Efecto de la calcinación de hidrocalumitas Fe-Ca como soporte de CoMo para la hidrodesulfuración de tiofeno e hidrogenación de ciclohexeno. / Calcination effect of Ca-Fe hydrocalumites supported CoMo for the hydrodesulfurization of thiophene and hydrogenation of cyclohexene.

• Carlos Linares Universidad de Carabobo
• Andri Campos Universidad de Carabobo
• Susana Mujica Universidad de Carabobo
• Freddy Ocanto Universidad de Carabobo
• Pablo Bretto Universidad de Carabobo

Abstract

Resumen

Se sintetizó una hidrocalumita de Fe-Ca, se calcinó entre 500 y 900°C, y se caracterizó por diferentes técnicas tales como: difracción de rayos X (DRX), espectroscopia de infrarrojo con transformada de Fourier (FT-IR) y área superficial. Luego, los soportes fueron impregnados con Mo y Co. Finalmente, los catalizadores fueron probados en la hidrodesulfuración de tiofeno e hidrogenación de ciclohexeno como reacciones modelo. Los resultados mostraron que la actividad catalítica depende de la temperatura de calcinación del soporte, y éstos fueron más activos cuando los soportes se calcinaron a la temperatura más alta lo cual podría estar asociado a las fases presentes.

Abstract

A Fe-Ca hydrocalumite was synthesized, calcined between 500 and 900°C, and characterized by different techniques such as: X-ray diffraction (XRD), Fourier-Transform infrared spectroscopy (FT-IR) and surface area. After that, supports were impregnated with Mo and Co. Finally, catalysts were tested in the thiophene hydrodesulfurization and cyclohexene hydrogenation as model reactions. Results showed that conversion depended of calcination temperature of support, and those were more active when the support was calcined to the highest temperature which could be associated to the present phases.

References

King D. A.: “Biggest opportunity of our age.” Sci., Vol.

, No 6269 (2016) 107.

Menz F. C. and Seip H. M.: “Acid rain in Europe and

the United State: an update.” Environ. Sci. Policy. Vol.

, No 4 (2004) 253-265.

Murali Dhar G., Srinivas B.N., Rana M.S., Kumar M.,

Manoj M. and Maity S.K.:“Mixed oxide supported

hydrodesulfurization catalyst –a review.” Catal.

Today. Vol. 86, No 1-4 (2003) 45-60.

Chary K.V.R., Rama Rao K.S., Murali Dhar G. and

Kanta Rao P.: “Hydrodeoxygenation of furan by

carbon supported molybdenum sulphide catalysts.”

Carbon. Vol. 29, No 3 (1991) 478-479.

Rawat K.S., Rana M.S. and Murali Dhar G.:

“Catalytic functionalities of USY zeolites supported

hydrotreating catalysts.” Stud. Surf. Sci. Catal. Vol.

(1998) 301.

Linares C.F., Amézqueta P. and Scott C.: “Mo/MCM41 type mesoporous materials doubly promoted

with Fe and Ni for hydrotreating reactions.” Fuel.

Vol. 87, No 12 (2008) 2817-2823.

Chary K.V.R., Ramakrishna H., Rama Rao K.S., Murali

Dhar G. and Kanta Rao P.: “Hydrodesulfurization on

MoS2/MgO.” Catal. Lett. Vol. 10, No 1-2 (1991) 27-

López-Salinas E., Llanos M.E., Cortés M.A. and Schifter

I.: “Characterization of synthetic hydrocalumitetype [Ca2 Al(OH)6]NO3.mH2

O.” J. Porous Mater. Vol. 2,

No 4(1995) 291-297.

Rousselot I., Taviot C., Leroux F., Léone P., Palvadeau

P. and Besse J.: “Insights on the structural chemistry

of hydrocalumite and hydrotalcite-like materials:

investigation of the series Ca2 M3+(OH)6 Cl·2H2 O (M3+:Al3+, Ga3+, Fe3+, and Sc3+) by X-ray powder diffraction.” J. Solid State Chem. Vol. 167, No 1(2002) 137144.

Linares C.F., Bretto P., Álvarez R., Ocanto F., Corao C.,

Betancourt P. and Brito J.L.: “Evaluation of calcined

hydrocalumite-type materials as supports of

CoMo and NiMo for thiophene hydrodesulfuration

reaction.” Mater. Res. Vol. 17, No 4(2014) 1516-

Scott C.E., Embaid S.P.. Luis M.A., González-Jimenez

F., Gengembre L., Hubaut R. and Grimblot J.:

“Bulk Fe-V mixed sulphides as hydroprocessing

catalysts: characterization and thiophene

hydrodesulphurization.” J. Bull. Soc. Chim. Belg. Vol.

(1995) 331-337.

Cornell U. and Schwertmann U. in: “The iron oxides

structures, properties, reactions, occurrences and

uses.”, Vol. 6, Wiley-Vch., 2nd Ed., Germany. 2003,

-398.

Breysse M., Afanasiev P., Geantet C. and Vrinat

M.: “Overview of support effects in hydrotreating

catalysts.” Catal. Today. Vol. 86, No 1-4 (2003) 5-16.

http://www.colby.edu/chemistry/PChem/notes/

NormalModesText.pdf.

Campos M., Santamaría J., Mérida J., Moreno R.,

Alburquerque M., Bruque S., Rodríguez E., Jiménez

A. and Maireles P.: “Base catalysts derived from

hydrocalumite for the transesterification of

sunflower oil.” Energy Fuels. Vol. 24, No 2(2009)

- 984.

Vieille L., Rousselot I., Leroux F., Besse J.P. and Taviot

C.: “Hydrocalumite and its polymer derivatives.

Reversible thermal behavior of Friedel’s salt: A

direct observation by means of high-temperature in

situ powder X-ray diffraction.” Chem Mater. Vol. 15,

No 23 (2003) 4361-4368.

Halikia L., Zoumpoulakis L., Christodoulou E.

and Prattis D.: “Kinetic study of the thermal

decomposition of calcium carbonate by isothermal

methods of analysis.” Eur. J. Miner. Process. Environ.

Prot. Vol. 1, No 2 (2001) 89-102.

Sohn J., Chun E. and Pae Y.: “Spectroscopic studies

on ZrO2 modified with MoO3 and activity for acid

catalysis.” Bull. Korean Chem. Soc. Vol. 24, No 12

(2003) 1785-1792.

Legrand L., Mazerolles L. and Chaussé A.: “The

oxidation of carbonate green rust into ferric phases:

solid-state reaction or transformation via solution.”

Geochim. Cosmochim J. Acta. Vol. 68, No 17 (2004)

-350.

García B., González G., Ocanto F. and Linares C.F.:

“CoMo/Zn-hydroxyapatites as catalysts for the

hydrodesulfurization reaction of thiophene.” Indian

J. Chem. Technol. Vol. 19, No 6 (2012) 403-408.

Pettre M., in: “ Heterogeneous Catalysis, Catalysis

and Catalysts”, Antin D., 3rd., Ed., Dover Publications

Inc, New York, 1961, 65-68.

Mey D., Brunet S., Canaft C., Maugé F., Bouchy C.,

Dielh F.: “HDS of a model FCC gasoline over a sulfide

CoMo/Al2O3 catalyst: Effect of the addition of

potassium.” J. Catal. Vol. 227, (2004) 436-447.