Cumene hydrocracking and thiophene HDS on niobia-supported Ni, Mo and Ni–Mo catalysts

Results are reported on the XPS characterization and catalytic activity in cumene hydrocracking (2.8 MPa, 623 K) and thiophene HDS (2.8 MPa, 523–573 K) of sulfided Ni, Mo and Ni–Mo catalysts supported on alumina and on pure and phosphated niobia. From the XPS results, evidence was obtained for the formation of a surface niobium sulfide with stoichiometry close to NbS₂ during catalyst sulfidation. Sintering of supported nickel during sulfidation occurred to a much smaller extent with the niobia-supported catalysts than with the alumina-supported ones. The dispersion of alumina-supported molybdenum was little influenced by sulfidation, whereas, with the niobia supports, the molybdenum surface concentration increased with sulfidation. With the alumina support, the Ni–Mo combination caused the dispersion of the sulfided nickel to be improved, possibly due to formation of a NiMoS phase. This was not observed with the niobia-supported catalysts.

Reasonable linear correlations were also found between the intrinsic activity for cumene hydrocracking and the amount of sulfided niobium in the catalysts, but the catalysts supported on phosphated niobia had a higher intrinsic activity than the ones supported on pure niobia. In thiophene HDS, the activity of the niobia-supported nickel catalysts was much larger than the activity of the alumina-supported ones. The activity of the niobia-supported molybdenum catalysts was smaller than that of the alumina-supported catalyst. With the bimetallic catalysts, little or no synergy was observed with the niobia-supported catalysts, in sharp contrast with the alumina case.     

Effect of the electronic properties of Mo sulfide phase on the hydrotreating activity of catalysts supported on Al2O3, Nb2O5 and Nb2O5/Al2O3

Activity in thiophene hydrodesulfurization (HDS) and in the three routes of 2,6-dimethylaniline (DMA) decomposition was examined on Mo sulfide catalysts supported on Al₂O₃, Nb₂O₅ and Nb₂O₅–Al₂O₃. Catalysts activity is enhanced when Mo phase is deposited on niobium-containing support. For HDS and for the hydrogenation route of DMA decomposition, the niobium-containing support strongly contributes to the catalyst activity whereas the activity of the Mo phase per Mo atom decreases with the increase of niobium amount in the support. By contrast, as for the DMA route, which leads to xylene formation (XYL), the activity of the Mo sulfide phase per Mo atom is strongly enhanced. The electronic properties of the MoS₂ phase were studied by means of IR spectroscopy of CO adsorption. Comparison of ν(CO/Mo) wavenumbers reveals an upward shift when Mo sulfide phase is deposited on Nb-containing support. The modification of the electronic properties of the sulfide phase is related to an interaction Mo–Nb either through the formation of a mixed Mo–Nb sulfide phase, or through the interaction MoS₂ slabs – support whose strength depends on the support acidity. Hence, the beneficial effect for xylene formation route is attributed to a decrease of the electron density of the Mo sulfide phase that should strengthen the DMA adsorption on the sulfide phase.     

Mesoporous silica–alumina as support for Pt and Pt–Mo sulfide catalysts: Effect of Pt loading on activity and selectivity in HDS and HDN of model compounds

The potential of mesoporous silica–alumina (MSA) material as support for the preparation of sulfided Pt and Pt–Mo catalysts of varying Pt loadings was studied. The catalysts were characterized by their texture, hydrogen adsorption, transmission electron microscopy, temperature programmed reduction (TPR) and by activity in simultaneous hydrodesulfurization (HDS) of thiophene and hydrodenitrogenation (HDN) of pyridine. Sulfided Pt/MSA catalysts with 1.3 and 2 wt.% Pt showed almost the same HDS and higher HDN activities per weight amounts as conventional CoMo and NiMo/Al₂O₃, respectively. The addition of Pt to sulfided Mo/MSA led to promotion in HDS and HDN with an optimal promoter content close to 0.5 wt.%. The results of TPR showed strong positive effect of Pt on reducibility of the MoS₂ phase which obviously reflects in higher activity of the promoted catalysts. The activity of the MSA-supported Pt–Mo catalyst containing 0.5 wt.% Pt was significantly higher than the activity of alumina-supported Pt–Mo catalyst. Generally, Pt–Mo/MSA catalysts promoted by 0.3–2.3 wt.% Pt showed lower HDS and much higher HDN activities as compared to weight amounts of CoMo and NiMo/Al₂O₃. It is proposed that thiophene HDS and pyridine hydrogenation proceed over Pt/MSA and the majority of Pt–Mo/MSA catalysts on the same type of catalytic sites, which are associated with sulfided Pt and MoS₂ phases. On the contrary, piperidine hydrogenolysis takes place on different sites, most likely on metallic Pt fraction or sites created by abstraction of sulfur from MoS₂ in the presence of Pt.     

Hydrodesulfurization over intrazeolite molybdenum nitride clusters prepared by using hexacarbonyl molybdenum as a precursor

Metal nitride catalysts have received extensive attention because of their potential high performance for hydrodesulfurization (HDS). In the present study, highly dispersed Mo nitride clusters having a composition of Mo₂N are synthesized in zeolite pores by means of a CVD method using Mo(CO)₆ as a precursor. The catalytic properties of the molybdenum nitride catalysts for the HDS of thiophene are compared with that of an intrazeolite molybdenum sulfide catalyst. The molybdenum nitride catalyst shows a more stable thiophene HDS activity than the molybdenum sulfide catalyst. Molybdenum nitride clusters are only partially sulfided even after a prolonged HDS reaction.     

Effect of EDTA on hydrotreating activity of CoMo/γ-Al2O3 catalyst

γ-Al₂O₃ supported Co (0–4.5 wt%) Mo (9.0 wt%) sulfide catalysts were prepared in the presence and the absence of ethylenediaminetetraacetic acid (EDTA). The hydrodenitrogenation (HDN) activity of these catalysts was studied in the model reaction of 2,6-dimethylaniline (DMA) at 300 °C under 4 MPa. The CoMo/Al₂O₃ catalysts prepared with the EDTA showed higher HDN of DMA than those prepared without EDTA. The maximum of 36% increase in rate constant of HDN of DMA was observed over the catalyst with 3% Co prepared using EDTA. The FT-IR spectroscopy of adsorbed CO on CoMo catalysts showed that EDTA addition promoted the formation of catalytically active “CoMoS” phase as evidenced from increases in intensity of band at 2070 cm⁻¹, which is maximum for 3% Co loaded catalysts. The HDN and hydrodesulfurization (HDS) activity of 3% Co loaded catalyst prepared using EDTA was tested and compared with those catalyst prepared without EDTA in a trickle bed reactor using heavy gas oil derived from Athabasca bitumen in the temperature range 370–400 °C and 8.8 MPa. Improved HDN and HDS conversion of heavy gas oil was obtained for the catalyst prepared with EDTA.     

The effects of fluorine, phosphate and chelating agents on hydrotreating catalysts and catalysis

The effects of fluorine, phosphate and chelating agents on hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) are reviewed. All three additives enhance the activity of NiMo/Al₂O₃ catalysts in HDN but have only a slightly positive or even a negative effect on the HDS activity of CoMo/Al₂O₃ and NiMo/Al₂O₃ catalysts. The positive effect on HDN is due to the enhancement of the hydrogenation of aromatic rings. On the other hand, these three additives diminish the rates of C–N bond breaking and alkene hydrogenation reactions.

All three additives are hard basic ligands that may interact strongly with hard acids such as coordinatively unsaturated Al³⁺ cations on the alumina surface. A strong interaction with the alumina support has several effects. First, molybdate and tungstate anions are no longer strongly bonded to the support and are predominantly present as polyanions, which can be easily sulfided to MoS₂ and WS₂ crystallites. The weaker interaction with the smaller support surface also leads to larger MoS₂ and WS₂ crystallites with a lower dispersion. Second, the Ni²⁺ and Co²⁺ cations will also interact more weakly with the alumina, and this makes the formation of Ni and Co promoter atoms in the catalytically active Ni–Mo–S and Co–Mo–S phases more efficient. Third, the weaker interaction of Mo and W with the support leads to a higher stacking of the MoS₂ and WS₂ crystallites and, thus, to the more active type II Ni–Mo–S and Co–Mo–S phases. The increased stacking is beneficial for geometrically demanding reactions such as the hydrogenation of aromatics. For less demanding reactions, such as alkene hydrogenation, aliphatic C–N bond breaking and thiophene HDS, the loss in dispersion is important.     

A model catalyst approach to the effects of the support on Co–Mo hydrodesulfurization catalysts

Co–Mo model sulfide catalysts, in which CoMoS phases are selectively formed, were prepared by means of a CVD technique using Co(CO)₃NO as a precursor of Co. It is shown by means of XPS, FTIR and NO adsorption that CoMoS phases form selectively when the Mo content exceeds monolayer loading. A single exposure of MoS₂/Al₂O₃ to a vapor of Co(CO)₃NO at room temperature fills the edge sites of the MoS₂ particles. It is suggested that the maximum potential HDS activity of MoS₂/Al₂O₃ and Co–Mo/Al₂O₃ catalysts can be predicted by means of Co(CO)₃NO as a “probe” molecule. An attempt was made to determine the fate of Co(CO)₃NO adsorbed on MoS₂/Al₂O₃. The effects of the support on Co–Mo sulfide catalysts in HDS and HYD were investigated by use of CVD-Co/MoS₂/support catalysts. XPS and NO adsorption showed that model catalysts can also be prepared for SiO₂-, TiO₂- and ZrO₂-supported catalysts by means of the CVD technique. The thiophene HDS activity of CVD-Co/MoS₂/Al₂O₃, CVD-Co/MoS₂/TiO₂ and CVD-Co/MoS₂/Al₂O₃ is proportional to the amount of Co species interacting with the edge sites of MoS₂ particles or CoMoS phases. It is concluded that the support does not influence the HDS reactivity of CoMoS phases supported on TiO₂, ZrO₂ and Al₂O₃. In contrast, CoMoS phases on SiO₂ show catalytic features characteristic of CoMoS Type II. With the hydrogenation of butadiene, on the other hand, the Co species on MoS₂/TiO₂, ZrO₂ and SiO₂ have the same activity, while the Co species on MoS₂/Al₂O₃ have a higher activity.     

Support effect on the properties of iron–molybdenum hydrodesulfurization catalysts

Two series of Mo and Fe containing catalysts have been prepared over alumina and titania supports using H₃PMo₁₂O₄₀ heteropolyacid (HPMo) and Fe salt of HPMo. Catalysts have been characterized by BET, SEM, IR, TPR, XPS methods and by their HDS activity in the reaction of thiophene conversion. The TiO₂-supported catalysts with low Mo concentration (6 wt%) show higher HDS activity than the catalyst with 12 wt% Mo. Iron promoting effect (Fe/Mo ~ 0.1) is observed with both, the alumina- and titania-supported catalysts. Iron supported over alumina increases Mo reducibility and decreases it on TiO₂-supported catalysts. Compared to alumina-supported catalysts, the TiO₂-supported catalysts show higher surface concentration of Mo⁶⁺ and Mo⁵⁺ in octahedral coordination – Mo(Oh). Iron increases the Mo(Oh) concentration even more. After sulfidation the Fe-containing catalysts show formation of different Mo valence states (Mo⁴⁺, Mo⁵⁺, Mo⁶⁺), Fe–P, Mo–P and/or Fe–Mo–P bonds, which affect the HDS catalytic activity.     

Hydrodesulfurization of thiophene on carbon nanofiber supported Co/Ni/Mo catalysts

Co, Mo, NiMo and CoMo catalysts supported on alumina, fishbone and platelet carbon nanofibers (CNFs) have been prepared. The dispersion of the oxide phases was qualitatively studied and compared using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The reducibility of the catalysts was studied by temperature programmed reduction (TPR). Hydrodesulfurization (HDS) of thiophene was used as a model reaction to compare the activity of different catalysts. The activity tests showed that the alumina supported catalysts exhibited higher activity compared to the corresponding CNF supported catalysts, and the NiMo catalysts were more active than the corresponding CoMo catalysts. The thiophene HDS activity was correlated with the dispersion of the molybdenum species and the reducibility of different catalysts. Interestingly, the CNF supported Co catalysts have higher thiophene HDS activity than the CNF supported Co(Ni)Mo catalysts.     

Hydrodenitrogenation of pyridine over alumina-supported iridium catalysts

The catalytic properties of alumina-supported Ir catalysts (≈1 wt% Ir) were studied in the hydrodenitrogenation (HDN) of pyridine at 320°C and 20 bar of pressure in the absence as well as presence of parallel hydrodesulfurization (HDS) of thiophene. The effects of Ir precursor (Ir(AcAc)₃, Ir₄(CO)₁₂, H₂IrCl₆, (NH₄)₂IrCl₆), metal dispersion and sulfur addition were investigated. Ir₄(CO)₁₂ gave the most active catalyst which was ascribed to a lower amount of contaminants originated from the starting Ir compounds rather than to a better Ir dispersion. The decrease of Ir dispersion by sintering in air led to much higher decrease of the rate of C–N bond hydrogenolysis than that of pyridine hydrogenation. The Ir dispersion determined partly the HDN selectivity; a better dispersed Ir phase gave a lower amount of intermediate piperidine. Presulfidation of the reduced catalyst led to 20% decline of the rates of both consecutive HDN steps. An additional and much larger activity decline was caused by the simultaneous execution of HDS. The competitive adsorption of thiophene (or H₂S) was selectively affecting C–N bond hydrogenolysis more than pyridine hydrogenation. The alumina-supported Ir catalysts possessed much higher HDN activity and HDN/HDS selectivity than a conventional NiMo system.     

Effect of temperature on activity and selectivity of carbon supported Mo sulfide in simultaneous hydrodenitrogenation of pyridine and hydrodesulfurization of thiophene

Activity and selectivity of carbon supported Mo catalyst was tested in parallel hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene in the temperature range 260–350 °C at 2 MPa of hydrogen pressure and compared with that of commercial NiMo-alumina catalyst Shell 324. The main advantages of carbon supported Mo sulfide over commercial NiMo catalyst can be summarized as follows: the markedly higher HDN and better HDS activities normalized to moles of active metals, the lower content of piperidine in the reaction products and the distinctly better selectivity towards HDN reaction.     

Hydrotreating of gas oil on SBA-15 supported NiMo catalysts

The siliceous and the metal substituted (B or Al)-SBA-15 molecular sieves were used as a support for NiMo hydrotreating catalysts (12 wt.% Mo and 2.4 wt.% Ni). The supports were characterized by X-ray diffraction (XRD), scanning electron microscopy and N₂ adsorption–desorption isotherms. The SBA-15 supported NiMo catalysts in oxide state were characterized by BET surface area analysis and XRD. The sulfided NiMo/SBA-15 catalysts were examined by DRIFT of CO adsorption and TPD of NH₃. The HDN and HDS activities with bitumen derived light gas oil at industrial conditions showed that Al substituted SBA-15 (Al-SBA-15) is the best among the supports studied for NiMo catalyst. A series of NiMo catalysts containing 7–22 wt.% Mo with Ni/Mo weight ratio of 0.2 was prepared using Al-SBA-15 support and characterized by BET surface area analysis, XRD and temperature programmed reduction and DRIFT spectroscopy of adsorbed CO. The DRIFT spectra of adsorbed CO showed the presence of both unpromoted and Ni promoted MoS₂ sites in all the catalysts, and maximum “NiMoS” sites concentration with 17 wt.% of Mo loading. The HDN and HDS activities of NiMo/Al-SBA-15 catalysts were studied using light gas oil at temperature, pressure and WHSV of 370 °C, 1300 psig and 4.5 h⁻¹, respectively. The NiMo/Al-SBA-15 catalyst with 17 wt.% Mo and 3.4 wt.% of Ni is found to be the best catalyst. The HDN and HDS activities of this catalyst are comparable with the conventional Al₂O₃ supported NiMo catalyst in real feed at industrial conditions.     

Catalytic properties of nickel molybdenum sulphides supported on nickel and magnesium aluminates

The hydrodesulphurization (HDS) of thiophene at atmospheric pressure, hydrodenitrogenation (HDN) of 2,6 diethylaniline (DEA) and of 1,2,3,4 tetrahydroquinoline (THQ) at 70 atm in a dynamic flow microreactor - these molecules being present alone or mixed in the feed - and finally HDN of mixtures of quinoline (Q) at 70 atm or of phenanthridine (Ph) at 140 atm with DEA in a batch reactor were the test reactions used to compare the performances of (Ni)---Mo---S catalysts supported on MgAl₂O₄ and NiAl₂O₄ with a classical Ni---Mo---S/γ Al₂O₃ commercial catalyst. Some of the catalysts supported on NiAl₂O₄ appeared to be superior to the commercial one, whereas those supported on MgAl₂O₄ were found to be less active. HDS of thiophene, as well as the amount of carbon monoxide adsorbed at 0°C by sulphided catalysts permitted the prediction of the order of HDN activity of the catalysts for the conversion of some nitrogen-containing molecules. A strong inhibiting effect of molecules like Q, THQ or Ph (or some of their products formed during the process) on the HDN of DEA has been found and attributed to the competitive adsorption of these molecules on the supported active phase.     

Catalytic properties of nickel molybdenum sulphide supported on zirconia

Zirconia has been investigated as a support material for Mo and NiMo sulphide catalysts. Thiophene HDS studies (1 atm, 400°C) reveal that the ZrO₂-supported Mo catalysts are twice as active as the corresponding Mo/Al₂O₃ catalysts. The promoting effect brought by nickel, however, is much smaller than expected in comparison with alumina supported catalysts; the use of zirconia induces higher hydrogenation selectivity. It is suggested that the promoter ions interact with both the Mo sulphide slab and the zirconia carrier, which results in a change in properties of the mixed catalytic sites.

The increased selectivity towards hydrogenation may be an important advantage when dealing with hydrodenitrogenation processes. Indeed, in catalytic tests carried out at 70 atm, 350°C, 2,6-diethylaniline reacts more rapidly over zirconia catalysts ; similarly, the hydrogenation route is well developed in the complex reaction scheme of quinoline. However the inhibiting effect of quinoline (or 1,2,3,4-tetrahydroquinoline) upon the reactivity of alkylanilines is as strong on zirconia supported as on alumina supported catalysts.

Nevertheless, the beneficial effect of the zirconia carrier is observed in the HDN of the less reactive phenanthridine molecule (140 atm, 340°C), and also in the HDN of real feed in a pilot test.     

Catalytic activities of Co(Ni)Mo/TiO2–Al2O3 catalysts in gasoil and thiophene HDS and pyridine HDN: effect of the TiO2–Al2O3 composition

The effect of the TiO₂–Al₂O₃ mixed oxide support composition on the hydrodesulfurization (HDS) of gasoil and the simultaneous HDS and hydrodenitrogenation (HDN) of gasoil+pyridine was studied over two series of CoMo and NiMo catalysts. The intrinsic activities for gasoil HDS and pyridine HDN were significantly increased by increasing the amount of TiO₂ into the support, and particularly over rich- and pure-TiO₂-based catalysts. It is suggested that the increase in activity be due to an improvement in reducing and sulfiding of molybdena over TiO₂. The inhibiting effect of pyridine on gasoil HDS was found to be similar for all the catalysts, i.e., was independent of the support composition. The ranking of the catalysts for the gasoil HDS test differed from that obtained for the thiophene test at different hydrogen pressures. In the case of gasoil HDS, the activity increases with TiO₂ content and large differences are observed between the catalysts supported on pure Al₂O₃ and pure TiO₂. In contrast, in the case of the thiophene test, the pure Al₂O₃-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also, in the thiophene test the difference in intrinsic activity between the pure Al₂O₃-based catalyst appeared relatively more active than the catalysts supported on mixed oxides. Also in the thiophene test, the difference in intrinsic activity between the pure Al₂O₃- and pure TiO₂-based catalysts is relatively small and dependent on the H₂ pressure used. Such differences in activity trend among the gasoil and the thiophene tests are due to a different sensitivity of the catalysts (by different support or promoter) to the experimental conditions used. The results of the effect of the H₂ partial pressure on the thiophene HDS, and on the effect of H₂S concentration on gasoil HDS demonstrate the importance of these parameters, in addition to the nature of the reactant, to perform an adequate catalyst ranking.     

磷添加方式对NiMo/Al2O3催化剂加氢脱硫性能的影响

采用分步浸渍法制备了不同磷添加方式改性的NiMo/Al₂O₃催化剂,在固定床微反装置上考察了该系列催化剂对焦炉煤气中噻吩加氢脱硫（HDS）性能的影响,采用BET、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、NH₃程序升温脱附（NH₃-TPD）、C₄H₄S(H₂)程序升温脱附[C₄H₄S(H₂)-TPD]、X射线光电子能谱（XPS）、高清透射电镜（HRTEM）和拉曼（Raman）等分析手段对催化剂进行表征。结果表明,不同磷添加方式制备NiMo/Al₂O₃催化剂的HDS性能存在较大差异。其中,催化剂PNi-Mo/Al和PMo-Ni/Al表面弱吸附解离活性位增强,对焦炉煤气中噻吩有较好的低温加氢脱硫活性,以含292.5mg/m³噻吩的模拟焦炉煤气为原料时,PNi-Mo/Al在250℃下对噻吩的脱硫率达61%。对于PNi-Mo/Al和PMo-Ni/Al催化剂,先浸渍P、Ni或者P、Mo时,P优先和载体Al₂O₃作用,减弱了活性金属组分Ni、Mo与载体间的相互作用,而又防止Ni或者Mo与载体间相互作用过低而聚集,提高了Ni、Mo在载体表面的均匀分散,生成能够促进硫化形成Ⅱ型活性相Ni-Mo-S的NiMoO₄物种。NiMoO₄和MoO₃之间的协同作用提高了催化剂的硫化度,使HDS活性得以提高。     

Synthesis,characterization and hydrotreating performance of supported tungsten phosphide catalysts

Supported tungsten phosphide catalysts were prepared by temperature-programmed reduction of their precursors (supported phospho-tungstate catalysts) in H₂ and characterized by X-ray diffraction (XRD), BET, temperature-programmed desorption of ammonia (NH₃-TPD) and X-ray photoelectron spectroscopy (XPS). The reduction-phosphiding processes of the precursors were investigated by thermogravimetry and differential thermal analysis (TG-DTA) and the suitable phosphiding temperatures were defined. The hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities of the catalysts were tested by using thiophene, pyridine, dibenzothiophene, carbazole and diesel oil as the feedstock. The TiO₂, ?-Al₂O₃ supports and the Ni, Co promoters could remarkably increase and stabilize active W species on the catalyst surface. A suitable amount of Ni (3%–5%), Co (5%–7%) and V (1%–3%) could increase dispersivity of the W species and the BET surface area of the WP/?-Al₂O₃ catalyst. The WP/?-Al₂O₃ catalyst possesses much higher thiophene HDS and carbazole HDN activities and the WP/TiO₂ catalyst has much higher dibenzothiophene (DBT) HDS and pyridine HDN activities. The Ni, Co and V can obviously promote the HDS activity and inhibit the HDN activity of the WP/?-Al₂O₃ catalyst. The G-Ni5 catalyst possesses a much higher diesel oil HDS activity than the sulphided industrial NiW/?-Al₂O₃ catalyst. In general, a support or promoter in the WP/?-Al₂O₃ catalyst which can increase the amount and dispersivity of the active W species can promote its HDS and HDN activities.     

Analysis of the hydrotreatment of Maya heavy crude with NiMo catalysts supported on TiO2-Al2O3 binary oxides: Effect of the incorporation method of Ti

Heavy Maya crude has been hydrotreated with NiMo/alumina-titania catalysts in which titania was incorporated by two different methods. Titania added to boehmite followed by calcination in order to promote formation of Ti–O–Al bonds, and Ti added to alumina in order to promote the formation of TiO₂ structures on the surface. The reaction results indicate that hydrodesulfurization (HDS), hydrodemetallization (HDM) and hydrodenitrogenation (HDN) activities are improved by the incorporation of Ti to the catalyst. In all cases, catalysts prepared by the method leading to the formation of surface TiO₂ structures show superior performance in the three functionalities (HDS, HDM and HDN). Raman analysis of the supports gives clear evidence of the differences in Ti oxide structures on the surface. The characterization of the catalysts indicates that Ti-modified catalysts have increased surface acidity (evaluated by pyridine adsorption) and greater number of coordinatively unsaturated sites (titrated by NO adsorption). Ti-containing catalysts seem to be also more stable with time-on-stream.     

Characteristics of bimetallic cobalt and molybdenum catalysts supported on activated carbon or alumina in hydrodesulfurization

A series of bimetallic cobalt (Co) and molybdenum (Mo) catalysts supported on activated carbon or alumina were prepared, and their activities in thiophene hydrodesulfurization and ethylene hydrogenation were compared. The nitric oxide (NO) chemisorption and temperature programmed desorption (TPD) were used to characterize the nature of the synergistic active sites. Carbon supported catalysts also demonstrated the synergism in activity, which is well known for alumina supported catalysts. The specific activity and the adsorption stoichiometry of each site were interpreted from NO chemisorption. The possibility of NO as a probe molecule for sulfide catalysts was provided by the present work.     

Hydrodesulfurization activity of highly dispersed Co sulfide clusters prepared in zeolite cages

Zeolite-supported highly dispersed Co sulfide clusters are synthesized using Co(CO)₃ (NO) as a precursor. The amount of Co inCoS_x/zeolite anchored by a CVD technique increases as the Al/Si ratio of the zeolite increases, whereas the activity per Co atomdecreases for thiophene hydrodesulfurization (HDS). When an Na-exchanged USY zeolite is used, the Co sulfide catalyst shows a muchhigher HDS activity than a conventional Co—Mo/Al₂ O₃ catalyst. It is considered from XAFS and NO adsorption techniques that thehigh HDS activity of CoS_x/USY-Na is due to an extremely high dispersion of Co sulfide clusters. This revised version was published online in July 2006 with corrections to the Cover Date.