Research On The Process And Intrinsic Kinetics Of Synthesis Of Morpholine Catalyzed By Diethylene Glycol

Morpholine as an important intermediates of fine chemicals and a wide range of applications in the industry such as medicine,rubber,and textiles.At present,the major method used for producing morpholine is catalytic amino lysis of diethylene glycol at domestic and foreign,but the low activity of catalysts and Low product selectivity are the main problems of this method.In order to put the high-performance catalyst into industrial production,the synthesis process and dynamics study is of great significance.In this paper,with copper and nickel as the main component,the activation treatment of ?-Al2O3 at 700 ? as carrier,ethylene glycol added as dispersant,Cu-Ni/?-Al2O3 catalysts were prepared by using ultrasonic assisted impregnation.In fixed bed reactor,this catalyst was used to study the synthesis of morpholine.by catalytic amination of diethylene glycol.The effect of reaction temperature,pressure,feed rate of diethylene glycol,and mole ratio to ammonia on the synthesis of morpholine was investigated by single factor experiments,and through the orthogonal test method to optimize the process conditions.Determined the optimum process conditions for the synthesis of morpholine,as follows:230 ?,1.7 Mpa,0.4 mL·g-1·h-1,and molar ratio of ammonia to diethylene glycol was 8:1.The yield of morpholine was highest,the diethylene glycol conversion rate was 98.63%,and the morpholine yield was 81.00%.The intrinsic kinetic experiments of diethylene glycol to morpholine over Cu-Ni/?-Al2O3 catalyst were carried out in a fixed bed integral reactor in the temperature range 483K?513 K,diethylene glycol/ammonia range 4:1?12:1 and 1.7 MPa.First,the reaction residence time range excluding external diffusion limitation and the average size range excluding internal diffusion were determined limitations by changing the loading amount and size of the catalyst,respectively.Then based on the kinetic experimental data obtained at different temperatures and feed concentrations,an exponential kinetics model for the synthesis of morpholine by diethylene glycol diamine over Cu-Ni/?-Al2O3 catalyst was established,and the kinetic model parameters were estimated using MATLAB.Finally,the obtained intrinsic kinetic model:r=22541×exp(-62581/RT)C-1.21 EDG C1.47 ammonia,it can pass the statistical test.The calculated value of the model fits well with the experimental value.The study of intrinsic kinetics provides a theoretical basis for the industrial production of morpholine through the catalytic amination of diethylene glycol on Cu-Ni/?-Al2O3 catalysts.