Yin 2013
Yin 2013
Yin 2013
DOI 10.1007/s10562-013-1131-2
Received: 12 July 2013 / Accepted: 4 October 2013 / Published online: 31 October 2013
Ó Springer Science+Business Media New York 2013
Abstract A novel binary promoter NiCoMo layered The cost effective and efficient choice is frequently
molybdate was synthesized as potential hydrodesulfuriza- achieved by the implementation of highly active hyd-
tion (HDS) catalyst precursor by chemical precipitation rodesulfurization (HDS) catalysts, and a great enhancement
from a solution containing nickel nitrate, cobalt nitrate and of HDS activity could be achieved by organic additives on
ammonium heptamolybdate. NiMo and CoMo layered supported HDS catalysts, like ethyleneglycol and triethyl-
molybdates were also prepared for comparison by the same eneglycol, which were attributed to the formation of so-
method. The NiCoMo, NiMo and CoMo layered molyb- called ‘‘NiMoS phase’’ or ‘‘CoMoS phase’’ [2, 3]. Another
dates were characterized by means of N2 physisorption, representative is the unsupported catalyst called NEBULA,
XRD, FT-IR, TG–DSC–MS, SEM and HRTEM, and cat- which is a Ni–Mo–W trimetallic catalyst and supposed to
alytic properties were evaluated in the continuous HDS of be catalytically active in hydrotreating, reaching four times
dibenzothiophene (DBT) and straight-run gas oil. The the activity of the conventional supported catalysts [4, 5].
characterization results indicated the three precursors were The success of NEBULA accelerate the investigation of
endowed with the same structure of ammonium nickel unsupported catalysts. Decomposition of thiosalts [5–7],
molybdate, and catalytic results showed that the NiCoMo sulfurization of oxide precursor [8], and homogeneous
catalyst exhibited higher HDS activity towards DBT and sulfide precipitation [9] were often tried out to prepare
straight-run gas oil, which might be more attractive for specialized unsupported catalysts, and some other studies
industrial applications. were carried out with the molybdenum carbide [10] or
nitride [11].
Keywords Nickel cobalt molybdate Nickel As groundbreaking work in the synthesis of molybdate
molybdate Cobalt molybdate Hydrodesulfurization material leaded by Pezerat [12] in identifying a series of
Dibenzothiophene ULSD molybdate compounds with the ideal formula (NH4)
H2xNi3-xO(OH)(MoO4)2, where 0 B x B 3/2, the crystal
structure, which consists of molybdate tetrahedral and
1 Introduction nickel octahedral forming layers perpendicular to the c
axis, was generated by Ying and coworkers [13]. The
More stringent legislation for cleaner environment and nonstoichiometry solid solution composing of unique
lower contents of sulfur in automotive fuels constrain the molybdate layered structure and promoter metal might be
refiners to update or improve the hydrotreating plants [1]. of great potential inspiration for design novel HDS catalyst.
More recently, we reported unsupported NiMo catalyst
derived from a novel porous ammonium nickel molybdate
C. Yin (&) H. Liu X. Li Y. Wang B. Liu (NH4)HNi2(OH)2(MoO4)2 and exhibited much high cata-
L. Zhao C. Liu lytic activity towards deep HDS of gas oil, which were
Key Laboratory of Catalysis, CNPC, State Key Laboratory of
attributed to efficient formation Ni–Mo–S structure from
Heavy Oil Processing, China University of Petroleum,
Qingdao 266555, Shandong, China the crystalline ammonium nickel molybdate [14]. In the
e-mail: yincl@upc.edu.cn light to explore efficient HDS catalyst, a novel binary
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promoter NiCoMo unsupported catalyst was firstly pre- Fourier-transform infrared (FT-IR) spectrum of the pre-
pared with NiCoMo layered molybdate synthesized cursor was collected on a Nexus spectrometer (NiColet,
through chemical precipitation, and the NiMo and CoMo USA) using KBr disks. Nitrogen adsorption–desorption
unsupported catalysts were prepared for comparison, and experiment was measured on a Micromeritics TRISTAR
evaluated in the continuous HDS of dibenzothiophene 3020 adsorption analyzer (USA). A FEI Quanta200 scan-
(DBT) and straight-run gas oil. ning electron microscope (SEM) was used to perform
morphological analysis. Thermogravimetry–differential
scanning calorimeters–mass spectrum (TG–DSC–MS)
2 Experimental Section analysis was carried out by applying a thermal analysis
instrument combined with a MS instrument (STA449c-
2.1 Synthesis of Layered Molybdates QMS403) at a heating rate of 10 °C min-1 under a high-
purity nitrogen atmosphere. The high-resolution transmis-
The layered molybdate were synthesized by chemical sion electron microscope (HRTEM) micrographs were
precipitation method as follows. The mixtures of ammo- recorded using a JEM 2010 microscope operated at 200 kV.
nium heptamolybdate with nickel nitrate or cobalt nitrate
were dissolved in deionized water, with the molar ratios 2.4 Catalyst Activity
1:1, 1:1 or 1:1:2 referring to NiMo, CoMo or NiCoMo,
respectively. The solution was added to flask, heated and Catalytic activity measurements were carried out in a high
stirred at 90 °C. The addition of concentrated ammonium pressure fixed bed down-flow micro-reactor with an inner
hydroxide (28.8 % NH3) to the solution containing NiMo diameter of 10 mm, 40 cm in length. Ten milliliter of the
precipitated a green solid that dissolved in an excess of catalyst was placed in the center of the reactor without any
ammonia, giving a dark blue solution, when it turns to diluent. The catalyst was first treated at 110 °C for 1 h and
CoMo and NiCoMo, the solid and solution changed to be maintained at 320 °C for 12 h by a liquid stream contain-
purple and dark blue, respectively. The solution was stirred ing 3.0 wt% CS2 in cyclohexane for sulfidation. 2.0 wt%
and heated for 12 h, resulting in the formation of the pre- DBT in petroleum ether (boiling range from 90 to 120 °C)
cipitate. The products were isolated by vacuum filtration, was then pumped into the reactor at the test temperature.
washed with deionized water, and dried overnight at 80 °C The reaction conditions were temperature 280 °C, pressure
and atmospheric pressure. The layered molybdate were 3.0 MPa, H2/feed ratio 300, and liquid hourly space
labeled as NiMo, CoMo and NiCoMo precursors according velocity (LHSV) 3.0 h-1. The product was cooled and
to the elemental composition. separated into gaseous and liquid products in a high-pres-
sure separator. The liquid products were analyzed by a
2.2 Preparation of Catalyst Varian 3800 gas chromatography equipped with flame
ionization detector (GC-FID) and a 50 m OV101 capillary
The catalyst preparation procedure has previously been column. The HDS of straight-run gas oil (produced by
described in detail elsewhere [14]. The layered molybdate West Pacific Petrochemical Company Ltd., Dalian) was
precursors were firstly grinded, then mixed evenly with operated at the same sulfidation conditions with above
alumina sol (alumina occupying 20 wt%) under the drop- mentioned and the reaction conditions were pressure
wise adding of deionized water. Then the mixture were 6.0 MPa, H2/feed ratio 600, temperature 350 °C and LHSV
extruded into rods 1.6 mm in diameter. After that, the rods 2.0 h-1. The sulfur composition of liquid products was
were dried in air at 110 °C for 12 h, followed by calcina- analyzed using Varian 3800 gas chromatography equipped
tion in a muffle furnace at 350 °C for 6 h. The catalysts with a pulse flame photometric detector (GC-PFPD) and a
were labeled as NiMo, CoMo and NiCoMo catalysts 30 m fused-silica capillary column.
according to the precursors used.
An industrial NiMo/Al2O3 catalyst (24 wt% MoO3,
4 wt% NiO, BET specific surface area of 225 m2 g-1) was 3 Results and Discussion
used as reference to compare the HDS activity of straight-
run gas oil with NiCoMo catalyst. 3.1 Characterization of Molybdate Precursors
X-ray powder diffraction (XRD) analysis was carried out The NiMo, CoMo and NiCoMo precursors through chem-
with a Rigaku D/max-IIA diffractometer using a graphite- ical precipitation reaction were characterized by XRD, and
filter Cu Ka radiation at a scan rate of 2° min-1. The the results were depicted in Fig. 1. Figure 1 exhibited that
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288 C. Yin et al.
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Novel Binary Promoter NiCoMo Layered Molybdate Catalyst 289
3.2.1 N2 Physisorption
Fig. 5 XRD patterns of sulfurized NiMo, CoMo and NiCoMo
catalysts
The BET specific surface, pore volume and pore size of
NiMo, CoMo and NiCoMo catalysts deriving from the
respective precursors were shown in Table 1. The unsup- 3.2.3 HRTEM
ported NiMo, CoMo and NiCoMo catalysts displayed
surface area in the range of 104–114 m2 g-1, and differ- The HRTEM photographs of sulfurized NiMo, CoMo and
ences of pore structure could also be found in the NiMo, NiCoMo catalysts were exhibited in Fig. 6. The black
CoMo and NiCoMo catalysts in Table 1. At the same time, thread-like fringes corresponding to typical stacking MoS2
CoMo unsupported catalyst exhibited higher pore volume slabs were observed in all sulfurized catalysts, which had a
(0.23 cm3 g-1) than that of NiCoMo catalyst, which was interplanar distance of about 0.61 nm, and this was attrib-
only 0.17 cm3 g-1, and the pore size of these three cata- uted to the characteristic of the (002) basal planes of the
lysts were in the range of 6.0–6.6 nm, which might provide crystalline MoS2. It could also be found that some smaller
suitable access for reactants. fringes were detected in sulfided catalysts, especially in
NiMo and CoMo catalysts. These fringes had a spacing of
3.2.2 XRD about 0.29 nm that was probably the characteristic of the
crystalline sulfurized nickel or cobalt containing species
The sulfurized NiMo, CoMo and NiCoMo catalysts were [14], which was in accordance with the foregoing sulfurized
characterized by XRD, and the results were presented in XRD results. However, there existed significant differences
Fig. 5. The phase of MoS2 (PDF card No. 89-5112) was in HRTEM photographs of these catalysts. It could be found
detected in NiMo and NiCoMo catalysts except CoMo that for sulfurized NiMo catalyst, the aggregated Ni3S2
catalyst, but in the NiCoMo catalyst, there exhibited poorly were covered with stacking MoS2 slabs, and as to CoMo
crystalline phase of MoS2, especially when the character- catalyst, the disordered MoS2 slabs placed around Co9S8,
istic degree of 2h was 14.4°, which was inclined to be which might not be suitable for the synergetic effects of
approximately amorphous phase, and the highly dispersed promoters in these cases [19, 20], while there existed
MoS2 played effective role in HDS reactions [18]. Ni3S2 obviously overlapping between MoS2 and sulfurized Ni or
(PDF card No. 044-1418) and Co9S8 (PDF card No. Co containing species in NiCoMo catalyst.
065-6801) were detected in NiMo and CoMo catalyst,
respectively, and both of these phases were confirmed by 3.2.4 Catalytic Results
XRD in binary promoter NiCoMo catalyst. The charac-
teristic peaks of Co9S8 phase were detected at 2h of 29.8° A model fuel containing 2 wt% DBT in petroleum ether
and 52.1° in CoMo catalyst, and the characteristic peak of was used to investigate the HDS activities for NiMo,
Ni3S2 phase was confirmed at 2h of 31.1° in NiMo catalyst, CoMo, and NiCoMo catalysts. Table 2 shows the distri-
which were also detected in NiCoMo catalyst with differ- butions of products after HDS reactions. The HYD/DDS
ent intensities. At the same time, the characteristic peaks of ratios of the three catalysts were calculated and also
MoS2 and Co9S8, Ni3S2 and Co9S8, were overlapped at shown in Table 2. Three Mo-based catalysts deriving from
about 47° and 30°, respectively. layered molybdate could efficiently convert DBT into
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Novel Binary Promoter NiCoMo Layered Molybdate Catalyst 291
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292 C. Yin et al.
Funds for the Central Universities (14CX06032A). Financial support 12. Pezerat H (1965) C R Acad Sci 261:5490
from PetroChina Corporation Limited is also greatly appreciated. 13. Levin D, Soled S, Ying J (1996) Inorg Chem 35:4191
14. Yin C, Zhao L, Bai Z, Liu H, Liu Y, Liu C (2013) Fuel 107:873
15. Lauritsen J, Helveg S, Lægsgaard E, Stensgaard I, Clausen B,
Topsøe H, Besenbacher F (2001) J Catal 197:1
References
16. Shaheen W (2002) Mater Lett 52:272
17. Levin D, Ying J (1999) J Electroceram 3:25
1. Stanislaus A, Marafi A, Rana M (2010) Catal Today 153:1 18. Wang A, Wang Y, Kabe T, Chen Y, Ishihara A, Qian W, Yao P
2. Nguyen T, Loridant S, Chantal L, Cholley T, Geantet C (2011) (2002) J Catal 210:319
Appl Catal B 107:59 19. Aray Y, Vega D, Rodriguez J, Vidal A, Grillo M, Coll S (2009) J
3. Escobar J, Barrera M, Toledo J, Cortés-Jácome M, Angeles- Phys Chem B 113:3058
Chávez C, Núñez S, Santes V, Gómez E, Dı́az L, Romero E, 20. Vissenberg M, Meer Y, Hensen E, Beer V, Kraan A, Santen R,
Pacheco J (2009) Appl Catal B 88:564 Veen J (2001) J Catal 198:151
4. Niefind F, Cruz-Reyes J, Valle M, Kienle L, Lotnik A, Alonso- 21. Lauritsen J, Kibsgaard J, Olesen G, Moses P, Hinnemann B,
Nuñez G, Armbrüster M, Bensch W (2012) Catal Lett 142:1312 Helveg S, Nørskov J, Clausen B, Topsøe H, Lægsgaard E, Be-
5. Sonj E, Bob L, Yoshimasa I, Katsuhisa F (2003) Div Fuel Chem senbacher F (2007) J Catal 249:220
48:494 22. Lauritsen J, Bollinger M, Lægsgaard E, Jacobsen K, Nørskov J,
6. Bocarando J, Alonso-Nuñez G, Bensch W, Huirache-Acuña R, Clausen B, Topsøe H, Besenbacher F (2004) J Catal 221:510
Valle M, Cruz-Reyes J (2009) Catal Lett 130:301 23. Wang A, Wang Y, Kabe T, Chen Y, Ishihara A, Qian W (2001) J
7. Poisot M, Bensch W, Fuentes S, Ornelas C, Alonso G (2007) Catal 199:19
Catal Lett 117:43 24. Harris S, Chianelli R (1986) J Catal 98:17
8. Quintana-Melgoza J, Alonso-Nuñez G, Homero-Galván D, 25. Caloch G, Santes V, Escobar J, Valle-Orta M, Barrera M, Her-
Ávalos-Borja M (2012) Catal Lett 142:1082 nández-Barrera M (2012) Int J Chem React Eng 10:A71
9. Inamura K, Prins R (1994) J Catal 147:515 26. Bataille F, Lemberton J, Michaud P, Pérot G, Vrinat M, Lemaire
10. Wang H, Wang X, Zhang M, Du X, Li W, Tao K (2007) Chem M, Schulz E, Breysse M, Kasztelan S (2000) J Catal 191:409
Mater 19:1801
11. Chouzier S, Czeri T, Roy-Auberger M, Pichon C, Geantet C,
Vrinat M, Afanasiev P (2011) J Solid State Chem 184:2668
123