CAJ | 학술논문

以硫酸为催化剂，间歇实验研究了276.2~285.2 K温度范围内混合丁烯/异丁烷烷基化反应动力学。实验结果表明，随着反应温度的降低，主产物三甲基戊烷（TMPs）生成量和烷基化油整体辛烷值增大，副产物二甲基己烷（DMHs）变化较小，高碳组分（HEs）的生成量降低明显。采用基于碳正离子反应机理建立的烷基化动力学模型对TMPs、DMHs、HEs 3类组分进行了计算分析，模拟计算结果表明，动力学模型对实验数据的拟合效果良好。链引发步骤异丁烯加氢离子反应表现出反 Arrhenius 行为，其本身及逆反应的活化能分别为45.14 kJ·mol?1和41.44 kJ·mol?1，增加对链传递部分C8正碳离子形成步骤的速率常数计算，部分涉及链传递和链终止反应步骤反应速率常数与文献值保持一致。
이류산위최화제，간헐실험연구료276.2~285.2 K온도범위내혼합정희/이정완완기화반응동역학。실험결과표명，수착반응온도적강저，주산물삼갑기무완（TMPs）생성량화완기화유정체신완치증대，부산물이갑기기완（DMHs）변화교소，고탄조분（HEs）적생성량강저명현。채용기우탄정리자반응궤리건립적완기화동역학모형대TMPs、DMHs、HEs 3류조분진행료계산분석，모의계산결과표명，동역학모형대실험수거적의합효과량호。련인발보취이정희가경리자반응표현출반 Arrhenius 행위，기본신급역반응적활화능분별위45.14 kJ·mol?1화41.44 kJ·mol?1，증가대련전체부분C8정탄리자형성보취적속솔상수계산，부분섭급련전체화련종지반응보취반응속솔상수여문헌치보지일치。
The alkylation kinetics of isobutane with mixed butenes using sulfuric acid as catalyst was investigated by batch experiments at temperatures from 276.2 K to 285.2 K under the conditions of industrial interest. With the decrease of reaction temperature, both the production of main product trimethylpentanes (TMPs) and RON of alkylates increased, and byproducts dimethylhexanes (DMHs) changed a little, but heavy ends components (HEs) reduced significantly. By using the alkylation kinetics model based on the classic carbonium ion mechanism, the concentration profiles with time regarding three groups of key alkylates, including TMPs, DMHs, and HEs, were compared against experiments. The regression results showed that the kinetics model fitted experimental data very well. An anti-Arrhenius behavior was found in the chain initiation step of the addition reaction of H+to isobutene, and the apparent activation energies of itself and the reverse reaction were 45.14 kJ·mol?1 and 41.44 kJ·mol?1. The calculation of reaction rates of the TMPs+and DMHs+forming steps was added, and most of the reaction rates of chain transfer and chain termination reactions remained the same as those in literature.