Abstract
CaO–Al2O3 mixed oxides were prepared by different preparation methods–such as sol–gel, co-precipitation, impregnation, and MW-assisted solution combustion synthesis (M-SCS)–and then impregnated with KOH to examine their activity in transesterification of canola oil to biodiesel. Synthesized nanocomposites were characterized by XRD, FTIR, BET/BJH, and SEM/EDX. The mixed oxides, except those prepared by M-SCS method, exhibited a nearly amorphous structure with some diffraction peaks of calcium oxide. Due to high combustion temperature during the M-SCS process, Ca ions could diffuse into the alumina lattice to form CaAl2O4. But upon impregnation with KOH, the former transformed to Ca12Al14O33. The KOH/Ca12Al14O33 nanocatalyst prepared by M-SCS method exhibited better basicity, mean pore size, and activity, as well as highest Ca/Al and K/Al ratios. In the presence of this catalyst, around 86% of canola oil were converted to biodiesel in the transesterification reaction carried out at 65°C, methanol/oil molar ratio 12: 1, 4 wt% catalyst, 4 h. Such parameters seem appropriate for industrial application. The M-SCS method is technically simple, cost effective, time/energy saving and requires no further thermal treatment.
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Abbaszaadeh, A., Ghobadian, B., Omidkhah, M.R. and Najafi, G., Current biodiesel production technologies: A comparative review, Energy Conv. Manage., 2012, vol. 63, pp. 138–148. doi https://doi.org/10.1016/j.enconman.2012.02.027
Jeenpadiphat, S. and Tungasmita, D.N., Acid-activated pillar bentonite as a novel catalyst for the esterification of high FFA oil, Powder Technol., 2013, vol. 237, pp. 634–640. doi https://doi.org/10.1016/j.powtec.2013.02.001
Borges, M.E. and Diaz, L., Recent developments on heterogeneous catalysts for biodiesel production by oil esterification and transesterification reactions: A review, Renewable Sustain. Energy Rev., 2012, vol. 16, no. 5, pp. 2839–2849. doi https://doi.org/10.1016/j.rser.2012.01.071
Atadashi, I.M., Aroua, M.K., Abdul Aziz, A.R., and Sulaiman, N.M.N., The effects of catalysts in biodiesel production: A review, J. Ind. Eng. Chem., 2013, vol. 19, no. 1, pp. 14–26. doi https://doi.org/10.1016/j.jiec.2012.07.009
Komintarachat, C. and Chuepeng, S., Solid acid catalyst for biodiesel production from waste used cooking oils, Ind. Eng. Chem. Res., 2009, vol. 48, no. 20, pp. 9350–9353. doi https://doi.org/10.1021/ie901175d
Vyas, A.P., Subrahmanyam, N. and Patel, P.A., Production of biodiesel through transesterification of Jatropha oil using KNO3/Al2O3 solid catalyst, Fuel, 2009, vol. 88, no. 4, pp. 625–628. doi https://doi.org/10.1016/j.fuel.2008.10.033
Arzamendi, G., Campo, I., Arguiñarena, E., Sánchez, M., Montes, M. and Gandia, L.M., Synthesis of biodiesel with heterogeneous NaOH/alumina catalysts: Comparison with homogeneous NaOH, Chem. Eng. J., 2007, vol. 134, nos. 1–3, pp. 123–130. doi https://doi.org/10.1016/j.cej.2007.03.049
Taufiq-Yap, Y.H., Abdullah, N.F., and Basri, M., Biodiesel production via transesterification of palm oil using NaOH/A12O3 catalysts, Sains Malays., 2011, vol. 40, no. 6, pp. 587–594.
Teo, S.H., Taufiq-Yap, Y.H., and Ng, F.L., Alumina supported/unsupported mixed oxides of Ca and Mg as heterogeneous catalysts for transesterification of Nannochloropsis sp. microalga’s oil, Energy Conv. Manage., 2014, vol. 88, pp. 1193–1199. doi https://doi.org/10.1016/j.enconman.2014.04.049
Wang, R., Yang, S., Yin, S., Song, B., Bhadury, P., Xue, W., Tao, S., Jia, Z., Liu, D., and Gao, L., Development of solid base catalyst X/Y/MgO/γ-Al2O3 for optimization of preparation of biodiesel from Jatropha curcas L. seed oil, Front. Chem. Eng. China, 2008, vol. 2, no. 4, pp. 468–472.
Sankaranarayanan, T.M., Pandurangan, A., Banu, M., and Sivasanker, S., Transesterification of sunflower oil over MoO3 supported on alumina, Appl. Catal. A, 2011, vols. 409–410, pp. 239–247. doi https://doi.org/10.1016/j.apcata.2011.10.013
Amani, H., Ahmad, Z., Asif, M., and Hameed, B.H., Transesterification of waste cooking palm oil by MnZr with supported alumina as a potential heterogeneous catalyst, J. Ind. Eng. Chem., 2014, vol. 20, no. 6, pp. 4437–4442. doi https://doi.org/10.1016/j.jiec.2014.02.012
Benjapornkulaphong, S., Ngamcharussrivichai, C., and Bunyakiat, K., Al2O3-supported alkali and alkali earth metal oxides for transesterification of palm kernel oil and coconut oil, Chem. Eng. J., 2009, vol. 145, no. 3, pp. 468–474. doi https://doi.org/10.1016/j.cej.2008.04.036
Umdu, E.S., Tuncer, M., and Seker, E., Transesterification of Nannochloropsis oculata microalga’s lipid to biodiesel on Al2O3 supported CaO and MgO catalysts, Bioresour. Technol., 2009, vol. 100, no. 11, pp. 2828–2831. doi https://doi.org/10.1016/j.biortech.2008.12.027
Umdu, E.S. and Seker, E., Transesterification of sunflower oil on single step sol–gel made Al2O3 supported CaO catalysts: Effect of basic strength and basicity on turnover frequency, Bioresour. Technol., 2012, vol. 106, no. 2, pp. 178–181. doi https://doi.org/10.1016/j.biortech.2011.11.135
Zabeti, M., Daud, W.M.A.W., and Aroua, M.K., Optimization of the activity of CaO/Al2O3 catalyst for biodiesel production using response surface methodology, Appl. Catal. A, 2009, vol. 366, no. 1, pp. 154–159. doi https://doi.org/10.1016/j.apcata.2009.06.047
Zabeti, M., Daud, W.M.A.W., and Aroua, M.K., Biodiesel production using alumina-supported calcium oxide: An optimization study, Fuel Process. Technol., 2010, vol. 91, no. 2, pp. 243–248. doi https://doi.org/10.1016/j.fuproc.2009.10.004
Noiroj, K., Intarapong, P., Luengnaruemitchai, A., and Jai-In, S., A comparative study of KOH/Al2O3 and KOH/NaY catalysts for biodiesel production via transesterification from palm oil, Renewable Energy, 2009, vol. 34, no. 4, pp. 1145–1150. doi https://doi.org/10.1016/j.renene.2008.06.015
Hájek, M., Skopal, F., Čapek, L., Černoch, M., and Kutálek, P., Ethanolysis of rapeseed oil by KOH as homogeneous and as heterogeneous catalyst supported on alumina and CaO, Energy, 2012, vol. 48, no. 1, pp. 392–397. doi https://doi.org/10.1016/j.energy.2012.06.052
Liao, C.-C. and Chung, T.-W., Optimization of process conditions using response surface methodology for the microwave-assisted transesterification of Jatropha oil with KOH impregnated CaO as catalyst, Chem. Eng. Res. Des., 2013, vol. 91, no. 12, pp. 2457–2464. doi https://doi.org/10.1016/j.cherd.2013.04.009
Xie, W., Peng, H. and Chen, L., Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst, Appl. Catal. A, 2006, vol. 300, no. 1, pp. 67–74. doi https://doi.org/10.1016/j.apcata.2005.10.048
Ma, G., Hu, W., Pei, H., Jiang, L., Ji, Y., and Mu, R., Study of KOH/Al2O3 as heterogeneous catalyst for biodiesel production via in situ transesterification from microalgae, Environ. Technol., 2014, vol. 36, no. 5, pp. 622–627. doi https://doi.org/10.1080/09593330.2014.954629
Yan, S., Lu, H., and Liang, B., Supported CaO catalysts used in the transesterification of rapeseed oil for the purpose of biodiesel production, Energy Fuels, 2007, vol. 22, no. 1, pp. 646–651. doi https://doi.org/10.1021/ef070105o
Moradi, G., Mohadesi, M., Rezaei, R., and Moradi, R., Biodiesel production using CaO/γ-Al2O3 catalyst synthesized by sol-gel method, Can. J. Chem. Eng., 2015, vol. 93, no. 9, pp. 1531–1538. doi https://doi.org/10.1002/cjce.22258
Mahdavi, V. and Monajemi, A., Optimization of operational conditions for biodiesel production from cottonseed oil on CaO–MgO/Al2O3 solid base catalysts, J. Taiwan Inst. Chem. Eng., 2014, vol. 45, no. 5, pp. 2286–2292. doi https://doi.org/10.1016/j.jtice.2014.04.020
Zhou, H., Sun, J., Ren, B., Wang, F., Wu, X., and Bai, S., Effects of alkaline media on the controlled large mesopore size distribution of bimodal porous silicas via sol–gel methods, Powder Technol., 2014, vol. 259, pp. 46–51. doi https://doi.org/10.1016/j.powtec.2014.03.060
González, E.A.Z., García-Guaderrama, M., Villalobos, M.R., Dellamary, F.L., Kandhual, S., Rout, N.P., Tiznado, H., and Arizaga, G.G.C., Potassium titanate as heterogeneous catalyst for methyl transesterification, Powder Technol., 2015, vol. 280, pp. 201–206. doi https://doi.org/10.1016/j.powtec.2015.04.030
López-Delgado, A., López, F.A., Gonzalo-Delgado, L., López-Andrés, S., and Alguacil, F.J., Study by DTA/TG of the formation of calcium aluminate obtained from an aluminum hazardous waste, J. Therm. Anal. Calorim., 2009, vol. 99, no. 3, pp. 999–1004. doi https://doi.org/10.1007/s10973-009-0597-z
Hashemzehi, M., Saghatoleslami, N., and Nayebzadeh, H., A study on the structure and catalytic performance of ZnxCu1–xAl2O4 catalysts synthesized by the solution combustion method for the esterification reaction, C. R. Acad. Sci. Chim., 2016, vol. 19, no. 8, pp. 955–962. doi https://doi.org/10.1016/j.crci.2016.05.006
Ebadzadeh, T. and Asadian, K., Microwave-assisted synthesis of nanosized α-Al2O3, Powder Technol., 2009, vol. 192, no. 2, pp. 242–244. doi https://doi.org/10.1016/j.powtec.2009.01.001
Ye, B., Qiu, F., Sun, C., Li, Y., and Yang, D., Biodiesel production from soybean oil using heterogeneous solid base catalyst, J. Chem. Technol. Biotechnol, 2014, vol. 89, no. 7, pp. 988–997. doi https://doi.org/10.1002/jctb.4190
Yang, L., Lv, P., Yuan, Z., Luo, W., Li, H., Wang, Z., and Miao, C., Synthesis of biodiesel by different carriers supported KOH catalyst, Adv. Mater. Res., 2012, vols. 581–582, pp. 197–201. doi https://doi.org/10.4028/www.scientific.net/AMR.581-582.197
Pasupulety, N., Gunda, K., Liu, Y., Rempel, G.L., and Ng, F.T.T., Production of biodiesel from soybean oil on CaO/Al2O3 solid base catalysts, Appl. Catal. A, 2013, vol. 452, no. 1, pp. 189–202. doi https://doi.org/10.1016/j.apcata.2012.10.006
Toniolo, J.C., Lima, M.D., Takimi, A.S., and Bergmann, C.P., Synthesis of alumina powders by the glycine–nitrate combustion process, Mater. Res. Bull., 2005, vol. 40, no. 3, pp. 561–571. doi https://doi.org/10.1016/j.materresbull.2004.07.019
Castro, C.S., Garcia Júnior, L.C.F., and Assaf, J.M., The enhanced activity of Ca/MgAl mixed oxide for transesterification, Fuel Process. Technol., 2014, vol. 125, pp. 73–78. doi https://doi.org/10.1016/j.fuproc.2014.03.024
Ruszak, M., Witkowski, S., Pietrzyk, P., Kotarba, A., and Sojka, Z., The role of intermediate calcium aluminate phases in solid state synthesis of mayenite (Ca12Al14O33), Funct. Mater. Lett., 2011, vol. 4, no. 2, pp. 183–186. doi https://doi.org/10.1142/S1793604711001907
Boysen, H., Kaiser-Bischoff, I., Lerch, M., Berendts, S., Hoelzel, M., and Senyshyn, A., Disorder and diffusion in mayenite, Acta Phys. Pol., 2010, vol. 117, no. 1, pp. 38–41. doi https://doi.org/10.12693/APhysPolA.117.38
Avci, N., Korthout, K., Newton, M.A., Smet, P.F., and Poelman, D., Valence states of europium in CaAl2O4:Eu phosphors, Opt. Mater. Express, 2012, vol. 2, no. 3, pp. 321–330.
Rahmani Vahid, B. and Haghighi, M., Urea–nitrate combustion synthesis of MgO/MgAl2O4 nanocatalyst used in biodiesel production from sunflower oil: Influence of fuel ratio on catalytic properties and performance, Energy Conv. Manage., 2016, vol. 126, pp. 362–372. doi https://doi.org/10.1016/j.enconman.2016.07.050
Jacobson, K., Gopinath, R., Meher, L.C., and Dalai, A.K., Solid acid catalyzed biodiesel production from waste cooking oil, Appl. Catal. B, 2008, vol. 85, nos. 1–2, pp. 86–91. doi https://doi.org/10.1016/j.apcatb.2008.07.005
Shao, G.N., Sheikh, R., Hilonga, A., Lee, J.E., Park, Y.-H., and Kim, H.T., Biodiesel production by sulfated mesoporous titania–silica catalysts synthesized by the sol–gel process from less expensive precursors, Chem. Eng. J., 2013, vols. 215–216, pp. 600–607. doi https://doi.org/10.1016/j.cej.2012.11.059
Chang, Y.-P., Chang, P.-H., Lee, Y.-T., Lee, T.-J., Lai, Y.-H., and Chen, S.-Y., Morphological and structural evolution of mesoporous calcium aluminate nanocomposites by microwave-assisted synthesis, Micropor. Mesopor. Mater., 2014, vol. 183, pp. 134–142. doi https://doi.org/10.1016/j.micromeso.2013.09.013
Meng, Y.-L., Wang, B.-Y., Li, S.-F., Tian, S.-J., and Zhang, M.-H., Effect of calcination temperature on the activity of solid Ca/Al composite oxide-based alkaline catalyst for biodiesel production, Bioresour. Technol., 2013, vol. 128, no. 2, pp. 305–309. doi https://doi.org/10.1016/j.biortech.2012.10.152
Alba-Rubio, A.C., Santamaría-González, J., Mérida-Robles, J.M., Moreno-Tost, R., Martín-Alonso, D., Jiménez-López, A., and Maireles-Torres, P., Heterogeneous transesterification processes by using CaO supported on zinc oxide as basic catalysts, Catal. Today, 2010, vol. 149, nos. 3–4, pp. 281–287. doi https://doi.org/10.1016/j.cattod.2009.06.024
Albuquerque, M.C.G., Azevedo, D.C.S., Cavalcante, C.L., Jr., Santamaría-González, J., Mérida-Robles, J.M., Moreno-Tost, R., Rodríguez-Castellón, E., Jiménez-López, A., and Maireles-Torres, P., Transesterification of ethyl butyrate with methanol using MgO/CaO catalysts, J. Mol. Catal. A, 2009, vol. 300, nos. 1–2, pp. 19–24. doi https://doi.org/10.1016/j.molcata.2008.10.033
Shahraki, H., Entezari, M.H., and Goharshadi, E.K., Sono-synthesis of biodiesel from soybean oil by KF/γ-Al2O3 as a nano-solid-base catalyst, Ultrason. Sonochem., 2015, vol. 23, pp. 266–274. doi https://doi.org/10.1016/j.ultsonch.2014.09.010
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Nayebzadeh, H., Saghatoleslami, N., Haghighi, M. et al. Catalytic Activity of KOH–CaO–Al2O3 Nanocomposites in Biodiesel Production: Impact of Preparation Method. Int. J Self-Propag. High-Temp. Synth. 28, 18–27 (2019). https://doi.org/10.3103/S1061386219010102
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DOI: https://doi.org/10.3103/S1061386219010102