CIESC Journal

• 化工学报 • 上一篇    下一篇

四氢萘催化脱氢反应动力学的研究

李成林,林洁,陈邦和,史士东,曹竹安   

  1. 清华大学化学化工系 ,清华大学化学化工系 ,清华大学化学化工系 ,清华大学化学化工系 ,清华大学化学化工系
  • 出版日期:1984-06-25 发布日期:1984-06-25

Kinetics of Catalytic Dehydrogenation of Tetralin Li Chenlin, Lin Jie, Chen Banghe, Shi Shidong and Cao Zhuan

Department of Chemistry and Chemical Engineering, Qinghua University   

  • Online:1984-06-25 Published:1984-06-25

摘要: 四氢萘在Ni Mo/Al_2O_3、Fe_2O_3、FeS_2上常压脱氢是典型的连串可逆反应,1,2-二氢萘及微量的1,4-二氢萘是反应的中间产物.脱氢反应速度随四氢萘分压提高和氢分压下降而提高.对二氢萘反应性能的考察表明它具有比四氢萘和萘高得多的反应活性,能迅速地催化转化为萘和四氢萘.氢加快二氢萘的加氢是它阻滞四氢萘脱氢的主要原因.各种催化剂对四氢萘脱氢、二氢萘转化和萘高压加氢都具有基本相同的活性顺序.根据可逆连串表面反应的历程及表面吸附的二氢萘为非常活泼的反应中间体的假设,作者推导了动力学模型,计算得到各反应物在Ni Mo/Al_2O_3、Fe_2O_3、Fe_2O_3/Al_2O_3上表面吸附常数和表面反应速率常数,并进行模拟计算.理论计算与实验能很好地吻合,证明了模型的合理性.模型及参数也进一步解释了一些实验事实.

Abstract: The dehydrogenation of tetralin over Ni-Mo/Al2O3, Fe2O3/Al2O3, Fe2O3 and FeS2 has been shown in this investigation to be a typical consecutive reversible reaction, with a small amount of 1, 2-dihydronaphthalene as an intermediate. On the less-active catalyst Fe2O3, a trace of 1, 4-dihydronaphthalene (DHN) is also formed-the more active the catalyst, the lower the concentration of DHN. The rate of dehydrogenation rises with an increase of the partial pressure of tetralin, and declines with an increase of the partial pressure of hydrogen. It was observed that DHN is much more active than tetralin and naphthalene, and in the presence of a catalyst, it can be converted rapidly into naphthalene and tetralin. The fact that hydrogen can accelerate the hydrogenation of DHN is thought to be the main reason for its inhibiting action on the dehydrogenation of tetralin. In the presence of a catalyst, 1,4-DHN is unstable and can be isomerized into 1,2-DHN very quickly. The different catalysts studied have almost the same order of activity for dehydrogenation of tetralin, conversion of DHN and hydrogenation of naphthalene. On the hypothesis that the reaction is a consecutive one on the catalyst surface and that the adsorbed DHN is a very active intermediate, a reaction model was deduced. The equilibrium constants of adsorption and the rate constants of the catalytic reaction were calculated. The curves so calculated fit very well the experimental data, thus showing the validity of this model. Certain experimental results were explained in the light of this model and the related parameters.