Water Contamination Impacts on Biodiesel Antioxidants and Storage Stability

Christensen, Earl D.; McCormick, Robert L.

doi:10.1021/acs.energyfuels.2c03911

Water Contamination Impacts on Biodiesel Antioxidants and Storage Stability

Journal Article · Tue Mar 14 04:00:00 EDT 2023 · Energy and Fuels

DOI:https://doi.org/10.1021/acs.energyfuels.2c03911· OSTI ID:1967957

^[1]; ^[1]

National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Biodiesel (fatty acid methyl esters) can oxidize in storage to form acids and gums that negatively impact engine performance and durability. Antioxidant additives are used to increase biodiesel storage stability, and previous studies that evaluated the effectiveness of antioxidants demonstrated that more polar antioxidants tend to be the most effective (provide the largest improvement in stability per unit of antioxidant added). However, polar antioxidants have significant water solubility, and diesel fuel storage tanks are commonly contaminated with water (forming a layer of water under the fuel). This study investigates whether nonpolar antioxidants, which are less effective in dry environments, might be more effective under wet conditions simulating real-world storage. Biodiesel blends treated with polar and nonpolar antioxidants were subjected to accelerated aging using the ASTM D4625 protocol (storage at 43 °C, open to air, for up to 24 weeks) both with and without added water. Fuels treated with polar/higher-effectiveness compounds and stored in contact with water (simulating water in a storage tank) or high humidity showed accelerated loss of stability compared to dry storage. The same fuel treated with a nonpolar antioxidant and stored in the same conditions did not exhibit accelerated stability loss and thus had higher storage stability over the long term despite treatment with an initially less effective additive. Analysis of the fuels during aging showed that this loss of stability was not due to oxidation but rather extraction of the polar antioxidant into the water layer. Antioxidant additives that are incompatible with wet or humid storage conditions were found to cause faster-than-anticipated loss of stability, which was preventable with use of nonpolar additives.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE; Clean Fuels Alliance America

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1967957

Report Number(s):: NREL/JA-4A00-84642; MainId:85415; UUID:ad4a3c8f-ec5e-4e53-bf96-3589d65c66f0; MainAdminID:69163

Journal Information:: Energy and Fuels, Journal Name: Energy and Fuels Journal Issue: 7 Vol. 37; ISSN 0887-0624

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (36)

Oxidative stability of biodiesel: recent insights Longanesi, Luca; Pereira, André P.; Johnston, Nigel Biofuels, Bioproducts and Biorefining, Vol. 16, Issue 1 https://doi.org/10.1002/bbb.2306	journal	October 2021
Antioxidants for improving storage stability of biodiesel Dunn, Robert O. Biofuels, Bioproducts and Biorefining, Vol. 2, Issue 4 https://doi.org/10.1002/bbb.83	journal	July 2008
Quality parameters evolution during biodiesel oxidation using Rancimat test Lacoste, Florence; Lagardere, Lionel European Journal of Lipid Science and Technology, Vol. 105, Issue 3-4 https://doi.org/10.1002/ejlt.200390030	journal	April 2003
Techniques to improve the stability of biodiesel: a review Hazrat, M. A.; Rasul, M. G.; Khan, M. M. K. Environmental Chemistry Letters, Vol. 19, Issue 3 https://doi.org/10.1007/s10311-020-01166-8	journal	February 2021
Oxidative stability and storage behavior of fatty acid methyl esters derived from used palm oil Loh, Soh-Kheang; Chew, Soo-Mooi; Choo, Yuen-May Journal of the American Oil Chemists' Society, Vol. 83, Issue 11 https://doi.org/10.1007/s11746-006-5051-9	journal	November 2006
The Effect of Natural and Synthetic Antioxidants on the Oxidative Stability of Biodiesel Tang, Haiying; Wang, Anfeng; Salley, Steven O. Journal of the American Oil Chemists' Society, Vol. 85, Issue 4 https://doi.org/10.1007/s11746-008-1208-z	journal	February 2008
Design and preliminary results of an NMR tube reactor to study the oxidative degradation of fatty acid methyl ester Chuck, Christopher J.; Jenkins, Rhodri W.; Bannister, Chris D. Biomass and Bioenergy, Vol. 47 https://doi.org/10.1016/j.biombioe.2012.09.043	journal	December 2012
Degradation of biodiesel under different storage conditions Leung, D. Y. C.; Koo, B. C. P.; Guo, Y. Bioresource Technology, Vol. 97, Issue 2 https://doi.org/10.1016/j.biortech.2005.02.006	journal	January 2006
Long term storage stability of Jatropha curcas biodiesel Jain, Siddharth; Sharma, M. P. Energy, Vol. 36, Issue 8 https://doi.org/10.1016/j.energy.2011.06.055	journal	August 2011
Long storage stability of biodiesel from vegetable and used frying oils Bouaid, Abderrahim; Martinez, Mercedes; Aracil, José Fuel, Vol. 86, Issue 16 https://doi.org/10.1016/j.fuel.2007.02.014	journal	November 2007
Long-term storage stability of biodiesel produced from Karanja oil Das, L. M.; Bora, Dilip Kumar; Pradhan, Subhalaxmi Fuel, Vol. 88, Issue 11 https://doi.org/10.1016/j.fuel.2009.05.005	journal	November 2009
Storage and oxidation stabilities of biodiesel derived from waste cooking oil Fu, Jinxia; Turn, Scott Q.; Takushi, Brandon M. Fuel, Vol. 167 https://doi.org/10.1016/j.fuel.2015.11.041	journal	March 2016
Effects of accelerated oxidation on the selected fuel properties and composition of biodiesel Tomić, M.; Đurišić-Mladenović, N.; Mićić, R. Fuel, Vol. 235 https://doi.org/10.1016/j.fuel.2018.07.123	journal	January 2019
Eugenol and TBHQ antioxidant actions in commercial biodiesel obtained by soybean oil and animal fat Ramos, T. C. P. M.; Santos, E. P. S.; Ventura, M. Fuel, Vol. 286 https://doi.org/10.1016/j.fuel.2020.119374	journal	February 2021
Some aspects of biodiesel oxidative stability Knothe, Gerhard Fuel Processing Technology, Vol. 88, Issue 7 https://doi.org/10.1016/j.fuproc.2007.01.005	journal	July 2007
Quality analysis of wintertime B6–B20 biodiesel blend samples collected in the United States Alleman, Teresa L.; Fouts, Lisa; McCormick, Robert L. Fuel Processing Technology, Vol. 92, Issue 7 https://doi.org/10.1016/j.fuproc.2011.02.004	journal	July 2011
Studies on the effect of antioxidants on the long-term storage and oxidation stability of Pongamia pinnata (L.) Pierre biodiesel Obadiah, Asir; Kannan, Ramanujam; Ramasubbu, Alagunambi Fuel Processing Technology, Vol. 99 https://doi.org/10.1016/j.fuproc.2012.01.032	journal	July 2012
Long-term storage oxidation stability of Karanja biodiesel with the use of antioxidants Agarwal, Avinash Kumar; Khurana, Deepak Fuel Processing Technology, Vol. 106 https://doi.org/10.1016/j.fuproc.2012.09.011	journal	February 2013
Long-term storage stability of biodiesel and biodiesel blends Christensen, Earl; McCormick, Robert L. Fuel Processing Technology, Vol. 128 https://doi.org/10.1016/j.fuproc.2014.07.045	journal	December 2014
Re-additization of commercial biodiesel blends during long-term storage Christensen, Earl D.; Alleman, Teresa; McCormick, Robert L. Fuel Processing Technology, Vol. 177 https://doi.org/10.1016/j.fuproc.2018.04.011	journal	August 2018
Improving butylhydroxytoluene activity with alternative secondary antioxidants: High synergistic effect in stabilizing biodiesel/diesel fuel blends in the presence of pro-oxidative metal Roveda, Ana Carolina; de Oliveira, Ivan Pires; Caires, Anderson Rodrigues Lima Industrial Crops and Products, Vol. 178 https://doi.org/10.1016/j.indcrop.2022.114558	journal	April 2022
Biodiesel fuels Knothe, Gerhard; Razon, Luis F. Progress in Energy and Combustion Science, Vol. 58 https://doi.org/10.1016/j.pecs.2016.08.001	journal	January 2017
Stability of biodiesel and its blends: A review Jain, Siddharth; Sharma, M. P. Renewable and Sustainable Energy Reviews, Vol. 14, Issue 2 https://doi.org/10.1016/j.rser.2009.10.011	journal	February 2010
Review of different test methods for the evaluation of stability of biodiesel Jain, Siddharth; Sharma, M. P. Renewable and Sustainable Energy Reviews, Vol. 14, Issue 7 https://doi.org/10.1016/j.rser.2010.04.011	journal	September 2010
Screening of antioxidant additives for biodiesel fuels Varatharajan, K.; Pushparani, D. S. Renewable and Sustainable Energy Reviews, Vol. 82 https://doi.org/10.1016/j.rser.2017.07.020	journal	February 2018
A comprehensive review of the selection of natural and synthetic antioxidants to enhance the oxidative stability of biodiesel Jemima Romola, C. V.; Meganaharshini, M.; Rigby, S. P. Renewable and Sustainable Energy Reviews, Vol. 145 https://doi.org/10.1016/j.rser.2021.111109	journal	July 2021
Insights into the effectiveness of synthetic and natural additives in improving biodiesel oxidation stability Lau, Chi Hou; Gan, Suyin; Lau, Harrison Lik Nang Sustainable Energy Technologies and Assessments, Vol. 52 https://doi.org/10.1016/j.seta.2022.102296	journal	August 2022
Effects of moisture content on biodiesel (B100) properties during storage: A comparative analysis between biodiesel produced from used cooking oil and beef tallow Kolobeng, Rebaone; Ketlogetswe, Clever; Jonas, Mbako Sustainable Energy Technologies and Assessments, Vol. 54 https://doi.org/10.1016/j.seta.2022.102844	journal	December 2022
Life Cycle Greenhouse Gas Emissions of Biodiesel and Renewable Diesel Production in the United States Xu, Hui; Ou, Longwen; Li, Yuan Environmental Science & Technology, Vol. 56, Issue 12 https://doi.org/10.1021/acs.est.2c00289	journal	May 2022
Impact of Antioxidant Additives on the Oxidation Stability of Diesel/Biodiesel Blends Karavalakis, Georgios; Stournas, Stamos Energy & Fuels, Vol. 24, Issue 6 https://doi.org/10.1021/ef1004623	journal	June 2010
Storage Stability of Biodiesel and Biodiesel Blends McCormick, Robert L.; Westbrook, Steven R. Energy & Fuels, Vol. 24, Issue 1 https://doi.org/10.1021/ef900878u	journal	January 2010
Studies on long-term storage stability of biodiesel (B100) and its blend (B20) using Box-Behnken response surface method Jayaraman, Pavalavana Pandian; Pugazhvadivu, M. International Journal of Ambient Energy, Vol. 39, Issue 3 https://doi.org/10.1080/01430750.2017.1303635	journal	March 2017
PubChem in 2021: new data content and improved web interfaces Kim, Sunghwan; Chen, Jie; Cheng, Tiejun Nucleic Acids Research, Vol. 49, Issue D1 https://doi.org/10.1093/nar/gkaa971	journal	November 2020
Investigation and enhancement on fuel stability characteristics of biodiesel dosed with various synthetic antioxidants Mohamed Shameer, P.; Nishath, P. Mohamed Energy & Environment, Vol. 29, Issue 7 https://doi.org/10.1177/0958305X18772415	journal	April 2018
Spectroscopic Study of Biodiesel Degradation Pathways Fang, Howard L.; McCormick, Robert L. SAE Technical Paper Series https://doi.org/10.4271/2006-01-3300	conference	October 2006
Impact of a Diesel High Pressure Common Rail Fuel System and Onboard Vehicle Storage on B20 Biodiesel Blend Stability Christensen, Earl; McCormick, Robert L.; Sigelko, Jenny SAE International Journal of Fuels and Lubricants, Vol. 9, Issue 1 https://doi.org/10.4271/2016-01-0885	journal	April 2016

Similar Records

Re-Additization of Commercial Biodiesel Blends During Long-Term Storage

Technical Report · Sun Nov 15 23:00:00 EST 2020 · OSTI ID:1721758

Improving storage stability of gasoline using elevated antioxidant concentrations

Conference · Fri Mar 31 23:00:00 EST 1995 · OSTI ID:68685

Storage Stability of 50% Biodiesel Blends and Neat Biodiesel Produced in North America

Technical Report · Sun Nov 23 19:00:00 EST 2025 · OSTI ID:3013240

Related Subjects

09 BIOMASS FUELS
33 ADVANCED PROPULSION SYSTEMS
biodiesel
fatty acids
fuel additives
fuel storage
stability
water treatment

Water Contamination Impacts on Biodiesel Antioxidants and Storage Stability

Citation Formats

References (36)

Similar Records

Related Subjects