Properties and Autoignition reactivity of diesel boiling range ethers produced from Guerbet alcohols

Fuel Communications Pub Date : 2025-03-01 Epub Date: 2024-12-22 DOI:10.1016/j.jfueco.2024.100131
Robert L. McCormick , Jon Luecke , Samah Y. Mohamed , Gina M. Fioroni , Nimal Naser , Teresa L. Alleman , Seonah Kim , Michael P. Lanci , Kenneth Kar
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Abstract

We examine the properties of diesel boiling range ethers made from coupling of alcohols produced by oligomerization of ethanol (Guerbet alcohols) for their utility as low-carbon liquid fuel blendstocks. Basic properties of boiling point, flash point, freezing point, density and viscosity are well suited for blending into diesel fuels. For the mixture of ethers the lightest component, di-n-butyl ether, can be present at up to 20 vol% while still having adequately high flashpoint for safe handling. Soot formation tendency (as yield sooting index) is well below that of conventional diesel. The ethers have similar compatibility with elastomers as conventional diesel, based on Hansen solubility parameter analysis. Oxidation stability was assessed for 30 vol% blends of individual ethers in a conventional diesel fuel using a long-term storage test. Over 6 weeks we observed no formation of peroxides or degradation. n-alkyl ethers with carbon number of 8 or higher have cetane number over 100, which is outside the defined range of cetane number, while branched ethers are over 70. The ethers also blend antagonistically into conventional diesel for cetane number, meaning that the blend cetane value is lower than predicted based on a linear by volume, mass, or mole model. We show that aromatics and naphthenes likely act as radical scavengers to slow or shut down autoignition of the highly reactive ethers at low to medium blend levels. Overall, diesel boiling range ethers show significant promise as high quality low-net carbon diesel blendstocks.
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格贝尔醇制柴油沸程醚的性质及自燃反应性
我们研究了由乙醇低聚产生的醇偶联而成的柴油沸程醚的性能,以作为低碳液体燃料混合物。沸点、闪点、凝固点、密度和粘度的基本特性都非常适合与柴油混合。对于醚的混合物,最轻的成分,二正丁基醚,可以以高达20 vol%的浓度存在,同时仍然具有足够高的闪点以安全处理。烟尘的形成趋势(如产烟指数)远低于传统柴油。根据汉森溶解度参数分析,这些醚与弹性体的相容性与传统柴油相似。使用长期储存试验,评估了传统柴油燃料中单个醚的30 vol%混合物的氧化稳定性。在6周的时间里,我们没有观察到过氧化物的形成或降解。碳数为8及以上的n-烷基醚的十六烷值超过100,超出了十六烷值的限定范围,而支链醚的十六烷值超过70。在十六烷值方面,这两种醚还会与传统柴油发生对抗性混合,这意味着混合十六烷值低于基于线性体积、质量或摩尔模型的预测。我们发现芳烃和环烷可能作为自由基清除剂,在低至中等混合水平下减缓或关闭高活性醚的自燃。总的来说,柴油沸程醚作为高质量低净碳柴油混合物具有重要的前景。
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