乙烯氢甲酰化反应动力学的研究——Ⅰ.以丙醛为反应介质

Kinetics Study of Ethylene Hydroformylation 1.Using Propanal as the Reaction Medium

以丙醛为反应介质、铑膦络合物为催化剂,对乙烯氢甲酰化反应的动力学进行了研究。通过对试验数据的关联,提出了丙醛生成速度的经验模型:r=649exp(-30400/RT)C_(Rh)^(0.949)C_T^(-0.076)P_E^(0.641)P_(H2)^(0.586)P_(CO)^(0.293)exp(0.044C_T^(-0.156)P_(CO))结果表明,C_(Rh)、T、P_(E)和 P(H2)是影响反应速度的主要因素,C_T 的影响很小,而 P_(CO)的影响在1.88bar 时有极大值,反应的表观活化能为30.4kJ/mol·K。

The kinetics of ethylene hydroformylation with rhodium phosphine complexcatalyst in propanal medium has been studied.The rate of propanal formation maybe expressed by the following empirical model:r=649exp(-30400/RT)C_(Rh)^(?)C_T^(0.076) p_B^(0.641) p_H_2^(0.586) p_(CO)^(0.293)·exp(0.044C_T^(-0.156)pco) where r is the rate of propanal formation(mol/1·h);R is 0.314 J/mol·K;T isthe reaction temperature(K);C_(Rh) is the concentration of rhodium catalyst basedon rhodium metal(ppm);C_r is the concentration of triphenyl phosphine(w%);p_B,p_H_2 and pco are the partial pressure of ethylene,hydrogen and carbon mono-xide respectively(bar).It shows that the C_(Rh),T,p_B and p_H_2 are the major factorsto influence the reaction rate.The influence of C_r is very small,whereas that of pcohas a maximum value at 1.88 bar.The apparent activation energy of the reactionis 30.4kJ/mol.K.