丁酮肟是一种性能优良的精细化学品,钛硅分子筛TS-1催化丁酮(MEK)氨氧化是合成丁酮肟的绿色工艺.本文研究了TS-1催化丁酮氨氧化直接合成丁酮肟的动力学.在实验条件下,当搅拌速率大于600 r/min时,外扩散的影响基本消除;TS-1催化剂的平均粒径约为170 nm,其内扩散的影响可以忽略,反应进入动力学控制区.本征动力学方程中丁酮、NH3和H2O2的反应级数分别为0.807、1.151和0.391,反应活化能为67.45 kJ/mol,反应指前因子为9.392×107 L1.349/(mol1.349?min).研究结果可为TS-1催化丁酮氨氧化合成丁酮肟工艺设计提供依据.%Methyl ethyl ketone oxime (MEKO) is an excellent fine chemical.The ammoximation of methyl ethyl ketone (MEK) to MEKO over titanium silicalites-1 (TS-1) is a novel and an environmentally friendly technology.The intrinsic kinetics of the MEK ammoximation reaction over TS-1 to produce MEKO was investigated.As the stirring rate was over 600 r/min and the average particle size of TS-1 catalyst was about 170 nm,both the effects of external diffusion and internal diffusion resistance on the ammoximation reaction could be ignored and the reaction was controlled only by the kinetics of ammoximation,and the reaction orders of MEK,NH3 and H2O2 were found to be 0.807,1.151 and 0.391,respectively.The reaction activation energy was 67.45 kJ/mol and the pre-exponential factor was 9.392×107 L1.349/(mol1.349?min).Results provided the fundamental data for the MEK ammoximation over TS-1 to prepare MEKO.
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