Abstract
The preparation and characterization of K-loaded Mg/Al mixed oxides as catalysts for the transesterification of nonfood Camelina sativa oil were studied. Transesterification was performed using three different potassium-loaded mixed oxides (MO) and the parent Mg/Al MO obtained from hydrotalcite by calcination and treated by impregnation. For K impregnation, three different K salt solutions were used as a K source. To observe the impact of K impregnation on the physicochemical properties of MO, analytical methods were used. X-ray diffraction, basicity, acidity, thermogravimetry, scanning electron microscopy, and textural properties showed a relationship between the type of K impregnation and the properties of the catalysts. Potassium caused an increase in the basicity of MO. The specific surface area (SBET) of the MO loaded by potassium acetate (MO–CH3COOK) increased after impregnation, but the pore volume decreased to half of the original value for all impregnated samples. However, impregnation led to an increase in acidity that negatively affected K-impregnated catalyst activity during the transesterification process. The highest ester content of 94.2 wt% was observed after 7 h of transesterification at 140 °C for the parent MO without impregnation. K-impregnated MO showed lower activity during transesterification and after 7 h reached around 65 wt% for both MO loaded with potassium nitrate (MO–KNO3) and MO–CH3COOK and almost 77 wt% for the MO loaded with potassium fluoride (MO–KF).
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Bacenetti J, Restuccia A, Schillaci G, Failla S (2017) Biodiesel production from unconventional oilseed crops (Linum usitatissimum L. and Camelina sativa L.) in Mediterranean conditions: Environmental sustainability assessment. Renew Energ 112:444–456. https://doi.org/10.1016/j.renene.2017.05.044
Balsamo N, Mendieta S, Oliva M, Eimer G, Crivello M (2012) Synthesis and characterization of metal mixed oxides from layered double hydroxides. Procedia Mater Sci 1:506–513. https://doi.org/10.1016/j.mspro.2012.06.068
Baskaran T, Christopher J, Sakthivel A (2015) Progress on layered hydrotalcite (HT) materials as potential support and catalytic materials. RSC Adv 120:98853–98875. https://doi.org/10.1039/C5RA19909C
Bhojaraj HP, Rajamathi M (2019) Cannizzaro reactions over calcined hydrotalcite. App Clay Sci 174:86–89. https://doi.org/10.1016/j.clay.2019.03.028
Canakci M, Van Gerpen J (2001) Biodiesel production from oils and fats with high free fatty acids. Trans ASAE 44:1429–1436. https://doi.org/10.13031/2013.7010
Cantrell DG, Gillie LJ, Lee AF, Wilson K (2005) Structure-reactivity correlations in MgAl hydrotalcite catalysts for biodiesel synthesis. Appl Catal a: Gen 287:183–190. https://doi.org/10.1016/j.apcata.2005.03.027
EN 14111, Fat and oil derivatives - Fatty Acid Methyl Esters (FAME) - Determination of iodine value
EN 14112, Fat and oil derivatives - Fatty Acid Methyl Esters (FAME) - Determination of oxidation stability (accelerated oxidation test)
EN 14214, Liquid petroleum products - Fatty acid methyl esters (FAME) for use in diesel engines and heating applications - Requirements and test methods
EN ISO 12185:1996, Methods of test for petroleum and its products. Crude petroleum, and petroleum products. Determination of density. Oscillation U-tube method.
EN ISO 3104, Petroleum products - Transparent and opaque liquids - Determination of kinematic viscosity and calculation of dynamic viscosity
Evans DG, Slade RCT (2006) Structural aspects of layered double hydroxides. In: Rvans XDG (ed) Structure and bonding. Springer-Verlag, Berlin Heidelberg, pp 1–87
Faria AC, Trujillano R, Rives V, Miguel CV, Rodrigues AE, Madeira LM (2022) Alkali metal (Na, Cs and K) promoted hydrotalcites for high temperature CO2 capture from flue gas in cyclic adsorption processes. Chem Eng J 427:131502. https://doi.org/10.1016/j.cej.2021.131502
Ferrie AMR, Caswell KL (2016) Applications of doubled haploidy for improving industrial oilseeds. In: McKeon TA, Hayes DG, Hildebrand DF, Weselake RJ (eds.) Industrial oil crops, Elsevier Inc, Canada, pp 359–378. https://doi.org/10.1016/B978-1-893997-98-1.00013-0
Frusteri L, Bonura G, Perathoner S (2018) Catalysts for biofuels production. In: Frusteri F, Aranda D, Bonura G (eds.) Sustainable catalysis for biorefineries, Royal Society of Chemistry pp 144–180. https://doi.org/10.1039/9781788013567
Fukuda H, Kondo A, Noda H (2001) Biodiesel fuel production by transesterification of oils. J Biosci Bioeng 92:405–416. https://doi.org/10.1016/S1389-1723(01)80288-7
Gao L, Xu B, Xiao G, Lv J (2008) Transesterification of palm oil with methanol to biodiesel over a KF/hydrotalcite solid catalyst. Energy Fuels 22:3531–3535. https://doi.org/10.1021/ef800340w
Gao L, Teng G, Lv J, Xiao G (2010) Biodiesel synthesis catalyzed by the KF/Ca−Mg−Al hydrotalcite base catalyst. Energy Fuels 24:646–651. https://doi.org/10.1021/ef900800d
Gupta S, Agarwal DD, Banerjee S (2012) Lithium aluminium layered double hydroxides: synthesis and application in poly (vinyl chloride). Int J Polym Mater 61:985–998. https://doi.org/10.1080/00914037.2011.610067
Helwani Z, Othman MR, Aziz N, Kim J, Fernando WJN (2009) Solid heterogeneous catalysts for transesterification of triglycerides with methanol: A review. Appl Catal a: Gen 363:1–10. https://doi.org/10.1016/j.apcata.2009.05.021
Jeswani KH, Chilvers A, Azapagic A (2020) Environmental sustainability of biofuels: A review. Proc R Soc A 476:20200351. https://doi.org/10.1098/rspa.2020.0351
Kalnes TN, McCall MM, Shonnard DR (2010) Renewable diesel and jet-fuel production from fats and oils. In: Crocker M (ed) Energy and environment series. Royal Society of Chemistry, pp 468–493. doi: https://doi.org/10.1039/9781849732260-00468
Kaur N, Ali A (2014) One-pot transesterification and esterification of waste cooking oil via ethanolysis using Sr: Zr mixed oxide as solid catalyst. RSC Adv 4:43671–43681. https://doi.org/10.1039/C4RA07178F
Lam MK, Lee KT, Mohamed AR (2010) Homogeneous, heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil (waste cooking oil) to biodiesel: A review. Biotechnol Adv 28:500–516. https://doi.org/10.1016/j.biotechadv.2010.03.002
Lee DW, Park YM, Lee KY (2009) Heterogeneous base catalysts for transesterification in biodiesel synthesis. Catal Surv Asia 13:63–77. https://doi.org/10.1007/s10563-009-9068-6
Lee HV, Juan JC, Taufiq-Yap YH, Kong PS, Rahman NA (2015) Advancement in heterogeneous base catalyzed technology: An efficient production of biodiesel fuels. J Renew Sustain Energy 7:032701. https://doi.org/10.1063/1.4919082
Lozano-Lunar A, Álvarez JI, Navarro-Blasco Í, Jiménez JR, Fernández-Rodriguez JM (2021) Optimisation of mortar with Mg-Al-Hydrotalcite as sustainable management strategy lead waste. App Clay Sci 212:106218. https://doi.org/10.1016/j.clay.2021.106218
Lv Y, Yu Q, Mou X, Lin R, Ding Y (2022) Revisiting the structural evolution of hydrotalcite-derived mixed metal oxides upon alkali doping and its impact on base catalysis. Eur J Inorg Chem 2022:e202100913. https://doi.org/10.1002/ejic.202100913
Macala GS, Robertson AW, Johnson CL, Day ZB, Lewis RS, White MG, Ford PC (2008) Transesterification catalysts from iron doped hydrotalcite-like precursors: solid bases for biodiesel production. Catal Lett 122:205–209. https://doi.org/10.1007/s10562-008-9480-y
Mališová M, Horňáček M, Mikulec J, Hudec P, Hájek M, Peller A, Hájeková E (2020) Transesterification of Camelina sativa oil catalyzed by Mg/Al mixed oxides with added divalent metals. ACS Omega 5:32040–32050. https://doi.org/10.1021/acsomega.0c04976
Murphy JE (2016) Camelina (Camelina sativa). In: McKeon TA, Hayes DG, Hildebrand DF, Weselake RJ (ed) Industrial oil crops. Elsevier Inc, Canada, pp 359–378. https://doi.org/10.1016/B978-1-893997-98-1.00013-0
Navajas A, Campo I, Moral A, Echave J, Sanz O, Montes M, Gandía LM (2018) Outstanding performance of rehydrated Mg-Al hydrotalcites as heterogeneous methanolysis catalysts for the synthesis of biodiesel. Fuel 211:173–181. https://doi.org/10.1016/j.fuel.2017.09.061
Nowicki J, Lach J, Organek M, Sabura E (2016) Transesterification of rapeseed oil to biodiesel over Zr-dopped MgAl hydrotalcites. Appl Catal a: Gen 524:17–24. https://doi.org/10.1016/j.apcata.2016.05.015
Olvera D, Rodriguez JA, Perez-Silva I, Chavez-Esquivel G, Tavizón-Pozos JA (2022) Catalytic evaluation of Li and K supported on CaO in the transesterification of triolein, tristearin, and tributyrin. Chem Pap. https://doi.org/10.1007/s11696-022-02305-x
Patil PD, Deng S (2009) Transesterification of Camelina Sativa oil using heterogeneous metal oxide catalysts. Energy Fuels 23:4619–4624. https://doi.org/10.1021/ef900362y
Patil PD, Gude VG, Camacho LM, Deng S (2010) Microwave-assisted catalytic transesterification of Camelina Sativa oil. Energy Fuels 24:1298–1304. https://doi.org/10.1021/ef9010065
Slezáčková M, Mikulec J, Blaško J (2021) Partial hydrogenation of double bonds in polyunsaturated fatty acid methyl esters. In: Proceedings from 8th international conference on chemical technology, Czech society of industrial chemistry, pp. 22–26, ISBN 978-80-88307-08-2.https://www.icct.cz/cs/Amca-ICCT/media/content/2021/proceedings/ICCT2021-Proceedings.pdf
Taipabu MI, Viswanathan K, Wu W, Nagy ZK (2021) Production of renewable fuels and chemicals from fats, oils and grease (FOG) using homogeneous and heterogeneous catalysts: design, validation, and optimalization. Chem Eng J 424:130199. https://doi.org/10.1016/j.cej.2021.130199
Trakarnpruk W, Porntangjitlikit S (2008) Palm oil biodiesel synthesized with potassium loaded calcined hydrotalcite and effect of biodiesel blend on elastomer properties. Renew Energ 33:1558–1563. https://doi.org/10.1016/j.renene.2007.08.003
Xu ZP, Zhang J, Adebajo MO, Zhang H, Zhou C (2011) Catalytic applications of layered double hydroxides and derivatives. Appl Clay Sci 53:139–150. https://doi.org/10.1016/j.clay.2011.02.007
Yan S, Salley SO, Simon Ng KY (2009) Simultaneous transesterification and esterification of unrefined or waste oils over ZnO-La2O3 catalysts. Appl Catal a: Gen 353:203–212. https://doi.org/10.1016/j.apcata.2008.10.053
Zaleckas E, Makarevičienė V, Sendžikienė E (2012) Possibilities of using Camelina sativa oil for producing biodiesel fuel. Transport 27:60–66. https://doi.org/10.3846/16484142.2012.664827
Acknowledgements
This research has been financially supported by the Slovak Research and Development Agency, grant number: APVV-16- 0097 and by Lanxess Central Eastern Europe s.r.o.. We are also thankful to The National Agricultural and Food Center in Vígľaš-Pstruša in the Slovak Republic for the cultivation of Camelina sativa seeds and to Association Energy 21 for cold pressing of CS oil.
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Mališová, M., Horňáček, M., Hudec, P. et al. Preparation and characterization of K-loaded Mg/Al mixed oxides obtained from hydrotalcites for transesterification of Camelina sativa oil. Chem. Pap. 76, 7585–7596 (2022). https://doi.org/10.1007/s11696-022-02434-3
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DOI: https://doi.org/10.1007/s11696-022-02434-3