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Kinetics, catalyst deactivation and modeling in the hydrogenation of β-sitosterol to β-sitostanol over microporous and mesoporous carbon supported Pd catalysts

机译:在微孔和介孔碳载Pd催化剂上将β-谷甾醇加氢成β-谷甾醇的动力学,催化剂失活和建模

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摘要

Kinetics of the hydrogenation of β-sitosterol to β-sitostanol is of industrial interest, since the desired product is used for suppressing cholesterol absorption in human body. The main drawback when using microporous Pd/C catalyst in this reaction is catalyst deactivation. In the current work the performance of microporous and mesoporous Pd catalysts in the hydrogenation of β-sitosterol was compared. The catalytic hydrogenations were performed in a shaking batch reactor in 1 -propanol as a solvent. With larger amounts of catalyst less catalyst deactivation occurred due to the fact that the catalyst support acted also as an adsorbent. The mesoporous 4 wt.% Pd/C (Sibunit) catalyst showed higher sitosterol conversions and less catalyst deactivation compared to a microporous 5 wt.% Pd/C catalyst. The kinetics of the hydrogenation of β-sitosterol to β-sitostanol was studied over 4 wt.% Pd/C (Sibunit) catalyst at different temperatures between 60 °C and 80 °C and by reusing the catalyst. The origin for catalyst deactivation was poisoning by phosphorus and sulphur, as well as coking. In situ catalyst potential measurements showed that there is a correlation between catalyst deactivation and decreasing catalyst potential with increasing sitosterol conversion. A mechanistic kinetic model including a deactivation factor was successfully applied to this reaction and the kinetic parameters were determined.
机译:β-谷甾醇氢化成β-谷甾烷醇的动力学是工业上有意义的,因为所需产物被用于抑制人体中胆固醇的吸收。在该反应中使用微孔Pd / C催化剂时的主要缺点是催化剂失活。在当前的工作中,比较了微孔和中孔钯催化剂在β-谷甾醇加氢中的性能。催化氢化在摇动间歇式反应器中在1-丙醇作为溶剂中进行。使用大量催化剂时,由于催化剂载体也起吸附剂的作用,所以发生了催化剂失活。与微孔的5wt%的Pd / C催化剂相比,中孔的4wt%的Pd / C(Sibunit)催化剂显示出更高的谷甾醇转化率和较少的催化剂失活。在60°C和80°C之间的不同温度下,通过重复使用催化剂,研究了在4 wt。%Pd / C(Sibunit)催化剂上β-谷甾醇氢化为β-谷甾醇的动力学。催化剂失活的根源是磷和硫以及焦化中毒。原位催化剂电势测量表明,随着谷固醇转化率的提高,催化剂失活与催化剂电势降低之间存在相关性。包括失活因子的机械动力学模型已成功应用于该反应,并确定了动力学参数。

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