ni crystals of 10–20 nm. The TEM images of the

fresh sulfided catalysts reveal the typical layer-like structures randomly
orientated, which can be attributed to MoS2 species [50]. As general
trend, the three catalysts show quite homogeneous distribution of sul-
fided phases.

3.2. LCO hydroprocessing

In this section the behavior of the catalysts has been compared,

focusing on their hydrodesulfurization and hydrodearomatization ac-
tivities and the coke formation. As it is widely known in the hydro-
processing of aromatic streams with remarkable sulfur content, the
catalyst suffers from a fast deactivation (in the first hour of reaction) as
a consequence of both coke deposition and the stabilization of the
oxidation-reduction and sulfurization states of the metallic phases [19].
Afterwards, a pseudoequilibrium state is reached, in which; the coke
formation rate is null because the coke precursors are effectively hy-
drogenated and/or cracked. As a consequence, the results that are
shown in this work are those obtained after this initial deactivation
period (1 h) and they remain steady during the following 7 h on stream
(figures that show the stability of the catalyst can be found as supple-
Fig. 5. H2-TPR patterns of the fresh catalysts.
mentary material, Figs. S1–S3).

species. The presence of Ni becomes evident with a well defined band at 3.2.1. Hydrodesulfurization
390 nm and a broad band in the 600–1000 nm range, with a maximum Fig. 9 shows the results for the hydrodesulfurization conversion and
at around 840 nm. These bands are related to octahedral Ni species and sulfur compounds content in the liquid products, for the three catalysts
to [Ni2+6O2−] species with octahedral coordination, respectively [49]. at studied temperatures. These results correspond to a relatively small
TEM micrographs of fresh catalysts before and after sulfurization space time (0.2 h) with the aim of comparing the catalysts and evaluate
are shown in Fig. 8. Analyzing the images of the fresh catalysts before the effect of the temperature, although under these conditions there is a
sulfurization, the corresponding morphology of every support can be partial sulfur removal. For the first stage of LCO hydroprocessing, as an

Fig. 6. XPS spectra of the fresh catalysts corresponding

235.6 eV 232.2 862.2 856.4
to Mo(3d) (a) and Ni(2p) (b).

a) b)

HY-Al2O3

MCM-41

SBA-15

245 240 235 230 225 875 870 865 860 855 850 845
Binding energy (eV) Binding energy (eV)

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R. Palos et al. Fuel 216 (2018) 142–152

Table 5 highly dispersed on the catalyst surface. Therefore the existence of

Surface elemental composition of the fresh catalysts. those structures added to the less acidic sites and the bigger porous
structure (accessible to bigger compounds present in LCO) favor all
Catalyst HY-Al2O3 MCM-41 SBA-15
kind of reactions that take place in hydroprocessing of LCO (cracking,
Ni (at.%) 4.13 0.39 0.38 hydrogenation, hydrogenolysis, chain scission, ring-opening).
Mo (at.%) 3.88 1.88 0.63 On the other hand, the high activity of the NiMoP/MCM-41 catalyst,
P (at.%) 1.89 – –
with a much lower average pore diameter, can be explained by the
Si (at.%) 13.26 24.51 25.93
O (at.%) 76.83 73.21 73.17 contribution of the high acidity and good dispersion of the metals (even
though lower than that of NiMoP/HY-Al2O3 catalyst).
Data obtained by XPS analyses.

220 260 300 390 840 nm 3.2.2. Hydrodearomatization

Fig. 10 compares the distribution of the components of the liquid
HY-Al2O3 products for the three catalysts at three different reaction temperatures.
According to the reaction mechanism established for the LCO hydro-
MCM-41
processing, one, two and three rings aromatic compounds are sequen-
SBA-15 tially hydrogenated in the metallic sites of the catalyst, leading to
naphthenes formation, leading them to the formation of paraffins and
isoparaffins after ring-opening reactions [53,54].
Absorbance (au)

According to this mechanism, in Fig. 10 it can be seen that the

polyaromatics compounds are partially converted into mono and dia-
romatics, diminishing the concentration of 2 and 3 ring aromatics and
increasing the concentration of 1 ring aromatics, as well as the con-
centration of paraffins and isoparaffins. Besides, it can be seen that the
hydrodearomatization is favored at higher temperatures, reaching a
minimum value for aromatics of 52.7 wt% with NiMoP/MCM-41 cata-
lyst at 400 °C. The increasing of the paraffins concentration reveals the
capacity of the three catalysts to crack CeC bonds of naphthenic rings,
which is also favored at higher temperatures obtaining a maximum
concentration of paraffins and isoparaffins of 42.3 wt% with NiMoP/
MCM-41 catalyst at 400 °C.
200 300 400 500 600 700 800 900 With NiMoP/MCM-41 catalyst, a reduction of the total content of
aromatics and polyaromatics of 15 and 74.6%, respectively, is
Wavelength (nm)
achieved, while for NiMoP/HY-Al2O3 and NiMoP/SBA-15 catalysts the
Fig. 7. UV–Vis spectra of the fresh catalysts. reduction of the total aromatic is of 9.7 and 11.8%, respectively, and
the polyaromatics reduction is of 50.3 and 59.7%, respectively.
industrial objective, it can be established a reduction of sulfur content According to the properties of the catalysts (Table 4), the higher hy-
from 10,212 ppm (Table 3) to values lower than 1000 ppm, to be able to drodearomatization activity of the NiMoP/MCM-41 catalyst could be
hydrocrack the hydroprocessed stream in a second stage with a noble attributed to its greater acidity as it is the required property for the
metal catalyst without a several poisoning of the metallic functions formation of mono-aromatics via hydrogenolysis of saturated rings, that
[51]. In Fig. 9 it can be seen that the hydrodesulfurization activity trend shifts the equilibrium of the previous hydrogenation reaction, obtaining
corresponds to: NiMoP/HY-Al2O3 > NiMoP/MCM-41 > NiMoP/SBA- a higher dehydrogenation conversion than that obtained with other two
15. Furthermore, NiMoP/HY-Al2O3 catalyst is the only one that reached catalysts. As it has been previously explained, the best results for the
a sulfur concentration lower than 1000 ppm at temperatures higher three catalysts have been obtained at 400 °C. However, high acidities
than 360 °C. With NiMoP/MCM-41 catalyst, this result is only reached bring drawbacks related to the cracking and to the blocking of micro-
at 400 °C. and mesopores due to the coke deposition that diminishes the accessi-
In Fig. 9 it is also clear the different reactivity of the sulfur com- bility of the LCO molecules to the acidic sites [15].
pound families present in the LCO [21]. On the one hand, benzotio- The liquid product is lumped into naphtha (< 216 °C), diesel
phene and its derivatives are almost completely removed at 400 °C with (216–350 °C) and gasoil (< 350 °C) fractions according to simulated
conversions of 99.4, 99.7 and 98.6% for the NiMoP/HY-Al2O3, NiMoP/ distillation tests. The results of the simulated distillation of the liquid
MCM-41 and NiMoP/SBA-15 catalysts, respectively. On the other hand, product (Fig. 11) reveal that diesel and naphtha are the main fractions,
the dibenzotiophene and its derivatives are more refractory and the with concentrations of 53.7–57.9 and 33.7–39.8 wt%, respectively.
highest conversion of these compounds (with an initial concentration of Gases production has been also evaluated being the average production
3609 ppm) is of 87.2% and it is achieved with NiMoP/HY-Al2O3 cata- at 320, 360 and 400 °C of 0.48, 1.41 and 4.63 wt%, respectively. Taking
lyst at 400 °C. into account these values, yields of the lumps have been calculated as
The aforementioned results can be justified considering the different the amount of each lump in the liquid products divided by the total
properties of the catalysts (Table 4) and the importance of the porous amount of feedstock. Obtained yields have been of 34.2–36.5 wt% for
structure and acidity in the hydroprocessing stages of LCO and other naphtha fraction, of 51.3–55.1 wt% for diesel fraction and 10.7–12.2 wt
streams of high molecular weight [19,22,52]. The greatest conversion % for gasoil lump. These facts indicate that the cracking is moderate,
achieved with NiMoP/HY-Al2O3 catalyst can be attributed to the mac- with an increase of the naphtha fraction compared to the naphtha
roporous structure of the support, which makes easier the access of the fraction on the LCO of about 27 wt% due to the cracking of the diesel
LCO components. Moreover, the conversion will be favored by its and gasoil fractions. The results for the different catalysts are very si-
higher metal content and superficial dispersion. The elevated dispersion milar, being slightly better the result obtained with NiMoP/MCM-41
is boosted by the higher amount of P (as it can be seen in ICP-AES catalyst at 400 °C, reducing the amount of gasoil to 4.3 wt%, which can
analyses) which favors the formation of type (II) Ni–Mo–S structures, be attributed to the higher acidity of this catalyst (Table 4).

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R. Palos et al. Fuel 216 (2018) 142–152

Fig. 8. TEM micrographs of the fresh HY-Al2O3 (a),

sulfided HY-Al2O3 (b), fresh MCM-41 (c), sulfided
MCM-41 (d), fresh SBA-15 (e), and sulfided SBA-15 (f).

3.3. Catalyst deactivation catalyst (HY-Al2O3) used as support. This macroporous matrix is sui-
table to make easier the entrance of the LCO molecules to the active
In Fig. 12, the N2 sweeping and coke combustion at programmed sites, but also to minimize the retention of the heaviest molecules as it
temperature (TPS and TPO, respectively) are shown for the three used favors their diffusion outside the catalyst particles.
catalysts. The contents of coke precursors and coke (displayed in Comparing the results of the coke combustion for the three used
Table 6) have been determined from the area below the curves. It can catalyst, it can be seen that coke content (Table 6), as well as, TPO
be seen the following trend for coke precursors content: NiMoP/SBA- profiles (Fig. 12) are different. The less coke content for the NiMoP/HY-
15 > NiMoP/MCM-41 > NiMoP/HY-Al2O3. This order corresponds to Al2O3 catalyst can be related to the properties of the FCC (HY-Al2O3)
the different capacity of the supports to retain the components of the catalyst (weak acidity and presence of a macroporous matrix). The role
reaction media in their porous structure. The lower value (16.03 wt%) of these properties have been well established in the catalytic cracking
corresponds to NiMoP/HY-Al2O3 catalyst, which also requires a lower and are crucial to mitigate the coke formation in the hydroprocessing
temperature for the desorption of retained compounds. This result can [55,56]. Wang et al. [57] have studied the mechanism of coke forma-
be attributed to the hierarchical porous structure of the discarded FCC tion in the deep hydroprocessing of vacuum residue, obtaining that

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R. Palos et al. Fuel 216 (2018) 142–152

M1BT M2BT M3BT DBT Naphtha Diesel Gasoil

M1DBT M2DBT M3DBT 100
7000 100
90

6000 90 80
Sulfur concentration (ppm)

80 70

HDS conversion (%)

5000

Composition (wt%)
60
70
4000
50
320 ºC 60
3000
40
50
2000 30
40
20
1000 360 ºC

320 °C
360 °C
400 °C
400 ºC
30 10
0
HY-Al2O3 MCM-41 SBA-15 0
LCO HY-Al2O3 MCM-41 SBA-15
Fig. 9. Comparison for the three catalysts of the distribution of the sulfur compounds and
hydrodesulfurization conversion, for different reaction temperatures. Catalyst
Fig. 11. Comparison for the three catalysts of the concentration of the liquid product
P+iP N A1 A2 A3 lumps, for different reaction temperatures.

100

90

80

70
Composition (wt%)

60

50

40

30

20
320 °C
360 °C
400 °C

10
Fig. 12. TPS and TPO profiles of the used catalysts.
0
LCO HY-Al2O3 MCM-41 SBA-15 Table 6
Catalyst Coke precursors and coke contents of spent catalysts.

Fig. 10. Comparison for the three catalysts of the composition of the liquid product, for Catalyst HY-Al2O3 MCM-41 SBA-15
different reaction temperatures.
a
Coke precursors (wt%) 16.03 31.43 39.81
Coke (wt%)b 2.42 6.82 4.62
coke is mainly formed by fast condensation of intermediate polyaro-
matics obtained after a hydrogenation and latter cracking of phenan- Data obtained by TPSa and TPOb analyses.
threne and pyrene molecules, to form heavier compounds.
Comparing the TPO profiles plotted in Fig. 12, it can be seen that these polyaromatics towards structures that burn at higher tempera-
coke combustion over NiMoP/SBA-15 and NiMoP/MCM-41 catalysts tures due to its low H/C ratio [58].
starts at lower temperature and leads to a well defined peak, with the Another remarkable fact is that combustion temperature and coke
maximum combustion rate at around 400 °C. However, the TPO profile content (2.42 wt%) of the used NiMoP/HY-Al2O3 catalyst are inside the
for NiMoP/HY-Al2O3 catalyst corresponds to the combustion of a het- usual range in the FCC unit, so it is expected that this catalyst can re-
erogeneous coke, which shows only a shoulder at 400 °C and a max- cover its activity by means of regeneration via coke combustion in
imum in the 500–520 °C range. The greater difficulty in the combustion oxidizing atmosphere. The character of equilibrated material of the
of the NiMoP/HY-Al2O3 catalyst can also be related with the porous support guarantees that it maintains its properties (porous structure and
structure of this catalyst that allows the entrance of big molecules from acidity) along reaction-regeneration cycles, which is an advantage for
LCO. The macroporous of the matrix ease the condensation reactions of the industrial use of the FCC catalyst as a support of LCO

150
R. Palos et al. Fuel 216 (2018) 142–152

HY-Al2O3 and NiMoP/SBA-15 is about half of that corresponding to the

fresh catalysts (Table 4), whereas, the specific surface of the NiMoP/
MCM-41 catalyst has decreased by the third part. Besides, the mesopore
average pore diameter of NiMoP/HY-Al2O3 catalyst has decreased from
26.6 to 15.0 nm, revealing that coke deposition takes place in macro
and mesopores of the catalyst, leading to smaller species. However, the
average pore volume of NiMoP/MCM-41 and NiMoP/SBA-15 catalysts
remains practically constant that indicates a homogeneous blocking of
mesopores in both catalysts.

4. Conclusions

NiMoP catalysts are suitable for a first stage of the REVAHS process
for LCO (hydroprocessing of LCO) because they lead to high hydro-
desulfurization conversion at 400 °C with a remarkable reduction of
polyaromatics and without an important reduction of diesel fraction. As
a consequence, with enough space time, an adequate composition of
treated LCO can be obtained for its subsequent valorization by means of
hydrocracking with noble metal based catalysts.
Discarded FCC (HY-Al2O3) catalyst (residua from industrial unit)
has turned out to be an appropriate support for the metallic function
(NiMoP), because it allows the impregnation of these metals with high
dispersion. This property and the hierarchical porous structure of the
catalyst particle are appropriate for favoring the hydroprocessing of
LCO components with less diffusional limitations than those meso-
porous supports usually employed in the synthesis of transition metal
catalysts. The low acidity of equilibrated FCC catalyst is also suitable
for mitigating the cracking of linear chains of diesel fraction in LCO.
Additionally, the hierarchical porous structure of the FCC (HY-
Al2O3) catalyst is suitable (the same as in catalytic cracking) to mini-
mize the polyaromatics retention in the NiMoP/HY-Al2O3 catalyst. In
this way, the amount of coke deposited is remarkably lower than that
for the other catalysts that attenuates the blocking of active sites.
The coke content and combustion characteristics are similar to those
Fig. 13. N2 adsorption-desorption isotherms (a) and pore size distribution (b) of the used of FCC unit, so the regeneration of NiMoP/HY-Al2O3 catalyst will be
catalysts. viable under similar operating conditions, without affecting the support
properties.

Table 7
Properties of the spent catalysts after N2 sweeping.
Acknowledgements

Catalyst HY-Al2O3 MCM-41 SBA-15 This work has been carried out with financial support of the
Ministry of Economy and Competitiveness (MINECO) of the Spanish
SBET (m2 g−1) 42 114 149
VP/P0=0,2Ads (mL g−1) 11.7 32.3 42
Government (CTQ2013-46172-P, CTQ2015-67425R), the ERDF funds
VP/P0=0,5Ads (mL g−1) 12.7 49.7 61 of the European Union, the Basque Government (IT748-13) and the
VP/P0=0,5Des (mL g−1) 12.9 55.7 63 University of the Basque Country UPV/EHU (UFI 11/39).
Mesopore volume (mL g−1) 0.045* 0.12 0.28 The authors thank for technical and human support provided by
Average pore diameter (nm) 16.0* 6.2 11.0
SGIker of UPV/EHU and European funding (ERDF and ESF).
Data obtained by N2 adsorption-desorption.
* Without considering the macropores of the matrix. Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the

hydroprocessing catalyst. The stability of the catalyst has been checked online version, at http://dx.doi.org/10.1016/j.fuel.2017.11.148.
by successive reactions after regeneration of the catalyst by coke
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