The influence of Al 2 O 3 –ZrO 2 and TiO 2 –ZrO 2 supports on NiMo-supported catalysts at a different sulfur concentration in a model hydrodeoxygenation (HDO)-hydrodesulfurization (HDS) co-processing reaction has been studied in this work. A competition effect between phenol and dibenzothiophene (DBT) for active sites was evidenced. The competence for the active sites between phenol and DBT was measured by comparison of the initial reaction rate and selectivity at two sulfur concentrations (200 and 500 ppm S). NiMo/TiO 2 –ZrO 2 was almost four-fold more active in phenol HDO co-processed with DBT than NiMo/Al 2 O 3 –ZrO 2 catalyst. Consequently, more labile active sites are present on NiMo/TiO 2 –ZrO 2 than in NiMo/Al 2 O 3 –ZrO 2 confirmed by the decrease in co-processing competition for the active sites between phenol and DBT. DBT molecules react at hydrogenolysis sites (edge and rim) preferentially so that phenol reacts at hydrogenation sites (edge and edge). However, the hydrogenated capacity would be lost when the sulfur content was increased. In general, both catalysts showed similar functionalities but different degrees of competition according to the highly active NiMoS phase availability. TiO 2 –ZrO 2 as the support provided weaker metal-support interaction than Al 2 O 3 –ZrO 2 , generating a larger fraction of easily reducible octahedrally coordinated Mo- and Ni-oxide species, causing that NiMo/TiO 2 –ZrO 2 generated precursors of MoS 2 crystallites with a longer length and stacking but with a higher degree of Ni-promotion than NiMo/Al 2 O 3 –ZrO 2 catalyst.

中文翻译：

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NiMo/Al2O3-ZrO2和NiMo/TiO2-ZrO2催化剂联合处理苯酚和二苯并噻吩的加氢脱氧和加氢脱硫

本文研究了模型加氢脱氧 (HDO)-加氢脱硫 (HDS) 共处理反应中不同硫浓度下 Al 2 O 3 –ZrO 2 和 TiO 2 –ZrO 2 载体对 NiMo 负载催化剂的影响。证明了苯酚和二苯并噻吩 (DBT) 对活性位点的竞争效应。通过比较两种硫浓度（200 和 500 ppm S）下的初始反应速率和选择性来测量苯酚和 DBT 之间活性位点的能力。NiMo/TiO 2 –ZrO 2 在与 DBT 共加工的苯酚 HDO 中的活性几乎是 NiMo/Al 2 O 3 –ZrO 2 催化剂的四倍。因此，与 NiMo/Al 2 O 3 -ZrO 2 相比，NiMo/TiO 2 -ZrO 2 上存在更多不稳定的活性位点，这可以通过苯酚和 DBT 之间对活性位点的共加工竞争减少来证实。DBT 分子优先在氢解位点（边缘和边缘）发生反应，因此苯酚在氢化位点（边缘和边缘）发生反应。然而，当硫含量增加时，氢化能力会下降。一般来说，根据高活性 NiMoS 相的可用性，两种催化剂都显示出相似的功能，但竞争程度不同。TiO 2 -ZrO 2 作为载体提供比 Al 2 O 3 -ZrO 2 更弱的金属-载体相互作用，产生更大比例的易还原八面体配位的 Mo-和 Ni-氧化物物质，导致 NiMo/TiO 2 -ZrO 2 生成与NiMo/Al 2 O 3 -ZrO 2 催化剂相比，MoS 2 微晶的前驱体具有更长的长度和堆积，但对Ni的促进程度更高。