Malaysian Journal of Analytical Sciences Vol 20 No 2 (2016): 393 – 400

 

 

 

EFFECT OF SUPPORT MATERIALS ON CATALYTIC ACTIVITY OF NANO RUTHENIUM CATALYST IN HYDROGENOLYSIS OF GLYCEROL

 

(Kesan Bahan Penyokong Terhadap Aktiviti Pemangkin Nano Ruthenium dalam Hidrogenolisis Gliserol)

 

Noraini Hamzah¹* and Mohd Ambar Yarmo²

 

¹School of Chemistry and Environmental, Faculty of Science and Technology

Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

²School of Chemical Sciences and Food Technology, Faculty of Science and Technology,

Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

 

*Corresponding author: pnoraini@salam.uitm.edu.my

 

 

Received: 24 February 2015; Accepted: 27 October 2015

 

 

Abstract

A series of heterogenous catalysts based on supported ruthenium were prepared from RuCl₃ precusor by impregnation method. The effect of support materials (bentonite, TiO₂, Al₂O₃ and SiO₂) on catalytic activity of Ru catalyst for hydrogenolysis of glycerol were investigated under mild reaction condition of 150°C and 20 bar initial hydrogen pressure for 7 hours reaction time and glycerol concentration was 20%(wt). It was found that the type of support material have significant effects on the activity and selectivity of glycerol hydrogenolysis. The order of Ru catalyst activity was Ru/bentonite > Ru/Al₂O₃ » Ru/TiO₂ > Ru/SiO₂. This study showed that bentonite supported Ru catalyst was the most active with glycerol conversion reaching 62.5% compared to other supports. All the tested catalyst exhibited high selectivity to 1,2-propanediol with more than 80%. Characterization of the catalysts was carried out using BET, XPS, FESEM-EDX and TEM to obtain the physicochemical properties of the catalysts.

 

Keywords: hydrogenolysis, ruthenium, bentonite, 1,2-propanediol, glycerol

 

Abstrak

Satu siri pemangkin heterogen berasaskan logam ruthenium berpenyokong disediakan daripada prekusor garam RuCl₃ menggunakan teknik impregnasi. Kesan bahan penyokong (bentonit, TiO₂, Al₂O₃ dan SiO₂) terhadap aktiviti pemangkin Ru dalam hidrogenolisis gliserol dilakukan pada keadaan tindak balas yang sederhana dengan suhu 150°C, tekanan awal hydrogen 20 bar, masa tindak balas 7 jam dan kepekatan gliserol 20%(wt). Keputusan yang diperolehi menunjukkan jenis bahan penyokong mempunyai kesan signifikan terhadap aktiviti dan pemilihan dalam hidrogenolisi gliserol. Turutan aktiviti pemangkin Ru adalah Ru/bentonit > Ru/Al₂O₃ » Ru/TiO₂ > Ru/SiO₂. Kajian ini menunjukkan pemangkin Ru yang disokong atas bentonit adalah pemangkin yang paling aktif dengan peratus penukaran mencapai 62.5% berbanding dengan penyokong lain. Semua pemangkin yang diuji menunjukkan peratus pemilihan terhadap produk 1,2-propandiol yang tinggi iaitu melebihi 80%. Pencirian pemangkin dilakukan menggunakan alat BET, XPS, FESEM-EDX dan TEM bagi mendapatkan sifat-sifat fizikokimia pemangkin.

 

Kata kunci: hidrogenolisis, ruthenium, bentonit, 1,2-propanediol, gliserol

 

 

References

1.       Maris, E. P. and Davis, R. J. (2007). Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts. Journal of Catalysis, 249(2): 328 - 337.

2.       Bolado, S., Treviño, R. E., García-Cubero, M. T., and Benito, G. G. (2010). Glycerol hydrogenolysis to 1, 2 propanediol over Ru/C catalyst. Catalysis Communications, 12(2): 122 - 126.

3.       Balaraju, M., Rekha, V., Prasad, P. S. S., Devi, B. L. A. P., Prasad R. B. N. and Lingaiah N. (2009). Influence of solid acids as co-catalysts on glycerol hydrogenolysis to propylene glycol over Ru/C catalysts. Applied Catalysis A: General, 354(1-2): 82 - 87.

4.       Balaraju, M., Rekha, V., Sai Prasad P. S., Prasad R. B. N. and Lingaiah N. (2008). Selective hydrogenolysis of glycerol to 1, 2 propanediol over Cu–ZnO catalysts. Catalysis Letters, 126(1): 119 - 124.

5.       Vasiliadou, E. S., Heracleous, E., Vasalos I. A., and Lemonidou A. A. (2009). Ru-based catalysts for glycerol hydrogenolysis - effect of support and metal precursor. Applied Catalysis B: Environmental, 92(1-2): 90-99.

6.       Maris, E. P., Ketchie, W. C., Murayama M. and Davis R. J. (2007). Glycerol hydrogenolysis on carbon-supported Pt/Ru and Au/Ru bimetallic catalysts. Journal of Catalysis, 251(2): 281- 294.

7.       Nakagawa, Y., Shinmi, Y., Koso S. and Tomishige K. (2010). Direct hydrogenolysis of glycerol into 1,3-propanediol over rhenium-modified iridium catalyst. Journal of Catalysis, 272(2):191 – 194

8.       Huang, L., Zhu, Y., Zheng, H., Ding, G. and Yongwang, Li. (2009). Direct conversion of glycerol into 1,3-propanediol over Cu-H₄SiW₁₂O₄₀/SiO₂ in Vapor Phase. Chemistry Letters, 131(1):312 – 320.

9.       Feng, J., Fu. H., Wang, J., Li, R., Chen, H. and Li, X. (2008). Hydrogenolysis of glycerol to glycols over ruthenium catalysts: Effect of support and catalyst reduction temperature. Catalysis Communications,  9(6): 1458 - 1464.

10.    Zhou, Z., Li, X. Zeng, T., Hong, W., Cheng Z. and Yuan, W. (2010). Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-A_l2O₃ Catalysts. Chinese Journal of Chemical Engineering,  18(3): 384 - 390.

11.    Shinmi, Y., Koso, S., Kubota, T., Nakagawa. Y. and Tomishige, K. (2010). Modification of Rh/SiO₂ catalyst for the hydrogenolysis of glycerol in water. Applied Catalysis B: Environmental, 94(3-4): 318 - 326.

12.    Miyazawa, T., Koso, S., Kunimori, K. and Tomishige, K. (2007). Glycerol hydrogenolysis to 1,2-propanediol catalyzed by a heat-resistant ion-exchange resin combined with Ru/C. Applied Catalysis A: General, 329: 30 – 35.

13.    Jiang, T., Zhou, Y., Liang, S., Liu H. and Han B. (2009) Improved utilisation of renewable resources: New important derivatives of glycerol. Green Chemistry, 7: 1000 - 1006.

14.    Yuan, Z. Wang, J., Wang, L., Xie, W., Chen, P., Hou Z. and Zheng. X., (2010). Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts. Bioresource Technology, 101: 7088 – 7092.

15.    Balaraju, M., Rekha, V., Devi, B. L. A. P., Prasad, R. B. N., Prasad P. S. S. and Lingaiah N. (2010). Surface and structural properties of titania-supported Ru catalysts for hydrogenolysis of glycerol. Applied Catalysis A: General   384: 107 - 114.