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A study on the conversion of glycerol to pyridine bases over Cu/HZSM-5 catalysts

机译:Cu / HZSM-5催化剂上甘油向吡啶碱的转化研究

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摘要

A catalyst of 4.6% Cu supported on HZSM-5 with Si/Al of 38 [4.6% Cu/HZSM-5(38)] was prepared in this work. Pyridine bases including pyridine and 2- and 3-picoline, were obtained over this catalyst from glycerol and ammonia. The parameters influencing the catalyst performance were studied thoroughly. An optimized process for the reaction of glycerol with ammonia to form the pyridine bases was also obtained. Under the optimized conditions, which include a reaction temperature of 520 degrees C, atmospheric pressure with an ammonia/glycerol molar ratio of 7 : 1, and a GHSV of 300 h(-1), the total carbon yield of the pyridine bases was nearly 42.8%. Characterization results from the IR of the adsorbed pyridine indicated that the doping of copper into HZSM-5(38) led to significant changes in the Lewis/Bronsted ratio. An appropriate proportion of the two types of acid sites is important to determine the total selectivity of pyridine bases. XRD analysis showed that copper was initially present in the CuO state and then converted into elemental Cu reduced by H-2 generated in situ in the catalytic run. TEM and nitrogen adsorption-desorption characterization revealed that the catalyst deactivation was mainly caused by carbonaceous deposits on the catalyst. The catalyst can be regenerated online by blowing air into the reactor at 550 degrees C for 6 h. The slight decrease of the activity of the regenerated 4.6% Cu/HZSM-5(38) compared with that of the fresh one could be ascribed to the partial sintering of copper particles and dealumination of the catalyst in the catalytic run.
机译:在这项工作中,制备了载于HZSM-5的4.6%Cu的催化剂,Si / Al为38 [4.6%Cu / HZSM-5(38)]。在该催化剂上由甘油和氨获得包括吡啶和2-和3-甲基吡啶的吡啶碱。深入研究了影响催化剂性能的参数。还获得了甘油与氨反应形成吡啶碱的优化方法。在最佳条件下,包括520摄氏度的反应温度,氨/甘油摩尔比为7:1的大气压和GHSV为300 h(-1),吡啶碱的总碳收率接近42.8%。吸附吡啶的红外光谱表征结果表明,向HZSM-5(38)中掺杂铜会导致Lewis /布朗斯台德比发生显着变化。两种酸位置的适当比例对于确定吡啶碱的总选择性很重要。 XRD分析表明,铜最初以CuO状态存在,然后被催化运行中的原位生成的H-2还原成单质铜。 TEM和氮吸附-解吸特性表明,催化剂失活主要是由催化剂上的碳沉积引起的。可以通过在550摄氏度下向反应器中吹入空气6小时来在线再生催化剂。与新鲜的相比,再生的4.6%Cu / HZSM-5(38)的活性略有下降,这可归因于铜颗粒的部分烧结和催化过程中催化剂的脱铝。

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