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Benzothiophene hydrodesulfurization over NiMo/alumina catalysts

modified by citric acid. Effect of addition stage of organic modifier

Article  in  Fuel Processing Technology · February 2017

DOI: 10.1016/j.fuproc.2016.09.028

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 Fuel Processing Technology 156 (2017) 33–42

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Benzothiophene hydrodesulfurization over NiMo/alumina catalysts

modified by citric acid. Effect of addition stage of organic modifier
José Escobar a,⁎, María C. Barrera b, Ana W. Gutiérrez a, José E. Terrazas b
a
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, San Bartolo Atepehuacan, Gustavo A. Madero, D.F., Mexico, 07730
b
Facultad de Ciencias Químicas-Centro de Investigación en Recursos Energéticos y Sustentables, Universidad Veracruzana, Campus Coatzacoalcos, Av. Universidad km. 7.5, Col. Santa Isabel,
Coatzacoalcos, Veracruz 96538, Mexico

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

Article history: NiMo/Al2O3 catalysts were obtained by one-pot simultaneous impregnation of Mo, Ni and P (at 12, 3 and 1.6 wt%,
Received 3 June 2016 respectively) over alumina. Citric acid (CA) was added (Ni/CA=1 mol ratio) to determine its influence over mo-
Received in revised form 30 August 2016 lybdenum species, as nickel precursor used was complexated Ni acetate. Three different preparation methodol-
Accepted 25 September 2016
ogies were used: (a) modification of calcined (400 °C) NiMo/Al2O3 by CA impregnation, (b) CA deposition
Available online xxxx
directly onto Al2O3 carrier, prior to Ni-Mo-P impregnation, (c) simultaneous Ni-Mo-P-CA deposition on alumina
Keywords:
support. Materials were characterized by N2 physisorption, infrared and UV-vis spectroscopies, temperature-pro-
Citric acid grammed reduction and thermal analysis (TG-DTG), and tested in liquid-phase benzothiophene (BT) conversion
NiMo catalysts in batch reactor. CA deposition over calcined NiMo/Al2O3 resulted in diminished proportion of refractory Mo6+(t)
Hydrodesulfurization tetrahedral species but also in octahedral Mo6+(o) reducible at higher temperature, as to those over non-modified
Benzothiophene NiMo/alumina. That was reflected in lower hydrodesulfurizating (HDS) ability. The highest BT HDS activity (70%
Chelating agent increase, as to the conventional calcined formulation with no organic additive) was found when CA was impreg-
nated over bare alumina prior to Ni-Mo-P deposition. In that case, decreased interaction between deposited mo-
lybdenum and nickel species and the support was evidenced, that due to surface “passivation” from citric
adsorption/decomposition on alumina surface. On the other hand, simultaneous Ni-Mo-P-CA deposition,
where low pH of impregnating solution (pH~1.4) devoided citric acid ionization, (then, no Mo-citrate complex
formation) was ineffective in providing catalyst of enhanced HDS activity.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction The beneficial influence of chelators that could complexate Ni or Co

Continuous tightening of environmental legislations that constrains
sulfur content in oil-derived fuels to extremely low concentration de-
mands for improved S-removal processes [1]. Posing an extra challenge,
low-quality heavy crudes of enhanced concentration of organic precur-
sors of atmospheric pollutants have to be used as raw materials in
obtaining those fuels, as light-oil resources are progressively worldwide
depleted. Thus, more efficient hydrodesulfurization (HDS) processes,
including both optimized industrial facilities set-up and improved cata-
lytic formulations are clearly needed.
Several approaches have been attempted in order to obtain mate-
rials of enhanced HDS activity as to that of traditional alumina-support-
ed Ni(Co)Mo(W) sulfided formulations. Those strategies have been
mainly focused on improving dispersion and sulfidability of supported
phases or in optimizing decoration of MoS2 crystals by promoters (co-
balt or nickel) that resulted in improved formation of the highly active
“Ni(Co)Mo(W)S” phase.
⁎ Corresponding author.
E-mail address: jeaguila@imp.mx (J. Escobar).
promoters has been addressed by various groups [2–4]. Most of authors
[5–8] coincide in that stable complexes formed by promoter chelation
could resist low-temperature sulfiding until conditions at which Mo
(or W) component could be transformed to corresponding sulfides.
Once those MoS2 (or WS2) particles are present, organo-Co or -Ni spe-
cies could be decomposed allowing promoters sulfidation. The highly
active “CoMo(W)S″ or “NiMo(W)S” phases could be then preferentially
formed by efficient Mo (W) sulfide slab edges decoration, precluding
segregation of sulfided Co/Ni phases that could result in catalysts of
minor HDS properties.
However, other positive roles could be played by chelating agents
added during hydrotreating catalysts synthesis. Among them, carbon
deposition [9] and decreased deposited phases-support interaction [2]
have been evidenced. Interaction between chelating ligands and car-
riers could strongly influence properties of final hydrotreating catalysts.
Isoelectric point and type of hydroxyls present on a given substrate
could determine that interaction degree [3]. For instance, carboxylate
groups in various chelators play an important role on those effects
through their affinity to OH groups on support surface [10]. For SBA
15-supported NiMo catalysts Badoga et al. [2] found that EDTA-support

http://dx.doi.org/10.1016/j.fuproc.2016.09.028
0378-3820/© 2016 Elsevier B.V. All rights reserved.
34 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42
interaction (via surface OH groups) weakened the Mo-carrier one favor-
ing molybdenum sulfiding that was reflected in improved activity in
light gas oil HDS.
Depending on pH and concentration citric acid could complexate
both Ni and Mo, contributing in formation of highly dispersed NiMoS
active phase of enhanced activity in refractory 4,6-dimethyl-
dibenzothiophene HDS [11]. In this case, the hydrogenation route was
strongly improved in KIT-6 mesoporous silica-supported NiMo catalysts
by adding citric acid at conditions where both Ni and Mo species could
be complexated. The organic acid provided efficient bridging between
impregnated species and the silica carrier enhancing their interaction,
the deleterious effect of the rather inert SiO2 surface being then
precluded.
In the opposite, different organics have also been used to deposit
carbon layers over alumina supports intending to weaken the strong in-
teraction between the carrier and impregnated Mo, W, Ni and Co
phases. In that line, Nikulshin et al. [12] found that depending on con-
tent of carbon deposited by pyrolyzing an isopropanol-glycerin (2
vol.%) mixture over Al2O3 sulfided NiW catalysts of enhanced properties
in dibenzothiophene HDS, naphthalene hydrogenation and quinoline
hydrodenitrogenation could be obtained. The best results were found
at approximate carbon monolayer (C ~5 wt%).
In a previous paper [13], the addition stage at which saccharose as
non-complexating additive should be added to obtain sulfide NiMo/
Al2O3 catalysts of improved HDS properties was determined. Among
preparation procedures studied, simultaneous one-pot Ni + Mo +
P + SA deposition rendered the material of the highest
dibenzothiophene desulfurization activity.
Similarly, the present contribution is focused on determining the
stage at which citric acid (complexing agent) should be added (at Ni/
CA = 1 mol ratio) to obtain materials of enhanced activity in organo-S
compounds removal. One-pot simultaneous Ni-Mo-P impregnation
was used as that preparation method is relevant to commercial catalysts
production. This work was focused on CA effect over molybdenum spe-
cies as nickel precursor was complexated Ni acetate. Differently to the
work of Wu et al. [11] where CA was added to increase interaction be-
tween KIT-6 mesoporous silica and Ni and Mo species, in our work we
tried to tune up the already strong affinity between those deposited
species and the alumina carrier. Prepared solids were characterized
through various instrumental techniques to try to explain the activity
trend found in benzothiophene HDS.
2. Experimental
2.1. Materials preparation
Al2O3 was obtained by annealing (500 °C, 5 h under static air) com-
mercial Pural SB sol-gel pseudo-boehmite (from Sasol) obtained from
Al-alkoxides. Oxidic catalyst precursors were prepared by one-pot im-
pregnation of Mo, Ni and phosphorous (at 12, 3 and 1.6 wt%, respective-
ly) by incipient wetness through an aqueous solution where MoO3 was
digested (at ~ 80 °C) in diluted H3PO4. After ~ 2 h nickel acetate
(NiC4H6O4·4H2O) was added, the solution being then digested by addi-
tional 12 h (~ 80 °C). Three different methodologies were followed to
obtain impregnated materials: Method I comprised Al2O3 impregnation
with aforementioned solution (at pH ~ 1.4 [14]) followed by drying (2 h,
120 °C, sample NM120) then calcining (400 °C for 5 h, key NM400).
Right after, part of that calcined material was impregnated with citric
acid at Ni/CA = 1 mol ratio (sample NMI) being then dried at 120 °C,
(2 h) high-temperature annealing being avoided to preserve organic ad-
ditive integrity. Citric acid decomposition could start at about 165 °C
[15]. Then, in order to effectively determine its influence on HDS cata-
lyst properties through various preparation steps it was crucial to
keep intact different functionalities (chelating agent, carbonaceous de-
posit precursor, etc.) by precluding annealing at severe conditions.
In the second methodology the carrier was firstly impregnated by
pore-filling with an aqueous CA solution (concentration corresponding
to Ni/CA = 1 mol ratio), then dried at aforementioned conditions. Sub-
sequently, Ni-Mo-P phases were simultaneously deposited over the
modified support by one-pot pore-filling impregnation by using the
previously described solution. Resulting solid was then dried at 120 °C
(2 h), sample NMII. In the third methodology CA was directly added
(at Ni/CA = 1 mol ratio) to the already prepared Ni-Mo-P aqueous solu-
tion that was then used to impregnate the Al2O3 carrier. The impregnat-
ed material was finally dried at 120 °C (2 h), sample NMIII.
2.2. Materials characterization
Textural properties of various materials were determined by N2
physisorption (at −198 °C), in an Autosorb-1 (Quantachrome) appara-
tus. Studied solids were previously degassed at 300 °C (2 h) at high vac-
uum (133.32 × 10−5 Pa) to eliminate any adsorbed molecules. Surface
area and average pore size were determined though BET equation and
Gurvich's rule [16], respectively.
FTIR (Fourier-transform infrared) spectra were acquired by a Perkin
Elmer Frontier FT-IR equipment with an attached Praying Mantis Dif-
fuse Reflection Accessory in the 3750–500 cm−1 range (alumina sup-
port in the 4000–1000 cm−1 range).
Cobalt and molybdenum coordination in oxidic impregnated mate-
rials were studied by UV–vis (diffuse reflectance spectroscopy) by uti-
lizing a Cary 100 equipment in the 200–800 nm wavelength range.
Supported Ni-Mo samples (approx. 100 mg in a quartz cell) were
studied by temperature-programmed reduction (TPR, in the 25–
900 °C range, 0.166 °C s−1 heating rate) by using an ICID SRyC-2 appa-
ratus equipped with thermal conductivity detector. A H2/N2 mixture (at
10 v/v %, 0.33 cm3 s−1 total flow) was used.
Thermogravimetric analysis (TGA) of impregnated samples were
carried out through a TA instruments Q2000 equipment. 15–50 mg
samples were analyzed in the 30–1000 °C temperature range (heating
ramp of 0.166 °C s−1). Differential thermogravimetric profiles were ob-
tained through derivatives of corresponding TG curves.
2.3. HDS reaction test
Prior to be tested in benzothiophene hydrodesulfurization NiMo/
alumina oxidic precursors were submitted to activation. Materials
were ex-situ sulfided in a pyrex glass tubular reactor under H2:H2S
8:1 gas flow (approx. 0.944 ml s−1). Heating rate from room tempera-
ture to 400 °C was 0.166 °C s−1, sulfiding stage taking place for 7200 s
at final conditions. Then, the system was cooled-down to room temper-
ature and ~ 240 mg of sulfided catalyst were recovered in 20 ml of n-
heptane under inert (N2) atmosphere provided by a glove box, preclud-
ing contact of activated catalysts with atmospheric oxygen to prevent
their oxidation to corresponding sulfates. In order to discard control
by internal diffusion/counterdiffusion of reactants/products catalyst
particle size was chosen from the fraction retained between U.S. mesh
size 80–100 (165 × 10−6 m average particle diameter) which according
to our extensive experience in HDS reaction tests effectively guarantee
testing under kinetic regime [13,14].
Sulfided catalysts were tested in benzothiophene (BT, ~0.30 g) HDS
in n-heptane in a slurry stainless-steel (T316 SS) Parr batch reactor 4570
(Scheme 1). BT well-represents less-reactive organo-sulfur species in
FCC naphtha (although it is also present in light middle distillates),
whereas n-heptane corresponds to hydrocarbons within naphtha boil-
ing range [17]. S concentration in the mixture was ~ 1040 ppm, value
typically found in fluid catalytic cracking naphtha. Reaction volume
was adjusted to 100 ml by adding the required amount of solvent. Reac-
tion conditions were 250 °C, 7.2 MPa and ~ 105 rad s−1 mixing speed
(Parr magnetic drive). The last value was carefully chosen based in pre-
vious experience to avoid reaction control by external diffusion phe-
nomena [13]. Reaction temperature was similar to those used in
 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42 35

naphtha hydrotreating commercial facilities [18]. Also, by operating at Table 1

used pressure it was assured that most of the solvent remains in liquid Textural properties of alumina support and NiMo impregnated materials (dried and cal-
cined), as determined by N2 physisorption (−198 °C).
phase (n-heptane boiling temperature ~264 °C) allowing proper opera-
tion of the slurry tri-phasic reactor. Operating pressure was monitored Sample SBET Vp Dpa
by both T316 stainless steel bourdon gage and stainless steel-housing (m2 g−1) (cm3 g−1) (nm)

transducer. Initial benzothiophene concentration was CBT0 = 0.0223 Al2O3 250 0.51 8.2
mol l−1 at room temperature and atmospheric pressure (0.01546 mol NM120 174 0.30 6.9
NM400 196 0.36 7.3
l−1 under reaction conditions, considering n-heptane density = 0.47 g
cm-3 [19]). a
From 4 × VpS−1
BET.

Nitrogen (at 7.5 MPa) was fed into the rector to remove air traces
then to check hermeticity of the experimental set-up. After confirming BT conversion (x) at a given time (t) was determined by (see
airtight system (0.5 h), N2 was evacuated and heating through corre- Nomenclature section):
sponding cylindrical oven (Scheme 1) started meanwhile stirring (at ~
105 rad s−1) uniformized radial thermal profile. Temperature monitor- AEB
xBT ¼ ð1Þ
ing and control was carried out through a type-J (iron-constantan) ther- ABT þ AEB
mocouple attached to corresponding 4848 Parr Instrument Company
controller. Once reaction temperature (250 °C) was reached, H2 was HDS kinetic constants (k) were calculated assuming pseudo-first
fed until getting 7.2 MPa total pressure. Zero time was considered at order kinetics referred to BT concentration:
that moment. A deep tube allowed periodically obtaining liquid sam-
−RBT ¼ k1 C BT C H2 ð2Þ
pling at various reaction times (from 0 to 7200 s, each 600 s, 11 samples
in total) to determine BT conversion. Operating pressure slightly de-
creased after sampling, H2 being then fed to recover original conditions. Constant H2 concentration in solvent (CH2) was assumed due to both
Liquid samples were analyzed in an Agilent 6890 N gas chromato- very high excess fed and negligible hydrogen consumption under reac-
graph provided with flame ionization detector and HP-5 (5% phenyl- tion conditions.
95% methyl-polysiloxane) non-polar capillary column (50 m, Then,
0.20 mm, 0.50 μm, length, diameter and film thickness, respectively).
−RBT ¼ kC BT ð3Þ
Good repeatability was confirmed by analyzing each liquid sample at
least twice. Under our reaction conditions, the only product detected
The mass balance of a batch reactor at constant volume,
was ethylbenzene (EB) which saturation to ethylcyclohexane was just
observed after total BT consumption. Although decompression (from Z
dC BT
7.2 MPa to atmospheric pressure) that took place during sampling RBT ¼ ð4Þ
dt
could provoke components evaporation we considered that due to its
higher volatility and corresponding required phase-change enthalpy
Integral reactor regime was considered as at high conversions HDS
[20] n-heptane rapid vaporization resulted in liquid samples cooling
reaction rate was dependent on BT transformation degree. As CBT =
fast enough to avoid BT and EB significant losses. Considerable higher
CBT0 (1-x), by combining Eqs. (3) and (4):
vaporization enthalpy of the latter [21] could also contribute to that. Al-
though due to solvent evaporation BT and EB concentration in analyzed Z
dC BT0 ð1−xÞ
liquid samples could differ from the actual one in the reactor, BT conver- −kC BT0 ð1−xÞ ¼ ð6Þ
dt
sion determinations could be considered accurate as they were calculat-
Z Z
ed from the proportion of those species in a given sample. dx
k dt ¼ ð7Þ
ð1−xÞ

− ln ð1−xÞ
k¼ ð8Þ
t

Fig. 1. Room temperature Fourier-transform infrared spectra (4000–1000 cm−1 region) of

Scheme 1. Tri-phasic slurry batch reactor used during catalytic tests (benzothiophene alumina-supported NiMo oxidic materials with and without citric acid prepared through
hydrodesulfurization) of various sulfided catalysts prepared. various protocols. Infrared spectrum of alumina support also included as reference.
36 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42
Fig. 2. Room temperature Fourier-transform infrared spectra (2000–1000 cm−1 region) of
alumina-supported NiMo oxidic materials with and without citric acid prepared through
various protocols. Infrared spectrum of alumina support also included as reference.
Kinetic constants were normalized by mass of catalyst (k in m3 kg−1
cat
s−1).
3. Results and discussion
3.1. Textural properties
Lower Sg of NM400 as to that of bare alumina support, nicely
corresponded to textural diminution by deposition of ~25 wt% of non-
porous Ni-Mo-P phases, Table 1. That suggested well-dispersed impreg-
nated species as significant textural losses by partial plugging of support
porous network was not observed.
3.2. FTIR (Fourier-transform infrared) spectroscopy
From FTIR spectra in Fig. 1 bands due to stretching vibrations of sur-
face OH groups at 3780 (type Ia, basic, single-bonded to one octahedral
aluminum [22]) and 3696 cm−1 (type IIb, neutral, bridged to two octa-
hedral Al3+ [23]) on Al2O3 were not evident in impregnated materials
due to preferential deposition of molybdate anions over those types of
surface OH groups [24].
Absorptions at 2970 and 2857 cm−1 related to –CH3 degenerated
stretching mode and –CH2 stretching symmetrical vibrations, respec-
tively, appeared in all spectra but in NM400 (no organic additive). In
general, in the 400–3000 cm−1 region studied samples spectra were
pretty similar to those of alike prepared with saccharose as modifier
[13].
Fig. 3. UV DRS spectra (Schuster-Kubelká-Munk function) of alumina-supported NiMo
oxidic materials prepared with and without citric acid through various protocols.
Fig. 4. Visible region DRS spectra (Schuster-Kubelká-Munk function) of alumina-
supported NiMo oxidic materials prepared with and without citric acid through various
protocols.
Undissociated water adsorbed on the carrier originated an intense
broadband in between 1500 and 1700 cm−1 [25], Fig. 2. For samples
prepared with CA the absorption at ~ 1570 cm−1 (more intense in
NMII) could be assigned to υas stretch of carboxylate groups [26] pre-
served after impregnation. The absorption at ~1460 cm−1 (more nota-
ble in NMI) was also related to carboxylates (υs OCO vibrations) [27]. A
band due to interactions between COO– and OH groups on the carrier
was recorded at ~ 1415 cm−1 [28]. That signal could correspond to υs
COO– (originally found at 1390 cm−1 in free citrate groups [29]) that
blue-shifted after deposition over the alumina substrate. The highest in-
tensity of that absorption in NMI suggested stronger interaction be-
tween carboxylate groups and acidic hydroxyls (type III, triply bonded
to Al3 + atoms in either octahedral or tetrahedral coordination [22])
remnant on Al2O3 carrier after Ni-Mo-P phases deposition-calcining.
Disappearance of shoulder at ~ 3550 cm−1 in NM400 spectrum after
CA impregnation (sample NMI in Fig. 1) supported that observation.
Also, absorptions due to C_O in carboxylates complexating Ni2+ [26]
were observed at 1621 cm− 1 for CA-modified solids (shoulder in
NMIII spectrum).
The absorption at 1660 cm−1 which intensity decreased following
the order NMII N NMI N NMIII was related to Mo complexation. The
presence of [(MoO2)2O(H2cit)2]2−·4H2O anions with infrared absorp-
tion at 1657 cm− 1 [30] was then suggested in our CA-impregnated
solids. From spectra in Fig. 2 it seemed that CA deposition over bare alu-
mina prio to Ni-Mo-P impregnation (sample NMII) was the most effec-
tive methodology to obtain chelated Mo species. By contacting alumina
with CA aqueous solutions at pH b 5 citrate anions could react with
Lewis acid sites on carrier [29] resulting in highly negative charged sur-
face then shifting the point of zero charge (usually between 7 and 9 for
Al2O3 [31]) to lower pH. Clearly, that could occur during NMII prepara-
tion when impregnating the carrier with CA solution [~1 M, pH ~ 2.95].
Formation of other complexated Mo species could also be consid-
ered. In this regard, the possible presence of [Mo4(C6H5O7)2O11]4− an-
ions could originate the signal at 1736 cm− 1 (in NMII, shoulder in
Table 2
Band-gap energy (BGE) and average number of nearest Mo6+ neighbors (NMo) in depos-
ited clusters, as determined from UV spectra of NiMo impregnated materials prepared
with and without citric acid.
Sample BGE NMo
(eV)
NM400 3.56 2.47
NMI 3.76 1.70
NMII 3.89 1.20
NMIII 3.83 1.46
 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42 37

Fig. 5. Temperature-programmed reduction profiles of alumina-supported NiMo oxidic Fig. 6. Thermogravimetrical analysis profiles of alumina-supported NiMo materials
materials prepared with and without citric acid through various protocols. prepared with and without citric acid through various protocols.

NMI) ascribed to non-bonding non-dissociated υ(C_O) in carboxylates addition provoked both increased intensity (much more notable ab-
[27]. Those molybdenum complexes could also produce bands at 1567 sorption in NMII and NMIII) and hypsochromic shift in that signal
and 1414 cm−1 due to υas(COO) in monodentated species and to with maximum at 258, 263, 267 and 275 nm for NMII, NMIII, NMI and
υs(COO) bridiging molybdenum atoms, respectively. NM400, respectively. As blue-shifted low-energy absorption edge has
The slight shoulder at approximately 1685 cm−1 in NMII and NMI, been related to smaller MoxOy domains [33] better dispersed oxo-mo-
associated to “free” noncoordinatively bonded\\CO\\OH groups [26], lybdates were strongly suggested in CA-modified formulations. CA im-
was more defined in NMIII pointing out to carboxylates not pregnation onto calcined sample NM400 (sample NMI) could not
complexating metallic atoms. That could be explained by the thermody- significantly improve molybdenum dispersion. Even more, the intense
namically non-favored CA dissociation in the highly acidic (pH ~ 1.4, signal in the 276–310 nm range in NMI spectrum strongly suggested
[14]) simultaneous one-pot Ni-Mo-P impregnating solution. Based on less-dispersed Mo6+ domains.
diagrams of Ni(II) and Mo(VI) species in CA aqueous solutions at differ- Regarding visible region spectra in Fig. 4, absorption at 401 nm in
ent pH Wu et al. [11] found no Mo complexes at conditions similar to NMII (shoulder in NMIII) was associated to octahedral Ni2+ [34]. That
those used during NMIII preparation (pH ~ 2, [Cit] = 1.3). Respecting signal was merged to low-energy Mo absorption edge in NM400 and
nickel, it could remain as corresponding acetate (from reactant used NMI spectra. Absorptions around 670 and 740 nm (3A2g → 3T1g (F) elec-
during impregnation, Section 2.1) under those impregnating conditions. tronic transitions) were also related to octahedral Ni2+ [35]. The former
Taking into account the CA amount added during catalysts synthesis nickel d-d transition blue-shifted from 676 nm in NM400 and NMIII to
(Section 2.1 Materials preparation) and the stoichiometry of aforemen- 669 nm in NMI and NMII pointing out to stronger coordinating ligands
tioned chelated Mo species, about 40–80% of molybdenum could be in the latter solids thus suggesting presence of complexated Ni2+ spe-
complexated whereas the rest could exist as polyoxomolybdates. cies [25]. Conversely, NM400 and NMIII could be associated to weaker
ligands (probably water molecules) in their coordination sphere.
3.3. UV–vis DRS spectroscopy For all samples but NMIII, the higher intensity of band at ~670 nm as
to that at 740 nm could indicate weak exchange interaction among Ni2+
From DRS UV–vis spectra of Fig. 3, all samples prepared with organic species suggesting well-dispersed supported nickel phases [35].
additive had high-energy absorption related to chromophore carbonyl The small shoulder at 588 nm for NM400 appearing just as hump in
in carboxylate groups (at 204 nm for NMI and NMII, at 208 nm for NMI suggested traces of tetrahedral Ni2+ thus pointing out to incipient
NMIII). The bathochromic shift in the latter suggested close interaction “surface spinel-like species” formation when submitting those solids at
of C_O moiety with OH groups [32] of undissociated carboxylate annealing (400 °C) [36].
under the strongly acidic conditions of one-pot Ni-Mo-P simultaneous
impregnation. 3.4. Band gap energy determinations
A broad inflexion which intensity decreased in the order NMII ≈
NMI N NMIII N NM400, suggested Mo species in different interaction de- To get better insight on oxidic molybdenum coordination in impreg-
grees with the alumina support. Position of that band precluded clear nated materials band-gap energy (BGE) of Mo6+ domains (from data
discrimination of tetrahedral and octahedral Mo6 + oxo-species. CA obtained through UV–vis spectra, Fig. 3) were determined. BGE values
were then correlated to molybdenum species of various coordination
states [33], Table 2.
Table 3
Maxima of signals from temperature-programmed reduction profiles of alumina-support-
ed NiMo materials (Fig. 5). Table 4
Weight losses at various temperature ranges from thermal analysis profiles of alumina-
6+ 4+ 2+ 0
Sample Mo (o) to Mo Ni to Ni Mo6+(t) to Mo 0
supported NiMo materials (Fig. 6).
(°C) (°C) (°C)
Sample b90 °C 175–310 °C 310–600 °C N800 °C Total
NM400 469 685 892c
(wt%) (wt%) (wt%) (wt%) (wt%)
NMI 498 750 892c
NMII 409, 462a 547b, 624b, 717 840b NM120 4.5 2.7 2.4 8.0 17.6
NMIII 451 669b, 825 891c NM400 3.4 2.3 1.8 9.6 17.1
a NMI 5.0 3.1 4.7 8.9 21.7
Shoulder.
b NMII 5.7 3.1 4.6 7.4 20.8
Hump.
c NMIII 3.5 3.6 3.8 6.2 17.1
And beyond.
38 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42
Fig. 7. Differential thermogravimetrical analysis profiles alumina-supported NiMo
materials prepared with and without citric acid through various protocols.
CA addition contributed in obtaining augmented BGE, NMII showing
the maximum value. By analyzing UV–vis spectra of defined Mo species,
Weber [33] found that larger iso-polymolybdates aggregates had lower
BGE. Conversely, decreased BGE corresponded to increased estimated
average aggregation degree of oxidic molybdenum clusters. Thus, en-
hanced BGE of CA-modified samples suggested higher Mo dispersion.
The average number of nearest neighbors in Mo clusters (NMo) could
be determined through: NMo = 16–3.8 × BGE [33]. CA addition over alu-
mina prior to Ni-Mo-P deposition rendered the material of the lowest
NMo related to smaller Mo6 + domains (Table 2). The low NMo values
of CA-modified catalysts suggested that the complexated Mo species
on those materials was [(MoO2)2O(H2cit)2]2− (see 3.2 FTIR (Fourier-
transform infrared) spectroscopy section).
Finally, it appeared that more efficient Mo chelation in NMII (Fig. 2)
contributed in obtaining the highest molybdenum dispersion. Also, Ni
species could be well-dispersed over that solid (Fig. 4). Expectably,
those properties could be reflected in improved HDS performance of
corresponding sulfided catalyst.
3.5. Supported phase characterization by temperature-programmed reduc-
tion (TPR)
Maxima of signals from TPR profiles of Fig. 5 are summarized in
Table 3. The signal around 469 °C in NM400 profile was attributed to re-
duction of octahedral Mo6+ in oxomolybdates (identified by UV–vis,
Section 3.3) to Mo4+ [37,38]. The shift to higher temperature (498 °C)
in NMI could be related to enhanced Mo6 + dispersion by CA-
complexated species formation [9] (Section 3.2 FTIR (Fourier-transform
infrared) spectroscopy). Indeed, Rinaldi et al. [9] found that CA-post-
treatment of calcined (500 °C) CoMo/Al2O3-B2O3 dissolved both depos-
ited CoMoO4 and polymolybdates, increasing then Co and Mo disper-
sion. Even more, enhanced amount of CoMoS sites after sulfidation
resulted in augmented activity in thiophene HDS. In full agreement to
Table 5
Maxima of signals from differential thermal analysis profiles of alumina-supported NiMo materials (Fig. 7).
Sample Low T Low T organics decomposition
evaporation (°C)
(°C)
NM400 84 – –
NMI 64 376
NMII 51 296
NMIII 50 296
that mentioned, NMI had enhanced Mo6 + dispersion as to that in
NM400 (Table 2). Very recently, others [39] have also reported molyb-
dates re-dispersion by citric acid addition over calcined (400 °C)
CoMo/alumina. In those cases, deposited Mo6 + redistribution was
more pronounced at CA/Co ratios of 1 and beyond.
Following similar trend to that of Mo, nickel reduction peak original-
ly observed at 685 °C in NM400 shifted to higher temperature in NMI
(750 °C), suggesting Ni-citrate complexes formation. The very wide sig-
nal related to Ni2+ reduction (~700 to 820 °C) in the latter pointed out
to supported species of various interaction degrees with the carrier. The
signal at ~890 °C and beyond from reduction of both Mo4+ (from octa-
hedral Mo6+ low-temperature partial reduction) and tetrahedral Mo6+
species strongly interacting with the support was significantly dimin-
ished by CA deposition over calcined NM400. That suggested partial car-
rier dissolution that could occur at the acidic pH (~ 2.95) of CA
impregnating solution resulting in extraction of Mo6+ species in high
interaction with the support. In full agreement, the shoulder at
588 nm in visible region spectrum of NM400 (Fig. 4) related to tetrahe-
dral Ni2+ in surface spinel-like species almost disappeared after CA ad-
dition over that formulation (sample NMI).
Low-temperature (~100–285 °C) signals in NMI profile could be re-
lated to evolution of products from decomposition of CA loosely bound
to deposited species, Fig. 5. Oxidic impregnated species present over
NM400 could catalyze organic additive degradation at some extent. In
this case, the broad signal in the aforementioned temperature range
could be due to alteration of the thermal conductivity detector by
evolved species, discarding H2 consumption events. In this line, low-
temperature signals (below 350 °C) in H2-TPR profiles of CA-modified
CoMo/alumina calcined at various conditions have been attributed
[38] to organics decomposition. Also, according to Ramírez et al. [40]
low-temperature TPR signal (~117 °C) in CA/SiO2/Al2O3 could be related
to organics reduction/decomposition.
Signals attributed to octahedral Mo6 + reduction shifted to lower
temperature (409 °C) in NMII, as to those in NM400 and NMI. That sug-
gested molybdenum species in weaker interaction with the carrier thus
pointing out to support surface “passivation” due to organics deposition
[40]. The shoulder at 462 °C could indicate non-complexated Mo con-
sidering that amount of CA used was not sufficient to chelate totality
of impregnated molybdenum. Nickel species in various interaction de-
grees with Al2O3 were suggested as corresponding reduction events
originated several humps in ample temperature range. In this case, the
main signal due to octahedral Ni2 + was observed at 717 °C. As NMII
was not submitted to high-temperature annealing formation of Mo6+
species in high interaction with the carrier was not expected. Thus,
the hump at 840 °C could be rather related to Mo4+ species (from for-
mer octahedral Mo6+ reduction) conversion to metallic Mo.
Octahedral Mo6+ reduction at 460 °C in simultaneously impregnat-
ed NMIII was accompanied by Ni2+ transformation to corresponding
metallic phase in a wide range of temperature (slight hump centered
at 669 °C) again suggesting species at various interactions degrees
with the support. At the highly acidic pH (~1.5 [14]) of impregnating so-
lution used the weak organic acid could not be dissociated existing then
as protonated acid ruling out complexation of either nickel or molybde-
num. In the same line, Li et al. [41] identified no Ni2+ chelation in acidic
(pH = 1.5) impregnating solutions obtained from nickel nitrate, ammo-
nium metatungstate and CA.
Medium T organics decomposition (°C) High T carbon residua combustion (°C) Mo6+
sublimation
(°C)
– 874
376, 453 – 857
– 503 842
– 503 869
 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42
Table 6
Pseudo first-order kinetic constant (benzothiophene HDS) over various sulfided NiMo/
alumina catalysts prepared with and without citric acid through various protocols. R-
squared values (coefficient of determination) of corresponding linear least squares fitting
also included. Batch reactor, n-heptane as solvent, P = 7.2 MPa, T = 250 °C, ~107 rads−1
(1030 rpm) mixing speed.
Catalyst k × 10−5 R-squared
(m3 kg−1
cat s
−1
) sample NM120) was included as reference in thermogravimetrical anal-
NM400 7.94 0.95
NMI 4.20 0.91
NMII 13.57 0.93
NMIII 7.61 0.96
A well-defined peak accompanied by an incipient signal (at 825 and
891 °C, respectively), could include contributions from Mo4+ transfor-
mation to metallic phase and tetrahedral Mo6 + reduction as well. In
our molybdophosphates impregnating solutions prepared from MoO3
digestion in diluted H3PO4 (see Section 2.1 Materials preparation) Daw-
son heteropolyanions could be formed (P2Mo18O6− 62 ) [42], in spite of the
large P/Mo ratio used (1/2.5 instead of 1/9). According to Blanchard et
al. [42] those anions could co-exist with H6PMo9O3−34 entities accompa-
nied by large phosphates excess. After impregnation over alumina the
pH in the pores could be high enough (out of the stability domain of
those species) to provoke Dawson anions decomposition, PMo9O934−
species and [Al(OH)6Mo6O18]3 − Anderson-type heteropolyanions
being then formed. Alumina partial dissolution is possible even at pH
values (between 4 and 6) at which that phenomenon could be consid-
ered as improbable [43], due to the effect of polymolybdates acting as
inorganic ligands. It seemed that by using our simultaneous impregna-
tion solution Al2O3 network disruption could contribute to tetrahedral
Mo6+ species in impregnated solids not submitted to high-temperature
annealing (see peak at 891 °C, NMIII profile in Fig. 5). The absence of
that signal in NMII profile suggested that alumina dissolution could
probably be precluded at some extent by surface “passivation” due to
Fig. 8. Linear regression fit of ln(1-x) against time plots for various tested materials. (a): NM400; (b): NMI; (c): NMII; (d) NMIII. Batch reactor, n-heptane as solvent, P = 7.2 MPa, T =
250 °C, ~107 rads−1 (1030 rpm) mixing speed.
39
organic moieties adsorption on the substrate, prior to Ni-Mo-P phases
deposition.
3.6. Materials characterization by thermal analysis (TG-DTG)
Impregnated material with no CA additive and dried at 120 °C (2 h,
ysis profiles shown in Fig. 6. Weight losses at temperature below 90 °C
(water boiling point in Mexico City) were related to physisorbed solvent
evaporation (Table 4). Losses between 175 and 310 °C could be originat-
ed by support dehydroxylation (surface and structural [44]) and or-
ganics decomposition [15], including elimination of coordination
water from Ni acetate [45]. In full agreement, weight losses in that
range were slightly enhanced in CA-containing samples. Between 310
and 600 °C rather similar weight losses for materials with CA strongly
suggested that in addition to nickel acetate decomposition burning of
carbon residua from citrates took place at that temperature range [15].
Thermal phenomena beyond 800 °C were attributed to MoO3 sublima-
tion [46].
Temperature maxima of weight loss rate (from DTG profiles of Fig.
7) are summarized in Table 5. Signal around 300 °C in NMII and NMIII
profiles nicely corresponded to Ni acetate decomposition [45]. The ab-
sence of that inflexion in NM400 and NMI could be expected as they
were submitted to high-temperature calcining conditions at which ace-
tates combustion could take place. Ni acetate decomposition under H2
atmosphere could occur at similar temperature as in air [45], meaning
that thermal phenomena occurring under either air combustion or cat-
alyst activation by sulfiding (see Section 2.3 HDS reaction test) could
present alike characteristics.
Main DTG signals related to CA residua combustion were observed at
376 and 453 °C in NMI whereas those inflexions were registered at more
severe conditions in NMII and NMIII. That pointed out to oxidic molyb-
denum catalyzing combustion of organic residua originally located on
deposited metals surface. In this line, Al2O3-supported Mo6+ materials
40 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42
Scheme 2. Benzothiophene HDS reaction pathways (from [48]).
have been tested as catalysts for diesel soot combustion where required
temperature was decreased by about 100 °C, as to the case of non-cata-
lyzed oxidation [46,47].
Finally, the high-temperature DTG signal attributed to MoO3 subli-
mation in Fig. 7 clearly shifted to lower values in CA-modified samples.
The maximum for that inflexion was observed at 842 and 874 °C for
NMII and NM400, respectively (see Table 5), again pointing out to de-
creased interaction between molybdenum species and carrier surface
“passivated” by CA deposition prior to Ni-Mo-P phases impregnation.
3.7. Hydrodesulfurization (HDS) activity test
Benzothiophene HDS activity (on pseudo first order kinetic constant
basis, k) of sulfided catalysts prepared are shown in Table 6. k values
were determined from slope of corresponding –ln(1-x) against time
plots shown in Fig. 8. Reaction pathways for BT transformation are
shown in Scheme 2 (from [48]). In agreement with Morooka and
Fig. 9. Concentration (at operating conditions) against time plots for BT and EB over various tested catalysts. Filled squares: benzothiophene. Open squares: ethylbenzene. Symbols:
experimental values. Lines: pseudo first order kinetics fitting. (a): NM400; (b): NMI; (c): NMII; (d) NMIII. Batch reactor, n-heptane as solvent, P = 7.2 MPa, T = 250 °C, ~107 rads−1
(1030 rpm) mixing speed.
Hamrin [49], no intermediate product from direct sulfur extrusion (sty-
rene) was registered under used reaction conditions probably due to its
rapid transformation to ethylbenzene (EB) [50]. According to Wang and
Prins [51] EB could be formed from BT beginning with breaking of the
aryl C\\S bond, then hydrogenation of the vinyl one, followed by alkyl
C\\S bond scission. Last two steps could occur much faster than desorp-
tion of corresponding intermediates resulting in EB kinetically behaving
as primary product although it actually requires of three distinctive
steps to be formed. Interestingly, in some cases aromatic ring hydroge-
nation of EB to ethylcyclohexane was observed after total BT conversion
over our sulfided catalysts. That was alike to biphenyl hydrogenation to
cyclohexylbenzene that coul take place right after total
dibenzothiophene (DBT) conversion [52], suggesting stronger adsorp-
tion of BT as to that of EB over active sites of tested catalysts. EB could
adsorb on sulfur vacancies available after total benzothiophene elimina-
tion, being then hydrogenated to corresponding alkylated cycloalkane.
Benzothiophene and ethylbenzene concentration (adjusted at actual
operating conditions) against time plots shown in Fig. 9 confirms that
essentially total organo-S species conversion was reached in the test du-
ration for the sample of the highest activity (NMII). After hydrotreating,
the liquid product had about 31 ppm S. Considering that FCC naphtha
comprises about 40% of the gasoline pool in refineries and that various
fractions composing the commercial product are essentially sulfur-free
(those from alkylation and reforming, for instance) the final mixed
stream with around 13 ppm S could fulfill stringent environmental reg-
ulations currently enforced in developed countries dictating 10–30 ppm
maximum S content.
Modification of calcined NM400 by CA impregnation (NMI sample)
was not effective in enhancing HDS activity, Table 6. That could proba-
bly be due to molybdenum content in prepared catalysts. Okamoto et
al. [53] found that by post-treatment of calcined alumina-supported
CoMo catalyst (20 wt% Mo) with citric acid (at CA/Mo = 2) the activity
of corresponding sulfided materials in DBT HDS could be enhanced by a
 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42
factor of more than two. They proposed that significant improvements
in organo-S removal activity could be related to transformation of crys-
talline MoO3 and CoMoO4 into well-dispersed Mo-CA surface com-
plexes that resulted in enhanced MoS2 particles edge dispersion after
sulfidation. However, in formulations of molybdenum content close to
monolayer (approximately 3 Mo atoms nm−2, as in our case) CA depo-
sition over annealed Mo phase could be even detrimental on HDS prop-
erties (as tested in thiophene conversion) [54]. It is worth mentioning
that those authors found positive effect of postreating with citric acid
at CA/Mo ratio much larger as to that used in the present work (2 and
0.4, respectively).
Although from UV data better dispersed Mo phases were found in
NMI as to those in NM400 (Table 2), TPR profiles (Fig. 5 and Table 3)
suggested that on the former deposited Mo phases were more difficult
to reduce, as to those over the latter. Thus, oxidic phases dispersion itself
was not determining on desulfurizating properties of corresponding
sulfided formulations.
HDS activity of simultaneously impregnated NMIII was inferior to
that of NM400. Due to low pH of acidic impregnating solution used dur-
ing NMIII preparation CA could not be ionized precluding then Mo com-
plexation. Li et al. [41] recently reported that citric (at CA/Ni = 1.2,
alumina-supported NiW materials not calcined after modifier addition)
simultaneously added in aqueous solution of nickel and tungsten pre-
cursors at pH alike to that in our NMIII impregnating solution did not re-
sulted in improved HDS activity (4,6-dimethyl-dibenzothiophene
conversion) of final sulfided catalyst. According to their XPS data that
could probably be attributed to decreased W and Ni sulfides dispersion
in corresponding formulation. In the same line, Okamoto et al. [54]
found negative effect of simultaneous CA addition in CoMo/alumina at
Mo loading alike to that used in the present work.
The catalyst obtained by impregnating CA on the bare carrier prior to
Ni-Mo-P phases deposition had the highest BT HDS activity (70% in-
crease as to that of the reference calcined formulation with no organic
additive), Table 6. From UV data that sample also had the highest
Mo6+ dispersion (Table 2). According to TPR profiles of Fig. 5 it seemed
that the “passivated” alumina surface provided by CA adsorption origi-
nated molybdenum species of enhanced reducibility due to their weak-
er interaction with the carrier. Even more, refractory tetrahedral Mo6+
entities strongly interacting with the Al2O3 substrate were absent in
NMII. Thus, the enhanced HDS properties of that sample seemed to be
consequence of those positive characteristics. In full agreement, Li et
al. [41] found enhanced activity of alumina-supported NiW catalysts
(at CA/Ni = 1.2) where part of the organic acid (equivalent to CA/
Ni = 0.3) was used firstly to modify the carrier being the rest added
during Ni-W-simultaneous impregnation. In that case, the CA-modified
Al2O3 was submitted to high-temperature pyrolysis resulting in carrier
surface passivation by carbonaceous residua deposition, prior to active
phases precursors impregnation. In our approach, our CA-modified
Al2O3 was just dried (120 °C) high-temperature annealing being
avoided in order to preserve the complexing ability of the adsorbed or-
ganic modifier.
It has been proposed [29] that during CA impregnation over alumina
carboxylate groups and deprotonated –OH groups as well could be
bonded to Lewis coordinatively unsaturated sites (Al3+) on the Al2O3
surface. However, significant number of carboxylate moieties in
adsorbed CA molecules could remain unbound being then available to
be coordinated to other atoms (presumably, molybdenum in our
case). Indeed, our FTIR data (see Section 3.2 FTIR (Fourier-transform in-
frared) spectroscopy) strongly suggested that Mo-citrate complexes
formation were favored in NMII.
It is worth mentioning that the amount of CA used in our work (CA/
Ni = 1) could not be enough to complexate all impregnated Mo6 +
pointing out to the possibility of optimizing the CA/Mo ratio to obtain
further improvements in HDS activity.
In full agreement with our findings, others have very recently pro-
posed [55] that under conditions relevant to commercial HDS
41
operations (P N 10 bar, as in our case) the most important role of CA
consisted in increasing the sulfiding degree of CoMo phases by weaken-
ing the interaction between deposited oxidic precursors and the Al2O3
carrier.
It was demonstrated that the preparation stage where the organic
modifier was added significantly affected the HDS properties of sulfided
alumina-supported NiMo catalysts. Others have also found that the
preparation step where chelating agent was contacted with metallic
components was crucial in determining HDS ability of corresponding
sulfided materials. For instance, it was recently reported [56] that
thioglycolic acid (TGA) effect on hydrotreating properties of Nb-HMS-
supported NiMo strongly depended on the stage at which it was
added (very negative when impregnated on calcined material, slightly
detrimental when simultaneously impregnated with the NiMo precur-
sors). The nature of the impregnated phases-support interaction is
also crucial regarding the effect of organic modifiers on HDS activity of
corresponding sulfided catalysts. In this line, by varying the carrier
from Nb-HMS to Nb SBA-15 [56], the TGA influence over sulfided
NiMo phases was strongly modified (good when on calcined materials,
very good when simultaneously impregnated with NiMo precursors).
Even more, in some cases the effect of organic additives could still be ev-
ident after their removal by calcining, as found for polyethylene glycol-
modified CoMo/alumina materials [57].
4. Conclusions
NiMo/Al2O3 formulations obtained by one-pot simultaneous im-
pregnation of Mo, Ni and P were modified by citric acid addition at Ni/
CA = 1 mol ratio at various preparation stages to assess the influence
of that parameter on HDS activity of final sulfided catalysts. Nickel ace-
tate was used as precursor to focus the investigation on molybdenum
complexation. CA deposition over calcined alumina-supported NiMo re-
sulted in diminished proportion of refractory tetrahedral Mo6+(t) spe-
cies but also in octahedral ones (Mo6 +(o)) reducible at higher
temperature, as to those over non-modified NiMo/Al2O3. That was
reflected in lower HDS ability. The highest BT HDS activity (70% in-
crease, as to the calcined formulation with no organic additive) was
found for the catalyst obtained by impregnating CA on bare alumina car-
rier prior to Ni-Mo-P deposition. In that case, molybdenum and nickel
species of decreased interaction with the support were evidenced due
to surface “passivation” from citric adsorption/decomposition on the
Al2O3 support. In the opposite, simultaneous Ni-Mo-P-CA deposition
where low pH of acidic impregnating solution (pH ~ 1.4) devoided citric
acid ionization (then, no citrate complex formation) was ineffective in
improving HDS activity.
Nomenclature
ABT Integrated area of benzothiophene chromatographic peak
(a.u.)
AEB Integrated area of ethylbenzene chromatographic peak (a.u.)
CBT0 Initial BT concentration (mol l−1)
CBT BT concentration at given time (mol l−1)
CH2 H2 concentration in saturated solvent (n-heptane) (mol l−1)
k Pseudo first order HDS kinetic constant (s−1)
k1 Pseudo first order HDS kinetic constant (l mol−1 s−1)
RBT BT HDS reaction rate (mol l−1 s−1)
t Reaction time (s)
x Benzothiophene conversion at time t
Acknowledgements
A. Gutiérrez acknowledges CONACYT (Mexico) for a graduate stu-
dent (Masters in Science) fellowship. The authors appreciate comments
and suggestions from the reviewers that significantly contributed in im-
proving this paper.
42 J. Escobar et al. / Fuel Processing Technology 156 (2017) 33–42
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