乙炔氢氯化均相催化反应动力学的初步研究

Kinetics of catalytic reactions for hydrochlorination of acetylene

初步研究了以PtCl4为催化剂,在十二烷/JM-T盐酸盐液相体系中,乙炔氢氯化制氯乙烯的均相反应动力学模型。根据测量组分在十二烷/JM-T体系中物料的气液平衡和反应动力学数据,并对实验数据进行回归方差分析,比较两个模型(Ⅰ)r=(K1′K2′PAPBCD0)/(K1′PA+K-1+K2′PB)和(Ⅱ)r=(Ke′K2′CD0PA0PB0)/(1+Ke′PA0),认为模型Ⅰ与实验数据拟合得更好,其中k1′=5.2,k2′=3.7和k-1=1287.8,回归分析的显著性检验F=3.801。根据模型Ⅰ初步推测该反应的反应过程是:C2H2先和催化剂Pt(Ⅳ)发生化学吸附,再和体系中的HCl反应;其中C2H2和催化剂络合为反应的控制步骤。

A preliminary kinetics model of the non-mercuric homogenous catalytic hydrochlorination of acetylene was established.Compared model（Ⅰ）r=（K1′K2′PAPBCD0）/（K1′PA＋K-1＋K2′PB） and model（Ⅱ）r=（Ke′K2′CD0PA0PB0）/（1＋Ke′PA0） by the phase equilibrium and reaction kinetics data in the PtCl4/primeneTM JM-T/dodecane system,it was concluded that model Ⅰ may outperform model Ⅱ in terms of goodness of fit.And k1′=5.2,k2′=3.7 and k-1=1287.8,test of significance F=3.801.According to model Ⅰ,the reaction mechanism is that catalyst Pt（Ⅳ）adsorbs with acetylene and then reacts with hydrogen chloride,and the former step is rate determining.