Dibenzothiophene Hydrodesulfurization over P-CoMo on Sol-Gel Alumina Modified by La Addition . E ff ect of Rare-Earth Content

Alumina-lanthana (La at 1, 3, or 5 wt%) supports were prepared by sol-gel from Al alkoxide sol where La(NO3)3 was added. Annealed (550 ◦C) xerogels were characterized by N2 physisorption, thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopyenergy dispersive spectroscopy (SEM-EDS), CO2-adsorption studied in IR region, Raman and ultraviolet-vis (UV-vis) spectroscopies. The texture of amorphous binary matrices of high La dispersion was adequate to applications in catalysts for middle distillates hydrodesulfurization (HDS). Generally, the amount and strength of surface basic sites increased with La content in solids. Mo (at 2.8 at. nm−2) and Co (at Co/(Co+Mo) = 0.3) were deposited over carriers by one-pot simultaneous impregnation in the presence of PO43− (P2O5/(NiO+MoO3) = 0.2 mass ratio). Calcined (400 ◦C) Co-Mo-P impregnated precursors had decreased basicity as to that of corresponding carriers, suggesting strong La-deposited species interaction. As La content in carriers increased Mo=O Raman stretching vibrations shifted to lower wave-numbers (949 to 935 cm−1) suggesting octahedral molybdates coordination change to tetrahedral. Although La at the lowest concentration (1 wt%) enhanced dibenzothiophene, HDS (~38% higher as to the Al2O3-supported formulation) desulfurization was significantly diminished at augmented content. Presence of hardly sulfidable tetrahedral Mo originated during impregnation at basic conditions in pores of La-modified carriers seemed to dictate observed behavior. Rare earth content in formulations enhanced selectivity to biphenyl.


Introduction
Improved catalytic formulations of enhanced properties in hydrodesulfurization (HDS) reactions that allow for compliance with ever stricter environmental regulations on S content in internal combustion engine fuels remains a challenging research field.In this context, one of the most relevant lines of investigation involves preparation of improved catalyst supports, where conventional active phases used in formulations applied at the industrial hydrotreating scale (sulfided Mo or W promoted by either Co or Ni) could have enhanced properties, including better dispersion and sulfidability or more efficient promoter integration [1][2][3].In this regard, the effects of using carriers with augmented surface basicity, as to that of conventionally used alumina, still remains a matter of debate.Some reports have shown that over carriers of increased basicity, by alkaline [4] or alkaline-earth metal [5] species addition, catalysts of enhanced selectivity to desulfurization and limited hydrogenating properties could be obtained.That effect has been attributed to several factors, for instance, decreased surface acidity by basic agent addition [4] or formation of oxidic species (magnesium molybdate and NiO-MgO solid solution, [5]) that resulted after sulfiding in MoS 2 (from MgMoO 4 , for example) phases of increased slab length and diminished saturation ability.However, decreased activity for organo-S species desulfurization (thiophene) was also observed [4], although in a lower degree, as to that registered for alkenes hydrogenation.Formation of K-decorated and K-intercalated MoS 2 phases supported on SBA-15 mesoporous materials of enhanced activity and selectivity to methanethiol from a H 2 S-CH 4 mixture have been recently reported [6].According to the authors, electron donation from K atoms could enhance the electron density of sulfided Mo species that facilitated formation of increased amounts of Mo-coordinatively unsaturated sites (CUS).
Environmentally friendly lanthanum is a cheap rare earth that has been added to catalyst carriers in order to increase their thermal resistance [7] and surface basicity [8].For instance, decreased acidity of alumina-La oxides contributed to augmented stability in ethanol conversion, due to diminished coke formation [9].Also, due to that diminished acidity, corresponding rare-earth-modified Al 2 O 3 had enhanced selectivity to ethylene (instead of to carbonaceous species) at high ethanol conversion [10].Augmented basicity provoked by La addition also resulted in improved activity in a rare-earth-modified Ni/alumina formulation tested in CO 2 methanation, that fact being originated by stronger carbon dioxide adsorption as surface carbonates that acted as so-called reactant reservoirs [11].Higher stability of La-modified HZSM-5 zeolite catalysts in methyl mercaptan decomposition, as to that of the non-doped material, has been attributed to decreased Brønsted acidity [12].
Regarding lanthanum-containing formulations applied as HDS catalysts carriers, to our best knowledge, the information available is rather scarce [13,14].Diminished activity in thiophene HDS of sulfided CoMo/alumina catalysts modified by La has been attributed to enhanced proportions of isolated MoO 4 2− refractory and less-sulfidable species adsorbed on lanthana domains [14].From their studies on molybdenum supported on La-modified alumina, Massoth et al. [13] found that strong interaction of rare earth oxidic domains with Al 2 O 3 resulted in LaO monolayer dispersion.At high La loadings, however, a second lanthanum oxide layer could be formed right over the first, the latter being partially sulfidable under 10% H 2 S/H 2 treatment (400 • C, 2 h).Higher activity, as to that of non-doped alumina-supported sulfided Mo catalysts, in both thiophene conversion and hexene saturation was found for formulations of high-La content (≥ 10 wt%).Different trends in those reactions, as a function of rare-earth concentration in tested formulations, were related to electronic support effects, which affected those reactions in distinctive ways.Also, a diminished proportion of disintegration reactions was observed, decreased cracking being originated by the neutralization of surface acidic sites over alumina, due to the basic agent deposition.Considering those contradictory results, the influence of basic La as a carrier additive on HDS catalyst properties deserves further investigation.
Respecting HDS catalysts' active phases (as opposed to corresponding supports), Chevrel phases (M x Mo 6 S 8 , where M could be La) have been synthesized and tested in HDS reaction schemes [15].Different to conventional MoS 2 -based hydrodesulfurization catalysts, where Mo is in 4 + oxidation state, in Chevrel phases Mo is in either 2 + or 2.666 + , depending on the type of second metal M. In general, HDS properties of Chevrel phases are not as good as those of MoS 2 -based catalysts, which explains why studies on those species (and particularly on those where La is the second metal) are very scarce.
In this work, lanthana modified-alumina at various rare-earth contents (1, 3, and 5 wt%) is used as CoMo-based HDS catalyst support.Textural, structural, and surface properties of carriers and corresponding impregnated materials, in an oxidic phase, were characterized through various techniques.Sulfided materials were tested in dibenzothiophene (most representative organo-S species present in middle distillates) hydrodesulfurization, in batch reactor at conditions close to those used in commercial-scale hydrotreaters aimed at diesel fuel production from oil-derived feedstocks.The activity trends found were correlated to physicochemical characteristics of studied catalysts.Some advances from this investigation have been recently reported [16].

N 2 Physisorption
N 2 physisorption isotherms (Figure S1) of alumina and La-modified supports (see Section 3.1.Materials Synthesis for samples nomenclature) were intermediate between types II and IV, according to IUPAC (International union of pure and applied chemistry) classification [17], suggesting mesoporous materials.All solids had type H1 hysteresis characterizing solids with porous networks of uniform size and shape [17], where capillary condensation started at ~P/P s = 0.5.
From Table 1, La addition was reflected in slightly increased (~10%) surface area (S gBET ) as to that of the pristine alumina carrier.More noticeable improvements were observed in both pore volume (V p ) and average pore diameter, that effect being more evident in materials at a higher rare earth content (in ALa3, 40% and 53% higher, respectively, as to sol-gel alumina).The texture of prepared binary matrices was adequate for carriers of catalysts applied in oil-derived middle distillate hydrotreatment aimed at diesel fuel production [18].Considering Co-Mo-P oxidic impregnated materials (see corresponding isotherms in Figure S2), CM/A had ~35% lower surface area as to that of the Al 2 O 3 carrier, commensurate with non-porous oxidic phase loading (~32%), which suggests well-dispersed deposited phases.On the other hand, La-modified supports had significant textural losses after Co-Mo-P impregnation (~60% diminished S g in CM/ALa1, as to that of the corresponding carrier), pointing to a partial collapse of the binary support matrix.Strandberg anions (phosphopentamolybdates), present in highly acidic impregnating solutions (see Section 3.1.Materials synthesis), could probably be decomposed under basic conditions in the interior of pores of rare earth modified materials (as indeed reported in Section 2.6.Raman spectroscopy), releasing PO 4 3− anions.Due to their strong affinity, lanthanum atoms in the solid matrices could strongly interact with those phosphate anions [20,21] being partially leached from the carriers, thus provoking the mentioned partial porous network destruction.Additionally, it has been reported [14] that, when impregnated through originally acidic solutions (as in our case), Mo could partially extract lanthanum atoms deposited over an alumina matrix, forming defined La molybdate domains.It seemed that particle growth could cause an enhanced average pore size (Table 1, as determined by Gurvich´s law [19]) of impregnated Co-Mo-P materials over La-doped carriers.Others [22] have also found that, during HDS catalysts preparation, impregnating conditions could be crucial in preserving textural properties of corresponding supports, avoiding then their collapse.Expectably, that fact could be reflected in improved catalytic activity.Pore size distributions (PSD) were determined through Barrett-Joyner-Halenda (BJH) methodology.In order to determine which PSD profile, obtained from an either adsorption or desorption data branch, better fits the actual ones, corresponding cumulative surface area values were compared to those obtained by the BET (Brunauer-Emett-Teller method, Table 1).Values from adsorption branch data (S gBJHa ) were closest to the BET ones as to those obtained from desorption data (S gBJHd ).Thus, PSD profiles from the former data were deemed the most suitable in describing the actual porous networks.PSD maxima of La-containing sol-gel carriers shifted to higher diameters as to that of non-modified alumina (~6.6 nm), ALa3 showing the maximum average value (~8.5 nm) (Figure S3a).Considering Co-Mo-P impregnated samples (Figure S3b), the maxima of CM/A and CM/ALa5 profiles shifted to larger diameters, as to those of corresponding supports (from 6.6 to 8.6 nm and from 6.4 to 8.1 nm, respectively).The amount of pores with diameters ≤ 5 nm, in the PSD of all carriers, strongly diminished after Co-Mo-P deposition.
2.2.Thermal Analyses (Thermogravimetric and Differential Thermal Analyses, TG and DTA) Thermogravimetric (TG) and differential thermal analyses (DTA) profiles of various carriers at different La contents were similar, with just small differences (not shown) in either weight losses (TG) or signal intensity (DTA).For example, corresponding plots for ALa5 are included in Figure 1.From room temperature to 550 • C, weight losses at a more or less constant rate were observed.The first part of the TGA curve (until approximately 140 • C) could be related to the evaporation of physisorbed water and alcohol from the sol-gel technique used during materials synthesis [23] (see Section 3.1.Materials synthesis).Further losses until 550 • C could be originated by the elimination of both nitrates (from La salt used) and organic remains from the Al alkoxide utilized.The endothermal signal centered at ~140 • C in the ALa5 DTA profile corresponded to aforementioned evaporation of water, alcohol, and structural hydroxyls.Meanwhile, the exothermal peak, at ~220 • C, could be provoked by NO 3 − anion decomposition [24].The intensity of this signal increased with La content in mixed formulations.The strong exothermal peak, centered at 277 • C, could be provoked by organic residua (from Al alkoxide) combustion [23].Due to crystallization phenomena (to any Al 2 O 3 , LaO or La 2 O 3 defined phases), no further signals were observed at more severe treatment conditions.In full agreement with our findings, it has been reported [25] that lanthanum addition during sol-gel alumina synthesis contributes to obtaining highly stable binary matrices delaying crystallization to the gamma phase, with defined La phases detected just after high-temperature (1000 • C) annealing.

X-ray Difracction (XRD)
Diffractograms of various supports at various compositions (not shown) showed no crystalline phases.The amorphousness of carriers suggested homogeneous materials, where La was both well-integrated and well-dispersed in alumina matrices.In Figure 2, diffractograms of the oxide at the highest La content and the corresponding Co-Mo-P impregnated material are shown.Both patterns did not show any diffraction peak, pointing to either well-dispersed deposited molybdates on the support surface or the presence of disordered amorphous Mo domains, undetectable by the used technique [26].

X-Ray Difracction (XRD)
Diffractograms of various supports at various compositions (not shown) showed no crystalline phases.The amorphousness of carriers suggested homogeneous materials, where La was both wellintegrated and well-dispersed in alumina matrices.In Figure 2, diffractograms of the oxide at the highest La content and the corresponding Co-Mo-P impregnated material are shown.Both patterns did not show any diffraction peak, pointing to either well-dispersed deposited molybdates on the support surface or the presence of disordered amorphous Mo domains, undetectable by the used technique [26].

Chemical Analysis (Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)
The chemical composition of the supports and the various impregnated materials prepared were determined from EDS (energy dispersive spectroscopy, equipment attached to a SEM, scanning electron microscope, with back-scattered electrons detector).Corresponding micrographs of La-

X-Ray Difracction (XRD)
Diffractograms of various supports at various compositions (not shown) showed no crystalline phases.The amorphousness of carriers suggested homogeneous materials, where La was both wellintegrated and well-dispersed in alumina matrices.In Figure 2, diffractograms of the oxide at the highest La content and the corresponding Co-Mo-P impregnated material are shown.Both patterns did not show any diffraction peak, pointing to either well-dispersed deposited molybdates on the support surface or the presence of disordered amorphous Mo domains, undetectable by the used technique [26].

Chemical Analysis (Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)
The chemical composition of the supports and the various impregnated materials prepared were determined from EDS (energy dispersive spectroscopy, equipment attached to a SEM, scanning electron microscope, with back-scattered electrons detector).Corresponding micrographs of La-

Chemical Analysis (Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS)
The chemical composition of the supports and the various impregnated materials prepared were determined from EDS (energy dispersive spectroscopy, equipment attached to a SEM, scanning electron microscope, with back-scattered electrons detector).Corresponding micrographs of La-modified carriers and Co-Mo-P impregnated materials are included in Figures S4 and S5, respectively.
No important differences in sample morphology were observed at this stage, all solids being constituted by faceted particles.Regarding Co-Mo-P impregnated solids, morphology of corresponding carriers is preserved (note higher mixrograph magnification in former samples).In Figure 3, representative EDS profiles of samples ALa5 and CM/ALa5 are shown.From Table 2, actual La loading (wt%) in sol-gel carriers nicely corresponded to nominal values, suggesting homogeneous binary matrices.

respectively.
No important differences in sample morphology were observed at this stage, all solids being constituted by faceted particles.Regarding Co-Mo-P impregnated solids, morphology of corresponding carriers is preserved (note higher mixrograph magnification in former samples).In Figure 3, representative EDS profiles of samples ALa5 and CM/ALa5 are shown.From Table 2, actual La loading (wt%) in sol-gel carriers nicely corresponded to nominal values, suggesting homogeneous binary matrices.S1), being slightly lower in the rest of samples.Additionally, Co and Mo contents in samples were alike in all impregnated samples.

Surface Bascity (CO2-Adsorption Studied In IR Region, CO2-FTIR)
The surface basic properties of the studied materials were estimated by integrating the area of peaks registered in the mid-infrared region, between 1800-1200 cm −1 , observed after CO2 roomtemperature adsorption [27], followed by thermo-desorption at various temperatures (Table 3).CO2 has been applied as a probe in determining the density and strength of surface basic sites of Lacontaining materials [28,29].Different surface species could be originated by carbon dioxide adsorption, namely, unidentate and bidentate carbonates and bicarbonates [30] (Scheme S1).Carbonates, related to CO2 adsorbed on surface sites with intermediate and high basic strengths,  Regarding Co-Mo-P impregnated solids, phosphorus content in CM/A and CM/ALa1 was very similar (Table S1), being slightly lower in the rest of samples.Additionally, Co and Mo contents in samples were alike in all impregnated samples.

Surface Bascity (CO 2 -Adsorption Studied In IR Region, CO 2 -FTIR)
The surface basic properties of the studied materials were estimated by integrating the area of peaks registered in the mid-infrared region, between 1800-1200 cm −1 , observed after CO 2 room-temperature adsorption [27], followed by thermo-desorption at various temperatures (Table 3).CO 2 has been applied as a probe in determining the density and strength of surface basic sites of La-containing materials [28,29].Different surface species could be originated by carbon dioxide adsorption, namely, unidentate and bidentate carbonates and bicarbonates [30] (Scheme S1).Carbonates, related to CO 2 adsorbed on surface sites with intermediate and high basic strengths, respectively, requires of surface basic oxygen atoms [31].Unidentate carbonates, characterized by symmetric and asymmetric O-C-O stretching at 1360-1400 cm −1 and 1510-1560 cm −1 , respectively, could be originated on isolated low-coordination surface O 2− anions in corners or edges.On the other hand, bidentate carbonates that could be formed on Lewis acid-base pairs (M-O 2− pair site, where M is La or Al cation, Scheme S1) are characterized by absorptions due to symmetric and asymmetric O-C-O stretching at 1320-1340 cm −1 and 1610-1630 cm −1 , respectively [31].Finally, bicarbonates involve CO 2 adsorption on low-strength basic surface hydroxyls [31], showing a C-OH bending mode at 1220 cm −1 and symmetric and asymmetric O-C-O stretching vibrations at 1480 cm −1 and 1650 cm −1 , respectively (Scheme S1).We arbitrarily classified the strength of various types of sites according to the temperature at which they could retain CO 2 (T d as weak (200 The number of surface basic sites of alumina augmented, by La addition, being that especially evident in samples of higher rare-earth concentration (see, for instance, values from room temperature spectra of ALa3 and ALa5, Table 3).Cui et al. [13] found a linear relationship between the amount of adsorbed CO 2 and La content (until ~20 wt%) in sulfided Mo/alumina samples prepared by rare-earth nitrate impregnation, although non-doped Mo/Al 2 O 3 had some surface basicity.In addition, the strength of sites as a function of CO 2 , retained after a progressively increased desorption temperature, was clearly enhanced in aforementioned solids.Most of the sites on sol-gel alumina, ALa1 and ALa5, were weak, mainly forming bicarbonates.In the opposite, ALa3 contained the strongest surface basic sites (those related to unidentate carbonates formation) among the studied materials, preserving around the third part of the total number of sites retaining CO 2 at room temperature and after treatment at 500 • C. Additionally, the relative amount of strong sites was three-fold to those over pristine alumina.In full agreement, it has been reported [32] that, on La-modified Al 2 O 3 at contents close to monolayer (~5.12 at.La 3+ nm −2 [33]) population of strong sites retaining CO 2 , was significantly enhanced.
For Co-Mo-P impregnated samples, the amount of adsorbed CO 2 was clearly diminished as to those of corresponding carriers, with the sole exception of the alumina-supported solid.In this case, significantly decreased basicity (~50%) was registered just in the case of weak sites, which could be related to the well-known strong interaction between molybdate anions and the most basic hydroxyl groups on Al 2 O 3 surface [34] (those related to bicarbonates formation during CO 2 adsorption experiments).Additionally, CM/ALa1 lost around 62% of sites adsorbing CO 2 at room temperature.The observed trend was even more marked regarding strong sites (~80% loss).Those facts could probably be related to strong deposited phases-La interaction.In the opposite, CM/ALa5 retained between 72%-83% of medium strength sites (mainly related to bidentate carbonates) of those on corresponding support.Due to strong Co [35], Mo [14] and P [20,21] interaction with La, it is probable that after impregnation the rare-earth could be lixiviated, to some extent, from the sol-gel matrix, with that fact explaining the partial textural collapse (Table 1).According to Cui et al. [13], during impregnation, Mo could preferably interact with La domains then with the alumina carrier.In addition, Ledford et al. [35] found that, in materials of La/Al ≥ 0.0075 atomic ratio (as in the case of our carriers with 3 and 5 wt% La), a Co-La phase could be formed that, being reflected in, lessened cobalt reducibility.The effects of lanthanum extraction could be more significant in the sample of the lowest rare earth content (CM/ALa1), rationalizing the important surface basicity lost.Conversely, the Co-Mo-P impregnated samples of enhanced La concentration had around 33% more sites retaining CO 2 at 400 • C as to the alumina-supported solid, pointing out the retention of mid-strength basic sites.

Raman Spectroscopy
Al 2 O 3 does not show any Raman band due to the low polarizability of light atoms and the ionic character of Al-O bonds [36].Characteristic peaks of lanthana at 104, 191 [37], 310, 350, and 415 cm −1 [38] were not evidenced, pointing to the absence of La 2 O 3 definite domains in our oxidic carriers.Raman signals at 225, 359, 911 (shoulder), and 949 cm −1 were observed in the CM/A spectrum (Figure 4a).The former two signals could be assigned to Mo-O-Mo and O-Mo-O vibrations [39].Meanwhile, those at higher wavenumbers were related to Mo=O bands.They were ascribed to Anderson species Al(OH) 6  five interconnected octahedral MoO 6 species) could, very probably, be preferentially present [40,41].
Although, due to their stability, those Strandberg heteropolyanions (H x P 2 Mo 5 O 23 (6−x)− ) [42] could exist in various protonation states over a wide pH range [41], they could be decomposed to phosphates and molybdates owing to their strong interaction with both basic hydroxyls and Al 3+ coordinatively unsaturated (CUS) Lewis acid sites on alumina surfaces [43].
basic sites.

Raman Spectroscopy
Al2O3 does not show any Raman band due to the low polarizability of light atoms and the ionic character of Al-O bonds [36].Characteristic peaks of lanthana at 104, 191 [37], 310, 350, and 415 cm −1 [38] were not evidenced, pointing to the absence of La2O3 definite domains in our oxidic carriers.Raman signals at 225, 359, 911 (shoulder), and 949 cm −1 were observed in the CM/A spectrum (Figure 4a).The former two signals could be assigned to Mo-O-Mo and O-Mo-O vibrations [39].Meanwhile, those at higher wavenumbers were related to Mo=O bands.They were ascribed to Anderson species Al(OH)6Mo6O18 3− [40], whose presence suggested partial support dissolution during contact with the acidic Co-Mo-P impregnating solution (pH ~2.5).Considering the Mo/P ratio in those solutions (~2.0) and their pH, H2P2Mo5O23 4− anions (two PO4 tetrahedrons surrounded by five interconnected octahedral MoO6 species) could, very probably, be preferentially present [40,41].Although, due to their stability, those Strandberg heteropolyanions (HxP2Mo5O23 (6−x)− ) [42] could exist in various protonation states over a wide pH range [41], they could be decomposed to phosphates and molybdates owing to their strong interaction with both basic hydroxyls and Al 3+ coordinatively unsaturated (CUS) Lewis acid sites on alumina surfaces [43].In spite of some fluorescence interference that decreased sensitivity of the technique used, CM/ALa1 and CM/ALa3, Raman spectra (Figure 4b) evidenced that the signal related to M=O stretching vibrations progressively shifted to a lower wavelength as the rare earth concentration increased, being registered at 935 cm −1 for CM/ALa5 (as compared to 949 cm −1 observed in CM/A spectrum, Figure 4a).That fact, accompanied by the apparition of a signal at 321 cm −1 (more evident in CM/ALa5), strongly suggested the co-existence of both octahedral and tetrahedral Mo species in La-containing samples.In full agreement, Payen et al. [14] reported that the Mo/ La ratio determined the type of oxomolybdenum entities adsorbed on lanthanum-modified alumina.Monomeric tetrahedral species (MoO4 2− ) could be preferably formed by an interaction with La-OH groups, whereas polymeric octahedral molybdates could be deposited on Al2O3 domains.For materials at a high La concentration (Mo/La~1), just tetrahedral molybdates were observed [14].In the same line, tetrahedral Mo species were mainly found [44] on basic magnesium-modified sol-gel alumina supports.It seemed that the high point of zero charge values of carriers with basic properties determined that behavior, as in contact with water those solids could produce high pH impregnating conditions where MoO4 2− species are favored.Additionally, coordination state modifications of Mo 6+ In spite of some fluorescence interference that decreased sensitivity of the technique used, CM/ALa1 and CM/ALa3, Raman spectra (Figure 4b) evidenced that the signal related to M=O stretching vibrations progressively shifted to a lower wavelength as the rare earth concentration increased, being registered at 935 cm −1 for CM/ALa5 (as compared to 949 cm −1 observed in CM/A spectrum, Figure 4a).That fact, accompanied by the apparition of a signal at 321 cm −1 (more evident in CM/ALa5), strongly suggested the co-existence of both octahedral and tetrahedral Mo species in La-containing samples.In full agreement, Payen et al. [14] reported that the Mo/ La ratio determined the type of oxomolybdenum entities adsorbed on lanthanum-modified alumina.Monomeric tetrahedral species (MoO 4 2− ) could be preferably formed by an interaction with La-OH groups, whereas polymeric octahedral molybdates could be deposited on Al 2 O 3 domains.For materials at a high La concentration (Mo/La~1), just tetrahedral molybdates were observed [14].In the same line, tetrahedral Mo species were mainly found [44] on basic magnesium-modified sol-gel alumina supports.It seemed that the high point of zero charge values of carriers with basic properties determined that behavior, as in contact with water those solids could produce high pH impregnating conditions where MoO 4 2− species are favored.Additionally, coordination state modifications of Mo 6+ species, from octahedral to tetrahedral (as determined by corresponding Raman shifts), by basic additive doping of alumina-supported unpromoted Mo (Mg, [5]) and CoMo formulations have been reported by others (K [45], Mg-Li [46]).Definite domains (although not large enough to be detectable by X-ray diffraction) of lanthanum molybdate have also been registered [14] by impregnating La-modified alumina with acidic solutions prepared from ammonium heptamolybdate.In our case, contributions of characteristic bands at 915 and 940 cm −1 could not be discarded, although, due to the low intensity of the registered peaks, they could remain masked.If existent, La 2 (Mo 4 ) 3 -like domains could also be responsible for tetrahedral molybdenum presence [47].According to the peaks' intensity in spectra, in Figure 4a,b, it seemed that samples CM/ALa1 and CM/ALa5 were the ones with the highest Mo dispersion (although with a high proportion of tetrahedral species).Small signals, at 1119 cm −1 , could be related to C-C bond stretching vibrations [48], probably originated by organic remains from either aluminum alkoxide used during carrier synthesis or due to acetate utilized during Co impregnation.

6+
species co-existed with them, as already suggested by our Raman spectroscopy studies (Section 2.6).
As proposed by Payen et al. [14], Mo (Th) 6+ species, related to molybdenum in strong interaction with the support, could be related to La domains, whereas Mo (Oh) 6+ ones could be deposited on alumina surfaces.As the former species were absent in the impregnating solutions (containing octahedral Mo 6+ heteropolyanions) their presence strongly pointed to the decomposition of the Strandberg species through their interaction with basic OH groups and CUS (Lewis sites) on the Al 2 O 3 carrier surface [43].
As aforementioned, basic conditions prevalent in the pores of La-modified carriers could also play a major role in tetrahedral Mo 6+ species formation.The bathochromic shift of the Mo (Oh) 6+ low-energy absorption edge strongly suggested an augmented oxomolybdates polymerization degree [52] in La-containing formulations as to that in CM/A following the order: CM/ALa1 > CM/ALa3 > CM/ALa5 > CM/A.The diminished surface area of lanthanum-modified CM materials (Table 1) could contribute to lowered octahedral Mo species dispersion.Indeed, a shoulder at ~370 nm, whose intensity increased according to the order CM/ALa1 > CM/ALa3 > CM/ALa5, pointed to the formation of MoO 3 domains [53].The triplet band related to 4 A2(F) → 4 T1(P) transitions of tetrahedral cobalt Co(Td) 2+ at 540, 580, and 625 nm [51] was augmented in rare earth-modified solids, but with no definite trend regarding La concentration.Those cobalt species could be originated in lanthanum cobaltate-like entities.Interestingly, the enhanced proportion of tetrahedral Co 2+ in alumina-supported CoMo oxidic formulations has been observed in the past by progressively increasing the basic additives concentration (Mg and Li) [46], with augmented CoAl2O4 formation being invoked in that case.For La-containing samples, shoulders at ~495 and ~563 nm could be related to octahedral Co 2+ species cobalt (Co(Oh) 2+ ) [54].These signals progressively increased in the order CM/ALa1 > CM/ALa3 > CM/ALa5, being essentially absent in the alumina-supported formulation.Additionally, a small 6.UV-vis spectra of Co-Mo-P impregnated oxidic formulations on La-modified Al 2 O 3 .Alumina-supported material included as reference.
The triplet band related to 4 A 2 (F) → 4 T 1 (P) transitions of tetrahedral cobalt Co (Td) 2+ at 540, 580, and 625 nm [51] was augmented in rare earth-modified solids, but with no definite trend regarding La concentration.Those cobalt species could be originated in lanthanum cobaltate-like entities.Interestingly, the enhanced proportion of tetrahedral Co 2+ in alumina-supported CoMo oxidic formulations has been observed in the past by progressively increasing the basic additives concentration (Mg and Li) [46], with augmented CoAl 2 O 4 formation being invoked in that case.For La-containing samples, shoulders at ~495 and ~563 nm could be related to octahedral Co 2+ species cobalt (Co (Oh) 2+ ) [54].These signals progressively increased in the order CM/ALa1 > CM/ALa3 > CM/ALa5, being essentially absent in the alumina-supported formulation.Additionally, a small shoulder at 518 nm (probably from 4 T 1g (F) → 4 T 1 g(P) electronic transition) suggested Co (Oh)

HDS Reaction Test
La content in supports of sulfided Co-Mo-P (see 3.3.HDS Reaction Test) catalysts clearly affected their dibenzothiophene HDS activity (Figure 7).The formulation with the lowest rare-earth content had the highest pseudo first order kinetic constant value (~38% enhanced as to that of the non-doped Al 2 O 3 -supported material).However, significant diminution in HDS properties was observed as lanthanum concentration augmented in tested materials.Payen et al. [14] reported progressive diminution in thiophene HDS activity as La content in alumina-supported CoMo formulations increased.Very probably, enhanced proportions of refractory tetrahedral MoO 4 2− (see Section 2.6. Raman spectroscopy), as rare earth content in formulations augmented, could be primarily responsible for that behavior.Those species are characterized by being hardly sulfidable under the used conditions [14], then precluding MoS 2 phase formation.
Al2O3-supported material).However, significant diminution in HDS properties was observed as lanthanum concentration augmented in tested materials.Payen et al. [14] reported progressive diminution in thiophene HDS activity as La content in alumina-supported CoMo formulations increased.Very probably, enhanced proportions of refractory tetrahedral MoO4 2− (see section 2.6.Raman spectroscopy), as rare earth content in formulations augmented, could be primarily responsible for that behavior.Those species are characterized by being hardly sulfidable under the used conditions [14], then precluding MoS2 phase formation.The increased amount of MoO4 2− species by the addition of basic agents in alumina-supported HDS catalysts has been reported in the past [14,56].For instance, Malet et al. [56] found augmented proportions of hardly-reducible tetrahedral molybdenum entities in Mo/TiO2 solids doped with Na (through NaOH impregnation) at various concentrations.The decreased reducibility of tetrahedral Mo 6+ species on Al2O3-supported oxidic Mo and CoMo formulations modified by basic agents (Mg and Li) was confirmed by temperature-programmed reduction studies [5,46].Regarding sulfided alumina-supported CoMo formulations modified by K addition (2.7 wt%), Maugé et al. [4] observed (by FTIR) decreased intensity in bands related to adsorbed CO as to that over the counterpart with a non-doped Al2O3 carrier.That could mean a lower proportion of sulfided phases, although the authors mainly attributed that to adsorption sites poisoning provoked by augmented sulfided phase electron density that could be reflected in diminished CO adsorption strength, under tested conditions (−173 °C).Similar to our case, those authors identified enhanced surface basicity of Kdoped solids by formation of hydrogen carbonates and bidentate carbonates (weak and medium strength sites, respectively [30]), as studied by CO2 adsorption followed by FTIR).Decreased conversion in the 2-methylthiophene in n-heptane was observed in the case of K-doped CoMo/alumina catalysts when tested in a model FCC (fluid catalytic cracking) naphtha mixture also ).Similar to our case, those authors identified enhanced surface basicity of K-doped solids by formation of hydrogen carbonates and bidentate carbonates (weak and medium strength sites, respectively [30]), as studied by CO 2 adsorption followed by FTIR).Decreased conversion in the 2-methylthiophene in n-heptane was observed in the case of K-doped CoMo/alumina catalysts when tested in a model FCC (fluid catalytic cracking) naphtha mixture also containing 2,3-dimethylbut-2-ene and orthoxylene.Regarding unpromoted sulfided alumina-supported Mo catalysts, Cui et al. [13] observed unaltered activity in thiophene HDS for materials at low La content (2 wt%), which was followed by decreased desulfurating properties in the solid modified with 5 wt% rare earth loading.
Regarding the effect of basic additives on dibenzothiophene (DBT) HDS activity of alumina-supported materials, strongly decreased activity was observed [44] in the case of NiMo formulations with a MgO-modified (5 mol%) Al 2 O 3 carrier.As the HDS activity of sulfided Mo has often been related to surface acidity [57], it seems reasonable to assume that diminished Brønsted or Lewis ones (or both) in formulations doped with basic additives could provoke limited organo-S species conversion.The high activity in DBT HDS of our sulfided alumina-supported Co-Mo-P formulation modified with lanthanum at the lowest content could result from a combination of factors.Our UV-vis results (Figure 6) suggested that, in CM/ALa1, extant octahedral molybdenum species were at lower interaction with the support.Although, according to Raman characterization (Figure 4), amount of refractory tetrahedral Mo entities augmented in that formulation, as to those over the non-doped material with an Al 2 O 3 carrier, the proportion of those monomeric species seemed to be not large enough to significantly affect proportion of sulfidable phases.In addition, the increased proportion of octahedral Co 2+ (as also observed by UV-vis, Figure 6) in the corresponding oxidic solid could be beneficial as that species is considered a precursor of cobalt that could efficiently form the highly active "CoMoS" phase during catalyst activation by sulfiding (see Section 3.3.HDS Reaction Test) [58].A linear relationship between Co (Oh) 2+ concentration in oxidic materials and HDS activity, in both gas-phase thiophene conversion and liquid phase real feedstock (vacuum gas oil and deasphalted oil) desulfurization, was found in that case.Interestingly, improved DBT HDS activity (as to that of corresponding non-modified catalysts) was observed in CoMo/alumina modified by basic agent addition, but just at a low doping agent content (1.2 wt% Mg or that solid with additional 4 wt% potassium loading) [59].However, and similarly to our case, HDS activity significantly diminished by augmenting basic species concentration in corresponding sulfided catalysts.Additionally, Cao et al. [60] reported decreased DBT HDS activity on magnesium modified (20 wt% MgO) CoMo/Al 2 O 3 materials.Very interestingly, it has been reported [61] that activity in the SO 2 conversion to sulfur, using coal gas as a reductant, of La-modified sulfided (at similar conditions to those used in the present work, Section 3.3.HDS Reaction Test) Co-Cu/γ-Al 2 O 3 catalysts was significantly improved over formulations at low rare earth content, as to that of the reference non-doped formulation.Activity was augmented by adding 0.5 wt% rare earth, the maximum being found at 1 wt% La.However, diminished SO 2 conversion was observed by augmenting dopant concentration (4 wt%).The authors attributed that to excessive La 2 O 3 loading that could accumulate around crystals of active components, generating an undesired phase change by embedding corresponding particles.Those facts clearly show that La-modified sulfided catalysts at low rare-earth contents deserve further studies, not just in HDS reaction schemes.It is also worth mentioning that recently [62] we reported on the increased activity in naphthalene conversion of Pt (1 wt%) supported on alumina modified with a basic additive (Mg in this case) at low content, as compared to the non-doped formulation with the Al 2 O 3 carrier.However, and similarly to what found during the present investigation, activity diminished in materials with a higher magnesium content (8 wt%).
Regarding selectivity to various products, DBT conversion could be carried out through direct desulfurization (DDS, to biphenyl, BP) and hydrogenation (HYD, firstly to hydrodibenzothiophenes, HDBT's) [63] reaction pathways (Scheme S2).At our reaction conditions (see Section 3.3.HDS Reaction Test), bicyclohexyl (BCH) saturation, from both aromatic rings, was observed just in trace amounts.Taking into account that BP hydrogenation to cyclohexylbenzene (CHB) could be strongly inhibited by DBT competitive adsorption under our HDS conditions, all CHB produced must have predominantly come from the HYD route through the sulfur removal of partially saturated HDBTs [64].Selectivity to BP was clearly enhanced with La content in sulfided formulations at isoconversion (x ~17%) (Figure 8).Previous studies in HDS of DBT [65,66] and benzothiophene (BT) [67] strongly evidenced that an augmented DDS/HYD ratio could be related to more efficient MoS 2 promotion by proper Co integration, then enhanced "CoMoS" phase formation.In this direction, Kaluža et al. [67] proposed that the amount of dihydrobenzothiophene (DHBT, formed from BT aromatic ring partial saturation) that could be then subsequently eliminated by C-S hydrogenolysis could be a measure of relative hydrogenation/hydrogenolysis selectivity.During their studies on CoMo sulfided formulations with various carriers, it was found that a very high promotion degree (17.9, over MgO-supported catalyst) was accompanied by a significantly decreased DHBT formation.
In the case of CoMo materials supported on alumina modified by basic agents, significantly augmented DDS/HYD selectivity in DBT HDS has been reported [46] in the past.For instance, by adding magnesia (0.05 mol ratio) to an Al 2 O 3 carrier CoMo catalysts producing strongly increased (100% enhancement at 30% conversion) DDS/HYD ratio were obtained.Even more, selectivity to biphenyl was further progressively augmented by additional lithium doping of the aforementioned formulation.Others [44] have also found decreased DBT transformation through the HYD route over sulfided NiMo catalysts supported on alumina modified by 5 mol% magnesia.
Catalysts 2019, 9, x FOR PEER REVIEW 13 of 20 proper Co integration, then enhanced "CoMoS" phase formation.In this direction, Kaluža et al. [67] proposed that the amount of dihydrobenzothiophene (DHBT, formed from BT aromatic ring partial saturation) that could be then subsequently eliminated by C-S hydrogenolysis could be a measure of relative hydrogenation/hydrogenolysis selectivity.During their studies on CoMo sulfided formulations with various carriers, it was found that a very high promotion degree (17.9, over MgOsupported catalyst) was accompanied by a significantly decreased DHBT formation.In the case of CoMo materials supported on alumina modified by basic agents, significantly augmented DDS/HYD selectivity in DBT HDS has been reported [46] in the past.For instance, by adding magnesia (0.05 mol ratio) to an Al2O3 carrier CoMo catalysts producing strongly increased (100% enhancement at 30% conversion) DDS/HYD ratio were obtained.Even more, selectivity to biphenyl was further progressively augmented by additional lithium doping of the aforementioned formulation.Others [44] have also found decreased DBT transformation through the HYD route over sulfided NiMo catalysts supported on alumina modified by 5 mol% magnesia.
Following this line of reasoning, the enhanced DDS/HYD ratio, in our case, could be originated by well-promoted (by Co) MoS2 slab edges, whose number could be restricted due to limited Mo 6+ sulfidation provoked by extant tetrahedral species.That could justify low DBT HDS activity of formulations of higher La content where cobalt could yet be properly integrated to molybdenum sulfide edges.In those catalysts, however, a certain proportion of the sulfided promoter could be as partially segregated CoxSy domains (of marginal HDS activity [66]) due to the reduced number of MoS2 layer edges, where they could be properly incorporated to produce the highly active "CoMoS phase".
Well-dispersed molybdenum sulfide phases (thus composed of short slabs) could be very efficient in aromatic ring hydrogenation [68].HYD sites have been related [46] to corner sites in Co-MoS2 slabs, whose proportion decreases as slab length grows.Those longer molybdenum sulfide layers could be originated by oxidic molybdates of lower dispersion, similarly to that proposed by Halachev et al. [69] in the case of alumina-supported P-modified NiW materials where the ratio Following this line of reasoning, the enhanced DDS/HYD ratio, in our case, could be originated by well-promoted (by Co) MoS 2 slab edges, whose number could be restricted due to limited Mo 6+ sulfidation provoked by extant tetrahedral species.That could justify low DBT HDS activity of formulations of higher La content where cobalt could yet be properly integrated to molybdenum sulfide edges.In those catalysts, however, a certain proportion of the sulfided promoter could be as partially segregated Co x S y domains (of marginal HDS activity [66]) due to the reduced number of MoS 2 layer edges, where they could be properly incorporated to produce the highly active "CoMoS phase".
Well-dispersed molybdenum sulfide phases (thus composed of short slabs) could be very efficient in aromatic ring hydrogenation [68].HYD sites have been related [46] to corner sites in Co-MoS 2 slabs, whose proportion decreases as slab length grows.Those longer molybdenum sulfide layers could be originated by oxidic molybdates of lower dispersion, similarly to that proposed by Halachev et al. [69] in the case of alumina-supported P-modified NiW materials where the ratio W=O/W-O-W, considered as a measure of dispersion of oxidic tungsten species, was related to naphthalene hydrogenation activity of corresponding sulfided formulations.Solids with a higher proportion of terminal M=O bonds resulted (after sulfiding) in catalysts with improved dispersion, and, thus, with enhanced saturation properties.In the opposite, materials with diminished dispersion resulted in decreased hydrogenating capabilities by generating longer MoS 2 with an increased edge sites/corner sites ratio.In this regard, it should be mentioned that, in our case, La-addition resulted in materials with lower oxidic Mo 6+ phases dispersion (Figure 6).Interestingly, sulfided CoMo/alumina catalysts with limited dispersion (longer slabs and augmented stacking) have also shown [70] enhanced HDS of thiophenic species, accompanied by decreased olefins hydrogenation in the selective hydrotreating of FCC naphtha focused on lowering octane number losses.
Bataille et al. [65] proposed that the main role of the promoter in DBT HDS is to enhance the reaction rate through the DDS pathway, or the C-S bond breakage activity in general.The involved mechanism could consist of attacking a hydrogen atom, in a β position relative to the S atom in a DBT molecule, by a basic sulfur anion.Primarily, both reaction routes (DDS and HYD) require a dihydrodibenzohiophene intermediate [65].Cleaving the C-S bond to produce two phenyl rings species (BP) could be carried out by hydrogenating one of the double bonds (in any of the aromatic rings) in the sulfur atom vicinity, resulting in the dihydrogenated DBT.Then, the C-S bond in the partially saturated ring could be opened by an elimination process.The second C-S bond cleavage, leading to BP, could possibly occur through a similar mechanism [65].
As the promoter (either Ni or Co) increases electron density of basic S anions, they could favor C-S bonds cleavage.The possibility of electron-rich alumina-lanthana supports contributing to increased sulfur anion basicity (then enhancing the DDS reaction pathway), as recently reported in the case of K-doped MoS 2 phases applied in methanethiol synthesis from a H 2 S-CH 4 mixture [6], remains a question that deserves to be answered.Mechanistic studies on DBT HDS over La-modified alumina supports are clearly needed, as information on reaction routes and kinetic parameters could provide valuable parameters that could be useful in investigations focused on applying that kind of catalyst under more realistic conditions in the presence of oil-derived middle distillates [71].
Regarding CoMo alumina formulations modified by La at various loadings, Payen et al. [14] found a similar promotion degree in the thiophene HDS as to that observed over a non-modified solid with an Al 2 O 3 carrier.Different trends, as to those reported by others, for corresponding catalysts doped with basic agents (in BT HDS, for instance [67]) could be originated in distinctive rate-limiting steps in tested reactions.Unfortunately, no data on selectivity through DDS and HYD reaction pathways were provided in that case [14].
From the results of the present investigation we consider that sulfided CoMo formulations, supported on alumina doped with La at low concentration (up to 1 wt%), clearly deserve deeper studies.These ongoing investigations will be the subject of further reports.
Finally, the development of HDS catalysts with enhanced activity and increased DDS/HYD selectivity ratio (as our CM/ALa1 formulation) results is promising considering their limited consumption of expensive hydrogen, mainly in the case of H 2 -constrained refineries.

Materials Synthesis
Al 2 O 3 -La 2 O 3 mixed oxides at three compositions (1, 3, and 5 wt%, ALa1, ALa3, and ALa5, respectively) were prepared by a sol-gel method.First, aluminum alkoxide was dissolved at 80 • C in corresponding alcohol (ROH/alkoxide = 60), under stirring and refluxing being kept during 2 h.Then, water and HNO 3 (3 N) hydrolysis catalysts [23] were added (H 2 O/alkoxide= 1, HNO 3 /alkoxide = 0.03, respectively), the mixture being kept under stirring and refluxing during approximately 1 more h until sol formation.Pertinent amounts of La(NO 3 ) 3 •6H 2 O in an alcoholic solution were added to the prepared alumina sol.Additional amounts of distillated water were supplied until total aluminum alkoxide hydrolysis.The mixtures were kept under stirring and reflux during 1 more h at room temperature until gelification.The obtained gels were aged, dried (~100 • C), and further calcined (550 • C, 4 h).
Over annealed mixed oxides Mo and Co were deposited (at 2.8 atoms Mo nm −2 and (Co/(Co+Mo)) = 0.3, respectively).Pore-filling simultaneous impregnation was carried out over previously dried supports (120 • C, 2 h) with an acidic solution (pH ~2.5) prepared from digestion (at ~80 • C, in water and under vigorous stirring, 4 h) of MoO 3 99.5 wt% (PQM) in the presence of H 3 PO 4 85.3 wt% (Tecsiquim, Mexico City, Mexico).H 2 O in excess (typically 250 ml of starting solution to impregnate 5 g of carrier) was used to accelerate molybdenum salt dissolution and digestion.A yellow transparent solution was obtained after hydrolysis.(CH 3 COO) 2 Ni•4H 2 O (Sigma-Aldrich, Darmstadt, Germany) was then added, with the stirring and processing temperature being maintained for 2 h.A P 2 O 5 /(NiO+MoO 3 ) = 0.2 mass ratio was fulfilled [72].A transparent dark wine solution was thus finally obtained.The solution volume was then reduced by evaporation until reaching the suitable one for pore-filling impregnation of the given mass of support.The described one-pot impregnation method was chosen as it constitutes a readily scalable methodology during catalyst preparation at the commercial scale.After impregnation materials were left aging overnight at room temperature for the diffusion of the impregnated species into the carrier porous network.Then, the materials were dried (2 h at 120 • C) and further calcined (400 • C for 5 h).Impregnated solids were identified by using the CM/ALaz key, where "z" represents La loading in corresponding supports.

Materials Characterization
Textural properties of prepared materials were determined by N 2 physisorption (at −198 • C, nitrogen saturation temperature at Mexico City barometric pressure) in a Micromeritics (Norcross, GA, USA) ASAP 2000 apparatus after ultra-high vacuum (133.32 × 10 −5 Pa) degassing at 300 • C for 2 h to eliminate adsorbed molecules.The surface area (BET, Brunauer-Emett-Teller method), pore volume, and average pore size of the materials (BJH, Barrett-Joyner-Halenda method) were determined from the corresponding isotherms.
Scanning electron microscopy pictures and chemical analysis by energy dispersive spectroscopy (EDS) of the prepared samples were performed in an environmental scanning electron microscope XL30 with an attached energy dispersive X-ray spectroscope (EDAX, Berwyn, PA, USA).
The surface basicity of alumina, alumina-lanthana supports, and the corresponding impregnated materials were characterized by CO 2 adsorption studied in the mid-infrared region.As an acid probe, carbon dioxide interacts with basic catalysts' surfaces, forming bidentate carbonates, unidentate carbonates, and bicarbonates (Scheme S1, [30]), depending on surface basic site strength.Previously, to corresponding studies, all materials (carefully weighed) were submitted to thermal treatments (500 • C), under an inert atmosphere, to eliminate adsorbed species.Samples were cooled down to room temperature with CO 2 being then fed to the system (at room temperature).Once samples were saturated, the flow of probe gas was suspended, with excess CO 2 being flushed by an inert gas stream.The corresponding spectra were acquired by using a Nicolet (Waltham, MA, USA) Magna 560 FTIR spectrometer at 4 cm −1 resolution (50 scans) in diffuse reflectance mode.The analyzed samples were treated at various progressively higher temperatures (25-500 • C) and detected peaks in the 1800-1200 cm −1 wavenumbers infrared range (corresponding to formed surface bicarbonates and carbonates) were then registered and integrated.
The Raman spectra of various impregnated samples were obtained using a Jobin Yvon Horiba (Northampton, UK) T64000 spectrometer, equipped with a CCD camera detector.As an excitation source, the 514.5 nm line of a Spectra Physics 2018 Argon/Krypton ion laser system was focused through an Olympus (Tokyo, Japan) BX41 microscope equipped with a 100× magnification objective.Laser power on the sample never exceeded 5 mW to avoid thermal effects on the samples studied.

HDS Reaction Test
Prepared catalysts were tested in sulfided form (see below) by using a batch reactor, as the main goal was to determine the effect of La content on the HDS properties of otherwise conventional P-modified CoMo/Al 2 O 3 catalysts.That approach allowed a simple, rapid comparison among the catalytic activity of various studied materials [44,46], although commercial-scale HDS applications in refineries are carried out in fixed-bed plug-flow reactors.Sulfided catalysts were obtained by submitting impregnated precursors to treatment at 400 • C (heating rate 6 • C min −1 ), under H 2 /H 2 S (Praxair, Mexico

Figure 1 .
Figure 1.Thermal analysis (TG and DTA) profiles of the ALa5 dried carrier.

Figure 2 .
Figure 2. X-ray diffraction patterns of ALa5 support and corresponding P-doped CoMo impregnated oxidic material.

Figure 1 .
Figure 1.Thermal analysis (TG and DTA) profiles of the ALa5 dried carrier.

Figure 1 .
Figure 1.Thermal analysis (TG and DTA) profiles of the ALa5 dried carrier.

Figure 2 .
Figure 2. X-ray diffraction patterns of ALa5 support and corresponding P-doped CoMo impregnated oxidic material.

Figure 2 .
Figure 2. X-ray diffraction patterns of ALa5 support and corresponding P-doped CoMo impregnated oxidic material.

Figure 6 .
Figure 6.UV-vis spectra of Co-Mo-P impregnated oxidic formulations on La-modified Al2O3.Alumina-supported material included as reference.

Figure 7 .
Figure 7. Pseudo first order kinetic constant (DBT HDS) of various tested catalysts.Batch reactor, n-hexadecane as solvent, P = 5.67 MPa, T = 320 • C, 107 rad s −1 (1030 rpm) mixing speed.The increased amount of MoO 4 2− species by the addition of basic agents in alumina-supported HDS catalysts has been reported in the past [14,56].For instance, Malet et al. [56] found augmented proportions of hardly-reducible tetrahedral molybdenum entities in Mo/TiO 2 solids doped with Na (through NaOH impregnation) at various concentrations.The decreased reducibility of tetrahedral Mo 6+ species on Al 2 O 3 -supported oxidic Mo and CoMo formulations modified by basic agents (Mg and Li) was confirmed by temperature-programmed reduction studies [5,46].Regarding sulfided alumina-supported CoMo formulations modified by K addition (2.7 wt%), Maugé et al. [4] observed (by FTIR) decreased intensity in bands related to adsorbed CO as to that over the counterpart with a non-doped Al 2 O 3 carrier.That could mean a lower proportion of sulfided phases, although the authors mainly attributed that to adsorption sites poisoning provoked by augmented sulfided phase electron density that could be reflected in diminished CO adsorption strength, under tested conditions (−173 • C).Similar to our case, those authors identified enhanced surface basicity of K-doped solids by formation of hydrogen carbonates and bidentate carbonates (weak and medium strength sites, respectively[30]), as studied by CO 2 adsorption followed by FTIR).Decreased conversion in the 2-methylthiophene in n-heptane was observed in the case of K-doped CoMo/alumina catalysts when tested in a model FCC (fluid catalytic cracking) naphtha mixture also containing 2,3-dimethylbut-2-ene and orthoxylene.Regarding unpromoted sulfided alumina-supported Mo catalysts, Cui et al.[13] observed unaltered activity in thiophene HDS for materials at low La content (2 wt%), which was followed by decreased desulfurating properties in the solid modified with 5 wt% rare earth loading.Regarding the effect of basic additives on dibenzothiophene (DBT) HDS activity of alumina-supported materials, strongly decreased activity was observed[44] in the case of NiMo formulations with a MgO-modified (5 mol%) Al 2 O 3 carrier.As the HDS activity of sulfided Mo has often been related to surface acidity[57], it seems reasonable to assume that diminished Brønsted or Lewis ones (or both) in formulations doped with basic additives could provoke limited organo-S species conversion.The high activity in DBT HDS of our sulfided alumina-supported Co-Mo-P formulation modified with lanthanum at the lowest content could result from a combination of factors.Our UV-vis results (Figure6) suggested that, in CM/ALa1, extant octahedral molybdenum species were at lower interaction with the support.Although, according to Raman characterization (Figure4), amount of refractory

Table 1 .
Textural properties (as determined by low-temperature N 2 physisorption) of ALaz supports and corresponding CoMo-impregnated oxidic materials.

Table 2 .
Chemical analysis (by SEM-EDS) of La-modified sol-gel alumina supports used.

Table 2 .
Chemical analysis (by SEM-EDS) of La-modified sol-gel alumina supports used.

Table 3 .
Relative surface basicity (CO 2 -FTIR, integrated area of peaks in the 1200-1800 cm −1 region) of supports used and corresponding Co-Mo-P oxidic impregnated materials.T d : Desorption temperature.ND: Non-determined.