丁辛醇工艺重组分副产物组成分析

利用气相色谱-谱联用(GC-S)技术对丙烯羰基化法生产丁辛醇工艺残液重组分进行了分析，确定了重组分中2个含量较高的组分——2,4-乙基-5-羟基-2-辛烯醛和2-乙基己酸-2-乙基己酯，推测了产生残液重组分可能的副反应。2,4-二乙基-5-羟基-2-辛烯醛可能是由于正丁醛发生深度缩合后，仅脱除了离羰基较近碳原子上的羟基而生成；2-乙基己酸-2-乙基己酯则可能是由2-乙基己醛发生季先科反应生成，或者是由2-乙基己酸和2-乙基己醇发生酯化反应而来。丁辛醇工艺残液重组分组成的确定为对其开展进一步有效利用研究奠定了基础。

Heavy-Component Byproducts Analysis in Butanol and 2-Ethylhexanol Synthesis Process

Heavy-component byproduct can be formed in propylene oxo-synthesis process to produce butanol and 2-ethylhexanol. The composition of these byproducts was identified with gas chromatography-mass spectrometer (GC-MS) analysis, and possible side-reaction pathways were also proposed based on analysis results. Two key components in the byproduct, i.e., 2,4-diethyl-5-hydroxy-2-octenal and 2-ethylhexanoic acid-2-ethylhexyl ester, were identified. Formation of 2,4-diethyl-5-hydroxy-2-octenal may be due to removal of hydroxyl group from the carbon atom adjacent to the carbonyl group in the molecule of butanal trimer, and 2-ethylhexanoic acid 2-ethylhexyl ester may be produced by Tishchenko reaction of 2-ethylhexanal, or by esterification reaction of 2-ethylhexanoic acid and 2-ethylhexanol. The determination of these heavy byproduct components can provide significant information for their future application.