The hydrogenation of trans,trans-muconic acid was investigated on a Pt/C 5% (wt) catalyst in a batch slurry reactor at constant hydrogen pressure (4 bar) and temperature (323, 333 and 343 K), with the purpose of developing a kinetic model able to predict conversions and product distributions. A dual-site Langmuir–Hinshelwood–Hougen–Watson (LHHW) model with hydrogen dissociation provided good fitting of the experimental data. The model parameters were regressed by robust numerical methods to overcome the computational challenges of the model parameters’ collinearity. Different reaction mechanisms were tested; the best model involved two subsequent hydrogenation steps. The first step yielded from trans,trans-muconic acid a monounsaturated intermediate (trans-2-hexenedioic acid), which was further hydrogenated to adipic acid in the second step. The intermediate was subjected to an equilibrium isomerization with cis-2-hexenedioic acid. The activation energy values and the rate constants were calculated for the reactions, providing the first reference for trans,trans-muconic acid hydrogenation.

中文翻译：

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反式，反式-葡糖酸加氢制生物己二酸：机理鉴定和动力学建模

在间歇式淤浆反应器中，在恒定氢气压力（4 bar）和温度（323、333和343 K）下，在Pt / C 5％（wt）催化剂上研究了反式，反式-粘康酸的氢化反应，目的是建立能够预测转化率和产品分布的动力学模型。具有氢离解的双位Langmuir-Hinshelwood-Hougen-Watson（LHHW）模型提供了很好的实验数据拟合。通过鲁棒的数值方法对模型参数进行回归，以克服模型参数共线性的计算难题。测试了不同的反应机理；最佳模型涉及两个后续的氢化步骤。第一步来自反式，反式-粘康酸-单不饱和中间体（反式-2-己烯二酸），其在第二步中进一步氢化成己二酸。中间体用顺-2-己烯二酸进行平衡异构化。计算了反应的活化能值和速率常数，为反式，反式-粘康酸加氢提供了第一个参考。