Application of dolomite as a heterogeneous catalyst of biodiesel synthesis
Abstract
Some of the more recent methods of obtaining biodiesel are based on heterogeneous catalysis, which has the advantage of multiple uses of a catalyst. Natural minerals, such as dolomite, opoca and serpentinites, could be promising for use in biodiesel synthesis. The purpose of this study was to optimise the reaction conditions for biodiesel synthesis from sunflower oil and methanol using dolomite as a catalyst. Optimum reaction conditions for the transesterification of sunflower oil with methanol, using dolomite calcined at the temperature of 850 °C, have been identified: the amount of the catalyst – 6%, the molar ratio of methanol to oil – 8:1, the reaction duration – 5 hours and the reaction temperature – 60 °C. The amount of Fatty Acid Methyl Esters (FAME) of the sunflower oil obtained – 97.6%. FAME is in conformity with the EN 14214:2003 standard, when 500 ppm of antioxidant Ionol and 500 ppm of depressant Infineum R-442 are added. The Cold Filter Plugging Point (CFPP) of FAME is reduced to7 °C by adding 500 ppm of Infineum R-442. This product can be used in summer in the countries that are placed in Class E, including Lithuania. It has been established that dolomite without regeneration can be used for the transesterification of sunflower oil 2 times.
Keyword : biodiesel, dolomite, heterogeneous catalysis, methanol, oil
How to Cite
Sendžikienė, E., Makarevičienė, V., & Kazancev, K. (2018). Application of dolomite as a heterogeneous catalyst of biodiesel synthesis. Transport, 33(5), 1155-1161. https://doi.org/10.3846/transport.2018.6723
This work is licensed under a Creative Commons Attribution 4.0 International License.
References
Arzamendi, G.; Campo, I.; Arguiñarena, E.; Sánchez, M.; Montes, M.; Gandía L. M. 2007. Synthesis of biodiesel with heterogeneous NaOH/alumina catalysts: Comparison with homogeneous NaOH, Chemical Engineering Journal 134 (1– 3): 123–130. https://doi.org/10.1016/j.cej.2007.03.049
Buasri, A.; Rochanakit, K.; Wongvitvichot, W.; Masa-ard, U.; Loryuenyong V. 2015. The application of calcium oxide and magnesium oxide from natural dolomitic rock for biodiesel synthesis, Energy Procedia 79: 562–566. https://doi.org/10.1016/j.egypro.2015.11.534
DIN EN 116:2018-04. Dieselkraftstoffe und Haushaltsheizöle – Bestimmung des Temperaturgrenzwertes der Filtrierbarkeit – Verfahren mit einem stufenweise arbeitenden Kühlbad [Diesel and Domestic Heating Fuels – Determination of Cold Filter Plugging Point – Stepwise Cooling Bath Method] (in German).
Dunn, R. O.; Ngo, H. L.; Haas, M. J. 2015. Branched-chain fatty acid methyl esters as cold flow improvers for biodiesel, Journal of the American Oil Chemists’ Society 92(6): 853–869. https://doi.org/10.1007/s11746-015-2643-2
EN 14104:2003. Fat and Oil Derivatives – Fatty Acid Methyl Esters (FAME) – Determination of Acid Value.
EN 14105:2011. Fat and Oil Derivatives – Fatty Acid Methyl Esters (FAME) – Determination of Free and Total Glycerol and Mono-, Di-, Triglyceride Contents.
EN 14203:2004. Blinds and Shutters – Capability for use of Gears with Crank Handle – Requirements and Test Methods.
EN 14112:2016. Fat and Oil Derivatives – Fatty Acid Methyl Esters (FAME) – Determination of Oxidation Stability (Accelerated Oxidation Test).
EN 14214:2003. Automotive Fuels – Fatty Acid Methyl Esters (FAME) for Diesel Engines – Requirements and Test Methods.
EN ISO 2160:1998. Petroleum Products – Corrosiveness to Copper – Copper Strip Test.
EN ISO 3104:1996. Petroleum Products – Transparent and Opaque Liquids – Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity.
EN ISO 5508:1990. Animal and Vegetable Fats and Oils – Analysis by Gas Chromatography of Methyl Esters of Fatty Acids.
EN ISO 12185:1996. Crude Petroleum and Petroleum Products – Determination of Density – Oscillating U-Tube Method.
EN ISO 12937:2000. Petroleum Products – Determination of Water – Coulometric Karl Fischer Titration Method.
Endalew, A. K.; Kiros, Y.; Zanzi, R. 2011. Inorganic heterogeneous catalysts for biodiesel production from vegetable oils, Biomass and Bioenergy 35(9): 3787–3809. https://doi.org/10.1016/j.biombioe.2011.06.011
Fan, M.; Liu, Y.; Zhang, P.; Jiang, P. 2016. Blocky shapes Ca–Mg mixed oxides as a water-resistant catalyst for effective synthesis of biodiesel by transesterification, Fuel Processing Technology 149: 163–168. https://doi.org/10.1016/j.fuproc.2016.03.029
Faungnawakij, K.; Yoosuk, B.; Namuangruk, S.; Krasae, P.; Viriya-empikul, N.; Puttasawat, B. 2012. Sr–Mg mixed oxides as biodiesel production catalysts, ChemCatChem 4(2): 209–216. https://doi.org/10.1002/cctc.201100346
Gui, X.; Chen, S.; Yun, Z. 2016. Continuous production of biodiesel from cottonseed oil and methanol using a column reactor packed with calcined sodium silicate base catalyst, Chinese Journal of Chemical Engineering 24(4): 499–505. https://doi.org/10.1016/j.cjche.2015.11.006
Ilgen, O. 2011. Dolomite as a heterogeneous catalyst for transesterification of canola oil, Fuel Processing Technology 92(3): 452–455. https://doi.org/10.1016/j.fuproc.2010.10.009
Jaiyen, S.; Naree, T.; Ngamcharussrivichai, C. 2015. Comparative study of natural dolomitic rock and waste mixed seashells as heterogeneous catalysts for the methanolysis of palm oil to biodiesel, Renewable Energy 74: 433–440. https://doi.org/10.1016/j.renene.2014.08.050
Long, Y.-D.; Fang, Z.; Su, T.-C.; Yang, Q. 2014. Co-production of biodiesel and hydrogen from rapeseed and Jatropha oils with sodium silicate and Ni catalysts, Applied Energy 113: 1819–1825. https://doi.org/10.1016/j.apenergy.2012.12.076
MacLeod, C. S.; Harvey, A. P.; Lee, F. A.; Wilson, K. 2008. Evaluation of the activity and stability of alkali-doped metal oxide catalysts for application to an intensified method of biodiesel production, Chemical Engineering Journal 135 (1–2): 63–70. https://doi.org/10.1016/j.cej.2007.04.014
Ngamcharussrivichai, C.; Nunthasanti, P.; Tanachai, S.; Bunyakiat, K. 2010. Biodiesel production through transesterification over natural calciums, Fuel Processing Technology 91(11): 1409–1415. https://doi.org/10.1016/j.fuproc.2010.05.014
Ngamcharussrivichai, C.; Wiwatnimit, W.; Wangnoi, S. 2007. Modified dolomites as catalysts for palm kernel oil transesterification, Journal of Molecular Catalysis A: Chemical 276(1–2): 24–33. https://doi.org/10.1016/j.molcata.2007.06.015
Niu, S.-L.; Huo, M.-J.; Lu, C.-M.; Liu, M.-Q.; Li, H. 2014. An investigation on the catalytic capacity of dolomite in transesterification and the calculation of kinetic parameters, Bioresource Technology 158: 74–80. https://doi.org/10.1016/j.biortech.2014.01.123
Santos, E. M.; Piovesan, N. D.; De Barros, E. G.; Moreira, M. A. 2013. Low linolenic soybeans for biodiesel: characteristics, performance and advantages, Fuel 104: 861–864. https://doi.org/10.1016/j.fuel.2012.06.014
Sendzikienė, E; Makarevicienė, V.; Ciutelytė, R. 2012. Sorption characteristics of dolomite suspension and methyldiethanolamine in gas treatment to remove carbon dioxide, Russian Journal of Applied Chemistry 85(12): 1910–1913. https://doi.org/10.1134/S1070427212120191
Sendzikienė, E.; Šinkūnienė, D.; Kazanceva, I.; Kazancev, K. 2016. Optimization of low quality rapeseed oil transesterification with butanol by applying the response surface methodology, Renewable energy 87(1): 266–272. https://doi.org/10.1016/j.renene.2015.10.024
Shajaratun Nur, Z. A.; Taufiq-Yap, Y. H.; Rabiah Nizah, M. F.; Teo, S. H.; Syazwani, O.N.; Islam, A. 2014. Production of biodiesel from palm oil using modified Malaysian natural dolomites, Energy Conversion and Management 78: 738–744. https://doi.org/10.1016/j.enconman.2013.11.012
Shibasaki-Kitakawa, N.; Honda, H.; Kuribayashi, H.; Toda, T.; Fukumura, T.; Yonemoto, T. 2007. Biodiesel production using anionic ion-exchange resin as heterogeneous catalyst, Bioresource Technology 98(2): 416–421. https://doi.org/10.1016/j.biortech.2005.12.010
Shimada, Y.; Watanabe, Y.; Sugihara, A.; Tominaga, Y. 2002. Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing, Journal of Molecular Catalysis B: Enzymatic 17(3–5): 133–142. https://doi.org/10.1016/S1381-1177(02)00020-6
Watanabe, Y.; Pinsirodom, P.; Nagao, T.; Yamauchi, A.; Kobayashi, T.; Nishida, Y.; Takagi, Y.; Shimada, Y. 2007. Conversion of acid oil by-produced in vegetable oil refining to biodiesel fuel by immobilized Candida antarctica lipase, Journal of Molecular Catalysis B: Enzymatic 44(3–4): 99–105. https://doi.org/10.1016/j.molcatb.2006.09.007
Zaleckas, E.; Makarevičienė, V.; Sendžikienė, E. 2012. Possibilities of using Camelina sativa oil for producing biodiesel fuel, Transport 27(1): 60–66. https://doi.org/10.3846/16484142.2012.664827
Buasri, A.; Rochanakit, K.; Wongvitvichot, W.; Masa-ard, U.; Loryuenyong V. 2015. The application of calcium oxide and magnesium oxide from natural dolomitic rock for biodiesel synthesis, Energy Procedia 79: 562–566. https://doi.org/10.1016/j.egypro.2015.11.534
DIN EN 116:2018-04. Dieselkraftstoffe und Haushaltsheizöle – Bestimmung des Temperaturgrenzwertes der Filtrierbarkeit – Verfahren mit einem stufenweise arbeitenden Kühlbad [Diesel and Domestic Heating Fuels – Determination of Cold Filter Plugging Point – Stepwise Cooling Bath Method] (in German).
Dunn, R. O.; Ngo, H. L.; Haas, M. J. 2015. Branched-chain fatty acid methyl esters as cold flow improvers for biodiesel, Journal of the American Oil Chemists’ Society 92(6): 853–869. https://doi.org/10.1007/s11746-015-2643-2
EN 14104:2003. Fat and Oil Derivatives – Fatty Acid Methyl Esters (FAME) – Determination of Acid Value.
EN 14105:2011. Fat and Oil Derivatives – Fatty Acid Methyl Esters (FAME) – Determination of Free and Total Glycerol and Mono-, Di-, Triglyceride Contents.
EN 14203:2004. Blinds and Shutters – Capability for use of Gears with Crank Handle – Requirements and Test Methods.
EN 14112:2016. Fat and Oil Derivatives – Fatty Acid Methyl Esters (FAME) – Determination of Oxidation Stability (Accelerated Oxidation Test).
EN 14214:2003. Automotive Fuels – Fatty Acid Methyl Esters (FAME) for Diesel Engines – Requirements and Test Methods.
EN ISO 2160:1998. Petroleum Products – Corrosiveness to Copper – Copper Strip Test.
EN ISO 3104:1996. Petroleum Products – Transparent and Opaque Liquids – Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity.
EN ISO 5508:1990. Animal and Vegetable Fats and Oils – Analysis by Gas Chromatography of Methyl Esters of Fatty Acids.
EN ISO 12185:1996. Crude Petroleum and Petroleum Products – Determination of Density – Oscillating U-Tube Method.
EN ISO 12937:2000. Petroleum Products – Determination of Water – Coulometric Karl Fischer Titration Method.
Endalew, A. K.; Kiros, Y.; Zanzi, R. 2011. Inorganic heterogeneous catalysts for biodiesel production from vegetable oils, Biomass and Bioenergy 35(9): 3787–3809. https://doi.org/10.1016/j.biombioe.2011.06.011
Fan, M.; Liu, Y.; Zhang, P.; Jiang, P. 2016. Blocky shapes Ca–Mg mixed oxides as a water-resistant catalyst for effective synthesis of biodiesel by transesterification, Fuel Processing Technology 149: 163–168. https://doi.org/10.1016/j.fuproc.2016.03.029
Faungnawakij, K.; Yoosuk, B.; Namuangruk, S.; Krasae, P.; Viriya-empikul, N.; Puttasawat, B. 2012. Sr–Mg mixed oxides as biodiesel production catalysts, ChemCatChem 4(2): 209–216. https://doi.org/10.1002/cctc.201100346
Gui, X.; Chen, S.; Yun, Z. 2016. Continuous production of biodiesel from cottonseed oil and methanol using a column reactor packed with calcined sodium silicate base catalyst, Chinese Journal of Chemical Engineering 24(4): 499–505. https://doi.org/10.1016/j.cjche.2015.11.006
Ilgen, O. 2011. Dolomite as a heterogeneous catalyst for transesterification of canola oil, Fuel Processing Technology 92(3): 452–455. https://doi.org/10.1016/j.fuproc.2010.10.009
Jaiyen, S.; Naree, T.; Ngamcharussrivichai, C. 2015. Comparative study of natural dolomitic rock and waste mixed seashells as heterogeneous catalysts for the methanolysis of palm oil to biodiesel, Renewable Energy 74: 433–440. https://doi.org/10.1016/j.renene.2014.08.050
Long, Y.-D.; Fang, Z.; Su, T.-C.; Yang, Q. 2014. Co-production of biodiesel and hydrogen from rapeseed and Jatropha oils with sodium silicate and Ni catalysts, Applied Energy 113: 1819–1825. https://doi.org/10.1016/j.apenergy.2012.12.076
MacLeod, C. S.; Harvey, A. P.; Lee, F. A.; Wilson, K. 2008. Evaluation of the activity and stability of alkali-doped metal oxide catalysts for application to an intensified method of biodiesel production, Chemical Engineering Journal 135 (1–2): 63–70. https://doi.org/10.1016/j.cej.2007.04.014
Ngamcharussrivichai, C.; Nunthasanti, P.; Tanachai, S.; Bunyakiat, K. 2010. Biodiesel production through transesterification over natural calciums, Fuel Processing Technology 91(11): 1409–1415. https://doi.org/10.1016/j.fuproc.2010.05.014
Ngamcharussrivichai, C.; Wiwatnimit, W.; Wangnoi, S. 2007. Modified dolomites as catalysts for palm kernel oil transesterification, Journal of Molecular Catalysis A: Chemical 276(1–2): 24–33. https://doi.org/10.1016/j.molcata.2007.06.015
Niu, S.-L.; Huo, M.-J.; Lu, C.-M.; Liu, M.-Q.; Li, H. 2014. An investigation on the catalytic capacity of dolomite in transesterification and the calculation of kinetic parameters, Bioresource Technology 158: 74–80. https://doi.org/10.1016/j.biortech.2014.01.123
Santos, E. M.; Piovesan, N. D.; De Barros, E. G.; Moreira, M. A. 2013. Low linolenic soybeans for biodiesel: characteristics, performance and advantages, Fuel 104: 861–864. https://doi.org/10.1016/j.fuel.2012.06.014
Sendzikienė, E; Makarevicienė, V.; Ciutelytė, R. 2012. Sorption characteristics of dolomite suspension and methyldiethanolamine in gas treatment to remove carbon dioxide, Russian Journal of Applied Chemistry 85(12): 1910–1913. https://doi.org/10.1134/S1070427212120191
Sendzikienė, E.; Šinkūnienė, D.; Kazanceva, I.; Kazancev, K. 2016. Optimization of low quality rapeseed oil transesterification with butanol by applying the response surface methodology, Renewable energy 87(1): 266–272. https://doi.org/10.1016/j.renene.2015.10.024
Shajaratun Nur, Z. A.; Taufiq-Yap, Y. H.; Rabiah Nizah, M. F.; Teo, S. H.; Syazwani, O.N.; Islam, A. 2014. Production of biodiesel from palm oil using modified Malaysian natural dolomites, Energy Conversion and Management 78: 738–744. https://doi.org/10.1016/j.enconman.2013.11.012
Shibasaki-Kitakawa, N.; Honda, H.; Kuribayashi, H.; Toda, T.; Fukumura, T.; Yonemoto, T. 2007. Biodiesel production using anionic ion-exchange resin as heterogeneous catalyst, Bioresource Technology 98(2): 416–421. https://doi.org/10.1016/j.biortech.2005.12.010
Shimada, Y.; Watanabe, Y.; Sugihara, A.; Tominaga, Y. 2002. Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing, Journal of Molecular Catalysis B: Enzymatic 17(3–5): 133–142. https://doi.org/10.1016/S1381-1177(02)00020-6
Watanabe, Y.; Pinsirodom, P.; Nagao, T.; Yamauchi, A.; Kobayashi, T.; Nishida, Y.; Takagi, Y.; Shimada, Y. 2007. Conversion of acid oil by-produced in vegetable oil refining to biodiesel fuel by immobilized Candida antarctica lipase, Journal of Molecular Catalysis B: Enzymatic 44(3–4): 99–105. https://doi.org/10.1016/j.molcatb.2006.09.007
Zaleckas, E.; Makarevičienė, V.; Sendžikienė, E. 2012. Possibilities of using Camelina sativa oil for producing biodiesel fuel, Transport 27(1): 60–66. https://doi.org/10.3846/16484142.2012.664827