MoO3负载对焦磷酸钙催化气相乳酸脱水产物选择性的影响

J. Mane, Dhananjay S. Doke, Vidhya C. Ghantani, M. Dongare, S. Umbarkar
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引用次数: 0

摘要

焦磷酸钙和羟基磷灰石催化剂具有不同的C/P比之前已被我们的团队用于乳酸气相脱水成丙烯酸,几乎100%的转化率和高达78%的丙烯酸选择性。活性对催化剂的酸碱度高度敏感。因此,对活性最高的催化剂焦磷酸钙进行MoO3改性,以改变其酸性,并研究其对乳酸脱水产物选择性的影响。在375℃、50%乳酸浓度、WHSV为3 h-1条件下,采用MoO3改性焦磷酸钙,MoO3负载率为5%进行乳酸气相脱水。并与未改性的焦磷酸钙催化剂进行了活性比较。令人惊讶的是,与脱水相比,脱氧是主要的。酸度被观察到在产品选择性中起关键作用。在酸性载体较少的情况下,与酸性载体γ-Al2O3和相同MoO3负载的SiO2相比,含5 wt% MoO3的焦磷酸钙表现出更强的脱氧活性。较高的酸度导致形成乙醛作为唯一的产物。结果证实了乳酸脱羧生成乙醛后,利用原位生成的氢对乳酸进行脱氧生成丙酸。
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Effect of MoO3 loading on product selectivity for calcium pyrophosphate catalyzed vapor phase lactic acid dehydration
Calcium pyrophosphate and hydroxyapatite catalysts with varying C/P ratios have been previously used by our group for vapor phase dehydration of lactic acid to acrylic acid with almost 100% conversion and up to 78% acrylic acid selectivity. The activity was highly sensitive to acidity and basicity of the catalyst. Hence the catalyst with maximum activity, calcium pyrophosphate, was modified with MoO3 for modifying its acidity and to study its effect on product selectivity for lactic acid dehydration. The MoO3 modified calcium pyrophosphate with 5% MoO3 loading was used for vapor phase dehydration of lactic acid at 375°C using 50% lactic acid concentration with WHSV of 3 h-1. The activity was compared with nonmodified calcium pyrophosphate catalyst. Surprisingly, deoxygenation was predominant compared to dehydration. Acidity was observed to play a crucial role in product selectivity (i.e,. with less acidic support, calcium pyrophosphate with 5 wt% MoO3 showed more deoxygenation activity as compared to acidic support γ-Al2O3 as well as SiO2 with same MoO3 loading). Higher acidity led to formation of acetaldehyde as the only product. The results confirmed formation of propionic acid by deoxygenation of lactic acid using in situ generated hydrogen after decarboxylation of lactic acid to acetaldehyde.
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