通过“毫秒”氧化裂解过程生产线性长链α-烯烃的清洁技术：反应物碳链长度的积极影响,New Journal of Chemistry

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通过“毫秒”氧化裂解过程生产线性长链α-烯烃的清洁技术：反应物碳链长度的积极影响
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2022-01-18 , DOI: 10.1039/d1nj05910f
Hugo Cruchade ₁ , Y. Pouilloux ₁ , R. Beauchet ₁ , Ludovic Pinard ₁

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正癸烷、正十二烷、正十四烷和正十六烷的氧化裂化在C/O摩尔比为1.8的铂催化剂上以毫秒接触时间进行评估。反应器的热映射显示所有反应物在稳态下毫秒反应器的热行为相似，对应于燃烧催化剂在 440-550°C 范围内的自热操作。提供的热量导致后催化气相中的热梯度，并维持有价值的线性α-烯烃（LAO）的吸热形成。LAO 产率随着反应物碳链长度的增加从正癸烷开始的 11.4 wt% 增加到从正癸烷开始的 20.2 wt%-十六烷。此外，当向 MSR 中加入较大的正构烷烃时，LAO 碳链长度往往会更高。两个数学模型能够预测有机产物的分布：（i）裂解产物的 Anderson-Schultz-Flory 定律，即LAO 和n-醛和（ii）基于含氧化合物的氢原子提取概率的模型，其形成不涉及碳-碳键断裂，即四氢呋喃、环氧乙烷和酮。

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Cleaner technology for the production of linear long-chain α-olefins through a “millisecond” oxidative cracking process: a positive impact of the reactant carbon chain length

The oxidative cracking of n-decane, n-dodecane, n-tetradecane and n-hexadecane was assessed at millisecond contact times on a platinum catalyst at a C/O molar ratio of 1.8. The thermal mapping of the reactor showed the similar thermal behaviour of the millisecond reactor at the steady-state for all reactants, corresponding to the autothermal operation of the combustion catalyst in the range of 440–550 °C. The heat provided led to a thermal gradient in the post-catalytic gas-phase and sustained the endothermic formation of valuable linear α-olefins (LAOs). The LAO yields increased with the carbon chain length of the reactant from 11.4 wt% starting from n-decane to 20.2 wt% starting from n-hexadecane. Furthermore, the LAO carbon chain length tends to be higher when feeding the MSR with larger n-alkanes. Two mathematical models are able to predict the distributions of organic products: (i) the Anderson-Schultz-Flory law for cracking products, i.e. LAO and n-aldehydes and (ii) a model based on the hydrogen atom abstraction probability for oxygenated compounds, the formation of which does not involve carbon–carbon bond cleavage, i.e. tetrahydrofurans, oxiranes and ketones.

更新日期：2022-01-18

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