用于苯甲醚低温加氢脱氧的镍铜基催化剂:二氧化硅和 γ-Al2O3 载体上金属比例的影响

Tom Vandevyvere , Maarten K. Sabbe , Pedro S.F. Mendes , Joris W. Thybaut , Jeroen Lauwaert
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摘要

在中性SiO2和酸性γ-Al2O3载体上考察了NiCu催化剂金属配比对苯甲醚低温加氢脱氧(HDO)的影响。sio2负载型催化剂的活性随着NiCu相中Ni含量的增加而增加,这与Ni的加氢能力有关。相反,在γ-Al2O3载体上,活性随Ni含量的增加而降低。总体而言,al2o3负载的催化剂表现出更小的NiCu合金粒度,比sio2负载的催化剂更具活性。在选择性方面,sio2负载的催化剂主要是将甲醚加氢为甲氧基环己烷,而γ- al2o3负载的催化剂能够进一步将甲氧基环己烷转化为环己烷,特别是在更高的转化率下,这表明酸位对低温HDO的重要性。Ni/Cu比对催化剂的选择性也有影响,但对催化剂的稳定性没有影响。失活现象仅依赖于载体:在负载sio2的催化剂上,由于载体对金属颗粒的弱稳定作用,活性位点发生烧结,而在负载γ- al2o3的催化剂上,酸催化结焦是失活的主要原因。
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NiCu-based catalysts for the low-temperature hydrodeoxygenation of anisole: Effect of the metal ratio on SiO2 and γ-Al2O3 supports

The effects of the metal ratio of NiCu catalysts on the low-temperature hydrodeoxygenation (HDO) of anisole were assessed on a neutral SiO2 and an acidic γ-Al2O3 support. The activity of SiO2-supported catalysts increases with the Ni content in the NiCu phase, related to Ni’s hydrogenation capacity. In contrast, on a γ-Al2O3 support, the activity decreases with the Ni content. Overall, Al2O3-supported catalysts, exhibiting a smaller NiCu alloy particle size, are more active than SiO2-supported ones. In terms of selectivity, SiO2-supported catalysts mainly hydrogenate anisole to methoxycyclohexane, while, particularly at higher conversions, γ-Al2O3-supported catalysts are able to further convert methoxycyclohexane to cyclohexane, demonstrating the importance of acid sites for low-temperature HDO. The Ni/Cu ratio also steers the selectivity, but not the catalyst stability. Deactivation phenomena are only support dependent: while on SiO2-supported catalysts, active site sintering occurs, attributed to weak stabilization of metal particles by the support, acid catalyzed coking is the main cause of deactivation on the γ-Al2O3-supported catalysts.

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