Hydrotreatment of Cellulose-Derived Bio-Oil Using Copper and/or Zinc Catalysts Supported on Mesoporous Silica-Alumina Synthesized from Lapindo Mud and Catfish Bone


Fahri Swasdika(1), Wega Trisunaryanti(2*), Iip Izul Falah(3)

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(*) Corresponding Author


Catalysts comprising copper and/or zinc supported on mesoporous silica-alumina (MSA) with a high Si/Al ratio were prepared by wet impregnation method. This study investigated the preparation, characterization, and catalytic application of the prepared catalysts for hydrotreatment cellulose-derived bio-oil. The wet impregnation was performed by directly dispersing Cu(NO3)2·3H2O and/or Zn(NO3)2·4H2O aqueous solution into MSA, followed by calcination and reduction under H2 gas stream. The acidity test revealed that metal addition on MSA support increases the acidity of catalysts. During hydrotreatment of cellulose-derived bio-oil CuZn/MSA with total acidity, copper loading, zinc loading, and specific surface area of 24.86 mmol g–1, 5.23 wt.%, 3.15 wt.%, and 170.77 m2 g–1, respectively, exhibited the best performance compared to other prepared catalysts with 90.49 wt.% conversion of liquid product.


hydrotreatment; bio-oil; catalysis; bifunctional catalyst; mesoporous silica-alumina

Full Text:

Full Text PDF


[1] Cheng, F., and Brewer, C.E., 2017, Producing jet fuel from biomass lignin: Potential pathways to alkyl-benzenes and cycloalkanes, Renewable Sustainable Energy Rev., 72, 673–722.

[2] Wang, S., Dai, G., Yang, H., and Luo, Z., 2017, Lignocellulosic biomass pyrolysis mechanism: A state-of-the-art review, Prog. Energy Combust. Sci., 62, 33–86.

[3] Czernik, S., and Bridgwater, A.V., 2004, Overview of applications of biomass fast pyrolysis oil, Energy Fuels, 18 (2), 590–598.

[4] Xiu, S., and Shahbazi, A., 2012, Bio-oil production and upgrading research: A review, Renewable Sustainable Energy Rev., 16 (7), 4406–4414.

[5] Hossain, A.K., and Davies, P.A., 2013, Pyrolysis liquids and gases as alternative fuels in internal combustion engines - A review, Renew. Sustain. Energy Rev., 21, 165–189.

[6] Saidi, M., Samimi, F., Karimipourfard, D., Nimmanwudipong, T., Gates, B.C., and Rahimpour, M.R., 2014, Upgrading of lignin-derived bio-oils by catalytic hydrodeoxygenation, Energy Environ. Sci., 7 (1), 103–129.

[7] Cheng, S., Wei, L., Julson, J., Muthukumarappan, K., Kharel, P.R., and Boakye, E., 2017, Hydrocarbon bio-oil production from pyrolysis bio-oil using non-sulfide Ni-Zn/Al2O3 catalyst, Fuel Process. Technol., 162, 78–86.

[8] He, Z., and Wang, X., 2012, Hydrodeoxygenation of model compounds and catalytic systems for pyrolysis bio-oils upgrading, Catal. Sustainable Energy, 1 (2013), 28–52.

[9] Wang, Y., Wu, J., and Wang, S., 2013, Hydrodeoxygenation of bio-oil over Pt-based supported catalysts: Importance of mesopores and acidity of the support to compounds with different oxygen contents, RSC Adv., 3 (31), 12635–12640.

[10] Lee, H., Kim, H., Yu, M.J., Ko, C.H., Jeon, J.K., Jae, J., Park, S.H., Jung, S.C., and Park, Y.K., 2016, Catalytic hydrodeoxygenation of bio-oil model compounds over Pt/HY catalyst, Sci. Rep., 6, 28765.

[11] Yuan, P., Liu, Z., Zhang, W., Sun, H., and Liu, S., 2010, Cu-Zn/Al2O3 Catalyst for the hydrogenation of esters to alcohols, Chin. J. Catal., 31 (7), 769–775.

[12] Gao, C., Xiao, X., Mao, D., and Lu, G., 2013, Preparation of L-phenylalaninol with high ee selectivity by catalytic hydrogenation of L-phenylalaninate over Cu/ZnO/Al2O3 catalyst, Catal. Sci. Technol., 3 (4), 1056–1062.

[13] Shi, Z., Xiao, X., Mao, D., and Lu, G., 2014, Effects of the preparation method on the performance of the Cu/ZnO/Al2O3 catalyst for the manufacture of L-phenylalaninol with high ee selectivity from L-phenylalanine methyl ester, Catal. Sci. Technol., 4 (4), 1132–1143.

[14] Zha, F., Ding, J., Chang, Y., Ding, J., Wang, J., and Ma, J., 2012, Cu-Zn-Al Oxide cores packed by metal-doped amorphous silica-alumina membrane for catalyzing the hydrogenation of carbon dioxide to dimethyl ether, Ind. Eng. Chem. Res., 51 (1), 345–352.

[15] Chiang, C.L., Lin, K.S., and Chuang, H.W., 2018, Direct synthesis of formic acid via CO2 hydrogenation over Cu/ZnO/Al2O3 catalyst, J. Cleaner Prod., 172, 1957–1977.

[16] Mascal, M., Dutta, S., and Gandarias, I., 2014, Hydrodeoxygenation of the angelica lactone dimer, a cellulose-based feedstock: Simple, high-yield synthesis of branched C7-C10 gasoline-like hydrocarbons, Angew. Chem. Int. Ed., 53 (7), 1854–1857.

[17] Brands, D.S., Poels, E.K., and Bliek, A., 1999, Ester hydrogenolysis over promoted Cu/SiO2 catalysts, Appl. Catal., A, 184 (2), 279–289.

[18] Loricera, C.V., Castaño, P., Infantes-Molina, A., Hita, I., Gutiérrez, A., Arandes, J.M., Fierro, J.L.G., and Pawelec, B., 2012, Designing supported ZnNi catalysts for the removal of oxygen from bio-liquids and aromatics from diesel, Green Chem., 14 (10), 2759–2770.

[19] Verma, D., Kumar, R., Rana, B.S., and Sinha, A.K., 2011, Aviation fuel production from lipids by a single-step route using hierarchical mesoporous zeolites, Energy Environ. Sci., 4 (5), 1667–1671.

[20] Vít, Z., Gulková, D., Kaluža, L., Bakardieva, S., and Boaro, M., 2010, Mesoporous silica-alumina modified by acid leaching as support of Pt catalysts in HDS of model compounds, Appl. Catal., B, 100 (3-4), 463–471.

[21] Vít, Z., Gulková, D., Kaluža, L., and Kupčík, J., 2015, Pd–Pt catalysts on mesoporous SiO2–Al2O3 with superior activity for HDS of 4,6-dimethyldibenzothiophene: Effect of metal loading and support composition, Appl. Catal., B, 179, 44–53.

[22] Marsuki, M.F., Trisunaryanti, W., Falah, I.I., and Wijaya, K., 2018, Synthesis of Co, Mo, Co-Mo and Mo-Co catalysts, supported on mesoporous silica-alumina for hydrocracking of α-cellulose pyrolysis oil, Orient. J. Chem., 34 (2), 955–962.

[23] Kusumastuti, H., Trisunaryanti, W., Falah, I.I., and Marsuki, M.F., 2018, Synthesis of mesoporous silica-alumina from Lapindo mud as a support of Ni and Mo metals catalysts for hydrocracking of pyrolyzed α-cellulose, Rasayan J. Chem., 11 (2), 522–530.

[24] Mahardika, I.B.P., Trisunaryanti, W., Triyono, T., Wijaya, D.P., and Dewi, K., 2017, Transesterification of used cooking oil using CaO/MCM-41 catalyst synthesized from Lapindo mud by sonochemical method, Indones. J. Chem., 17 (3), 509–515.

[25] Ahmad, M., and Benjakul, S., 2011, Characteristics of gelatin from the skin of unicorn leatherjacket (Aluterus monoceros) as influenced by acid pretreatment and extraction time, Food Hydrocolloids, 25 (3), 381–388.

[26] Xu, S., Yang, H., Shen, L., and Li, G., 2017, Purity and yield of collagen extracted from southern catfish (Silurus meridionalis Chen) skin through improved pretreatment methods, Int. J. Food Prop., 20 (Suppl. 1), S141–S153.

[27] Trisunaryanti, W., Lisna, P.S., Kartini, I., Sutarno, Falah, I.I., and Triyono, 2016, Extraction of gelatin from bovine bone and its use as template in synthesis of mesoporous silica, Asian J. Chem., 28 (5), 996–1000.

[28] Saraswathi, P., and Makeswari, M., 2017, Preparation and characterization of alumina and silica modified chitosan, Rasayan J. Chem., 10 (3), 759–765.

[29] Gustian, I., Ghufira, and Oktiarni, D., 2017, Composite membranes based on sulfonated polysulfone and natural zeolite for proton exchange membrane fuel cells, Rasayan J. Chem., 10 (3), 689–694.

[30] Saber, O., and Gobara, H.M., 2014, Optimization of silica content in alumina-silica nanocomposites to achieve high catalytic dehydrogenation activity of supported Pt catalyst, Egypt. J. Pet., 23 (4), 445–454.

[31] Wang, X., Ma, K., Guo, L., Tian, Y., Cheng, Q., Bai, X., Huang, J., Ding, T., and Li, X., 2017, Cu/ZnO/SiO2 Catalyst synthesized by reduction of ZnO-modified copper phyllosilicate for dimethyl ether steam reforming, Appl. Catal., A, 540, 37–46.

[32] Karnjanakom, S., Guan, G., Asep, B., Du, X., Hao, X., Yang, J., Samart, C., and Abudula, A., 2015, A green method to increase yield and quality of bio-oil: Ultrasonic pretreatment of biomass and catalytic upgrading of bio-oil over metal (Cu, Fe and/or Zn)/γ-Al2O3, RSC Adv., 5 (101), 83494–83503.

[33] Pongsendana, M., Trisunaryanti, W., Artanti, F.W., Falah, I.I., and Sutarno, 2017, Hydrocracking of waste lubricant into gasoline fraction over CoMo catalyst supported on mesoporous carbon from bovine bone gelatin, Korean J. Chem. Eng., 34 (10), 2591–2596.

DOI: https://doi.org/10.22146/ijc.50558

Article Metrics

Abstract views : 82 | views : 26

Copyright (c) 2020 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 / 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.