CIESC Journal

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A STUDY ON KINETICS OF OXIDATION OF CYCLOHEXANE TO ADIPIC ACID BY ONE-STEP PROCESS

王润俦; 谢敏明; 汪仁   

  1. East China Institute of Chemical Technology
  • 收稿日期:1900-01-01 修回日期:1900-01-01 出版日期:1984-12-28 发布日期:1984-12-28
  • 通讯作者: 王润俦

A STUDY ON KINETICS OF OXIDATION OF CYCLOHEXANE TO ADIPIC ACID BY ONE-STEP PROCESS

WANG Runchou; XIE Minming; WANG Ren   

  1. East China Institute of Chemical Technology
  • Received:1900-01-01 Revised:1900-01-01 Online:1984-12-28 Published:1984-12-28
  • Contact: WANG Runchou

摘要: The cobalt catalyzed oxidation of cyclobexane in acetic acid solution to adipid acid by pure oxygenhas been studied.Under the following conditions of investigation:reaction temperature 80—90℃,con-centration of cyclobexane 1.08-2.97 mol/l,concentration of Co (OAC)_2·4H_2O 0.031-0.0803 mol/l,aceticacid/cyclohexane 10—20 (by weight) and oxygen pressure 5-30 kg/cm~2.,it is found that the kinetics ofadipic acid formation could be expressed by the follwoing equationr=k[C_6H_(12)][Co~(+++)]~2[Co~(++)]~(-1)[P_(o_2)]~(1/2)where r rate of formation of adipic acid;[C_6H_(12)] concentration of cyclohexane;[Co~(+++)] concentration of cobaltic ion;[Co~(++)] concentration of cobaltous ion;[P_(o_2)] pressure of oxygen;k rate constant of reaction.The temperature dependence of rate constant can be correlated with the Arrhenius equation:lnk=(-ΔE)/(RT)+AThe apparent activated energy ΔE is 32.74 kcal/g-mol.A tentative reaction mechanism is presented to explain the phenomena observed,in which the ratedetermining step is the formation of cation radical species through the interaction of Co~(+++) and cyclohex-ane molecules with Co~(+++) and Co~(++) serving as chain carriers.

Abstract: The cobalt catalyzed oxidation of cyclobexane in acetic acid solution to adipid acid by pure oxygenhas been studied.Under the following conditions of investigation:reaction temperature 80—90℃,con-centration of cyclobexane 1.08-2.97 mol/l,concentration of Co (OAC)_2·4H_2O 0.031-0.0803 mol/l,aceticacid/cyclohexane 10—20 (by weight) and oxygen pressure 5-30 kg/cm~2.,it is found that the kinetics ofadipic acid formation could be expressed by the follwoing equationr=k[C_6H_(12)][Co~(+++)]~2[Co~(++)]~(-1)[P_(o_2)]~(1/2)where r rate of formation of adipic acid;[C_6H_(12)] concentration of cyclohexane;[Co~(+++)] concentration of cobaltic ion;[Co~(++)] concentration of cobaltous ion;[P_(o_2)] pressure of oxygen;k rate constant of reaction.The temperature dependence of rate constant can be correlated with the Arrhenius equation:lnk=(-ΔE)/(RT)+AThe apparent activated energy ΔE is 32.74 kcal/g-mol.A tentative reaction mechanism is presented to explain the phenomena observed,in which the ratedetermining step is the formation of cation radical species through the interaction of Co~(+++) and cyclohex-ane molecules with Co~(+++) and Co~(++) serving as chain carriers.