Samara Soares*, , , Luís C. Martins, , , Donato A. G. Aranda, , and , Luiz A. Martinelli,
{"title":"用δ13C测定可再生柴油和化石柴油混合物中原料的分析方法","authors":"Samara Soares*, , , Luís C. Martins, , , Donato A. G. Aranda, , and , Luiz A. Martinelli, ","doi":"10.1021/acs.energyfuels.5c03793","DOIUrl":null,"url":null,"abstract":"<p >Renewable diesel is an innovative fuel derived from renewable feedstocks (vegetable oils and frying oils) mainly via hydrodeoxygenation, yielding hydrocarbons chemically similar to fossil diesel. Its use reduces greenhouse gas emissions, decreases dependence on fossil fuels, and is compatible with conventional engines. However, ensuring authenticity is essential to prevent adulteration. This study proposes an analytical method using δ<sup>13</sup>C to differentiate renewable diesel from fossil diesel. Renewable diesel exhibited δ<sup>13</sup>C values ranging from −30.8‰ (soybean) to −28.1‰ (macauba), indicating its renewable origin. Fossil diesel showed δ<sup>13</sup>C values around −25‰, enabling a clear distinction. A calibration curve using soybean-based renewable diesel blends with fossil diesel showed linear range of 10 to 100%v/v, described by the equation (<i>C</i> = −0.06RD −24.7; <i>r</i> = 0.999). The approach achieved detection and quantification limits of 3.3%v/v and 10.0%v/v, respectively, and coefficient of variation of 1.5% (<i>n</i> = 10), representing the lowest renewable diesel content in fossil diesel blends that can be reliably detected and accurately quantified for regulatory compliance. Matrix-matched calibration yield recoveries of 93–120% and 71–99% with 10 and 50%v/v renewable diesel, respectively. Mixtures of fossil diesel and renewable diesel (1–3% v/v), from soybean oil and used frying oil, were classified using hierarchical and <i>K</i>-means clustering. Clustering by renewable diesel content showed distances of 12–24, within-cluster sum of squares (WCSS) = 143, intracluster distance = 3; clustering by feedstock showed distances of 2.0–2.5, WCSS = 82.7, intracluster distance = 1.4. ANOVA confirmed significant group differences (<i>F</i> = 12.82; <i>p</i> = 0.0339). The method is robust and effective for monitoring the authenticity and detecting low-level of renewable diesel in blends with fossil diesel.</p>","PeriodicalId":35,"journal":{"name":"Energy & Fuels","volume":"39 39","pages":"18916–18923"},"PeriodicalIF":5.3000,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.energyfuels.5c03793","citationCount":"0","resultStr":"{\"title\":\"Analytical Method for Determining Renewable Diesel and Identifying Feedstock in Fossil Diesel Blends Using δ13C for Fuel Traceability\",\"authors\":\"Samara Soares*, , , Luís C. Martins, , , Donato A. G. Aranda, , and , Luiz A. Martinelli, \",\"doi\":\"10.1021/acs.energyfuels.5c03793\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Renewable diesel is an innovative fuel derived from renewable feedstocks (vegetable oils and frying oils) mainly via hydrodeoxygenation, yielding hydrocarbons chemically similar to fossil diesel. Its use reduces greenhouse gas emissions, decreases dependence on fossil fuels, and is compatible with conventional engines. However, ensuring authenticity is essential to prevent adulteration. This study proposes an analytical method using δ<sup>13</sup>C to differentiate renewable diesel from fossil diesel. Renewable diesel exhibited δ<sup>13</sup>C values ranging from −30.8‰ (soybean) to −28.1‰ (macauba), indicating its renewable origin. Fossil diesel showed δ<sup>13</sup>C values around −25‰, enabling a clear distinction. A calibration curve using soybean-based renewable diesel blends with fossil diesel showed linear range of 10 to 100%v/v, described by the equation (<i>C</i> = −0.06RD −24.7; <i>r</i> = 0.999). The approach achieved detection and quantification limits of 3.3%v/v and 10.0%v/v, respectively, and coefficient of variation of 1.5% (<i>n</i> = 10), representing the lowest renewable diesel content in fossil diesel blends that can be reliably detected and accurately quantified for regulatory compliance. Matrix-matched calibration yield recoveries of 93–120% and 71–99% with 10 and 50%v/v renewable diesel, respectively. Mixtures of fossil diesel and renewable diesel (1–3% v/v), from soybean oil and used frying oil, were classified using hierarchical and <i>K</i>-means clustering. Clustering by renewable diesel content showed distances of 12–24, within-cluster sum of squares (WCSS) = 143, intracluster distance = 3; clustering by feedstock showed distances of 2.0–2.5, WCSS = 82.7, intracluster distance = 1.4. ANOVA confirmed significant group differences (<i>F</i> = 12.82; <i>p</i> = 0.0339). 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Analytical Method for Determining Renewable Diesel and Identifying Feedstock in Fossil Diesel Blends Using δ13C for Fuel Traceability
Renewable diesel is an innovative fuel derived from renewable feedstocks (vegetable oils and frying oils) mainly via hydrodeoxygenation, yielding hydrocarbons chemically similar to fossil diesel. Its use reduces greenhouse gas emissions, decreases dependence on fossil fuels, and is compatible with conventional engines. However, ensuring authenticity is essential to prevent adulteration. This study proposes an analytical method using δ13C to differentiate renewable diesel from fossil diesel. Renewable diesel exhibited δ13C values ranging from −30.8‰ (soybean) to −28.1‰ (macauba), indicating its renewable origin. Fossil diesel showed δ13C values around −25‰, enabling a clear distinction. A calibration curve using soybean-based renewable diesel blends with fossil diesel showed linear range of 10 to 100%v/v, described by the equation (C = −0.06RD −24.7; r = 0.999). The approach achieved detection and quantification limits of 3.3%v/v and 10.0%v/v, respectively, and coefficient of variation of 1.5% (n = 10), representing the lowest renewable diesel content in fossil diesel blends that can be reliably detected and accurately quantified for regulatory compliance. Matrix-matched calibration yield recoveries of 93–120% and 71–99% with 10 and 50%v/v renewable diesel, respectively. Mixtures of fossil diesel and renewable diesel (1–3% v/v), from soybean oil and used frying oil, were classified using hierarchical and K-means clustering. Clustering by renewable diesel content showed distances of 12–24, within-cluster sum of squares (WCSS) = 143, intracluster distance = 3; clustering by feedstock showed distances of 2.0–2.5, WCSS = 82.7, intracluster distance = 1.4. ANOVA confirmed significant group differences (F = 12.82; p = 0.0339). The method is robust and effective for monitoring the authenticity and detecting low-level of renewable diesel in blends with fossil diesel.
期刊介绍:
Energy & Fuels publishes reports of research in the technical area defined by the intersection of the disciplines of chemistry and chemical engineering and the application domain of non-nuclear energy and fuels. This includes research directed at the formation of, exploration for, and production of fossil fuels and biomass; the properties and structure or molecular composition of both raw fuels and refined products; the chemistry involved in the processing and utilization of fuels; fuel cells and their applications; and the analytical and instrumental techniques used in investigations of the foregoing areas.