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<p>This study systematically investigates the intrinsic kinetics of the liquid-phase hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate (DMCD) over a Cr-free CuFe<sub>5</sub> catalyst in a fixed-bed reactor. The complex reaction network involves the sequential hydrogenation of the two ester groups in DMCD, proceeding via the intermediate methyl 4-(hydroxymethyl)cyclohexane-1-carboxylate (MHMCC) to yield the target diol, 1,4-cyclohexanedimethanol (CHDM). This main pathway is accompanied by a parallel side reaction that generates 1-((4-(hydroxymethyl)cyclohexyl)methyl) 4-methyl cyclohexane-1,4-dicarboxylate (HCMMCD). Four dissociative adsorption kinetic models based on the dual-site Langmuir–Hinshelwood-Hougen-Watson (LHHW) mechanism were developed. Kinetic parameters for each model were estimated via the nonlinear least-squares method using the Levenberg–Marquardt algorithm in MATLAB. Model discrimination identified the mechanism with the surface reaction as the rate-determining step as optimal, showing excellent agreement with experimental data (correlation coefficient <i>R</i><sup>2</sup> = 0.943) and satisfying statistical validation criteria. The optimized model indicates that DMCD undergoes dissociative adsorption on the catalyst surface, with stepwise hydrogenation of acyl species constituting the rate-limiting step. Activation energies for the key surface reactions were determined to be 133.66 kJ/mol (DMCD → MHMCC) and 189.62 kJ/mol (MHMCC → CHDM). These findings establish a fundamental kinetic basis for scaling up the liquid-phase hydrogenation process employing the environmentally benign CuFe<sub>5</sub> catalyst.</p>

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Hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate to 1,4-cyclohexanedimethanol: a kinetic study over a CuFe5 catalyst

  • 期刊论文

  • 发表日期：

    2026年4月10日

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  • Kun Jiang,
  • Qian Zhang,
  • Yuanbo Zheng,
  • Kai Wu,
  • Weiqiang Wang,
  • Qinwei Yu,
  • Jianming Yang

摘要

This study systematically investigates the intrinsic kinetics of the liquid-phase hydrogenation of dimethyl 1,4-cyclohexanedicarboxylate (DMCD) over a Cr-free CuFe5 catalyst in a fixed-bed reactor. The complex reaction network involves the sequential hydrogenation of the two ester groups in DMCD, proceeding via the intermediate methyl 4-(hydroxymethyl)cyclohexane-1-carboxylate (MHMCC) to yield the target diol, 1,4-cyclohexanedimethanol (CHDM). This main pathway is accompanied by a parallel side reaction that generates 1-((4-(hydroxymethyl)cyclohexyl)methyl) 4-methyl cyclohexane-1,4-dicarboxylate (HCMMCD). Four dissociative adsorption kinetic models based on the dual-site Langmuir–Hinshelwood-Hougen-Watson (LHHW) mechanism were developed. Kinetic parameters for each model were estimated via the nonlinear least-squares method using the Levenberg–Marquardt algorithm in MATLAB. Model discrimination identified the mechanism with the surface reaction as the rate-determining step as optimal, showing excellent agreement with experimental data (correlation coefficient R2 = 0.943) and satisfying statistical validation criteria. The optimized model indicates that DMCD undergoes dissociative adsorption on the catalyst surface, with stepwise hydrogenation of acyl species constituting the rate-limiting step. Activation energies for the key surface reactions were determined to be 133.66 kJ/mol (DMCD → MHMCC) and 189.62 kJ/mol (MHMCC → CHDM). These findings establish a fundamental kinetic basis for scaling up the liquid-phase hydrogenation process employing the environmentally benign CuFe5 catalyst.