Hydrodesulfurization of dibenzothiophene over alumina-supported nickel molybdenum phosphide catalysts

The activity of nickel molybdenum phosphide catalysts was studied for the hydrodesulfurization of dibenzothiophene at 573 K and total pressure of 2.0 MPa. The Al₂O₃-supported NiMo phosphide catalysts were prepared by successive and simultaneous methods. The effect of the reduction temperature on the catalyst activity was also studied. The simultaneous preparation was determined to be the best method for the preparation of the active supported catalyst for dibenzothiophene HDS. The 623 K-reduced catalyst had the highest HDS rate of the catalysts. Nickel migrated from the inside to the surface during the reaction and promoted the HDS activity. The active species in the dibenzothiophene HDS and the oxidation states of Mo, Ni and P in the catalyst before and after reaction and of S after the reaction were studied on the basis of an XPS analysis.     

Ni2P催化剂的制备及其在加氢脱硫的研究进展

现在油品重质化越来越严重,为了满足环境保护局和人们的要求,对油品加氢脱硫已是一项急迫的任务。过渡金属磷化物具有优异的加氢脱硫活性和稳定性,尤其是Ni2P催化剂,将成为催化材料领域研究的热点。本文综述了Ni2P催化剂制备方法和加氢脱硫活性。Ni2P催化剂有望成为继硫化物、碳化物催化剂之后的又一代深度加氢脱硫催化剂。     

Performance of CoMoS catalysts supported on nanoporous carbon in the hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

A new type of nanoporous carbon with a large surface area and mesoporosity was prepared and used as a support for a hydrodesulfurization (HDS) catalyst. The overall activity of CoMoS catalysts for the HDS of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) is affected by the type of support used for preparing the catalyst and decreases in the order of CoMo/(nanoporous carbon)>CoMo/(activated carbon)>CoMo/Al₂O₃. The surface area of activated carbon is the largest among these three types of supports but is significantly lowered after metal loading during the preparation of the catalyst. On the other hand, the surface areas of the other two supports are largely preserved after metal loading. The intrinsic activity of the catalysts, estimated by dividing the overall HDS rate by the amount of NO adsorbed on the catalyst, shows a trend that is different from that for the overall activity, and follows the order of CoMo/(nanoporous carbon)≈CoMo/Al₂O₃>CoMo/(activated carbon). The low intrinsic activity of CoMo/(activated carbon) compared to that of the other two catalysts, particularly in the case of 4,6-DMDBT HDS, is obtained because the diffusion of reactants into the catalyst pores is significantly limited. This is not observed with other catalysts supported on nanoporous carbon and alumina. From the results of this study, we conclude that nanoporous carbon is a promising support for HDS catalysts, compared to conventional supports such as alumina and activated carbon, because it has a large surface area and a high mesoporosity, both of which are beneficial to the preparation of highly dispersed metal catalysts without significant pore blocking due to the dispersed metal particles.     

Kinetics of dibenzothiophene hydrodesulfurization over MoS2 supported catalysts: modelization of the H2S partial pressure effect

The influence of H₂S partial pressure over the catalytic activity of MoS₂, supported on three different oxides: Al₂O₃, TiO₂ and ZrO₂, was studied in the hydrodesulfurization of dibenzothiophene (DBT). A complex inhibiting effect is observed and two orders of reaction relative to H₂S were determined: −1/2 and 0, as a function of H₂S partial pressure. The experimental results are in good agreement with the kinetic models whereby the DBT transformation takes place through a dihydrogenated intermediate (DH-DBT). The associated mechanism considers that the heterolytic dissociative adsorption of H₂ and H₂S occurs over an unsaturated Mo ion and over a stable sulfur ion.     

Mesoporous molecular sieve MCM-41 supported Co–Mo catalyst for hydrodesulfurization of petroleum resids

In this work, we explored the potential of mesoporous zeolite-supported Co–Mo catalyst for hydrodesulfurization of petroleum resids, atmospheric and vacuum resids at 350–450°C under 6.9 MPa of H₂ pressure. A mesoporous molecular sieve of MCM-41 type was synthesized; which has SiO₂/Al₂O₃ ratio of about 41. MCM-41 supported Co–Mo catalyst was prepared by co-impregnation of Co(NO₃)₂·6H₂O and (NH₄)₆Mo₇O₂₄ followed by calcination and sulfidation. Commercial Al₂O₃ supported Co–Mo (criterion 344TL) and dispersed ammonium tetrathiomolybdate (ATTM) were also tested for comparison purposes. The results indicated that Co–Mo/MCM-41(H) is active for HDS, but is not as good as commercial Co–Mo/Al₂O₃ for desulfurization of petroleum resids. It appears that the pore size of the synthesized MCM-41 (28 Å) is not large enough to convert large-sized molecules such as asphaltene present in the petroleum resids. Removing asphaltene from the resid prior to HDS has been found to improve the catalytic activity of Co–Mo/MCM-41(H). The use of ATTM is not as effective as that of Co–Mo catalysts, but is better for conversions of >540°C fraction as compared to noncatalytic runs at 400–450°C.     

MCM-41负载Pt-Al催化剂的制备及其表征

以介孔硅MCM-41为载体、无水乙醇为溶剂、氯化铝为促进剂,采用浸渍法制备了Pt-Al/MCM-41催化剂。利用XRD、XPS、TEM、FTIR、N₂吸附-脱附、NH₃-TPD对催化剂进行了表征,重点讨论了不同Pt-Al负载顺序对催化剂结构和性能的影响,并将其应用于硅氢加成反应。结果表明,Pt和Al的负载顺序不同会影响催化剂的有序度、Pt颗粒的分散程度和酸性,其中,Pt-Al/MCM-41催化剂的有序度和Pt颗粒的分散程度相对最好,酸性相对较强。在七甲基三硅氧烷与烯丙醇聚氧乙烯醚的硅氢加成反应中,不同催化剂对七甲基三硅氧烷的转化率影响顺序为Pt-Al/MCM-41 > Pt+Al/MCM-41 > Al-Pt/MCM-41 > Pt/MCM-41。     

Hydrodesulfurization of dibenzothiophene over supported and unsupported molybdenum carbide catalysts

A series of γ-Al₂O₃ supported molybdenum carbides [carbided Mo/γ-Al₂O₃ (MCS), Co-Mo/γ-Al₂O₃ (CMCS), and Ni-Mo/γ-Al₂O₃ (NMCS)] and unsupported molybdenum carbide (MCUS) were prepared by the temperature-programmed carburization of their corresponding molybdenum nitrides with 20 % CH₄/H₂. XRD and SEM studies show that unsupported molybdenum carbide catalyst possesses a typical crystalline Mo₂C (FCC structure), while supported molybdenum carbide catalysts possess highly dispersed surface molybdenum carbide species on an alumina oxide support. The results of dibenzothiophene (DBT) hydrodesulfurization over molybdenum carbide catalysts show that the reactivity is strongly dependent on the type of catalyst. Supported molybdenum carbide catalysts possess a higher reactivity than the unsupported molybdenum carbide catalyst. In addition, Co or Ni promoted, supported molybdenum carbide catalyst possesses a higher reactivity than the unpromoted, supported molybdenum carbide catalyst. The reactivity, which is also dependent on the reaction conditions, increases with increasing reaction temperature and pressure and contact time. The CO uptakes of the molybdenum carbide catalysts correlate well with overall activity (total rate) for DBT hydrodesulfurization. The major reaction product is biphenyl, with cyclohexylbenzene next in abundance regardless of the type of catalysts and reaction conditions. It was also found that the molybdenum carbide catalysts exhibit stable initial reactivity due to the stable and weak acidic characteristics of these catalysts.     

Sulfided Mo and CoMo supported on zeolite as hydrodesulfurization catalysts: transformation of dibenzothiophene and 4,6-dimethyldibenzothiophene

The hydrodesulfurization (HDS) of dibenzothiophene (DBT) and of 4,6-dimethyldibenzothiophene (4,6-DMDBT) was carried out on sulfided Mo and CoMo on HY catalysts, and also on sulfided Mo and CoMo on alumina catalysts (fixed bed reactor, 330°C, 3 MPa hydrogen pressure). On all the catalysts, the two reactants transformed through the same parallel pathways: direct desulfurization (DDS) leading to biphenyl-type compounds, and desulfurization after hydrogenation (HYD) leading first to tetrahydrogenated intermediates, then to cyclohexylbenzene-type products. However, additional reactions were observed with the zeolite-supported catalysts, namely methylation of the reactants, cracking of the desulfurized products, and, in the case of 4,6-DMDBT, displacement of the methyl groups and transalkylation. The global activity of Mo/zeolite in DBT or 4,6-DMDBT transformation as well as its activity for the production of desulfurized products (HDS) were much higher than those of Mo/alumina. On the other hand, cobalt exerted a promoting effect on the activity in the transformation of DBT or 4,6-DMDBT of all the molybdenum catalysts. However, this effect was much less significant with the zeolite support than with the alumina support, which indicated that the promoter was not well associated to molybdenum on the zeolite support. Therefore, the activity of CoMo/zeolite in the HDS of DBT was much lower than that of CoMo/alumina. On the contrary, in the case of 4,6-DMDBT CoMo/zeolite was more active in HDS than CoMo/alumina. This increase in HDS activity was attributed to the transformation of 4,6-DMDBT into more reactive isomers through an acid-catalyzed methyl migration. The consequence was that on the zeolite-supported catalyst 4,6-DMDBT was more reactive than DBT.     

Ni2P/Al-MCM-41催化剂的制备及其加氢脱硫性能

以硅酸钠为硅源、硫酸铝为铝源、十六烷基三甲基溴化铵（CTAB）作模板剂,采用共沸蒸馏与超声波分散技术相结合的方法制备了介孔分子筛Al-MCM-41。以Al-MCM-41为载体、硝酸镍和磷酸氢二氨为原料,采用超声波振荡、程序升温还原法制备了Ni₂P/Al-MCM-41催化剂,并对Al-MCM-41和Ni₂P/Al-MCM-41进行了傅里叶变换红外光谱、比表面积测定、X射线衍射、扫描电镜表征。考察了Ni₂P/Al-MCM-41催化剂对噻吩加氢脱硫的催化性能。结果表明：采用超声波制得的Al-MCM-41其比表面积、孔容和孔径明显高于常规搅拌制得的Al-MCM-41,共沸蒸馏制得的Al-MCM-41其比表面积、孔容和孔径高于未共沸蒸馏的Al-MCM-41;在反应时间为5 h、548 K、3.5 MPa条件下,Ni₂P/Al-MCM-41催化剂对噻吩加氢脱硫的转化率接近100%。     

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.     

A simple method to prepare highly active and dispersed Ni/MCM-41 catalysts by co-impregnation

A simple method for preparing highly active and dispersed supported metal catalysts was developed by co-impregnation. Compared with conventional wetness impregnation, addition of moderate ethylene glycol into the metal nitrate aqueous solution could enhance interaction with MCM-41 surface, resulting in formation of very small NiO particle size (3.5 nm) and high dispersion of the active phase. The Ni/MCM-41 catalysts using co-impregnation exhibited excellent catalytic performance for low temperature hydrogenation of naphthalene with 100% conversion at 55 °C, which could rival the activity of commercial Raney Ni catalyst. The obtained catalysts were characterized by XRD, TEM, TG-DSC, FT-IR, BET and TPR.     

Hydrodesulfurization of dibenzothiophene over exfoliated MoS2 catalyst

The activity of exfoliated MoS₂ in hydrodesulfurization of dibenzothiophene (DBT) was compared to crystalline MoS₂, molybdenum naphthenate (MoNaph) derived MoS₂ and ammonium heptamolybdate (AHM) derived MoS₂. The prepared catalysts had significantly different morphologies, as described by the crystallite stack height and slab length, measured by both XRD and TEM. These data were used to estimate the fraction of rim and edge sites in the crystallites. The DBT turnover frequency (TOF) was highest on the exfoliated MoS₂, whereas the selectivity for hydrogenolysis and hydrogenation reactions was shown to correlate with the fraction of rim or edge sites. Selectivity for hydrogenolysis increased as the fraction of edge sites increased.     

The effect of neodymium content on dibenzothiophene HDS performance over a bulk Ni2P catalyst

Neodymium (Nd)-modified Ni₂P catalysts (Nd_xNi₂P, where x is the molar fraction of Nd to Ni₂P) have been successfully prepared. An appropriate amount of Nd can dramatically increase the surface area and promote the formation of smaller and highly dispersed Ni₂P particles. The Nd_xNi₂P catalyst with x = 0.10 exhibited the highest dibenzothiophene hydrodesulfurization activity of 97.4%, which is an increase of 35% when compared with that found for bulk Ni₂P.     

Comparison of molybdenum carbide and tungsten carbide for the hydrodesulfurization of dibenzothiophene

The molybdenum and tungsten carbides (Mo₂C and W₂C) were synthesized, characterized and tested in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The phase purity of these catalysts was established by X-ray diffraction (XRD), and the surface properties were determined by N₂ BET specific surface area (Sg) measurements, CO chemisorption and high-resolution transmission electron microscopy (HRTEM). The activities of catalysts were determined during the HDS of DBT at a temperature of 613 K and under a 6 MPa total pressure. Both molybdenum and tungsten carbides were active in HDS of DBT. The reactivity studies showed that molybdenum carbide was more active than tungsten carbide related to weight. However, W₂C was shown to possess stronger hydrogenating properties.     

负载型功能化离子液体的催化性能

用MCM-41为载体,通过化学法合成了负载羟基功能化的咪唑类离子液体催化剂HIILsBr/MCM-41,考察了在碳酸丙烯酯（PC）合成中的催化作用。考察了负载温度、负载时间、离子液体与载体的配比、溶剂等负载反应条件对催化剂催化性能的影响。结果表明： 在115 ℃,2.0 MPa,4 h条件下,PC产率为89.9%,选择性为99.5%。     

Preparation and characterization of highly active ruthenium sulphide supported catalysts

Ruthenium sulphide catalysts supported on alumina were prepared using different precursor salts [ruthenium (III) chloride trihydrate, ruthenium (III) acetylacetonate and triruthenium dodecacarbonyl] and sulphided under various atmospheres. The properties of the catalysts in thiophene hydrodesulphurization are interpreted in relation to the XPS characterizations. These results show the importance of the sulphidation step in the absence of hydrogen in order to obtain a well sulphided, well dispersed and highly active catalyst.On leave from the Central Research Institute for Chemistry of the Hungarian Academy of Sciences, 1025 Budapest, Pusztaszeri ut 56–57, Hungary.     

Thioreduction of cyclopentanone and hydrodesulfurization of dibenzothiophene over sulfided nickel or cobalt-promoted molybdenum on alumina catalysts

Two series of sulfided Ni or Co promoted Mo/alumina catalysts, having different Ni or Co loadings, were characterized by their activities for the transformation of cyclopentanone into cyclopentanethiol (flow reactor, 220°C, atmospheric pressure) and for the hydrodesulfurization of dibenzothiophene (flow reactor, 340°C, 3 MPa hydrogen pressure). The addition of the promoter increased significantly the activity of the Mo/alumina catalyst for both reactions, up to a maximum obtained with the catalysts having a (promoter)/(promoter+Mo) molar ratio equal to 0.3–0.4. This increase in activity was due in part to an increase in the hydrogenating properties of the Mo/alumina catalyst. However, an additional modification of the catalyst (basic and nucleophilic properties) must be considered to account for the spectacular effect of the promoter on the rate of the dibenzothiophene direct desulfurization reaction.     

Ni_2P/MCM-41催化剂的制备及其加氢脱氧反应工艺条件的优化

采用程序升温还原次磷酸盐法合成了Ni2P/MCM-41催化剂,并结合X射线衍射(XRD)、N2等温吸附手段对催化剂进行了表征。以苯并呋喃(BF)为模型化合物进行加氢脱氧(HDO)反应性能研究。考察了反应温度、反应压力、空速、氢油比对Ni2P/MCM-41 HDO反应的影响。反应温度300 oC,反应压力3 MPa,氢油比500(V/V),空速4.0 h-1时,连续反应100 h,BF HDO活性稳定在90%以上。     

Effect of the hydrogen spillover on the selectivity of dibenzothiophene hydrodesulfurization over CoSx/γ-Al2O3, NiSx/γ-Al2O3 and MoS2/γ-Al2O3 catalysts

Dibenzothiophene (DBT) hydrodesulphurization (HDS) reaction at 3 MPa and 325–375 °C on Mo/γ-Al₂O₃ single-bed and Me/γ-Al₂O₃//SiO₂//Mo/γ-Al₂O₃ (Me = Co or Ni) double-bed catalysts were investigated. Results indicate that ratio cyclohexylbenzene (CHB)/biphenyl (BP) or selectivity is higher when using double-beds rather than a single-bed. Synergy in dibenzothiophene hydrodesulphurization on Co//Mo and Ni//Mo double-beds is also detected. Changes in selectivity and conversion are attributed to the action of spillover hydrogen (Hso) formed in the first bed that reaches the second bed.