Nanocatalysts of Sulfated Zirconia and Calcium Oxide/Zirconia for Microwave-Assisted Biodiesel Synthesis from Castor Oil

Abstract:

Nanocatalysts of sulfated zirconia (SZ) and CaO/zirconia for microwave assisted-biodiesel synthesis from castor oil have been successfully prepared. The aim of the research was to determine the effectiveness and the selectivity of catalysts in biodiesel production. The sulfated zirconia catalyst was prepared by the wet impregnation method while the calcium oxide/zirconia catalyst was prepared through the wet impregnation by microwave-assisted method. The catalysts were used for the esterification and transesterification reaction with the highest acidity and the basicity value of 7.16 mmol NH₃ g^-1, 87.76 mmol HCl g^-1, respectively. The acidity and basicity of the catalysts are directly related to the catalyst active site in the esterification and transesterification process. The results showed that catalyst 0.5 M SZ 500 and 1: 0.2 CaO/ZrO₂ 800 had excellent stability that can be seen from their high crystallinity and large surface area. The biodiesel products characterized by ¹H-NMR, GC-MS and Bomb calorimeter also showed excellent results. After purification, ¹H-NMR result shows the conversion of castor oil into methyl ester is close to 100%. This was supported by GC-MS where the highest area of methyl ester is 93.91% of methyl ricinoleate.

• Periodical: Materials Science Forum (Volume 1067)
• Pages: 167-176
• DOI: https://doi.org/10.4028/p-4320g2
• Online since: August 2022
• Authors: Resty Zama Andiena*, Karna Wijaya, Akhmad Syoufian
• Keywords: Biodiesel, Calcium/Oxide Zirconia, Microwave, Sulfated Zirconia

References

[1] Kitla A, Safonova O.V, Föttinger K, Infrared Studies on Bimetallic Copper/ Nickel Catalysts Supported Zirconia and Ceria/Zirconia. Catal. Lett. 143 (2013) 517–530. https://doi.org/10.1007/s10562-013-1001-y.

DOI: 10.1007/s10562-013-1001-y

[2] Pratiwi S, Juerges N, Review of the impact of renewable energy development on the environment and nature conservation in Southeast Asia. Energ. Ecol. Environ. 5 (2020) 221–239. https://doi.org/10.1007/s40974-020-00166-2.

DOI: 10.1007/s40974-020-00166-2

[3] Elder M, Romero J, Bhattacharya A, Sano D, Matsumoto N, Hayashi S Socioeconomic Impacts of Biofuels in East Asia. In: Takeuchi K, Shiroyama H, Saito O, Matsuura M, (eds) Biofuels and Sustainability, Science for Sustainable Societies, Springer, Tokyo, 2018, pp.87-118. https://doi.org/10.1007/978-4-431-54895-9_8.

DOI: 10.1007/978-4-431-54895-9_8

[4] Djustiana N, Febrida R, Panatarani C, Imarundha Y, Karlina E, & Joni, I.M, Microstructure Analysis of Zirconia-Alumina-Silica Particles Made from Indonesia Natural Sand Synthesized Using Spray Pyrolysis Method, Key Eng. Mater. 720 (2016) 285–289. https://doi.org/10.4028/ www.scientific.net/kem.720.285.

DOI: 10.4028/www.scientific.net/kem.720.285

[5] Kiss A.A, Dimian A.C, and Rothenberg G, Solid Acid Catalysts for Biodiesel Production-Towards Sustainable Energy, Adv. Synth. Catal. 348 (2006) 75-81. https://doi.org/10.1002/adsc.200505160.

DOI: 10.1002/adsc.200505160

[6] Dehghani S, Haghighi M, Sono-sulfated zirconia nanocatalyst supported on MCM-41 for biodiesel production from sunflower oil: Influence of ultrasound irradiation power on catalytic properties and performance, Ultrasonics Sonochemistry, Vol.35 (2017) A 142-151, ISSN 1350-4177. https://doi.org/10.1016/j.ultsonch.2016.09.012.

DOI: 10.1016/j.ultsonch.2016.09.012

[7] Booramurthy VK, Kasimani R, Pandian, S. et al, Nano-sulfated zirconia catalyzed biodiesel production from tannery waste sheep fat. Environ. Sci. Pollut. Res. 27, (2020) 20598–20605. https://doi.org/10.1007/s11356-020-07984-1.

DOI: 10.1007/s11356-020-07984-1

[8] Utami M, Wijaya K, and Trisunaryanti W, Effect of Sulfuric Acid Treatment and Calcination on Commercial Zirconia Nanopowder. Key Eng. Mater. 757 (2017) 131-137. https://doi.org/10.4028/ www.scientific.net/KEM.757.131.

DOI: 10.4028/www.scientific.net/kem.757.131

[9] Murzin, D.Y, On Apparent Activation Energy of Structure Sensitive Heterogeneous Catalytic Reactions, Catal. Lett. 149 (2019) 1455–1463. https://doi.org/10.1007/s10562-019-02772-0.

DOI: 10.1007/s10562-019-02772-0

[10] Zein Y.M, Anal A.K, Prasetyoko D, and Qoniah I Biodiesel Production from Waste Palm Oil Catalyzed by Hierarchical ZSM-5 Supported Calcium Oxide, Indo. J. Chem 16 (2016) 1:98 – 104. https://doi.org/10.22146/ijc.21184.

DOI: 10.22146/ijc.21184

[11] Kaur N, and Ali A Kinetics and Reusability of Zr/CaO as Heterogeneous Catalyst for the Ethanolysis and Methanolysis of Jatropha Crucas Oil, Fuel Process. Technol. 119 (2014) 174-184. https://doi.org/10.1016/j.fuproc.2013.11.002.

DOI: 10.1016/j.fuproc.2013.11.002

[12] Said A.E.A, El-Wahab M.M.A, and El-Aal, M.A. The Catalytic Performance of Sulfated Zirconia in the Dehydration of Methanol to Dimethyl Ether, J. Mol. Catal. A: Chem., 394 (2014) 40–47. https://doi.org/10.1016/j.molcata.2014.06.041.

DOI: 10.1016/j.molcata.2014.06.041

[13] Kaur N, and Ali A, Preparation and Application of Ce/ZrO2-TiO2/SO42- as Solid Catalyst for the Esterification of Fatty Acids, Renew. Energy. 81 (2015) 421-431. https://.

[14] Fu B, Gao L, Niu L, Wei R, and Xiao G Biodiesel from Waste Cooking Oil via Heterogeneous Superacid Catalyst SO42-/ZrO2, Energy Fuels, 23 (2009) 569–572. https://doi.org/10.1021/ef800751z.

DOI: 10.1021/ef800751z

[15] Ardizzone S, Bianchi CL, Cattagni W, and Ragaini V Effects of the Precursor Features and Treatments on the Catalytic Performance of SO4/ZrO2 Catal. Lett. 49 (1997) 193–198. https://doi.org/10.1023/A:1019049103916.

DOI: 10.1023/a:1019049103916

[16] Rachmat A, Trisunaryanti W, Sutarno, Wijaya K., Synthesis and characterization of sulfated zirconia mesopore and its application on lauric acid esterification. Mater Renew Sustain Energy 6 (2017) 13. https://doi.org/10.1007/s40243-017-0097-1.

DOI: 10.1007/s40243-017-0097-1

[17] Lesbani A, Ceria Sitompul S, Mohadi, R, & Hidayati, N. (2016). Characterization and Utilization of Calcium Oxide (CaO) Thermally Decomposed from Fish Bones as a Catalyst in the Production of Biodiesel from Waste Cooking Oil. Makara J. Technol. 20(3) (2016) 121-126. https://.

DOI: 10.7454/mst.v20i3.3066

[18] Margaretha Y.Y, Prastyo H.S, Ayucitra A, Ismadji S, Calcium oxide from Pomacea sp. shell as a catalyst for biodiesel production. Int. J. Energy Environ. Eng. 3 (2012) 33. https://doi.org/10.1186/2251-6832-3-33.

DOI: 10.1186/2251-6832-3-33

[19] Galván-Ruiz M, Hernández J, Baños L, Noriega-Montes J, and Rodríguez-García M.E, Characterization of Calcium Carbonate, Calcium Oxide, and Calcium Hydroxide as Starting Point to the Improvement of Lime for Their Use in Construction, J. Mater. Civ. Eng. 21 (2009) 694- 698. https://doi.org/10.1061/(ASCE)0899-1561(2009)21:11(694).

DOI: 10.1061/(asce)0899-1561(2009)21:11(694)

[20] Kamalanathan P, S. Kannan, & S. Rajeswari, Development and Characterisation of Zirconia and Hydroxyapatite Composites for Orthopaedic Applications. Trends Biomater. Artif. Organs, 18 (2005) 114-116. https://www.researchgate.net/publication/281297064.

[21] Xia S, Guo X, Mao D, Shi Z, Wu G, and Lu G, Biodiesel Synthesis over the CaO-ZrO2 Solid Base Catalyst Prepared by A Urea-Nitrate Combustion Method, RSC Adv. (2014) 4:51688-51695. https://doi.org/10.1039/C4RA11362D.

DOI: 10.1039/c4ra11362d

[22] Hsiao M–C, Lin C–C, Chang Y–H Microwave irradiation–assisted transesterification of soybean oil to biodiesel catalyzed by nanopowder calcium oxide. Fuel (2011) 90:1963–7. https://.

DOI: 10.1016/j.fuel.2011.01.004

[23] Dehkordi A.M, Ghasemi M, Transesterification of waste cooking oil to biodiesel using Ca and Zr mixed oxides as heterogeneous base catalysts. Fuel Process. Technol. 97 (2012) 45-51. https://.

DOI: 10.1016/j.fuproc.2012.01.010

[24] Knothe G, Monitoring A Progressing Transesterification Reaction by Fiber-Optic Near Infrared Spectroscopy with Correlation to 1H-Nuclear Magnetic Resonance Spectroscopy J. Am. Oil Chem. Soc. 77 (2000) 489-493. http://lib3.dss.go.th/fulltext/Journal/J.AOCS/J.AOCS/2000/no.5/may2000vol77, no5,pp.489-493.pdf.

DOI: 10.1007/s11746-000-0078-5

[25] Pratama L, Yoeswono, Triyono, Tahir I, Effect of temperature and speed of Stirrer to Biodiesel Conversion from Coconut Oil with The Use of Palm empty fruit bunches as Heterogenous Catalyst, Indo. J. Chem. 9 (2009) 1:54-61. https://doi.org/10.22146/ijc.21562.

DOI: 10.22146/ijc.21562

[26] Rahmat B, Setiasih IS, and Kastaman R, Effect of glycerol separation on palm oil transesterification, Indo. J. Chem. 12 (2012) 3:255-260. https://.

DOI: 10.22146/ijc.21339

[27] Qiqmana A.M, Sutjahjo D. H, Karakteristik Biodiesel dari Minyak Biji Nyamplung dengan Proses Degumming Menggunakan Asam Sulfat dan Asam Cuka, JTM. Vol. 2 (2014) (2):132-139. https://jurnalmahasiswa.unesa.ac.id/index.php/jtm-unesa/article/view/6534/7297.

DOI: 10.36055/tjst.v9i1.6687