(617aa) Effect of the Preparation Method on the Porosity of Amorphous Silica-Alumina to be Used in Hydrocracking Reactions | AIChE

(617aa) Effect of the Preparation Method on the Porosity of Amorphous Silica-Alumina to be Used in Hydrocracking Reactions

Authors 

Coconubo Díaz, A. L. - Presenter, Universidad Industrial de Santander
Ballesteros Rueda, L. M., Universidad Industrial de Santander

EFFECT OF THE PREPARATION METHOD ON THE POROSITY OF
AMORPHOUS SILICA-ALUMINA TO BE USED IN HYDROCRACKING REACTIONS

Angélica L. Coconubo-Díaz1A, Alexander
Guzmán-Monsalve2B, Luz M. Ballesteros-Rueda1C

 

1: Centro de Investigaciones en Catálisis, Escuela de Ingeniería Química,
Carrera 27 Calle 9 Universidad Industrial de Santander, Bucaramanga, Santander,
Colombia

2: Km 7 Vía Piedecuesta, Instituto Colombiano del Petróleo, Piedecuesta,
Santander, Colombia

e-mail: angelica.coconubo@gmail.com A, alexander.guzman@ecopetrol.com.co B, luzmabal@uis.edu.co C 

 

ABSTRACT

Catalyst for heavy oil and vacuum gas oil hydrocracking (HCK) require high pore diameter
to treat the bulky molecules present in such kind of feedstocks,  in order to allow the access of large
molecules into the active sites of the catalyst, avoiding
diffusional limitations [1,
2]. Amorphous AluminoSilicates
(ASAs) are widely used as catalyst support in the heavy oil refining
industry because of its physico-chemical properties (acidity and large pore size)
[1, 3, 4].  On the other hand, several
authors have stated that the
synthesis methods of ASAs impacts the textural properties such as surface area and pore size [4]. Particulary, in the sol-gel method, the control of the hydrolysis process and condensation is very important
to obtain the desired gel [3, 5].

In the present study, bifunctional catalysts consisting of nickel-molybdenum (NiMo) supported on amorphous
silica-alumina were prepared using two different sol-gel methods. It is
well known that the characteristics
of the obtained oxides depend on the
sol-gel parameters such as
precursor molecules, concentration,
solvent type, temperature, amount of water and pH [6, 7]. The sol-gel methods used were:
sol-gel using PolyEthylene Glycol (PEG) as an organic template [8], and sol-gel
with gel skeletal reinforcement [9]. In the first method the
amount of PEG was varied taking into
account the amount of silica precursor used which, in this study, was
TetraEthyl OrthoSilicate
(TEOS); on the other hand, in the second method
was varied the amount of TEOS used in the reinforcement
solution (RS). In addition,
in both methods the calcination were carried out
at two different values of temperature, in order to compare its effect in the textural properties of the supports.  The supports (ASAs) and the NiMo catalysts were characterized by means of N2-physisorption,
X-ray diffraction, SEM-spectroscopy, and NH3-adsorption; in order to determine their chemical and physical properties.

Amorphous silica-alumina prepared
by the first
method, showed both type of porosities:
micro and mesopores, and it
was found that surface area
and mesoporosity area increased while the amount of PEG added increased as well. On the
other hand, ASAs prepared by the
second method showed only mesoporosity,
meaning that RS helps avoiding the formation of micropores. Additionally, surface area, pore
volumen and pore size, increased while increasing the TEOS amount in the RS.  Furthermore, it was found, that
the calcination temperature affects the porosity of the material using both methods, since
the surface area decreased when the highest
calcination temperature was used likely
ocurring by sinterization of the material.

Keywords: Hydrocracking, Amorphous Aluminosilicates, Ni-Mo
Catalyst, Sol-Gel method, Polyethylene Glycol, Gel Skeletal Reinforcement, Vacuum Gas Oil.

REFERENCES

[1] LEYVA, C., et al,  “Activity and
Surface Properties of NiMo/SiO2-Al2O3Catalysts for Hydroprocessing of Heavy Oils,” Appl. Catal. A Gen.,
vol. 425–426, pp. 1–12, 2012

[2] PASHKOVA, V. O., SARV, P., and DEREWIŃSKI, M., “Composite Porous Materials Containing Zeolitic Domains Prepared by Controlled
Partial Recrystallization
of Amorphous Aluminosilicates,”
Stud. Surf. Sci. Catal., vol. 170, pp. 289–296, 2007.

[3] ISHIHARA, A., et al, “Catalytic Properties of Amorphous Silica-Alumina Prepared using Malic Acid
as a Matrix in Catalytic
Cracking of n-dodecane,” Appl.
Catal. A Gen.
, vol. 388, pp. 68–76, 2010.

[4] CAILLOT, M., et al, “Synthesis of Amorphous Aluminosilicates by Grafting: Tuning
the Building and final Structure of the Deposit by Selecting
the Appropriate Synthesis Conditions,” Microporous Mesoporous
Mater.
, vol. 185, pp. 179–189, 2014.

[5] OKAMOTO, Y., et al, “A study on the Preparation
of Supported Metal Oxide Catalysts
using JRC-reference Catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index,” Appl. Catal. A Gen.,
vol. 170, pp. 359–379, 1998.

[6] ALI, M.A., TATSUMI, T., and MASUDA, T., “Development
of Heavy Oil Hydrocracking Catalysts using Amorphous Silica-Alumina and Zeolites as Catalyst Supports,” Appl. Catal. A Gen., vol. 233, pp. 77–90, 2002.

[7] PÉREZ-MARTÍNEZ, D. J., GAIGNEAUX, E. M., and GIRALDO, S. A., “Improving the Selectivity
to HDS in the HDT of Synthetic
FCC Naphtha using Sodium Doped Amorphous
Aluminosilicates as Support
of CoMo Catalysts,” Appl. Catal. A Gen., vol.
421–422, pp. 48–57, 2012.

[8] ISHIHARA, A., et al, “Preparation of Amorphous Silica-Alumina using Polyethylene Glycol and its role for Matrix in Catalytic
Cracking of n-dodecane,” Appl.
Catal. A Gen.
, vol. 478, pp. 58–65, 2014.

[9] ISHIHARA, A., HASHIMOTO, T., and NASU, H., “Large
Mesopore Generation in an Amorphous Silica-Alumina
by Controlling the Pore Size
with the Gel Skeletal Reinforcement and its Application to Catalytic Cracking,” Catalysts,
vol. 2, pp. 368–385, 2012.