New approach to unsupported ReS2 nanorod catalyst for upgrading of heavy crude oil using methane as hydrogen source

Highly active ReS₂ nanocatalysts were prepared by CVD method and characterized by XRD, BET -BJH, Raman spectroscopy, XPS, TPR, NH₃-TPD, SEM, and HRTEM techniques. Catalytic activities were used in upgrading heavy crude oil using methane as hydrogen source. The results showed a significant increase in API and decrease in sulfur and nitrogen content of crude oil. RSM technique was used to investigate the interactive effects of temperature (200–400 °C), pressure (20–40 bar) and dosage of nanocatalyst (0.5–2 wt. %) on the performance of HDS reaction. The results represent that the maximum predicted HDS activity (74.375%) was estimated under the optimal conditions (400 °C, 20 bars, and 2 wt % of nanocatalyst). Also, the effect of reaction temperature, pressure and dosage of ReS₂ nanorods catalyst on HDN of heavy crude oil was investigated and highest efficiency in the HDN process (93%) occurred at 400 °C and 40 bar using 2 wt % ReS₂.     

Mixed oxide supported hydrodesulfurization catalysts—a review

Support effects form important aspect of hydrodesulfurization (HDS) studies and mixed oxide supports received maximum attention in the last two decades. This review will focus attention on studies on mixed oxide supported Mo and W catalysts. For convenience of discussion, these are divided into Al₂O₃ containing mixed oxide supports, TiO₂ containing mixed oxide supports, ZrO₂ containing mixed oxide supports and other mixed oxide supports containing all the rest. TiO₂ containing mixed oxides received maximum attention, especially TiO₂–Al₂O₃ supported catalysts. A brief discussion about their prospects for application to ultradeep desulfurization is also included. An overview of the available literature with emphasis on research carried out in our laboratory form the contents of this publication.     

Kinetic study of the deep hydrodesulfurization of dibenzothiophene over molybdenum carbide supported on a carbon black composite: Existence of two types of active sites

Hydrodesulfurization (HDS) is part of the hydrotreating process, which is an ensemble of several reactions (HDN, HDO, HDS, etc.) taking place simultaneously at the industrial scale. Only sulfur is currently submitted to drastic Europeans specifications and conventional commercial catalysts cannot reach the specifications at low cost. This paper presents the behavior of a potential substitute catalyst tested for the deep HDS of a model molecule such as the dibenzothiophene (DBT). The substitute is molybdenum carbide supported on a mesoporous carbon black composite of surface area 240 m² g⁻¹. A global kinetic study of the deep HDS of DBT (300 ppm S) was performed at 623 K and 5.0 MPa and a global kinetic model was proposed as well as global rate constants were calculated to obtain theoretical plots of concentration versus contact time to compare with the experimental data. The kinetic model and global kinetic orders were confirmed as an acceptable correlation was found between calculated and experimental data. Furthermore, the determination of the global kinetic orders indicated that two types of active sites must be present on the surface in order to explain the observed results.     

The morphology of MoS2, WS2, Co–Mo–S, Ni–Mo–S and Ni–W–S nanoclusters in hydrodesulfurization catalysts revealed by HAADF-STEM

HAADF-STEM studies have provided detailed morphological insight regarding MoS₂, WS₂, Co–Mo–S, Ni–Mo–S and Ni–W–S nanostructures in graphite-supported catalysts. It is found that the technique allows the catalytically active edges to be imaged even for single layer metal sulfide structures. Unpromoted MoS₂ and WS₂ are predominantly present as slightly truncated triangular clusters containing only a single S–M–S layer (M = Mo, W). The addition of promoter atoms results in more heavy truncations consistent with the expected tendency for the Co–Mo–S structures to expose promoted S-type edges at the expense of unpromoted Mo-type edges. However, the HAADF-STEM (High-Angle Annular Dark-field Scanning Transmission Electron Microscopy) results show for the first time that Co–Mo–S and Ni–W–S may also expose extended high index truncations.     

Performance of fluorine-added CoMoS/Al2O3 prepared by sonochemical and chemical vapor deposition methods in the hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

The performance of a new type of CoMoS/Al₂O₃ catalyst, with added fluorine and prepared by sonochemical and chemical vapor deposition (CVD) methods, was investigated in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). The catalyst, which was designed to contain optimum amounts of fluorine and cobalt, exhibited a higher activity, ca. 4.6 times higher activity particularly in the HDS of 4,6-DMDBT, than a fluorine-free catalyst prepared by a conventional impregnation method. The enhanced activity of the new catalyst can be attributed to the cumulative effects of individual factors involved in the catalyst preparation. That is, the use of a sonochemical synthesis led to a high dispersion of small MoS₂ crystallites on the alumina, and the addition of the Co species to the catalyst by CVD caused a close interaction between the Co species and the MoS₂ crystallites to produce numerous CoMoS species, which are the catalytically active species for HDS. The addition of fluorine increased the amounts of acidic sites in the catalyst, which promoted hydrogenation (HYD) route to a greater extent than the direct desulfurization (DDS) route in DBT HDS and both HYD and DDS routes to similar extents in the case of 4,6-DMDBT HDS. Accordingly, the addition of fluorine led to a greater increase in catalytic activity for 4,6-DMDBT HDS than for DBT HDS.     

A comparative study on the effect of promoter content of hydrodesulfurization catalysts at different evaluation scales

CoMo and NiMo supported Al₂O₃ catalysts have been investigated for hydrotreating of model molecule as well as industrial feedstock. Activity studies were carried out for thiophene and SRGO hydrodesulfurization (HDS) in an atmospheric pressure and batch reactor respectively. These activities on sulfided catalysts were evaluated as a function of promoter content [M/(M + Mo) = 0.30, 0.34, 0.39; M = Co or Ni] using fixed (ca. 8 wt.%) molybdenum content. The promoted catalysts were characterized by textural properties, XRD, and temperature programmed reduction (TPR). TPR spectra of the Co and Ni promoter catalysts showed that Ni promotes the easy reduction of Mo species compared with Co. With the variation of promoter content NiMo catalyst was found to be superior to CoMo catalyst for gas oil HDS, while at low-promoter content the opposite trend was observed for HDS of thiophene. The behavior was attributed to the several reaction mechanisms involved for gas oil HDS. A nice relationship was obtained for hydrodesulfurized gas oil refractive index (RI) and aromatic content, which corresponds to the Ni hydrogenation property.     

Hydrodesulfurization of model diesel using Pt/Al2O3 catalysts prepared by supercritical deposition

Pt/Al₂O₃ catalysts with Pt loadings ranging from 0.5 to 11 wt.% were synthesized by supercritical carbon dioxide (scCO₂) deposition method. Transmission electron microscopy (TEM) images showed that the synthesized catalysts contained small Pt nanoparticles (1–4 nm in diameter) with a narrow size distribution, no observable agglomeration, and uniformly dispersed on the alumina support. The catalysts were found to be active for hydrodesulfurization of dibenzothiophene (DBT) dissolved in n-hexadecane (n-HD) without sulfiding the metal phase. The reaction proceeded only via the direct hydrogenolysis route in the temperature range 310–400 °C and at atmospheric pressure. The activity increased with increasing the metal loading. Increasing [H₂]₀/[DBT]₀ by either increasing [H₂]₀ or decreasing [DBT]₀, increased the DBT conversion. At a fixed weight hourly space velocity and feed concentration, conversion did not increase with increasing temperature beyond 330 °C. The presence of toluene inhibited the catalyst activity presumably due to competitive adsorption between DBT and toluene. Under the operating conditions, the reaction was far from equilibrium.     

Effect of water on HDS of DBT over a dispersed Mo catalyst using in situ generated hydrogen

A novel process was developed for the bitumen emulsion upgrading, wherein emulsion breaking and upgrading occurred in the same reactor using H₂ generated in situ from the water in the emulsion via the water gas shift reaction (WGSR). In this study, dibenzothiophene (DBT) was chosen as a model compound to investigate the effect of water and in situ H₂ on hydrodesulfurization (HDS). All the experiments were performed in a 1-L autoclave reactor at temperatures between 300 and 380 °C using in situ H₂ and ex situ H₂ (externally supplied H₂) over a dispersed Mo catalyst formed from phosphomolybdic acid (PMA). At very low water content, water was found to promote the HDS reaction in the ex situ H₂ run probably because it facilitates the formation of more active dispersed MoS_x species. At higher water content, however, water inhibits every individual reaction in the reaction network in the HDS of DBT, blocking the hydrogenation pathway more than the hydrogenolysis pathway. The relative reactivity of the in situ and ex situ H₂ depends on the water content present in the reaction system. At an optimized mole ratio of H₂O:CO (1.35), higher HDS activity was observed in the in situ H₂ run compared to ex situ H₂ run, and particularly, the hydrogenation pathway was promoted in the in situ H₂ run.     

Removal of refractory S-containing compounds from liquid fuels on novel bifunctional CoMo/HMS catalysts modified with Ti

This study shows that titanium incorporation into hexagonal mesoporous silica (HMS) material has a positive effect on the activity of supported CoMo catalysts in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4-ethyl,6-methyl-dibenzothiophene (4E6MDBT). All catalysts showed the highest activity in the HDS of DBT than in the HDS of 4E6MDBT. The low reactivity observed in the HDS of 4E6MDBT is caused by the steric hindrance of the two alkyl groups at positions 4 and 6. The HDS of DBT over Ti-free catalyst proceeds exclusively via the direct desulfurization (DDS) route whereas over Ti-containing catalysts proceed via DDS (main route) and hydrogenation (HYD) pathway. The catalyst with a Si/Ti = 40 (molar ratio) was the most active in the HDS of DBT. A further increase in the Ti-content led to a decrease in Brønsted acidity and the S_BET specific area of the catalysts, which implies a decrease in the bifunctional character of the catalysts. Raman spectroscopy demonstrated that Ti-incorporation into HMS material leads to a decrease in the degree of polymerization of Mo species, and this implies a better dispersion of MoS₂, in good agreement with the XPS measurements. Regarding the HDS-resistant 4E6MDBT, the HDS reaction over the Ti-free catalyst was found to proceed exclusively via the dealkylation (DA) route. After Ti-incorporation into HMS material, additional acid-catalyzed isomerization occurs. With respect to industrial sample, the catalyst with Si/Ti = 40 showed lower intrinsic activity as well as greater selectivity toward isomerization route products.     

纳米自组装大孔催化剂对催化裂化柴油的加氢催化性能

采用二次纳米自组装方法制备出具有大孔道的催化剂0106、1227,两种纳米自组装催化剂在30～100 nm孔径分布分别占11％、28％。纳米自组装催化剂具有低堆积密度和高金属含量等特点。在10 mL固定床微型反应器中,以镇海炼化的催化裂化柴油为原料,在温度360℃、压力7 M Pa、氢油体积比为600∶1、体积空速为1．5 h-1条件下,考察了两种纳米自组装催化剂的初活性评价,并与现有工业催化剂作对比。结果表明,两种纳米自组装催化剂0106、1227可使催化裂化柴油的含硫质量分数从12400μg/g分别最低降到483、283μg/g ,最高脱硫率分别为96．10％、97．71％;将含氮质量分数从1507μg/g分别最低降到35．7、14．0μg/g ,最高脱氮率分别为97．63％和99.00％;其最高芳烃饱和率分别为67．99％和68．88％;而参比催化剂仅可使催化裂化柴油的含硫质量分数从12400μg/g最低降到537μg/g ,最高脱硫率为94．57％;将含氮质量分数从1507μg/g最低降到64．6μg/g ,最高脱氮率为95．54％;其最高芳烃饱和率为65．65％。