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.     

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.     

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.     

States of carbon nanotube supported Mo-based HDS catalysts

As HDS catalysts, the supported catalysts including oxide state Mo, Co–Mo and sulfide state Mo on carbon nanotube (CNT) were prepared, while the corresponding supported catalysts on γ-Al₂O₃ were prepared as comparison. Firstly, the dispersion of the active phase and loading capacity of Mo species on CNT was studied by XRD and the reducibility properties of Co–Mo catalysts in oxide state over CNTs were investigated by TPR while the sulfide Co–Mo/CNT catalysts were characterized by XRD and LRS techniques. Secondly, the activity and selectivity of hydrodesulfurization (HDS) of dibenzothiophene with Co–Mo/CNT and Co–Mo/γ-Al₂O₃ were studied. It has been found that the main active molybdenum species in the oxide state MoO₃/CNT catalysts were MoO₂, rather than MoO₃ as generally expected. The maximum loading before formation of the bulk phase was lower than 6%m (calculated in MoO₃). The TPR studies revealed that that active species in oxide state Co–Mo/CNT catalysts were more easily reduced at relatively lower temperatures in comparison to those in Co–Mo/γ-Al₂O₃, indicating that the CNT support promoted the reduction of active species. Among 0–1.0 Co/Mo atomic ratio on Co–Mo/CNT, 0.7 has the highest reducibility. It shows that the Co/Mo atomic ratio has a great effect on the reducibility of active species on CNT and their HDS activities and that the incorporation of cobalt improved the dispersion of molybdenum species on CNT and mobilization. It was also found that re-dispersion could occur during the sulfiding process, resulting in low valence state Mo₃S₄ and Co–MoS_2.17 active phases. The HDS of DBT showed that Co–Mo/CNT catalysts were more active than Co–Mo/γ-Al₂O₃ and the hydrogenolysis/hydrogenation selectivity of Co–Mo/CNT catalyst was also much higher than Co–Mo/γ-Al₂O₃. For the Co–Mo/CNT catalysis system, the catalyst with Co/Mo atomic ratio of 0.7 showed the highest activity, whereas, the catalyst with Co/Mo atomic ratio of 0.35 was of the highest selectivity.     

Redispersion effects of citric acid on CoMo/γ-Al2O3 hydrodesulfurization catalysts

Calcined CoMo/γ-Al₂O₃ catalysts were modified by citric acid (CA) with different CA/Co ratios and the corresponding structure evolutions were systematically characterized. Then combined with HDS activity results, potential redispersion effects of CA were suggested: (i) weaken the MoO₃-Al₂O₃ interaction via competitive interacting with the OH groups of alumina surface to realize the redispersion of Mo oxides; (ii) transform tetrahedral MoO₄^2 − or β-CoMoO₄ into octahedral polymolybdate species and promote bulk MoO₃ to form well-dispersed MoO₃; (iii) remove the CoAl₂O₄-like species. These effects probably together promote the resulting sulfided catalysts with more type II CoMoS active sites, thus enhancing the HDS activity.     

Highly active hydrotreatment catalysts prepared with chelating agents

Hydrotreatment catalysts (Co–Mo/Al₂O₃, Ni–Mo/Al₂O₃ and Ni–W/Al₂O₃) were prepared by an impregnation method using an aqueous solution containing a chelating agent (nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) or trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CyDTA)). Co–Mo/Al₂O₃ and Ni–W/Al₂O₃ prepared with the chelating agents showed higher hydrodesulfurization (HDS) activity as well as hydrogenation (HYD) activity under high pressure (5.1 MPa) than those prepared without the chelating agents. Co–Mo/Al₂O₃ prepared with CyDTA showed ca. 70% higher HDS activity for benzothiophene (BT) than that prepared without it. HYD activity of Ni–W/Al₂O₃ for o-xylene was promoted about 65% by the addition of CyDTA. FT-IR of nitric oxide (NO) adsorbed on the sulfided Co–Mo/Al₂O₃'s suggested that Co was highly dispersed over the catalyst surface when the catalysts were prepared with the chelating agents.     

Co–ZSM-5 catalysts in the decomposition of N2O and the SCR of NO with CH4: Influence of preparation method and cobalt loading

Co–ZSM-5 prepared via different methods with Co/Al ratios ranging from 0.03 to 0.83 are investigated in both the direct N₂O decomposition and the selective catalytic reduction (SCR) of NO with CH₄. UV–vis and H₂-TPR are used to get an insight in the active species in these reactions. It is observed that in catalysts with low Co loadings (Co/Al < 0.3) Co is predominantly present as mono-atomic Co species, located at ion exchange positions in ZSM-5. Higher Co loadings result in the formation of different kinds of Co-oxides, which constitute the majority of species in the over-exchanged catalysts (Co/Al > 0.5). The mono-atomic species show the highest activity in the direct decomposition of N₂O, whereas the oxidic Co species do not seem to contribute much to the overall decomposition. In the SCR, the Co-oxide species catalyze the combustion of CH₄ whereas the selectivity towards NO reduction is much increased at low Co loadings. Therefore, over-exchange of Co–ZSM-5 does not seem to be favorable for both the direct N₂O decomposition and the SCR of NO with CH₄. Co/Al ratios <0.3 give the best results both in terms of conversion and activity per Co atom in both reactions.     

Deactivation of Co---Mo/A12O3 hydrodesulfurization catalysts during a one-year commercial run

A series of Co---Mo catalysts with different Co and Mo loadings were prepared and exposed to a commercial HDS run for a year. From the activity tests using model compounds, the HDS activity of the fresh catalyst was found to increase up to 4.0 Mo atoms nm⁻² with increasing Co---Mo loading. However, no significant difference in the activity was observed in the used catalysts. TEM and EXAFS analyses revealed that the MOS₂ stacks aggregated in the lateral direction but did not grow in the normal direction to the layers during the run.     

The functionalities of Pt/γ-Al2O3 catalysts in simultaneous HDS and HDA reactions

A Pt/γ-Al₂O₃ catalyst was tested in simultaneous hydrodesulfurization (HDS) of dibenzothiophene and hydrodearomatization (HDA) of naphthalene reactions. Samples of it were subjected to different pretreatments: reduction, reduction–sulfidation, sulfidation with pure H₂S and non-activation. The reduced catalyst presented the best performance, even comparable to that of Co(Ni)Mo catalysts. All catalyst samples were selective to the HDS reaction over HDA, and to the direct desulfurization pathway of dibenzothiophene HDS over the hydrogenation reaction pathway of HDS. The effect of H₂S partial pressure on the functionalities of the reduced Pt/γ-Al₂O₃ catalyst was studied. The results showed that an increase in H₂S partial pressure does not cause poisoning, but an inhibition effect, without changing the catalyst selectivity. Accordingly, the activity trends were ascribed to adsorption differences between the different reactive molecules over the same catalytic active site. TPR characterization along with a thermodynamics analysis showed that the active phase of reduced Pt/γ-Al₂O₃ is constituted by Pt⁰ particles. However, presulfidation of the catalyst leads to a mixture of PtS and Pt⁰ which has a negative effect on the catalytic performance without changing catalyst functionalities.     

Magnesia-Supported Mo, CoMo and NiMo Sulfide Catalysts Prepared by Nonaqueous Impregnation: Parallel HDS/HDN of Thiophene and Pyridine and TEM Microstructure

MgO-supported Mo, CoMo and NiMo sulfide catalysts were prepared by impregnation using slurry MoO₃/methanol and solutions of Ni and Co nitrates in methanol. The catalysts exhibited very high hydrodesulfurization activity and low hydrodenitrogenation activity in competitive reactions of thiophene and pyridine. The promotion effect for HDS of Ni and Co was higher for our MgO-supported MoS₂ catalysts than for conventional Al₂O₃-supported catalysts. The specific features in the TEM images of MgO-supported catalysts as compared to conventional Al₂O₃-supported catalysts were fairly broad MoS₂ slab length distribution and the presence of unusually long MoS₂ slabs.     

W-promoted Co–Mo–K/γ–Al2O3 catalysts for water–gas shift reaction

The effects of incorporating tungsten into the traditional Co–Mo–K/γ–Al₂O₃ catalysts on the catalytic performances for water–gas shift reaction were investigated. Activity tests showed that W-promoted Co–Mo–K/γ–Al₂O₃ catalysts exhibited higher activity than W-free Co–Mo–K/γ–Al₂O₃ catalyst. Raman and H₂-TPR studies indicated that part of the octahedrally coordinated Mo–O species on Co–Mo–K catalysts transformed into tetrahedrally coordinated Mo–O species in the presence of W promoter.     

Catalytic activity of Co,Mo and CoMo supported on NaY zeolite: hydrodesulfurization of gas oil at high pressure

Three series of Co/NaY, Mo/NaY and CoMo/NaY zeolite catalysts with variable metal content, prepared by a conventional impregnation method, were characterized by XRD, IR spectroscopy (oxide state) and acidity measurements (sulfide state), and tested in hydrodesulfurization (HDS) of gas oil at high pressure in the temperature range 275–350°C. The combined results of surface area, XRD and IR showed that in the catalysts with high metal loading a small loss in crystallinity and a partial blockage of the zeolite supercages were produced by Mo oxide species. The number of acid sites, which was lower for the Co/NaY than for the Mo/NaY catalysts, increased with increasing Co or Mo loading, but the strength of the acid sites was stronger for the Co/NaY series. HDS specific activities of the Co/NaY and Mo/NaY monometallic catalysts reached a maximum at very low loadings of Co ( 0.10 at. nm^–2) or Mo ( 0.16 at. nm^–2) by the double action of the metal sulfide species and the strong acid sites generated on the zeolite by the Co or Mo incorporation. In the binary CoMo/NaY catalysts, the synergy between Co and Mo species was significant for high Mo contents only.     

Selectivity enhancement of Co-Mo/Al2O3 FCC gasoline hydrodesulfurization catalysts via incorporation of mesoporous Si-SBA-15

Mesoporous Si-SBA-15 was applied to enhance the FCC gasoline selective hydrodesulfurization (HDS) performance of conventional Co-Mo/Al₂O₃ catalysts and the physicochemical properties of the resulting catalyst were compared with those of Co-Mo/Al₂O₃ catalysts incorporated with macroporous kaolin, mesoporous Si-MCM-41 and microporous Si-ZSM-5. The selective HDS performances of all the catalysts were assessed with different FCC gasolines as feedstocks. The results showed that the HDS selectivity of the catalysts was closely related to the Mo sulfidation that depends on catalyst surface area and metal-support interaction. With the superior Mo sulfidation, the Co-Mo/Si-SBA-15-Al₂O₃ catalyst had the optimal HDS selectivity for not only the full-range FCC gasolines but also the heavy fractions thereof. The present article demonstrates the significance of enhancing Mo sulfidation in improving HDS selectivity and thus sheds a light on the development of highly selective HDS catalysts.     

Cobalt-Molybdenum Sulfide Catalysts Prepared by In Situ Activation of Bimetallic (Co-Mo) Alkylthiomolybdates

Unsupported cobalt-molybdenum sulfide catalysts were prepared from bimetallic CoMo alkyl precursors by in situ activation during the hydrodesulfurization (HDS) of dibenzothiophene (DBT). The bimetallic CoMo precursors were prepared by reaction of tetraalkylammonium thiomolybdate salts, (R₄N)₂MoS₄ (where R = H, methyl, butyl, pentyl or hexyl), with CoCl₂ in water at a Co/Mo molar ratio of 0.3. These catalysts exhibit a Swiss-cheese-like morphology, high surface areas (from 52 up to 320 m²/g), high content of carbon (C/Mo = 2.2-3.3) and type IV adsorption-desorption isotherms of nitrogen. The in situ activation of these tetraalkylammonium thiobimetalate precursors leads to a mesoporous structure with pore size ranging from 2 to 4.5 nm. X-ray diffraction showed that the structure of unsupported cobalt-molybdenum sulfide catalysts corresponds to a poorly crystalline structure characteristic of 2H-MoS₂ with low-stacked layers. The nature of the alkyl group strongly affects both the surface area and the HDS activity. The catalytic activity is strongly enhanced when using carbon-containing precursors; the CoMo catalysts prepared by in situ activation of Co/[N(C₄H₉)₄]₂MoS₄ presents the highest HDS activity. The highest surface area of the catalysts was observed for the CoMo catalyst formed from Co/[N(C₆H₁₃)₄N]₂MoS₄.     

On the formation of cobalt–molybdenum sulfides in silica‐supported hydrotreating model catalysts

Model catalysts, consisting of a conducting substrate with a thin SiO₂ layer on top of which the active catalytic phase is deposited by spincoating impregnation, were applied to study the formation of the active CoMoS phase in HDS catalysts. The catalysts thus prepared showed representative activity in the hydrodesulfurization of thiophene, confirming that these models of HDS catalysts are realistic. Combination of the sulfidation behaviour of Co and Mo studied by XPS and activity measurements shows that the key in the formation of the CoMoS phase is the retardation of the sulfidation of Co. Complexing Co to nitrilotriacetic acid complexes retarded the Co sulfidation, resulting in the most active catalyst. Due to the retardation of Co in these catalysts, the sulfidation of Mo precedes that of Co, thereby creating the ideal conditions for CoMoS formation. In the CoMo catalyst without NTA the sulfidation of Co is also retarded due to a Co–Mo interaction. However, the sulfidation of Mo still lags behind that of Co, resulting in less active phase and a lower activity in thiophene HDS. This revised version was published online in June 2006 with corrections to the Cover Date.     

Characterization of hydrodesulfurization catalyst prepared by impregnating cobalt nitrate solution onto the sulfided MoO3/Al2O3 catalyst

CoMo/Al₂O₃ catalysts were prepared by impregnating Cobalt nitrate solution into oxidic or sulfided Mo/Al₂O₃. The properties of CoMo/Al₂O₃ catalysts were characterized by XRD, TPS, oxygen chemisorption and ESR. Catalytic activity of CoMo/Al₂O₃ catalyst was evaluated by thiophene HDS as a probe reaction. When CoMo/Al₂O₃ catalyst was prepared by impregnating Cobalt nitrate solution into sulfided Mo/Al₂O₃, the interaction between Mo and alumina became weaker and the formation of synergic phase was facilitated. These structural changes may explain higher HDS activity of CoMo/Al₂O₃ catalyst prepared by impregnating Cobalt nitrate solution into sulfided Mo/Al₂O₃.     

Hydrodesulphurization performance of NiW/TiO2-Al2O3 catalyst for ultra clean diesel

TiO₂-Al₂O₃ binary oxide supports were obtained by sol–gel methods from Tetra-n-butyl-titanate and pseudoboehmite/aluminium chloride resources. The typical physico-chemical properties of NiW/TiO₂-Al₂O₃ catalysts with different TiO₂ loadings and their supports were characterized by means of BET, XRD and UV–vis DRS, etc. The BET results indicated that the specific surface areas of NiW/TiO₂-Al₂O₃ catalysts were as higher as that over pure γ-Al₂O₃ support, and the pore diameters were also large. The XRD and UV–vis DRS analyzing results showed that the Ti-containing supported catalysts existed as anatase TiO₂ species and the incorporation of TiO₂ could adjust the interaction between support and active metal, and impelled the higher reducibility of tungsten. The hydrodesulphurization (HDS) performance of the series catalysts were evaluated with diesel feedstock in a micro-reactor unit, and the HDS results showed that NiW/TiO₂-Al₂O₃ catalysts exhibited higher activities of ultra deep hydrodesulphurization of diesel oil than that of NiW/Al₂O₃ catalyst. The optimal TiO₂ content of NiW/TiO₂-Al₂O₃ catalysts was about 15 m%, and the corresponding HDS efficiency could reach to 100%. The sulphur contents of diesel products over NiW/TiO₂-Al₂O₃ (from pseudoboehmite/AlCl₃) catalysts with suitable TiO₂ content could be less than 15 ppmw, which met the sulphur regulation of Euro IV specification of ultra clean diesel fuel.     

In situ QEXAFS investigation at Co K-edge of the sulfidation of a CoMo/Al2O3 hydrotreating catalyst

In situ sulfidation of a commercial alumina-supported CoMo hydrotreating catalyst (3 wt% Co, 12.3 wt% Mo) has been studied by QEXAFS at Co K-edge. Sulfidation was performed by heating progressively the oxide precursor from room temperature (RT) up to 673 K in a H₂/10% H₂S flow (ramp 4 K/min). XAFS spectra were recorded each 10 K with an acquisition time of only 30 s. The obtained XANES and EXAFS data were compared with those of a Co/Al₂O₃ (2.36 wt% Co) used as reference sample. It is evidenced that sulfidation of Co atoms in a CoMo/Al₂O₃ catalyst starts at room temperature while the sulfidation of a Co/Al₂O₃ catalyst begins at 473 K.     

Preparation and characterization of nano-sized CoMo/Al2O3 catalyst for hydrodesulfurization

CoMo on Al₂O₃ catalyst prepared by spray pyrolysis method was found in the form of spheres of 0.5–1.2 μm, which consisted of tiny primary particles of ca. 10–20 nm diameter. The materials shows comparable activity to those of commercial catalysts in HDS of straight run gas oil, in particular, refractory 4,6-dimethyldibenzothiophene (4,6-DMDBT). Weaker interactions between CoMo and Al₂O₃ are suggested by temperature-programmed reduction (TPR), Raman spectroscopy, to give more active species than those over the impregnated catalysts. This accounts for its comparable activity in spite of its smaller surface area.     

Hydrotreating of Heavy Gas Oil Derived from Athabasca Bitumen Over Co–Mo/γ-Al2O3 Catalyst Prepared by Sonochemical Method

Co–Mo/γ-Al₂O₃ oxide containing 9.8 wt% Mo and 2.9 wt% Co was prepared by high-intensity ultrasonic irradiation of Mo(CO)₆, Co₂(CO)₈, and γ-Al₂O₃ in decahydronapthalene under air flow. The oxidic Co–Mo catalyst thus formed was characterized by elemental analysis, BET N₂ adsorption and XRD. The surface sites on the sulfided Co–Mo/γ-Al₂O₃ catalyst were characterized by infrared spectroscopy of CO adsorption. Hydrodenitrogenation (HDN) and hydrodesulfurization (HDS) activities were evaluated for heavy gas oil derived from Athabasca bitumen in a trickle bed reaction system using the following conditions: temperatures ranging from 370 to 400 °C, a pressure of 8.8 MPa, a liquid hourly space velocity of 1 h⁻¹, and a H₂/feed ratio of 600 ml/ml. The dispersion, nature of active sites and hydrotreating activity of this catalyst were compared with the conventionally prepared Co–Mo/γ-Al₂O₃ catalyst containing similar wt% of Mo and Co. The Co–Mo catalyst prepared by sonochemical method has higher HDN and HDS rate constants than the conventional catalyst due to an improved dispersion of MoS₂.