Hemijska industrija 2023 Volume 77, Issue 1, Pages: 85-93
https://doi.org/10.2298/HEMIND220808003D
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Stability evaluation of biodiesel supplemented with synthetic and bio-based antioxidants by a pressurized accelerated oxidation method
Đurišić-Mladenović Nataša 
(University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia), natasa.mladenovic@uns.ac.rs
Tomić Milan (University of Novi Sad, Faculty of Agriculture, Novi Sad, Serbia)
Pajin Biljana (University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia)
Buljovčić Maja (University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia)
Lončarević Ivana (University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia)
Rankov-Šicar Milica (University of Novi Sad, Faculty of Technology Novi Sad, Novi Sad, Serbia + SP Laboratorija a.d., Bečej, Serbia)
This work examines pressurized accelerated oxidation by a RapidOxy tester as an alternative method for determination of biodiesel oxidation stability. Sunflower oil-based biodiesel was synthesized and treated with antioxidants: tert-butylhydroquinone (TBHQ) - a synthetic antioxidant known for its powerful protective effect, and a mixture of bio-based antioxidant compounds extracted from vinery waste, VWEeth. The antioxidant potency of TBHQ was evaluated at varying temperatures (110 - 140 °C) and concentrations (250 - 2,000 mg dm-3) by the RapidOxy method; assessment of selected results was performed by comparison with relevant data obtained by the standard Rancimat method. VWEeth was added in two high dosages to biodiesel (87,500 and 150,000 mg dm-3) and analyzed at 140°C by the RapidOxy method. Both antioxidants at all applied dosages showed beneficial effects on improving the oxidative stability of biodiesel, but not all of the achieved improvements reached the stability minimum identified by the EN14214 standard. The lowest addition of TBHQ seemed to have a similar effect as the tested dosages of VWEeth but these additions did not increase the induction period above the limit of 8 h; two-fold higher quantity of TBHQ was successful in this respect, increasing the initial oxidation stability by a factor of about 2, which was determined by both methods. The RapidOxy method proved to be a very fast method suitable for testing a large number of samples, which is particularly important for efficient testing of different types and doses of antioxidants.
Keywords: induction period, Rancimat, RapidOxy, tert-butylhydroquinone TBHQ, vinery waste ethanolic extract
Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 451-03-68/2022-14/200134 and Grant no. 451-03-68/2022-14/200117
Show references
Tomić M, Đurišić-Mladenović N, Mićić R, Simikić M, Savin L. Effects of accelerated oxidation on the selected fuel properties and composition of biodiesel. Fuel. 2019; 235: 269-276 https://doi.org/10.1016/j.fuel.2018.07.123
Alves-Fortunato M, Ayoub E, Bacha K, Mouret A, Dalmazzone C. Fatty Acids Methyl Esters (FAME) autoxidation: New insights on insoluble deposit formation process in biofuels. Fuel. 2020; 268: 117074 https://doi.org/10.1016/j.fuel.2020.117074
Sia CB, Kansedo J, Tan YH, Lee KT. Evaluation on biodiesel cold flow properties, oxidative stability and enhancement strategies: A review. Biocatal Agric Biotechnol 2020; 24: 101514. https://doi.org/10.1016/j.bcab.2020.101514
Bacha K, Ben-Amara A, Vannier A, Alves-Fortunato M, Nardin M. Oxidation stability of diesel/biodiesel fuels measured by a PetroOxy device and characterization of oxidation products. Energy Fuels. 2015; 29: 4345-4355 https://doi.org/10.1021/acs.energyfuels.5b00450
Yaakob Z, Narayanan BN, Padikkaparambil S, Surya Unni K, Akbar MP. A review on the oxidation stability of biodiesel. Renew Sustain Energy Rev 2014; 35: 136-153 https://doi.org/10.1016/j.rser.2014.03.055
Lawan I, Zhou W, Garba ZN, Zhang M, Yuan Z, Chen L. Critical insights into the effects of bio-based additives on biodiesels properties. Renew Sustain Energy Rev. 2019; 102: 83-95 https://doi.org/10.1016/j.rser.2018.12.008
Kumar D, Singh B. Tinospora cordifolia stem extract as an antioxidant additive for enhanced stability of Karanja biodiesel. Ind Crops Prod. 2018; 123: 10-16 https://doi.org/10.1016/j.indcrop.2018.06.049
Valenga MGP, Boschen NL, Rodrigues PRP, Maia GAR. Agro-industrial waste and Moringa oleifera leaves as antioxidants for biodiesel. Ind Crops Prod 2019; 128: 331-337 https://doi.org/10.1016/j.indcrop.2018.11.031
Devi A, Das VK, Deka D. Evaluation of the effectiveness of potato peel extract as a natural antioxidant on biodiesel oxidation stability. Ind Crops Prod 2018; 123: 454-460 https://doi.org/10.1016/j.indcrop.2018.07.022
Tongcumpou C, Usapein P, Tuntiwiwattanapun N. Complete utilization of wet spent coffee grounds waste as a novel feedstock for antioxidant, biodiesel, and bio-char production. Ind Crops Prod 2019; 138: 111484 https://doi.org/10.1016/j.indcrop.2019.111484
Roveda AC, de Oliveira IP, Caires ARL, Rinaldo D, Ferreira VS, Trindade MAG. Improving butylhydroxytoluene activity with alternative secondary antioxidants: High synergistic effect in stabilizing biodiesel/diesel fuel blends in the presence of prooxidative metal. Ind Crops Prod 2022; 178: 114558 https://doi.org/10.1016/j.indcrop.2022.114558
Alberici RM, Simas RC, Abdelnur P V, et al. A highly effective antioxidant and artificial marker for biodiesel. Energy Fuel. 2010; 24(11): 6522-6526 https://doi.org/10.1021/ef100968b
van der Westhuizen I, Focke WW. Stabilizing sunflower biodiesel with synthetic antioxidant blends. Fuel. 2018; 219: 126- 131 https://doi.org/10.1016/j.fuel.2018.01.086
Rankov Šicar M, Mićić R, Tomić M, Đurišić-Mladenović N. Efficiency of different additives in improvement of oxidation stability of fatty acid methyl esters with different properties. J Serb Chem Soc. 2021; 86: 739-752 https://doi.org/10.2298/JSC210209029R
Botella L, Bimbela F, Martín L, Arauzo J, Sánchez JL. Oxidation stability of biodiesel fuels and blends using the Rancimat and PetroOXY methods. Effect of 4-allyl-2,6-dimethoxyphenol and catechol as biodiesel additives on oxidation stability. Front Chem. 2014; 2: 43 https://doi.org/10.3389/fchem.2014.00043
Neumann A, Jebens T, Wierzbicki V. A method for determining oxidation stability of petrodiesel, biodiesel, and blended fuels. Am Lab. 2008; 40: 22-26 https://www.americanlaboratory.com/914-Application-Notes/34716-A-Method-for-Determining-Oxidation-Stability-of-Petrodiesel-Biodiesel-and-Blended-Fuels/
Araújo S V, Luna FMT, Rola Jr EM, Azevedo DCS, Cavalcante Jr CL. A rapid method for evaluation of the oxidation stability of castor oil FAME: influence of antioxidant type and concentration. Fuel Process Technol. 2009; 90(10): 1272-1277 https://doi.org/10.1016/j.fuproc.2009.06.009
Đurišić-Mladenović N, Kiss F, Škrbić B, Tomić M, Mićić R, Predojević Z. Current state of the biodiesel production and the indigenous feedstock potential in Serbia. Renew Sustain Energy Rev 2018; 81: 280-291 https://doi.org/10.1016/j.rser.2017.07.059
Dunn RO. Effect of oxidation under accelerated conditions on fuel properties of methyl soyate (biodiesel). J Am Oil Chem Soc 2002; 79(9): 915-920 https://doi.org/10.1007/s11746-002-0579-2
Agarwal S, Singhal S, Singh M, Arora S, Tanwer M. Role of Antioxidants in Enhancing Oxidation Stability of Biodiesels. ACS Sustain Chem Eng 2018; 6(8): 11036-11049 https://doi.org/10.1021/acssuschemeng.8b02523
Zhou J, Xiong Y, Shi Y. Antioxidant Consumption Kinetics and Shelf-Life Prediction for Biodiesel Stabilized with Antioxidants Using the Rancimat Method. Energy Fuels. 2016; 30(12): 10534-10542. https://doi.org/10.1021/acs.energyfuels.6b02199
Spacino KR, Silva ET da, Angilelli KG, Moreira I, Galão OF, Borsato D. Relative protection factor optimisation of natural antioxidants in biodiesel B100. Ind Crops Prod 2016; 80: 109-114. https://doi.org/10.1016/j.indcrop.2015.11.034
Devi A, Das VK, Deka D. Ginger extract as a nature based robust additive and its influence on the oxidation stability of biodiesel synthesized from non-edible oil. Fuel. 2017; 187: 306-314 https://doi.org/10.1016/j.fuel.2016.09.063