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Influence of the W-CyDTA solution in

impregnation and HDS activity of NiWS/-Al2O3


catalyst
C.E. Santolalla-Vargas,V.A. Surez-Toriello, D. Garca-Ramrez, P. Peralta-Valerio, J.A. de los Reyes*
INTRODUC The synthesis of catalysts for hydrodesulfurization
1 Universidad (HDS) of sulfursDepartamento
A. Metropolitana-Iztapalapa, molecules in de
diesel has relevance
Ingeniera to environmental
de Procesos e Hidrulica,requirements
D.F. (Mxico) of 10 ppm of S in this fuel.
However, sulfur compounds have to be removed selectively to prevent the hydrogenation routes and maintain
* jarh@xanum.uam.mx thelosquality
(J.A. de Reyes) of diesel. The conventional HDS catalysts contain MoS2 or WS2
TION
promoted by Co or Ni supported on alumina. However, to improve the catalytic properties, new synthesis methods have been implemented. In this sense, the incorporation of chelating
agents plays an essential role in enhancing the catalytic properties of HDS catalysts[1]. In particular, 1,2 diamino cyclohexane tetra acetic acid (CyDTA) has been studied in Co-Mo and Ni-Mo
catalysts preparation[1]. Furthermore, NiWS system has been less studied despite the interesting results obtained in contrast with conventional systems. In these systems, the Ni promotion in
the WS2 phase is improved by forming the so-called "NiWS" phase. However, the amount of Ni in this phase has not yet been optimized. Also, it has been found that the active phase
dispersion can be improved. One alternative to solve the above problems is the formation of W-CyDTA complexes to impregnate on Al2O3 surface. In this case, the W-CyDTA complex interacts
with Al2O3 surface to avoiding the strong interaction metal-support. The surface modification using CyDTA has generated highly active catalysts in 4.6 dimethyl dibenzothiophene HDS on W
based catalysts[2]. Therefore, in this study NiW/Al2O3 catalysts with W-CyDTA complex addition at different molar ratio CyDTA/W were synthesized and characterized. Finally, considering their
potential application in diesel processing, the catalysts activity was evaluated in dibenzothiophene (DBT) HDS.

METHODS Supported NiW catalyst was prepared by subsequent incipient wetness impregnation method using a mixed W-CyDTA solution and nickel nitrate. Commercial -
Al2O3 (245 m2g-1) was used as support. Various W-CyDTA solutions ( CyDTA/W=0.0, 0.5, 1.0, 2.0) were prepared at different molar ratios. The W loading was 10 wt.-% and 2.0 wt.-% for Ni.
The catalysts are called W-CyDTA(x)Ni, where x is the molar ratio value of the W-CyDTA solution. A NiW/-Al2O3 catalyst without CyDTA was prepared and used as a reference. The catalysts
were characterized by different physicochemical techniques: DRS UV-Vis and TPR. The sulfide catalysts were tested in DBT HDS reaction and performed at 593 K, 5.5 MPa of H2 and 1200 rpm
in a batch reactor (PARR).

RESULTS
CATALITYC PROPERTIES

TPR

DRS-UV VIS
A re-dispersion of W species after the
impregnation of Ni solutions was
evidenced. Figure 4. Shematic representation of possible interations on
Intensity (a.u.)

W-CyDTA (x)Ni/Al2O3 catalyst in oxide state

Charge transfer O2- W6+

Temperature (C)

Figure 3. DRS UV VIS spectra for Ni W/Al2O3 at different


molar ratio CyDTA /W: 0.0(a) ,0.5(b), 1.0(c) and 2.0(d)
Figure 1. DRS UV VIS spectra for Ni W/Al2O3 at different molar
ratio CyDTA /W: 0.0(a) ,0.5(b), 1.0(c) and 2.0(d)
TPR profiles of the catalysts showed several peaks
reduction at high temperature (> 600 C) with Figure 5. Correlation W6+ reduction vs Initial reaction rate for NiW/-Al2O3 with
The spectra of nickel region suggest more stable CyDTA/W molar ratio is incremented. These peaks CyDTA at different W/CyDTA molar ratio (0.0,0.5,1.0,2.0).
correspond to W species with strong metal-support
nickel complex a high content of CyDTA. interaction

Table 1. temperature reduction of W


Ni electron transitions Hydrodesulfurization of DBT
Catalyst Temperature reduction of
Table2. conversion and products (at(16-24)% conversion ) in the HDS of DBT
W (C) over NiW sulfide catalysts

NiW/Al203 503 DDS Initial Rate


HYD reaction route reaction HYD/DDS (mol DBT/gr CAT
W-CyDTA(0.5) Ni 473 Catalyst route
Conv. ratio S)

(%) THDBT CHB BCH BP 10-7


16 .36 2.6 4.0 9.0 0.77 4.4
NiW/Al2O3
W-CyDTA(1.0) Ni 491
NiW/Al2O3 18 1.2 2.1 3.4 11.5 0.58 8.0
(0.5)
NiW/Al2O3 24 13 0.13 4.2 6.6 2.6 2.6
W-CyDTA(2.0) Ni 511 (1.0)

NiW/Al2O3 19 0.09 0.36 6.9 11.9 0.62 3.3


(2.0)
Figure 2. DRS UV VIS spectra for Ni W/Al2O3 at different
molar ratio CyDTA /W: 0.0(a) ,0.5(b), 1.0(c) and 2.0(d)

CONCLUSIO REFERENC
N Sun, M.; Nicosia, D.; Prins, R. Catal. Today 86, 173 (2003).
ES
In this work, the synthesis of sulfide NiW/-Al2O3 catalysts synthesized with W-CyDTA solutions Santolalla-Vargas,C.E.;Surez Toriello,V.A.; de los Reyes, J.A.; Cromwell, D.K.; Pawelec, B. and Fierro, J.L.G. Mat. Chem.
Phys. 166, 105 (2015).
at various CyDTA/W values was studied. The variation CyDTA/W ratio of impregnation W-CyDTA
helps to increase the W species reduction < 600 C, highly active in HDS.
We acknowledgment financial support from CONACYT-SENER-HIDROCARBUROS (2137). CONACYT-SENER-Hidrocarburos
2009-01, proyecto 117373.