Study of Carbon Nanotube Supported Co-Mo Selective Hydrodesulphurization Catalysts for Fluid Catalytic Cracking Gasoline

In this paper, carbon nanotube supported Co-Mo catalysts for selective hydrodesulphurization （HDS） of fluid catalytic cracking （FCC） gasoline were studied, using di-isobutylene, cyclohexene, 1-octene and thiophene as model compounds to simulate FCC gasoline. The results show that the Co-Mo/CNT has very high HDS activity and HDS/hydrogenation selectivity comparing with the Co-Mo/γ-Al2O3 and Co-Mo/AC catalyst systems. The saturation ratio of cyclohexene was lower than 50%, and the saturation ratio of 1,3-di-isobutylene lower than 60% for the Co-Mo/CNT catalysts. Co/Mo atomic ratio was found to be one of the most important key factors in influencing the hydrogenation selectivity and HDS activity, and the most suitable Co/Mo atomic ratio was 0.4. Co/CNT and Mo/CNT mono-metallic catalysts showed lower HDS activity and selectivity than the Co-Mo/CNT bi-metallic catalysts.     

准“原位”XPS技术研究加氢精制催化剂的硫化过程

用准“原位”XPS技术研究了Mo/Al_2O_3、Mo/TiO_2-Al_2O_3、CO/Al_2O_3、CO/TiO_2-Al_2O_3、Co-Mo-Al_2O_3和Co-Mo/TiO_2-Al_2O_3等催化剂的硫化过程．结果表明：对以Al_2O_3为载体的催化剂，当Mo或Co载量较低(分别低于0.05 gMoO_3/gAl_2O_3或0.03gCoO/gAl_2O_3)时，没有Mo或Co硫化物的生成，而以TiO_2改性的Al_2O_3为载体的催化剂，Mo/TiO_2-Al_2O_3催化剂的硫化较Mo/Al_2O_3容易得多, 表现为在较低温度下，负载在TiO_2改性Al_2O_3载体上的MoO_3，能很快硫化并达到相当大的硫化度, 对Co/Al_2O_3催化剂而言，即使在较高温度400 ℃时，载体上高分散的CoO物种仍难以硫化；而Co_3O_4微晶的硫化却容易得多, 载体用TiO_2改性，并不影响高分散形态的CoO催化剂的硫化，却明显地影响Co_3O_4微晶的硫化．噻吩加氢脱硫(HDS)的活性测量指出，对Co-Mo/Al_2O_3和Co-Mo/TiO_2-Al_2O_3催化剂而言，HDS活性和硫化度之间存在着良好的相关性．并用TiO_2改性载体，可以增加Co-Mo催化剂的HDS活性和硫化度.     

Novel MWCNT-Support for Co-Mo Sulfide Catalyst in HDS of Thiophene and HDN of Pyrrole

With home-made multi-walled carbon nanotubes (MWCNTs, simplified as CNTs in later text) as support, CNT-supported Co-Mo-S catalysts, denoted as x%(mass percentage) MoiCoj/CNTs, were prepared. Their catalytic performance for thiophene hydrodesulfurization (HDS) and pyrrole hydrodenitrification (HDN) reactions was studied, and compared with the reference system supported by AC. Over the 7.24%Mo3Co1/CNTs catalyst at reaction condition of 1.5 MPa, 613 K, C4H4S/H2=3.7/96.3(molar ratio) and GHSV≈8000 mlSTp/(g-cat·h), the specific HDS activity of thiophene reached 3.29 mmolc4H4s/(s·molMo), which was 1.32 times as high as that (2.49 mmolC4H4s/(s·molMo)) of the AC-based counterpart, and was 2.47 times as high as that (1.33 mmolC4H4s/(s·molMo)) of the catalysts supported by AC with the respective optimal Mo3Co1-loading amount, 16.90%Mo3Co1/AC. Analogous reaction-chemical behaviours were also observed in the case of pyrrole HDN. It was experimentally found that using the CNTs in place of AC as support of the catalyst caused little change in the apparent ac-tivation energy for the thiophene HDS or pyrrole HDN reaction, but led to a significant increase in the concentration of catalytically active Mo-species (Mo4 ) at the surface of the functioning catalyst. On the other hand, H2-TPD measurements revealed that the CNT-supported catalyst could reversibly adsorb a greater amount of hydrogen under atmospheric pressure at temperatures ranging from room temperature to about 673 K. This unique feature would help to generate microenvironments with higher stationary-state concentration of active hydrogen-adspecies at the surface of the functioning catalyst. Both factors mentioned above were favorable to increasing the rate of thiophene HDS and pyrrole HDN reactions.     

碳纳米管负载Co-Mo催化剂在孤岛减压渣油加氢裂化反应中的应用

采用等体积浸渍法制备了一系列不同Co/Mo原子比的碳纳米管（CNT）负载Co Mo催化剂。将该系列催化剂用于孤岛减压渣油加氢裂化反应,评价其催化效果,并在相同反应条件下与 γAl2O3负载Co-Mo催化剂的催化性能进行比较。结果表明,Co-Mo/CNT催化剂的催化效果略低于Co-Mo/γAl2O3催化剂。Co/Mo原子比对Co-Mo/CNT催化剂的催化效果有较大的影响。与相同载体的催化剂相比,当Co/Mo原子比为0.50时,Co-Mo/CNT催化剂具有最佳的催化效果,而Co-Mo/γAl2O3催化剂在Co/Mo原子比为0.35时具有最佳的催化效果。     

States of Carbon Nanotube Supported Mo-Based HDS Catalysts

The dispersion of the active phase and loading capacity of the Mo species on carbon nanotube (CNT) was studied by the XRD technique. The reducibility properties of Co-Mo catalysts in the oxide state over CNTs were investigated by TPR, while the sulfided Co-Mo/CNT catalysts were characterized by means of the XRD and LRS techniques. The activity and selectivity with respect to the hydrodesulfurization (HDS) performances on carbon nanotube supported Co-Mo catalysts were evaluated. It was found that the main active molybdenum species in the oxide state MoO3/CNT catalysts were MoO2, but not MoO3, as generally expected. The maximum loading before the formation of the bulk phase was lower than 6% (percent by mass, based on MoO3). TPR studies revealed that the active species in the oxide state Co-Mo/CNT catalysts were reduced more easily at relatively lower temperatures in comparison to those of the Co-Mo/γ-Al2O3 catalysts, indicating that the CNT support promoted or favored the reduction of the active species. The active species of a Co-Mo-0.7/CNT catalyst were more easily reduced than those of the Co-Mo/CNT catalysts with Co/Mo atomic ratios of 0.2, 0.35, and 0.5, respectively, suggesting that the Co/Mo atomic ratio has a great effect on the reducibility of the active species. It was found that the incorporation of cobalt improved the dispersion of the molybdenum species on the support, and a phenomenon of mobilization and re-dispersion had occurred during the sulfurization process, resulting in low valence state Mo3S4 and Co-MoS2.17 active phases. HDS measurements showed that the Co-Mo/CNT catalysts were more active than the Co-Mo/γ-Al2O3 ones for the desulfurization of DBT, and the hydrogenolysis/hydrogenation selectivity of the Co-Mo/CNT catalysts was also much higher than those of the Co-Mo/γ-Al2O3. The Co-Mo/CNT catalyst with a Co/Mo atomic ratio of 0.7 showed the highest activity, whereas the catalyst with a Co/Mo atomic ratio of 0.35 had the highest selectivity.     

Co-Mo/γ-Al2O3催化剂的原位红外光谱表征研究

采用CO和NO作为探针分子,应用原位红外光谱法(in-situ FT-IR)和程序升温还原(H₂-TPR)对Mo/γ-Al₂O₃和Co-Mo/γ-Al₂O₃加氢催化剂进行表征,并对催化剂进行了加氢脱硫(HDS)活性评价。实验结果表明,在Co-Mo/γ-Al₂O₃催化剂表面存在三个吸附位;在Mo/γ-Al₂O₃催化剂中加入助剂钴对钼吸附位起到显著的改性作用,并且引入新的活性中心,提高了催化剂的催化活性;随着钼含量的增加,活性中心数目逐渐增多;用CO-NO共吸附原位红外光谱研究了Co-Mo/γ-Al₂O₃催化剂表面活性中心的信息,证明不同的Mo中心分别吸附CO和NO,并将它们区分开来,解决了不同活性中心的光谱互相重叠的问题。     

Pt/γ-Al2O3催化剂活性位的表征及其噻吩加氢脱硫催化活性

A series of Pt/γ Al 2O 3 catalysts with different content of Pt were characterized by using low temperature FT IR spectroscopy of adsorbed CO, while their catalytic activity for HDS was investigated with thiophene as a model substrate. On the basis of the experimental results, it has been obtained that the pseudo zero order rate of the thiophene HDS reaction is well linearly proportional to the total area of the two IR bands at 2?080 and 1?850 cm -1 of CO adsorbed on Pt/γ Al 2O 3, and that the Pt sites for CO adsorption may be the active centers for thiophene HDS reaction.     

β-Mo2N0.78/γ-Al2O3催化剂的制备及其噻吩加氢脱硫活性的研究

以γ-Al2O3为载体，钼酸铵为氧化钼前驱体，采用在N2-H2气氛下的程序升温还原氮化反应，制备β-Mo2N0.78/γ-Al2O3催化剂，以噻吩为模型化合物，考察了该催化剂的加氢脱硫反应性能，以及反应温度、氢还原预处理和钴、镍助剂的引入等因素对催化剂活性的影响。结果表明，在320 ℃～400 ℃之间，随着反应温度的升高，催化剂的活性逐渐增加；预还原则降低了催化剂的活性；添加钴、镍均在一定负载量范围内可以改善β-Mo2N0.78/γ-Al2O3催化剂的加氢脱硫活性，但镍对催化剂活性的影响要小于钴。     

钴掺杂对碳化钼催化噻吩加氢脱硫性能的影响

以MoO3和CoMo混合氧化物为前驱体, 制备了碳化钼和碳化钼-钴催化剂, 采用XRD, BET, SEM和XPS等技术对其进行了表征, 研究了Co掺杂对碳化钼催化剂噻吩加氢脱硫性能的影响. 结果表明, 掺入适量的Co后制得的CoMo双金属混合氧化物为MoO3和CoMoO4的两相混合体, 经CH4/H2气氛程序升温还原碳化反应生成共生共存的Co-Mo2C, Co以金属细颗粒的形态均匀地分散在生成的Mo2C组分之间. 在共生过程中含Co物种的掺入可降低制备碳化钼所需要的还原碳化温度, 使制备的碳化钼颗粒变小, 比表面积增大, 表面Mo2+含量增多, 从而对碳化钼的噻吩加氢脱硫活性有较好的促进作用, Co的添加量以Co/Mo摩尔比为0.2左右较为适宜. 用化学共沉淀法制得的Co-Mo2C共生共存体系的噻吩加氢脱硫反应活性, 好于由金属Co与Mo2C机械混合法制得的Co+Mo2C二相共存体系. 这表明当两个活性相共存时, 只有经过相互共生过程才能发挥其最佳的协同效应.     

Ru—Co—Mo／Al2O3还原催化剂：CO和NO吸附的红外光谱研究

本文采用CO、NO作为探针分子,应用红外光谱法对其在还原态Mo/Al_2O_3,Co-Mo/Al_2O_3,Ru-Mo/Al_2O_3,Ru-Co-Mo/Al_2O_3系列催化剂上的吸附态进行了表征。CO和NO在Mo,Co,Ru中心上的吸附峰随着它们的担载量增加而增强。Co和Ru作为助剂对Mo中心的吸附能力产生显著不同的影响,增加Co担载量大大减少了Mo中心的吸附NO量,并且NO在Co中心上的吸附红外谱带1775,1860 cm~(-1)位移到1800,1879 cm~(-1);而增加Ru担载量则加强了CO和NO在Mo中心上的吸附量,并使得NO在Mo中心上的吸附红外谱带1706,1812 cm~(-1)红移至1679,1801 cm~(-1)。根据实验结果,本文分别对Co和Ru的助剂功能进行了讨论。     

Simultaneous operation of dibenzothiophene hydrodesulfurization and methanol reforming reactions over Pd promoted alumina based catalysts

In the current study simultaneous reactions of hydrodesulfurization(HDS) of dibenzothiophene(DBT) and reforming of methanol in a micro-autoclave reactor were studied over bi-metallic(Co-Mo/Al2O3 and Ni-Mo/Al2O3) and tri-metallic(Pd-Co-Mo/Al2O3 and Pd-Ni-Mo/Al2O3) catalyst systems which were prepared by incipient impregnation method.In situ hydrogen utilization and low Pd loadings were the major targets of this study.For comparison purpose,catalytic activity was separately determined for both the methanol reforming and HDS of DBT reactions as well.Ni based catalysts were confirmed with better activity than Co ones for both the reactions with Pd promoted ones ranking at the top i.e.Pd-Ni-Mo/Al2O3 > Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3 > Co-Mo/Al2O3 where Pd-Ni-Mo/Al2O3 showed 91% DBT conversion at 380 ℃ and 12 h reaction time.Some of the selected organic additives on catalytic activity were tested for their effect toward HDS reaction which was unique with close relation to their chemical nature.Reaction products were quantitatively and qualitatively analyzed via HPLC and GC-MS techniques respectively which helped in elucidating reaction mechanism.     

The studies of hydrodesulfurization activity over molybdenum catalysts supported on Al-MCM-41 modified by lanthanum

A series of lanthanum modified Al-MCM-41 substrates served as supports to prepare the Mo/La-Al-MCM-41 catalysts. The catalysts were characterized by XRD, BET, FT-IR, XPS, TPR and TPD, and their catalytic activities were determined for thiophene hydrodesulfurization (HDS).     

Ru作为Co—Mo／Al2O3加氢脱硫催化剂助剂的研究

用Ru改性的Ru-Co-Mo/Al_2O_3对噻吩加氢脱硫的催化性能进行了考察。结果表明,与Co-Mo/Al_2O_3相比,Ru-Co-Mo/Al_2O_3的加氢脱硫活性增高。通过CO、NO吸附的红外光谱实验证实,由于Ru的加入,吸附在Co和Mo中心上的特征谱带向低波数移动,且峰强度增强,这些结果提出了在硫化态Ru-Co-Mo/Al_2O_3上,Ru中心的部分d电子转移到Co、Mo中心的周围或由于Ru的存在促进了Co、Mo中心的还原。     

硫代硫酸铵预硫化的Mo/AC催化剂加氢脱硫性能的研究

采用等体积浸渍法将硫代硫酸铵(ATS)负载在Mo/AC催化剂上,制备了器外预硫化的Mo/AC-ATS催化剂;以噻吩加氢脱硫(HDS)为探针反应,考察了活化温度和活化时间对预硫化催化剂加氢脱硫活性的影响。研究发现,300 ℃下活化0.5 h所得到的预硫化催化剂具有最好的加氢脱硫活性。与传统硫化剂CS₂和DMDS硫化的催化剂相比,采用Mo/AC-ATS催化剂,在最佳活化条件下,噻吩转化率分别提高了34%和42%。XPS、TPR-MS和TEM等表征结果显示,预硫化的Mo/AC-ATS催化剂中Mo⁴⁺含量较高,这是其具有较高加氢脱硫活性的主要原因。     

1-辛烯在Co/CNTs催化剂上的氢甲酰化研究： 钌的促进作用

采用等体积浸渍法制备了碳纳米管负载的钴及钴-钌双金属催化剂，并以1-辛烯的氢甲酰化反应为探针，研究了所制催化剂的催化性能；用TEM、XRD、TPR、TG技术对催化剂的形貌、物相结构、还原行为和热稳定性进行了研究。结果表明，金属钌能够促进金属钴在碳纳米管上的均匀担载，并有助于金属钴的还原，降低了催化剂的还原温度。1-辛烯的氢甲酰化反应结果表明，少量钌的加入，可明显提高反应的转化率和C9-醛的选择性；在双金属催化剂中，金属催化剂的粒径更小，分布更均匀，钌的加入对钴金属催化剂有促进作用。     

Unsupported Molybdenum and Cobalt-Molybdenum Nitrides for Thiophene Hydrodesulfurization

The catalytic activity and the structure of unsupported Mo and CoMo nitrided catalysts were investigated. It was found that the structure and catalytic activity of the nitrided catalysts are influenced by the conditions of nitridation. Molybdenum oxynitrides are more active in hydrodesulfurization (HDS) of thiophene than MoS₂. The addition of cobalt to nitrided Mo improves its HDS activity, however, sulfided CoMo catalyst is still more active than the nitrided one. Synergy between Co and Mo for the nitrided unsupported CoMo catalyst exists at lower degree than for the sulfided form of CoMo.     

CO吸附原位红外光谱结合分子模拟计算研究FCC汽油加氢脱硫催化剂的选择性

以脱硫选择性不同的2组催化裂化汽油加氢脱硫催化剂为研究对象, 采用CO吸附原位红外光谱表征了2组催化剂的活性相特征, 并通过分子模拟计算方法比较了助剂Co加入前后噻吩和1-己烯在催化剂表面的电荷分布、吸附能及其加氢反应的活化能等, 探讨了助剂Co的加入对选择性加氢脱硫催化剂脱硫选择性的作用机理. 结果表明, 加氢脱硫催化剂CoMoS活性相的增加有利于提高催化剂的加氢脱硫/加氢降烯烃(HDS/HYD)选择性. 与1-己烯加氢位相比, Co的加入显著提高了噻吩分子加氢位的缺电子性, 噻吩在催化剂表面的吸附度增强, 显著降低噻吩加氢反应的能垒, 从而使噻吩加氢反应更易进行. 这也表明CoMoS为高HDS活性、高HDS/HYD选择性的活性相.     

高表面积复合氧化物Co-O-Si的制备及其催化1-己烯骨架异构和噻吩加氢脱硫活性

通过硝酸钴与硅酸钠共沉淀、辅以正丁醇干燥技术制备了具有原子分散度的Co-O-Si复合氧化物（Co/Si原子比 ≈ 0.65）,该催化剂具有较大的比表面积（562 m²/g）和较强表面酸性. 在硫化处理后,能够形成高度分散的硫化物活性组分,在模型汽油加氢处理反应中显示了较高的催化活性,在573 K时,噻吩的加氢脱硫活性可达99.4%,同时,1-己烯的骨架异构收率达到了35%. 该催化剂虽然不含Mo,其加氢脱硫活性可与工业催化剂Co-Mo/γ-Al₂O₃相当. 而在汽油深度加氢脱硫过程中,直链烯烃往往被加氢饱和,造成辛烷值损失. 该催化剂则可使部分直链烯烃发生骨架异构而生成异构烷烃,可减少深度加氢脱硫过程中的辛烷值损失.     

Weakening internal diffusion effect in selective hydrodesulfurization of FCC gasoline by novel designed eggshell CoMoS/Al2O3 catalysts

A simple method for preparation of presulfided eggshell CoMoS/γ-Al2O3 catalysts with sharp boundary is developed, through which the eggshell thicknesses of Co and Mo could be easily regulated by controlling the impregnation time. According to the results characterized by EDS, XRD, HRTEM and FT-IR of adsorbed CO, the active component structures, the nature and/or the amount of active sites on the eggshell catalyst are similar to these on the uniform catalyst. The evaluation results of the catalytic performance in selective hydrodesulfurization (HDS) of FCC gasoline show the presence of significant internal diffusion inhibition effect on HDS of S-compounds especially in the uniform catalyst. Compared with uniform catalyst, the eggshell catalyst could remarkably reduce such an internal diffusion inhibition effect due to a shortened diffusion path of the reactants, thus showing higher HDS activity and selectivity.     

Support effects on the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery

Effects of carbon nanotubes (CNT) and alumina (γ-Al2O3) supports on the catalytic activities of hydrodesulfurization (HDS) process over CoMo catalyst have been studied. XRD results indicated that the main active phases in CNT and γ-Al2O3 supported Co-Mo catalysts are MoO2 and MoO3, respectively. The TPR results reveal that the reduction peak temperatures of the active species on CNT supported Co-Mo catalyst is lower than those on alumina supported Co-Mo catalyst, indicating that the CNT supports favor the r...