Fuel 100 (2012) 34–42

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Fuel
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Hydrodesulfurization and hydrocracking of Maya crude with P-modified

NiMo/Al2O3 catalysts
Patricia Rayo a,⇑, Jorge Ramírez a,b, Pablo Torres-Mancera b, Gustavo Marroquín a, Samir K. Maity a,
Jorge Ancheyta a
a
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, México, DF 07730, Mexico
b
UNICAT, Departamento de Ingeniería Química, Facultad de Química, UNAM, Ciudad Universitaria, México, DF 04510, Mexico

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

Article history: In the present work we analyze the changes in hydrocracking, hydrodesulfurization, hydrodeasphalteni-
Received 9 June 2011 zation, and hydrodesmetallization, during the hydrotreating of Maya crude, when 3.4 wt.% of P2O5 is
Received in revised form 3 December 2011 incorporated by two different routes to a NiMo/Al2O3 catalyst. The catalysts were characterized by nitro-
Accepted 7 December 2011
gen physisorption, XRD, HRTEM, SEM, and CO adsorption analyzed by FTIR. Additionally, to obtain deeper
Available online 24 December 2011
knowledge on the reaction system, the catalysts were also tested in the HDS of 4,6-DMDBT, and hydro-
cracking of cumene. NiMo/PAl2O3 shows the highest HDS activity for 4,6-DMDBT, the better hydrogenat-
Keywords:
ing properties, and the best performance in all the reactions during hydrotreating of Maya crude. The
NiMo catalysts
Hydrodesulfurization
acidity and porosity of the catalyst are determinant factor for the conversion of atmospheric residue.
Hydrocracking of Maya crude oil At similar acidity, the porosity defines the best catalyst and conversely, at similar porosity, acidity will
Phosphorous define the activity of the catalyst. However, an excess of acidity in the catalyst can lead to rapid deacti-
vation. NiMo/PAl2O3 displays superior performance compared to NiMo/Al2O3 and NiMoP/Al2O3 because it
presents the best combination of acidity, porosity and distribution of the sulfided Ni and Mo phases,
which provide the hydrodesulfurization and hydrogenating functions.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction textural and acidic properties of the catalyst. How these changes
in catalyst formulation will affect the catalyst performance during
The demand of light fractions continues to increase progres- the hydrotreatment of heavy Maya crude is not well understood.
sively in the recent years. To this day, the reserves of light crudes The use of phosphorus as an additive for hydrotreating catalyst is
are decreasing while those of heavy crudes increase, making an alternative because it can tune the acidity of the catalyst,
important to develop efficient catalysts for hydroprocessing heavy reduces the metal-support interaction, and therefore improves
crudes and residua. the sulfidation of the active phases. In the literature there are a large
The catalyst formulation for hydroprocessing of heavy crude number of studies on the effect of P on NiMo/Al2O3 catalysts using
oils and residues needs a balance between Ni–Mo–S active phase sulfur containing model molecules (thiophene, benzothiophene, 4.6
(hydrogenation and hydrogenolysis functionalities) and acidity of dimethyl dibenzothiophene, etc.) [1–13]. These studies have shown
the catalyst support. The catalyst should have ability to transform that phosphorus has different effects, such as: (a) Improves the
the bulk molecules present in the vacuum residue to high value stability of impregnating solutions helping the dispersion of the
liquid fractions of light and medium distillates. At the same time metals on the support [3–6]. (b) Inhibits the formation of inactive
it must have good capabilities to reduce the sulfur, nitrogen, and species like NiAl2O4 and increases the formation of octahedral
metals present in the feedstock. Ni2+ ions. (c) Modifies the strength and distribution of acid sites
The addition of phosphorous to a NiMo/Al2O3 catalyst may lead on alumina [7]. (d) Improves the thermal stability of -alumina [7].
to some improvement in the catalyst performance. However, the (e) Inhibits coke formation during hydrotreating reactions [8,9].
way in which phosphorous is incorporated in the catalyst can alter (f) Increases hydrocracking activity [10]. (g) Changes the morphol-
in different ways the dispersion of the Mo and Ni phases, and the ogy of the active species (size and stacking of MoS2 crystallites
[11–13]. (h) Decreases the metal-support interaction [14]. (i)
⇑ Corresponding author. Address: Instituto Mexicano del Petróleo, Eje Central
Modifies the textural properties of catalysts [15].
Lázaro Cárdenas Norte152, San Bartolo Atepehuacan, Gustavo A. Madero, México, The effect of P on the HDN of model compounds like quinoline,
DF 07730, Mexico. Tel.: +52 55 9175 8416; fax: +52 55 9175 8418. aniline [16] and pyridine [17] has also been studied. It was
E-mail address: prayo@imp.mx (P. Rayo). reported that P promotes the formation of a new type of AlPO4 sites

0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.12.004
 P. Rayo et al. / Fuel 100 (2012) 34–42 35

that facilitate the CN bond breaking [18]. However, a negative ef- Table 1
fect of P on HDN of quinoline [19] and pyridine [16] has also been Analysis and properties of Maya crude feed.

reported. This negative effect was ascribed to the different route of Properties ASTM method Maya crude oil
C–N bond breaking for different model compounds. Elemental analysis (wt.%)
In spite of the numerous studies with model compounds, the ef- C D5291 84.5
fect of phosphorous when hydrotreating real heavy feedstocks has H D5291 11.6
not been extensively studied and remains uncertain. It has been N D5291 0.3
S D4294 3.5
found that the effects induced by P depend in many cases of the Metals (ppm)
method in which P is incorporated to the catalyst. For example, dif- Ni D5863 57.2
ferences in activity have been found depending if P is incorporated V D5863 262.7
before or after the metal active phases [8,9,11]. (Ni + V) D5863 319.9
Asphaltenes (wt.%) D4124 12.6
Kang et al. [20]studied the effect of P catalysts in HDS and
Physics properties
HDM activities with Kuwait vacuum residue. They found that Density, 20/4 °C D1298 0.9251
the HDS and HDM activities increase with increasing concentra- API gravity 21.5
tion of P in the range of 0.5–1.0 wt.%. It was also observed that
the activity increases when the catalyst is prepared by co-impreg-
nation. Kushiyama et al. [21,22] found that an appropriate concen-
tration of P improves the catalytic activity in heavy oil and calcined at 450 °C/4 h. For the preparation of NiMo/PAl2O3
hydrotreating, but that an excess of P may decrease the activity. were impregnated 8 g of support using the incipient wet method
The authors assume that P interacts strongly with the V com- with a solution of phosphoric acid (Aldrich 85%) with the amount
pounds present in heavy oil and thereby prevents the deactivation required to obtain a concentration of 3.4 wt.% P2O5. This support
of active Mo species. Rayo et al. [8] studied the changes of HDS, was dried at 120 °C/4 h and calcined at 550 °C/4 h. On this modi-
HDN, HDA and HDM activities using a hydrotreated Maya crude fied support was impregnated the active phases of Ni and Mo using
oil diluted with diesel 50/50 wt.%. The results show that P does the same route as for the first catalyst. The NiMoP/Al2O3 catalyst
not affect equally these catalytic functionalities. The hydrocrack- was prepared by impregnating of alumina support (Saint Gobain
ing performance and the selectivity to different liquid fractions S6175) with a solution containing the precursors of Mo + Ni + P.
were not analyzed. In a flask with 20 mL of deionized H2O and vigorous stirring was
For CoMo/Al2O3 catalysts, Maity et al. [9–24] found that the slowly added ammonium heptamolybdate. Once the solution was
effect of P in the hydrotreating of heavy crude is not only related dissolved was slowly added nickel nitrate dissolved in 7 mL of
to the active sites but also to the porous structure of catalyst. It deionized H2O, resulting a green solution. Subsequently was added
is concluded that P increases activity and inhibits coke formation. drops of phosphoric acid (Aldrich 85%) up to 1.0 mL, resulting a fi-
Some patents claim that P incorporation increases hydrodesul- nal yellow solution with pH = 3.2. This catalyst has a content of
furization (HDS), hydrodenitrogenation (HDN), hydrodemetalliza- MoO3, NiO, and P2O5 of 15, 3.3, and 3.4 wt.%, respectively.
tion (HDM) and improves hydrocracking [3–6].
To enquire more on the performance of NiMo catalysts during
the hydrotreating of heavy petroleum, in the present work we ana- 2.3. Catalyst and support characterization
lyze the changes in the hydrocracking, hydrodesulfurization,
hydrodeasphaltenization, and hydrodemetallization, during the Specific BET surface area (SBET) and pore size distribution (PSD)
hydrotreating of Maya crude when 3.4 wt.% of P2O5 is incorporated measurements were carried out in a Quantachrome Nova 4000
by two different routes to a NiMo/Al2O3 catalyst. Additionally, to equipment by nitrogen physisorption 77 K). Prior to the adsorp-
obtain deeper knowledge on the reaction system, the catalysts tion, the supports and catalysts were outgassed for 3 h at 473 K.
were also tested in the HDS of 4,6 DMDBT, and the hydrocracking Before analysis by nitrogen physisorption, the spent catalysts were
of cumene. Changes in the conversion of vacuum residue and the washed with hot toluene using a Soxhlet extractor in order to
composition of the liquid products (SARA) are also analyzed. remove organic residues, and then dried at room temperature for
18 h and at 393 K for 3 h. The used catalysts were regenerated at
a temperature of 773 K/6 h in a flow of air 50 mL/min.
2. Experimental section
X-ray powder diffraction spectra were obtained using a Siemens
D500 diffractometer from 10 to 70 2h at 2.5°-min 1 scan rate using
2.1. Feed composition
CuK radiation. The analysis of metals, Ni and V, in the used cata-
lysts was carried out in a Perkin Elmer 2380 atomic absorption
The catalytic tests were performed in a high pressure microre-
spectrophotometer.
actor in up flow mode using Maya heavy crude oil as feedstock.
The surface morphology and composition of the catalysts was
The chemical analysis of the Maya crude oil used as feed is pre-
studied by SEM–EDX using an xT Nova NanoLab 200 microscope.
sented in Table 1.
The sample was deposited on a carbon holder and evacuated at
high vacuum (10 5 Torr) before images were taken.
2.2. Catalysts preparation For FT-IR experiments on sulfided samples, the powered cata-
lysts were pressed into self supporting wafers (6 mg/cm2). The
Three catalysts were prepared, NiMo/Al2O3, NiMo/PAl2O3, and wafers were introduced into a special IR cell with KBr windows
NiMoP/Al2O3, using a commercial alumina support (Saint Gobain and presulfided at atmospheric pressure and at 673 K for 4 h using
S6175) in the form of extrudates with a diameter of 1/8 in. a 15% H2S/H2 gas mixture. Then, they were pretreated by outgas-
NiMo/Al2O3 was prepared by impregnating of 10 g of support using sing during 4 h at 723 K. Afterwards, small doses of CO were intro-
the simultaneous method by wet incipient impregnation with a duced at low temperature (100 K) into the cell until an
solution containing nickel nitrate (Fluka 98.5%) and ammonium equilibrium pressure of 1.0 Torr was reached. After each pulse an
heptamolybdate (Fluka 99.0%) dissolved in water (pH = 5.2) in ade- IR spectrum was taken. The spectra were taken with a Nicolet
quate concentrations to obtain a final content of 3.3 wt.% NiO and 6700 FTIR spectrometer with a resolution of 4 cm 1 and 100 scans
15.0 wt.% MoO3, respectively. This catalyst was dried at 120 °C/4 h per spectrum.
36 P. Rayo et al. / Fuel 100 (2012) 34–42

2.4. Catalytic activity test poured into the columns adapted in series and washed with
25 mL of pentane. Pentane is added in enough amount to complete
Cumene (C9H12) cracking was used as model reaction to deter- 280 10 mL. After washing, columns are decoupled and washed
mine the relative acidity of the catalysts. The reactions were car- again individually. The column packed with clay is washed with
ried out in a fixed-bed reactor operating at atmospheric pressure a toluene–acetone mixture (50/50 vol.%/vol.%) to recover the polar
and 673 K with a flow of 50 mL/min of H2/C9H12. A saturator tem- fraction (resins) whereas saturate fraction is recovered with pen-
perature of 278 K was used in order to have 0.02 mol% cumene in tane and aromatics with toluene in the column packed with
hydrogen. Prior to the reaction, the catalyst was sulfided at 473 K alumina.
for 2 h in a flow of 40 mL of CS2/H2. Catalyst particle size was
20–40 mesh. Product analysis was performed by online gas chro- 3. Results and discussion
matography using a Varian 4700 gas chromatograph using a FID
equipped with an OV17 3% column kept at 373 K. 3.1. Characterization of supports and catalysts
Catalytic activity tests for HDS of 4,6-DMDBT were performed in
a batch Parr reactor. Prior to the activity measurement the cata- The results from nitrogen physisorption show that the surface
lysts were presulfided ‘‘ex situ’’ in a continuous flow reactor oper- area, pore diameters and pore volume of the support were not af-
ating at atmospheric pressure and at 673 K for 4 h using a 15% H2S/ fected by the modification with P. However, the distribution of
H2 gas mixture. The batch reactor was loaded with approximately pore diameters shows an increase of 25.2% of pores <5 nm, (Table
200 mg of sulfided catalyst. The experiments were conducted at 2). In line with this, we observe a decrease of 20.9% in the pores
1100 psi and 593 K. The feed was 40 mL of a solution of 4,6-DMDBT with diameters between 5 and 10 nm.
in n-decane with a concentration of 0.1 wt% sulfur. The experi- These effects can be due to the deposition of P species in the
ments were performed during 6 h taking samples each hour. The pore walls [12,15]. The change of surface area and pore diameter
products of the reaction were analyzed on a Hewlett Packard gas distribution varies with the incorporation of the Mo and Ni precur-
chromatograph HP 5860 equipped with a FID detector. sors. The surface area of NiMo/Al2O3, NiMo/PAl2O3, and NiMoP/
The HDT reaction experiments using Maya crude as feedstock Al2O3 catalysts decreases 7, 20, and 27 m2/g respectively. This
were conducted in a continuous flow microplant unit equipped trend is also observed for the average pore diameter and pore vol-
with a 0.5 in. diameter tubular reactor to which 10 mL of catalyst ume, the being more prominent for the NiMoP/Al2O3 catalyst. In
was loaded. The time-on-stream of each catalytic test was 200 h. general, the addition of Ni and Mo species causes a reduction of
A homogeneous mixture of the catalyst together with equal vol- pore diameter in all the pore diameter range. In the pore size dis-
ume of diluent, carborundum (0.2 mm size), was loaded to the tribution we observe an increment of 40% in the percentage of
reactor. First, the catalyst was dried at 393 K and atmospheric pores in the range of <5 nm for NiMoP/Al2O3, whereas this incre-
pressure during 2 h using a flow of hydrogen (66 L/h). After drying, ment is only 13.8 and 8.3% for NiMo/PAl2O3, NiMo/Al2O3 respec-
the catalyst was allowed for soaking in straight-run gas oil (SRGO, tively. In line with this, there is a decrease of pores in the range
2.0 wt.% ‘‘S’’) at 423 K for 2 h. Finally, the sulfiding agent, a mixture of 5–10 nm most notable in the catalyst NiMoP/Al2O3.
of the same SRGO with dimethyl disulfide (DMDS, 1.0 wt.%), was Specific surface area and total pore volume of all three used cat-
introduced. Sulfidation was done at 2.7 Mpa under a two level tem- alysts (Table 3) are drastically reduced with respect to their respec-
perature program, 533 K (3 h) and 593 K (5 h), using a H2/HC ratio tive fresh calcined counterparts (Table 2). This reduction of surface
of 353 m3/m3 and 2.0 h 1 LHSV [8]. area is larger for NiMo/PAl2O3. The pores having pore diameter be-
After sulfidation the reaction test is conducted at 6.8 Mpa, reac- low 5 nm increase drastically due to coke and metals deposits;
tion temperature of 653 K, LHSV of 1.0 h 1, and hydrogen-to-oil ra- whereas the pores having pore diameter 5–10 nm decrease (Table
tio of 890 m3/m3. Product samples were collected each 12 h for 3). It is also observed that surface area regains around 80–89% by
analysis. regeneration of the used catalysts. When we compare the pore size
distribution of NiMo/Al2O3 with the P-containing catalysts, it is ob-
2.5. Liquid products and feed characterization served that a greater amount of small pores are lost during the
regenerating coke burning process for the catalyst without P
Metals (Ni, V) were analyzed in the feed and products using (Fig. 1). This could be due to the collapse of small pores during
flame atomic adsorption spectrometry (ASTM D 5863 method). the burning of coke indicating that the incorporation of P to the
The total S content was analyzed by UV–fluorescence (ASTM D catalyst strengthens the pore walls and therefore less collapse of
5453 method) while nitrogen was measured by oxidative combus- small pores is observed. It is also possible that the amount of coke
tion and chemiluminescence (ASTM D 4629 method) at high tem- burned in the NiMo/Al2O3 catalyst is larger and therefore, a greater
perature in an oxygen rich atmosphere. The amount of asphaltenes amount of small pores collapse in this catalyst. In fact, the results
is defined as the insoluble fraction in n-heptane. The solid carbona-
ceous material on spent catalysts (toluene washed) was analyzed
with a Leco SC-444 instrument using ASTM: C 1408 method by di- Table 2
rect combustion-infrared detection. Textural properties of support and catalysts.

The product yields of the hydrocracking reaction were deter- Properties Supports Catalysts
mined by thermogravimetric analysis (TGA) using Perkin-Elmer Al2O3 PAl2O3 NiMo/ NiMo/ NiMoP/
instrument. In this experiment the sample was heated from room Al2O3 F PAl2O3 F Al2O3 F
temperature to 811 K at a rate of 277 K/min in the presence of he- SSA (m2/g) 204 199 197 184 177
lium (flow 60 mL/min). Table 1 shows the properties of the Maya PV (mL/g) 0.73 0.72 0.64 0.6 0.52
crude oil. APD 14.6 14.4 13.1 12.8 11.7
SARA fractionation was carried out in two chromatographic col- PSD (%)
umns packed with clay and alumina. In this procedure, asphaltenes <5 (nm) 15.6 40.8 29.4 49.1 56.6
were separated from the sample by adding pentane. During the 5–10 (nm) 69 48.1 62.4 42.5 36
>10 (nm) 15.4 11.1 8.2 8.5 7.4
test, 2.0 g of sample are mixed with 25 mL of pentane and the mix-
ture is stirred during 24 h. Then, the mixture is filtered and SSA = specific surface area, PV = pore volume, APD = average pore diameter,
asphaltenes are recovered. The filtrate (pentane + maltenes) is PSD = pore size distribution, F = fresh calcined.
 P. Rayo et al. / Fuel 100 (2012) 34–42 37

Table 3
Textural properties of used and regenerated catalysts.

Properties Used catalysts Regenerated catalysts

NiMo/Al2O3 U NiMo/PAl2O3 U NiMoP/Al2O3 U NiMo/Al2O3 R NiMo/PAl2O3 R NiMoP/Al2O3 R
SSA (m2/g) 54 33 62 158 162 157
PV (mL/g) 0.14 0.11 0.2 0.57 0.48 0.45
APD 10.5 13.1 10.5 14.2 11.8 11.6
PSD (%)
<5 (nm) 63.5 56.3 79.9 7.5 26.8 17.1
5–10 (nm) 24.6 26.4 12.2 61.4 65.5 68.3
>10 (nm) 11.9 17.3 7.9 31.1 7.7 14.6

U = used, R = regenerated.

3.0 3.0
NiMo/Al2O3 F NiMo/PAl2O3 F
2.5 2.5
NiMo/Al2O3 R NiMo/PAl2O3 R
dV (log d), cc/g

dV (log d), cc/g

2.0 2.0

1.5 1.5

1.0 1.0

0.5 0.5

0.0 0.0
0 5 10 15 20 0 5 10 15 20
Pore diameter, nm Pore diameter, nm

3.0
NiMoP/Al2O3 F
2.5
NiMoP/Al2O3 R
dV (log d), cc/g

2.0

1.5

1.0

0.5

0.0
0 5 10 15 20
Pore diameter, nm

Fig. 1. Pore size distribution in fresh (F) and regenerated (R) catalysts.

regeneration process described above resulted in the formation

Table 4 of new larger pores.
Metal content as determined by SEM–EDX for fresh calcined catalysts.
The X-ray diffractograms of the fresh catalysts (Fig. 2), show
wt% Catalysts peaks corresponding to poorly crystallized alumina and the ab-
NiMo/Al2O3 NiMo/PAl2O3 NiMoP/Al2O3 sence of reflections associated to MoO3 or crystalline species of P,
O 41.2 43.7 44.8
suggesting a homogenous dispersion of P, Mo and Ni species on
Al 43.1 39.9 42.05 the support surface. It is reported in the literature that with the
P – 1.0 1.2 incorporation of phosphorous to the catalyst some AlPO4 sites
Mo 13.4 13.3 9.8 may be formed and that the phosphorous species change the distri-
Ni 2.3 2.1 2.2
bution and dispersion of Mo and Ni [11].
Table 4 shows that the average percentages of the different ele-
ments present in the fresh catalysts, as measured by SEM–EDX, are
in Table 5 indicate that a greater amount of coke is deposited on close to the theoretical ones. For the used catalysts, additional ele-
the NiMo/Al2O3 catalyst. These results indicate that P inhibits coke ments like S, V, Ni and coke have been deposited (Table 5). The
formation. coke deposition is less on the catalysts having P. The lower coke
It is worth mentioning that in the regenerated catalysts there is deposition on P-containing catalysts is also reported in the litera-
an increase of large pores compared with the fresh counterparts ture [8,9,12,24]. After regeneration, coke and sulfur are removed
(Fig. 1), indicating that, the collapse of small pores during the from the catalysts whereas V and Ni remain.
38 P. Rayo et al. / Fuel 100 (2012) 34–42

Table 5
Metal content as determined by SEM–EDX for used and regenerated catalysts.

Used catalysts Regenerated catalysts

NiMo/Al2O3 U NiMo/PAl2O3 U NiMoP/Al2O3 U NiMo/Al2O3 R NiMo/PAl2O3 R NiMoP/Al2O3 R
C 34.8 22.9 27.5 – – –
O 18.6 29.4 23.5 39.3 37.3 36.7
Al 22 22.6 21.3 45.6 42.8 41.1
P – 1.6 1.5 – 1.4 1.7
Mo 10.9 9.6 10.8 8.3 8.0 8.8
S 10.7 9.6 10.7 0.8 – –
V 2.3 5.5 1.9 2.0 7.0 8.5
Ni 3.1 2.7 2.8 3.8 3.5 3.2
S/Mo 3.1 2.7 3.0

MoO3 NiMoP/Al2O3 0.1

Al2O3

Absorbance (a.u.)
NiMoP/Al2O3
arbitrary units

NiMo/Al2O3 0.1

NiMo/PAl2O3

NiMo/PAl2O3
0.1
NiMo/Al2O3

2200 2150 2100 2050 2000

10 20 30 40 50 60 70
Wavenumber (cm-1)
2θ
Fig. 4. FT-IR spectra of CO adsorbed on sulfided catalysts at 1.0 Torr at equilibrium.
Fig. 2. X-ray diffraction of oxide catalysts.

cracking activity [26]. From DFT calculation it was reported that

–SH groups are located on the edges of the MoS2 crystallites [27].
25
19.7 20.0 Some of the anionic vacancies, which are converted to acid sites
during activation, are also sites for HDS and hence both HDS and
Cumene conversion, %

20 cumene cracking follow the same trend.

15 3.3. FT-IR of adsorbed CO

For the three catalysts studied, the IR spectra of CO absorbed at

10
5.0 1.0 Torr at equilibrium and its deconvolution are shown in Fig. 4.
The assignation of each band was established in agreement with
5 earlier findings on CO adsorbed on NiMo-based catalysts [28].
Two bands due to CO adsorbed on the support, Al3+ Lewis sites
0 and OH’s (2196 and 2156 cm 1respectively), and four bands asso-
NiMo/Al2O3 NiMo/PAl2O3 NiMoP/Al2O3
ciated to coordinatively unsaturated sites (CUS) on sulfided phases
Catalysts
at 2128 cm 1 (NiMoS phase), 2110 cm 1 (MoS2), 2085 cm 1 (NiSx)
Fig. 3. Cumene hydrocracking over NiMo/Al2O3, NiMo/PAl2O3, and NiMoP/Al2O3. and 2055 cm 1 (Mo sites at NiMoS phase). The area of each band
obtained from the IR spectra corresponding to 1.0 Torr of CO at
equilibrium is summarized in the Table 6. NiMo/PAl2O3 presents
3.2. HDC of cumene the highest amount of promoted NiMoS sites as well as the lowest
amount of non-promoted MoS2 and NiSx sites.
Characterization of the acidity of the catalysts through hydro- The amount of CO adsorbed at Al3+ and OH’s sites reflects the
cracking of cumene shows that NiMo/Al2O3 and NiMo/PAl2O3 have fraction of support uncovered in the sulfided catalysts. Therefore,
similar HDC activities and higher than that displayed by NiMoP/ a high amount of CO adsorbed on the support means less coverage
Al2O3, which is about four times less active (Fig. 3). Cumene crack- of the support by the active phase. The results indicate that the
ing requires Brönsted acidity; it is reported in the literature that density of hydroxyl groups is about the same for NiMoP/Al2O3
cumene cracking also indicates the presence of acid OH groups in and NiMo/PAl2O3 and slightly higher in NiMo/Al2O3 (band at
the support surface and –SH group associated to molybdenum sul- 2156 cm 1), whilst Al3+ Lewis acid sites (band at 2196 cm 1) fol-
fide active sites [25]. It has been suggested that anion vacancies are lows the order NiMo/Al2O3 > NiMo/PAl2O3 > NiMoP/Al2O3. Hence
converted to acid–SH groups during the activation of catalyst; in it can be inferred that the active phase coverage is NiMoP/
fact, there is a correlation between chemisorbed oxygen and the Al2O3 > NiMo/PAl2O3 > NiMo/Al2O3.
 P. Rayo et al. / Fuel 100 (2012) 34–42 39

Table 6
Deconvolution results for FT-IR spectra of CO adsorbed on the sulfided catalysts.

NiMoP/Al2O3 NiMo/Al2O3 NiMo/PAl2O3

Area (%) Area (%) Area (%)
Al3+ 0.7 3.2 1.8 7.6 1.0 5.0
Al-OH 0.2 0.8 0.3 1.2 0.2 0.8
NiMoS 5.7 27.3 6.1 25.5 6.4 31.7
MoS2 4.7 22.5 5.4 22.8 4.4 21.7
NiSx 7.6 36.3 8.3 34.6 7.1 35.1
Mo–NiMoS 2.1 9.8 2.0 8.5 1.2 5.8

1
Fig. 7. Reaction rate constants (gcat-h) for the HDS of 4,6-DMDBT.

0.6 6.5

NiMo/Al 2O3
HDS of 4,6-DMDBT, k (gcat*h)-1
6.0

NiMo/PAl 2 O3
4,6-DMDBT

0.4
5.5
o
Ci / C

NiMoP/Al2 O3
5.0
0.2

4.5

4.0
0.0
0.0 0.2 0.4 0.6 0.8 1.0
4,6-DMDBT conversion 3.5
5.50 5.75 6.00 6.25 6.50
Fig. 5. Products distribution during HDS of 4,6-DMDBT for NiMo/PAl2O3. CO/NiMoS FT-IR Band area

Fig. 8. HDS of 4,6-DMDBT vs NiMoS CUS titrated by CO.

kHYD and also kHYD/kDDS shows the order NiMo/PAl2O3 > NiMo/
Al2O3 > NiMoP/Al2O3. Consistently, the amount of CUS associated
to promote NiMoS sites follows the same tendency. In fact, there
is a linear correlation between the amount of NiMoS sites probed
by CO and whichever of the parameters: kHDS, kHYD and kHYD/kDDS.
Fig. 8 shows the correlation for HDS activity and the amount of Ni-
MoS sites probed by CO.
The HDS activity is related to the number of vacancies associ-
ated with the promoted sites. Therefore, the highest HDS activity
of NiMo/PAl2O3 is in line with the highest amount of promoted Ni-
MoS sites detected by CO adsorption. By comparing NiMo/Al2O3
and NiMoP/Al2O3, the former has a higher amount of promoted Ni-
MoS sites; hence it displays better hydrotreatment activity than
the latter despite its slightly higher amount of non-promoted
Fig. 6. Reaction scheme for 4,6-DMDBT.
MoS2 and NiSx sites.

3.4. HDS of 4,6-DMDBT 3.5. HDT real feed (Maya heavy crude)

The values of the pseudo-first order kinetic constants of the HDS The conversion after 204 h time-on-stream for the different cat-
of 4,6-DMDBT are 4.1, 5.3 and 6.1 (gcat-h) 1 for NiMoP/Al2O3, alyst functionalities HDS, HDM, HDN, and HDAs when processing
NiMo/Al2O3 and NiMo/P/Al2O3 respectively. The distribution of Maya crude also indicate slightly better performance of NiMo/
HDS products for NiMoP/Al2O3 is shown in Fig. 5; the other two PAl2O3 compared to NiMo/Al2O3, both being better than NiMoP/
catalysts generated similar distribution of products (not shown). Al2O3 (Fig. 9). The performance of the catalyst in each one of the
Based on the scheme of the HDS of 4,6-DMDBT shown in Fig. 6, functionalities will be mainly related to one or several of the cata-
the kinetic constants for each step in reaction network were deter- lyst properties such as the acidity, the dispersion of the Ni and Mo
mined. In this reaction scheme, the kinetic constant for the hydro- sulfided phases, the number of CUS in sulfided catalysts as mea-
genation route (kHYD) is commonly related with hydrogenation sured by CO adsorption, or the surface area and porosity.
functionality, the kinetic constant for direct desulfurization kDDS The activity in HDS follows the same trend as the one obtained
is associated with hydrogenolysis functionality and the quotient in the HDS of 4,6 DMDBT (NiMo/PAl2O3 > NiMo/Al2O3 > NiMoP/
kHYD/kDDS to the hydrogenation selectivity [29–31]. The results in Al2O3). Accordingly, the results from CO adsorption show that the
Fig. 7 show that kDDS is the same in the three catalysts whereas HDS conversion of using Maya crude as feedstock correlates with
40 P. Rayo et al. / Fuel 100 (2012) 34–42

100 25.5
NiMo/Al2O3 24.4
NiMo/PAl2O3 24.5 23.9
80
NiMoP/Al2O3
23.5

API Gravity
Conversion, %

60
22.0
22.5
38.4 40.1
40 36.2 34.9
21.5
25.1
21.8 23.8 20.8 Maya
20 17.5 20.5
6.8 7.8
3.1
19.5
0 NiMo/Al2O3 NiMo/PAl2O3 NiMoP/Al2O3
HDS HDM HDAs HDN
Catalysts
HDT reactions
Fig. 10. API Gravity of liquid product after 204 h time-on stream.
Fig. 9. HDT conversions at 204 h using Maya crude oil as feed.

that: NiMo/PAl2O3  NiMo/Al2O3 > NiMoP/Al2O3. The first two

the amount of NiMoS in the catalyst. This means that possibly the catalysts have almost the same acidity, as determined by cumene
sulfur containing molecules that are transformed at the HDS con- cracking, wider pores (see Table 2) and higher dispersion of the
versions, 60–40%, shown by the catalysts during the operating time NiMoS sulfided phase (see CO results, Table 6).
(204 h), are not bulky molecules contained in the asphaltenes. In For the elimination of asphaltenes, HDA’s, it is necessary to have
any case, for the fresh catalysts, the average pore diameter for strong acidity to hydrocrack first the aliphatic chains in the asphal-
the two most active ones is similar (13.1 nm for NiMo/Al2O3 and tene molecules and then to hydrogenate the polyaromatic struc-
12.8 nm for NiMo/PAl2O3), with the less active catalyst presenting tures and open the rings in asphaltenes. In this case, the following
a slightly smaller average pore diameter, 11.7 nm. So, it appears catalyst activity trend was observed: NiMo/PAl2O3 > NiMo/Al2O3 >
that for catalysts with pore diameters in the same range, the rank- NiMoP/Al2O3. As Fig. 9 shows, NiMo/PAl2O3 is slightly more active
ing of HDS activity will be defined by the dispersion of the active than NiMo/Al2O3 possibly because the former has slightly more
sulfide MoS2 and NiMoS phases and particularly by the amount Brönsted acidity (Fig. 3), and shows higher dispersion of the NiMoS
of promoted NiMoS sites. It is also observed that the decrease in sulfided phase (Table 6), and higher hydrogenating capability as
average pore diameter with time on stream is smaller for the P- reflected in the HDS of 4,6-DMDBT (Fig. 7).
containing catalysts (Table 3). This indicates that the presence of The changes in API gravity are the result of the combined effects
P in the catalyst helps to prevent coke deposits. of hydrocracking, HDM and HDA’s (Fig. 10). So in this case the lar-
For HDN it is necessary to hydrogenate first the aromatic ring in ger increases in API gravity will be defined by the acidity, the
order to be able to break the C–N bond. So, usually the most active porosity and the hydrogenating power of the catalyst [35].
catalysts for HDN are the ones with a strong hydrogenating func- NiMo/Al2O3 and NiMo/PAl2O3 showed, after 204 h time on
tion. The experimental results show that the HDN activity trend stream, an increment of API gravity above that of Maya crude of
is similar to that found for the HDS of 4,6-DMDBT. This is not sur- 2.9° and 2.4° API, whereas NiMoP/Al2O3 only achieved an increase
prising since for the transformation of 4,6-DMDBT it is also neces- of 0.5° API. This latter catalyst presents the lowest acidity, the nar-
sary to hydrogenate first the aromatic ring in order to eliminate the rower pores, with 56% of the pores below 5 nm, and the lowest
steric hindrance imposed by the sulfur adjacent methyl groups. In dispersion of the active phase, according to the CO adsorption
fact, it has been found previously [32] that the hydrogenation of results.
the aromatic ring in 4,6-DMDBT takes place on the brim sites of
the sulfided catalyst. For this reason the aromatics and nitrogen-
containing molecules poison this type of sites [33]. So, it appears
that in this case the HDN reaction activity is also governed by Variation (products-feed), %
the dispersion of the active sulfided phase, showing an activity -12 -10 -8 -6 -4 -2 0 2 4 6
trend equal to: NiMo/PAl2O3 > NiMo/Al2O3 > NiMoP/Al2O3. The cat-
>811
alyst acidity will also help since the C–N bond is more difficult to
break than the C–S bond.
It is known that 60–70% of the metals are in the asphaltenes, 727-811
with the remaining being in the form of porphyrin isolated mole-
Crude oil fraction, K

cules [34]. In other words, metals are contained in large molecules 616-727
present in the feed. The deposition of metals on the surface of the
catalyst creates a permanent deactivation that does not go away 316-616
with a normal regeneration under oxidizing atmosphere. Therefore,
this reaction needs wide pores to allow the diffusion of the large 547-589
molecules that contain the metals (Ni and V) and that at the same NiMoP/Al2O3
time act as reservoirs for the deposited metals. Besides porosity 477-547
the catalyst needs acidity and a good hydrogenating metallic phase. NiMo/PAl2O3
Demetallization catalysts are normally constituted by low Mo load NiMo/Al2O3 < 477
that acts as hydrogenating function, large pores to allow diffusion
and deposition of metals, and surface acidity to break the necessary
metal–nitrogen bonds in the porphyrinic structures. The activity Fig. 11. Percentages of product fractions obtained after 204 h time-on-stream,
trend found for this reaction follows the above statements showing using Maya crude oil as feed.
 P. Rayo et al. / Fuel 100 (2012) 34–42 41

SATURATED AROMATICS
6
(a) (b) 15
4 10

2 5
Difference (products-feed)

Diference (products-feed)
0 0

-2 -5

-4 -10

-6 -15
NiMo/Al2O3 NiMo/Al2O3
-8 NiMo/PAl2O3 -20 NiMo/PAl2O3
NiMoP/Al2O3 NiMoP/Al2O3
-10 -25
0 20 40 60 80 100 120 140 160 180 200 220 0 20 40 60 80 100 120 140 160 180 200 220
Time-on stream, h Time-on-stream, h

RESINS ASPHALTENES
(c) 15 (d) 5
NiMo/Al2O3 NiMo/Al2O3
4
NiMo/PAl2O3 NiMo/PAl2O3
10
NiMoP/Al2O3 3 NiMoP/Al2O3
Differece (products-feed)
Differece (products-feed)

2
5
1

0 0

-1
-5
-2

-3
-10
-4

-15 -5
0 20 40 60 80 100 120 140 160 180 200 220 0 20 40 60 80 100 120 140 160 180 200 220
Time-on-strem, h Time-on-strem, h

Fig. 12. Difference in product composition with respect to the Maya crude oil feed.

During Maya crude hydroprocessing, the vacuum residue (VR) is 3.6. SARA fraction conversion
converted to different liquid fractions as can be observed in Fig. 11,
where the difference above or below that present in Maya crude is To characterize the chemical composition of crude oil and its
displayed. It appears that the conversion of VR is determined by heavy fractions, it is necessary to separate and quantify the differ-
the acidity and porosity of the catalyst. At similar acidities the con- ent hydrocarbon groups in the oil mixture. One such separation is
version increases with the porosity of the catalyst, whereas at simi- the SARA fractionation that separates crude oil or its heavy frac-
lar porosity the acidity defines the best catalyst. Fig. 11 shows that tions into saturates, aromatics, resins, and asphaltenes.
NiMo/Al2O3 and NiMo/PAl2O3 catalysts give higher conversion of To emphasize how much of each fraction was obtained above or
residue (>811 K) compared with NiMoP/Al2O3. This is due to the below that contained in the original feed, here we present the
presence of higher acidity and porosity of NiMo/Al2O3 and NiMo/ SARA results in terms of SARA product minus SARA feed (Fig. 12).
PAl2O3 catalysts. In fact, most of the pores of NiMo/Al2O3 are in the It is observed that saturate and aromatics increase in the products,
5–10 nm range. Comparing NiMo/PAl2O3 and NiMoP/Al2O3, the lat- whereas resin and asphaltenes are consumed from the feedstock.
ter has more Brönsted acidity. So the results suggest that catalyst The acidity of the catalysts follows the order NiMo/PA-
acidity is not only factor that determines the conversion of VR but l2O3  NiMo/Al2O3 > NiMoP/Al2O3. So, it is expected that NiMo/
that catalyst porosity also plays an important role. Al2O3 and NiMo/PAl2O3 will crack more resins and asphaltenes
It is noted that NiMo/Al2O3 and NiMo/PAl2O3 catalysts produce (Fig. 12c and d). The asphaltenes are converted to resins and resins
more light fractions of turbosine (477–547 K), kerosene (547– to aromatics (Fig. 12c). Unexpectedly, NiMoP/Al2O3, which has low
589 K), gas oil (589–616 K) and VGO (616–727 K). The increment acidity, produces more saturates, Fig. 12a. A possible explanation is
of these light fractions contributes to the higher API gravity of that NiMoP/Al2O3 could be hydrogenating the aromatic fraction to
the final product. According to Fig. 11 these two catalysts also pro- saturates, so a lower quantity of aromatic fraction is found in the
duce a 2% increment in the gasoline fraction (<477 K). product (Fig. 12b).
42 P. Rayo et al. / Fuel 100 (2012) 34–42

4. Conclusions [12] Topsoe H, Clausen BS, Massoth FE. In: Anderson JR, Boudard M, editors.
Catalysis-science and technology, vol. 11. Berlin: Springer; 1996.
[13] McMillan M, Brinen JS, Haller GL. Solid-state magic-angle spinning 27Al NMR
It has been found that the method of incorporation of P to a used to study alumina support and surface compound structures of catalysts. J
NiMo/Al2O3 hydrocracking catalyst for heavy oils can change sig- Catal 1986;97:243–7.
[14] Jian M, Rico J, Cerda L, Prins R, Jian M, Prins R. Kinetics of the
nificantly the performance of the catalyst. For the hydrocracking
hydrodenitrogenation of deacahydroquinoline over NiMo(P)/Al2O3. Catal Ind
of heavy Maya crude, the incorporation of first, phosphorous to Eng Chem Res 1998;37:834–40.
the alumina support and then the active Ni and Mo phases leads [15] Poulet O, Hubaut R, Kasztelan S, Grimblot J. Modification of the site structure
of MoS2/c-Al2O3 catalysts by addition of P, F and alkaline elements. Stud Surf
to higher conversions of vacuum residue, less coke deposited on
Sci Catal 1993;75:2075–8.
the catalyst, and higher HDS, HDN, HDM, and HDAs activity. For [16] Eijsbouts S, van Gestel JNM, van Veen JAR, Beer VHJ, Prins R. The effect of
the conversion of VR the acidity and porosity of the catalyst are phosphate on the hydrodenitrogenation activity and selectivity of alumina
determinant; at similar acidity the porosity defines the best cata- supported sulfided Mo, Ni, and Ni-Mo catalysts. J Catal 1991;131:412–32.
[17] van Veen JAR, Colijn HA, Hendriks PAJM, van Welsenes AJ. On the formation of
lyst and conversely, at similar porosity, acidity will define the type I and type II NiMoS phases in NiMo/Al2O3 hydrotreating catalysts and its
activity of the catalyst. However, an excess of acidity will lead to catalytic implications. Fuel Process Technol 1993;35:137–57.
rapid deactivation of the catalyst. [18] Ramírez J, Castaño VM, Leclercq C, López Agudo A. High-resolution electron
microscopy study of phosphorus-containing MoS2/A1203 hydrotreating
When tested in HDS of 4,6-DMDBT NiMo/PAl2O3 also shows the catalysts. Appl Catal 1992;83:251–61.
highest activity and better hydrogenating properties. In part, this is [19] Spojakina A, Damyanova S, Petrov L. Effect of phosphorus on the surface state of
so because of the higher number of NiMoS active sites present in alumina-supported nickel-molybdenum catalysts for hydrodesulphurization.
Appl Catal 1989;56:163–76.
this catalyst. NiMo/PAl2O3 displays superior performance com- [20] Kang BC, Wu ST, Tsai HH, Wu JC. Effect of catalyst composition on the
pared to NiMo/Al2O3 and NiMoP/Al2O3 because it presents the best hydrodesulphurization and hydrodemetallization of atmospheric residual oil.
combination of acidity, porosity and distribution of the sulfided Ni Appl Catal 1988;45:221–38.
[21] Kushiyama S, Aizawa R, Kobayashi S, Koinuma Y, Uemasu I, Ohushi H. Effect of
and Mo phases, which provide the hydrodesulfurization and
addition of sulphur and phosphorus on heavy oil hydrotreatment with
hydrogenating function. dispersed molybdenum-based catalysts. Appl Catal 1990;63:279–92.
[22] Kushiyama S, Aizawa R, Kobayashi S, Koinuma Y, Uemasu I, Ohushi H. A novel
effect of phosphorus addition on the activity of dispersed molybdenum-based
Acknowledgments catalysts in heavy oil hydrotreatment. Ind Eng Chem Res 1991;30:107–11.
[23] Cruz J, Avalos M, Borja R, López Cordero, Bañares MA, Fierro JLG, et al. Influence
of pH of the impregnation solution on the phosphorus promotion in W/Al2O3
We thank Instituto Mexicano del Petróleo (IMP) for its financial hydrotreating catalysts. Appl Catal 2002;224:97–110.
support. We also express our appreciation to Mrs. Bertha Núñez [24] Maity SK, Flores GA, Ancheyta J, Rana MS. Effect of preparation methods and
Muñoz and Mr. Rafael Rivera Bermudez for helping in adsorp- content of phosphorus on hydrotreating activity. Catal Today 2008;130:
374–81.
tion-desorption and liquid products characteristic. JR acknowl- [25] Topsøe NY, Topsøe H. FTIR studies of Mo/Al2O3-based catalysts: II. Evidence for
edges sabbatical grant from DGAPA-UNAM and financial support the presence of SH groups and their role in acidity and activity. J Catal
from UNAM-PAPIIT-IN-102709. 1993;139:641–51.
[26] Rana MS, Srinivas BN, Maity SK, Murali Dhar G, Prasada Rao TSR. Origin of
cracking functionality of Sulfided (Ni) CoMo/SiO2-ZrO2 catalysts. J Catal
References 2000;195:31–7.
[27] Byskov LS, Nørskov JK, Clausen BS, Topsøe H. DFT calculations of unpromoted
and promoted MoS2-based hydrodesulfurization catalysts. J Catal
[1] Iwamoto R, Grimblot J. Influence of phosphorous on the properties of alumina-
1999;187:109–22.
bases hydrotreating catalysts. Adv Catal 1999;44:417–505.
[28] Travert AC, Dujardin F, Maugé E, Veilly S, Cristol JF, Payen E. CO adsorption on
[2] Muralidhar G, Massoth FE, Shabta J. Catalytic functionalities of supported
CoMo and NiMo sulfide catalysts: a combined IR and DFT study. J Phys Chem B
sulfides: I effect of support and additives on the CoMo catalyst. J Catal
2006;110:1261–70.
1984;85:44–52.
[29] Kwak C, Kim MY, Choi K, Moon SH. Effect of phosphorus addition on the
[3] Hilfman L. US Patent 3.617.528; 1971.
behavior of CoMoS/Al2O3 catalyst in hydrodesulfurization of
[4] Morales A, Ramirez M, Agudelo M. Promoter role of octahedral Co (and Ni) in
dibenzothiophene and 4,6-dimethyldibenzothiophene. Appl Catal A
modified Co(Ni)Mo–Al2O3 catalysts for hydrodesulfurization reactions. Appl
1999;185:19–27.
Catal 1986;23:23–34.
[30] Isoda T, Nagao S, Ma X, Korai Y, Mochida I. Hydrodesulfurization of refractory
[5] Gishti K, Iannibello A, Marengo S, Morelli G. On the role of phosphate anion in
sulfur species. 1. Selective Hydrodesulfurization of 4,6-dimethyldibenzo-
the MoO3–Al2O3 based catalysts. Appl Catal 1984;12:381–93.
thiophene in the major presence of naphthalene over CoMo/Al2O3 and Ru/
[6] Mickelson GA. US Patent 3.749.663; 1973.
Al2O3. Blend Catal Energy Fuels 1996;10:482–6.
[7] Stanislaus S, Asi-Habi A, Dolana C. Effect of phosphorus on the acidity of c-
[31] Michaud P, Lemberton JL, Perot G. Hydrodesulfurization of dibenzothiophene
alumina and on the thermal stability of c-alumina supported nickel–
and 4,6-dimethyldibenzo-thiophene: effect of an acid component on the
molybdenum hydrotreating catalysts. Appl Catal 1988;39:239–53.
activity of a sulfided NiMo on alumina catalyst. Appl Catal A 1998;169:
[8] Rayo P, Ramírez J, Ancheyta J, Rana MS. Hydrodesulfurization,
343–53.
hydrodenitrogenation, hydrodesmetallization, and hydrodeasphaltenization
[32] Topsøe H. Developments in operando studies and in situ characterization of
of Maya crude over NiMo/Al2O3 Modified with Ti and P. Petrol Sci Technol
heterogeneous catalysts. J Catal 2003;216:155–64.
2007;25:215–29.
[33] Lauritsen JV, Kibsgaard J, Olesen GH, Moses PG, Hinnemann B, Helveg S, et al.
[9] Maity SK, Ancheyta J, Rana MS, Rayo P. Effect of phosphorus on activity of
Location and coordination of promoter atoms in Co- and Ni-promoted MoS2-
hydrotreating catalyst of Maya heavy crude. Catal Today 2005;109:42–8.
based hydrotreating catalysts. J Catal 2007;249:220–33.
[10] Lewis JM, Kydd RA, Boorman PM, van Rhyn PH. Phosphorus promotion in
[34] Trejo F, Ancheyta J, Centeno G, Marroquín G. Effect of hydrotreating conditions
nickel-molybdenum/alumina catalysts: model compound reactions and gas oil
on Maya asphaltenes composition and structural parameters. Catal Today
hydroprocessing. Appl Catal 1992;84:103–21.
2005;109:178–84.
[11] Atanasova P, Tabakova T, Vladov Ch, Halachev T, Lopez Agudo A. Effect of
[35] Ancheyta J, Centeno G, Trejo F, Speight JG. Asphaltene characterization as
phosphorus concentration and method of preparation on the structure of the
function on-stream during hydroprocessing of Maya crude. Catal Today
oxide form of phosphorus-nickel-tungsten/alumina hydrotreating catalysts.
2005;109:162–6.
Appl Catal 1997;161:105–19.