异丁醛加氢制异丁醇宏观动力学研究

Macro-Kinetics of Isobutyraldehyde Hydrogenation to Isobutyl Alcohol

在内循环无梯度反应器中研究了铜系催化剂上异丁醛加氢的反应性能,实验采用工业原粒度φ6 mm×6 mm柱状催化剂。实验条件为温度130～180℃,压力为0.3～0.8 MPa,液体空速为1.5～4 h-1,考察了反应温度、压力和液体空速对异丁醛加氢反应的影响。结果表明,反应温度和压力升高,异丁醇收率增大;液体空速增大,异丁醇收率减小。选取各组成以分压表示的异丁醛加氢反应的幂函数动力学模型,根据测定的30套动力学数据,运用非线性最小二乘法,通过计算机数值模拟确定动力学参数,异丁醛加氢制备异丁醇的表观活化能Ea为15.89 kJ/mol,对异丁醛和H2分压的反应级数分别为0.16和0.30。残差分析和统计检验表明,动力学模型是适定的。

In an internal gradientless recycle reactor, the experiments of isobutyraldehyde hydrogenation were performed over Cu catalyst which was cylindrical particles with the size of φ6 mm×6 mm. The experiments were performed at the temperature of 130-180 ℃, liquid space velocities of 1.5-4 h-1 and pressures of 0.3-0.8 MPa. The results showed that the yield of isobutyl alcohol increased with increasing temperature and pressure and decreased with increasing liquid space velocities. The power-low kinetics model was used to express the macro-kinetics of the above hydrogenation process. In the proposed models, the reactant components were expressed by their partial pressure. The factors of the proposed models were determined by fitting 30 sets of experimentally obtained partial pressure of both reactants. In order to estimate the kinetic parameters of the proposed models, the nonlinear least squares method was used. The calculations showed that the apparent activation energy for hydrogenation of isobutyraldehyde was 15.89 kJ/mol, and the reaction orders for isobutyraldehyde and Hz were 0.16 and 0.30 respectively. The residual error distributions and the statistic tests showed that the proposed macro-kinetic models were reliable and adequate.