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.     

Structure of molybdenum oxide clusters prepared in zeolite cages

Molybdenum hexacarbonyl entrapped in NaY zeolite was oxidized with molecular oxygen by UV-irradiation at room temperature or by thermal treatment at 343–373 K. Both oxidation procedures resulted in the identical molybdenum(VI) oxide; molybdenum dimer species (Mo-Mo distance: 0.321 nm). The Mo-Mo bonding of the oxide species was degraded on an evacuation at 673 K, while it was considerably stable in the presence of gaseous oxygen.     

The effects of catalysts on the carbothermic reduction of zinc sulfide in the presence of calcium oxide

The effects of the type and the amount of various catalysts on the rate of the carbothermic reduction of zinc sulfide in the presence of calcium oxide were studied using thermogravimetric analysis system (TGA). Experimental results revealed that the order of the effects of the catalysts is Li₂CO₃ ≈ Na₂CO₃ ≈ Na₂SO₄ > Li₂SO₄ > K₂CO₃ > K₂SO₄. It was also observed that with more Li₂CO₃ the reaction is faster, when the amount of Li₂CO₃ was less than 2.0 wt.%.     

Synthesis of mixed alcohols from CO2 contained syngas on supported molybdenum sulfide catalysts

The performances of active carbon supported molybdenum sulfide catalysts prepared by different procedures or promoted by different elements in the synthesis of mixed alcohols from CO₂ containing syngas were examined. The results showed that high alcohol activity and selectivity could be obtained by employing a rapid drying procedure and employing a H₂S---H₂ stream for (NH₄)₂MoS₄ decomposition. Addition of Co, Cr and Cl to K---Mo/C catalyst led to an increase in the alcohol activity or selectivity. The presence of CO₂ in the feed caused a greater amount of water to be produced but reduced the formation of CO₂. The product distribution was also strongly influenced by the presence of either CO₂ or H₂S in the feed. Addition of CO₂ reduces the formation of higher alcohols while H₂S increases higher alcohol formation.     

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.     

The effect of additives on hydrodesulfurization of dibenzothiophene over bulk molybdenum sulfide: Increased catalytic activity in the presence of phenol

The effect of various additive organic reagents on the activation of MoS₃ as molybdenum sulfide catalyst precursor during hydrodesulfurization reaction of dibenzothiophene was studied. It was found that the presence of phenol or 1-naphthol greatly promoted the activity of the catalyst, while tetralin, 9,10-dihydrophenanthrene, ethylbenzene, and pyridine reagents were found to be detrimental for the activity of the catalyst.     

A role of molybdenum and shape selectivity of catalysts in simultaneous reactions of hydrocracking and hydrodesulfurization

The hydrocracking and hydrodesulfurization (HDS) of n-heptane containing 0.2 mole% dibenzothiophene (DBT) were performed simultaneously using NiPtMo catalysts supported on HZSM-5, LaY and γ-Al₂O₃ in a high pressure fixed bed reactor. Molybdenum played an important role in both hydrocracking and hydrodesulfurization (HDS). We found that the sulfur compound, dibenzothiophene (DBT). in the reactant was adsorbed on a molybdenum site and converted to hydrogen sulfide so that the active sites of the catalysts for hydrocracking were less poisoned by DBT and the conversion of n-heptane over molybdenum impregnated catalyst was higher than that over molybdenum-free catalyst. The crystal structures of the molybdenum supported on the zeolite and γ-Al₂O₃ were mainly MoO_2.5 (OH)_0.5[021] and MoO₃[210] respectively as shown by XRD analysis. The structure of MoO_2.5(OH)_0.5 was easily reduced to MoS₂[003] during the reaction. After the reaction of 100 hours over the catalyst supported on γ-Al₂O₃ the crystal structure of MoO₃[210] partially changed to MoO₃[300] and the structure of MoS₂[003] was not observed. Because of the reactant shape selectivity of zeolite, the acid and the metal sites in the intracrystalline of the catalysts supported on zeolites were less poisoned by DBT. Therefore, both hydrocracking and HDS using n-heptane containing 0.2 mole% of DBT were successfully demonstrated over the prepared catalysts.     

Tailoring the pore size of zeolite Y as the support of diesel aromatic saturation catalyst

The molecular dimensions of typical aromatics and sulfur-containing compounds in diesel cuts were simulated. A pore configuration design was proposed for sulfur-tolerant metal catalyst. Modified zeolite Y with and without the presence of mesopores were used as a catalyst support. Pyrene and naphthalene were used as the model compounds for hydrogenation. Sulfur tolerance of the catalyst was investigated with naphthalene hydrogenation in the presence of thiophene. It was demonstrated that the generation of mesopores in zeolite Y can enhance the activity of pyrene hydrogenation, but lower the tolerance to thiophene.     

Amine-immobilized HY zeolite for CO2 capture from hot flue gas

Solid amine-based adsorbents were widely studied as an alternative to liquid amine for post-combustion CO₂ capture (PCC). However, most of the amine adsorbents suffer from low thermal stability and poor cyclic regenerability at the temperature of hot flue gases. Here we present an amine loaded proton type Y zeolite (HY) where the amines namely monoethanolamine (MEA) and ethylenediamine (ED) are chemical immobilized via ionic bond to the zeolite framework to overcome the amine degradation problem. The MEA and ED of 5%, 10% and 20% (mass) concentration – immobilized zeolites were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, and N₂ -196 ℃ adsorption to confirm the structure integrity, amine functionalization, and surface area, respectively. The determination of the amine loading was given by C, H, N elemental analysis showing that ED has successfully grafted almost twice as many amino groups as MEA within the same solvent concentration. CO₂ adsorption capacity and thermal stability of these samples were measured using thermogravimetric analyser. The adsorption performance was tested at the adsorption temperature of 30, 60 and 90 ℃, respectively using pure CO₂ while the desorption was carried out with pure N₂ purge at the same temperature and then followed by elevated temperature at 150 ℃. It was found that all the amine@HY have a substantial high selectivity of CO₂ over N₂. The sample 20% ED@HY has the highest CO₂ adsorption capacity of 1.76 mmol·g^-1 at 90 ℃ higher than the capacity on parent NaY zeolite (1.45 mmol·g^-1 only). The amine@HY samples presented superior performance in cyclic thermal stability in the condition of the adsorption temperature of 90 ℃ and the desorption temperature of 150 ℃. These findings will foster the design of better adsorbents for CO₂ capture from flue gas in post-combustion power plants.     

Exhausted fluid catalytic cracking catalysts as raw materials for zeolite synthesis

The utilization of exhausted fluid catalytic cracking (FCC) catalysts as raw materials for the zeolite synthesis was analyzed. Samples of the catalysts directly released from FCC units and the corresponding impact grinding pretreated samples were used. Mechanical treatment was observed to decrease catalyst crystallinity and particle size. The catalyst reactivity was analyzed in terms of conversion in zeolite and product properties. Hydrothermal synthesis experiments in NaOH medium were performed. Catalysts conversion in A and X type zeolites was obtained for treated and not treated samples. In particular, high conversion in NaX type were achieved using the more siliceous catalyst, whereas grinding activation produces a decrease of particle size and Al/Si ratio of the zeolites obtained.     

Selective Hydrogenation of Citral in an Organic Solvent,in a Ionic Liquid,and in Substance

It is investigated whether the catalyst system Ag‐In/SiO₂ can be applied in the selective hydrogenation of citral, with the aim of synthesizing the acyclic, allylic terpene alcohols geraniol/nerol with high selectivity and space‐time yield. In addition, as liquid‐phase hydrogenations are often also influenced by the choice of solvent, it is of interest to know how the solvent, in particular in terms of its polarity and hydrogen solubility, affects the activity and the selectivity of catalysts during hydrogenation of the α,β‐unsaturated aldehyde citral.     

Deep hydrodesulphurization and hydrogenation of diesel fuels on alumina-supported and bulk molybdenum carbide catalysts

Deep hydrodesulphurization (HDS) of diesel fuels has been carried out on P (Ni)-promoted or non-promoted Mo₂C-supported γ-Al₂O₃ and bulk Mo₂C under standard industrial conditions (613 K, 3 MPa). The effect of the promoter was investigated for different feedstocks on HDS and hydrogenation (HYD) with very low levels of sulfur. The temperature effect was also followed. The HDS conversion indicates that phosphorus promoted alumina supported carbide catalysts are as active as a commercial Co-Mo/Al₂O₃ catalyst for low levels of sulfur in the feed. Furthermore, the refractory compounds such as 4,6-dimethyldibenzothiophene are only transformed on molybdenum carbide catalyst in industrial conditions for hydrotreated gas oils. With gas oils with less than 50 wt ppm in sulfur, phosphorus promoted molybdenum carbide catalysts become more active than commercial catalysts for the HYD of the aromatic compounds and the HDS or the HDN of the feedstock.     

Catalytic functionality of unsupported molybdenum sulfide catalysts prepared with different methods

The catalytic functionality and structural properties of three kinds of unsupported molybdenum sulfide catalysts were investigated by model test reactions and BET, TEM, XPS and XRD analyses. The results indicated that highly bent multi-layered MoS₂ structures were more catalytically active, while a well crystallized MoS₂ structure was more favorable for direct S-extrusion during the reactions of dibenzothiophene. It was proposed that the curvature of MoS₂ basal planes was catalytically active, though they were less active for hydrodesulfurization than the edge planes.     

Niobium sulfide as a dopant for hydrotreating NiMo catalysts

Niobium sulfide has been recently found to be an interesting new active phase for hydrodesulfurization. In this work, niobium was used as a dopant for a conventional hydrotreating catalyst. A NiMo hydrotreating catalyst in the oxide form was doped with various contents of Nb precursor salt (02 sulfiding agent in a high pressure vessel. The use of this new dopant increased the catalytic activity in both HDS and HYD model reactions. Highest activities were obtained with an optimum Nb content of 5 wt.%. The selectivity of the products was also modified since more isomerized compounds where produced. Various techniques were used to determine structural and morphological characteristics of the materials. TEM pictures only showed the presence of lamellar particles similar to MoS₂. EDX analysis demonstrated the homogeneous distribution of the transition metal elements (Ni, Mo, Nb) even with small electron probes at high magnification. EXAFS was used to determine the local environment of Nb atoms and showed that Nb was present in the form of “NbS₂” entities similar to the bulk phase.     

Hydrotreating of light cycle oil using WNi catalysts containing hydrothermally and chemically treated zeolite Y

One W–Ni catalyst supported on hydrothermally treated zeolite Y and two W–Ni catalysts supported on chemically treated zeolite Y were prepared. The catalysts were characterized by NH₃-TPD, pyridine-IR, TEM, BET, and XPS. Their performance of hydrodesulfurization, hydrodenitrogenation, and hydrodearomatization were compared using light cycle oil (LCO) as the feed. The results showed that the hydrothermal treatment promotes HDS activity whereas the chemical approach favours the HDA activity. The HDN activity of the three catalysts was similar. Addition of zeolite Y with high proportion of Brønsted acidity in the catalysts helps to enhance the hydrodearomatization activity.     

Role of zeolite structure on NO reduction with diesel fuel over Pt supported zeolite catalysts

A highly desirable selective catalytic reduction (SCR) of NO with real life diesel fuel over Pt supported zeolites with different topologies (Pt-ZSM-5, Pt-FER, Pt-MOR and Pt-BEA) is studied under simulated exhaust conditions. The catalysts are characterized by CO chemisorption, NH₃-TPD and TGA. The NO conversion ability of these catalysts has been correlated with zeolite structure and acidity. Pt-MOR is found to be the most active catalyst, 90% NO conversion at 300 °C, however Pt-FER showed highly desirable low temperature window, 77% NO conversion below 260 °C. Over ZSM-5, BEA and Y with three dimensional pore structures extensive carbonaceous deposits are observed by TGA which are detrimental to NO conversion. On the other hand, FER zeolite having one dimensional pore structure did not allow extensive coke formation resulting in a highly desired low temperature NO conversion. The results suggest that, NO reduction mainly take place near the zeolite pore opening, which is in reasonable agreement considering the long and bulky molecules in diesel fuel.     

Hydrogenation of Cinnamaldehyde over Pt‐Modified Molecular Sieve Catalysts

The catalytic properties of various Pt‐modified molecular sieves were tested in liquid‐phase hydrogenation of cinnamaldehyde and compared to Pt/MgO and commercial Pt/C catalysts. The type of support considerably influenced the catalytic properties. The superior selectivity performance of microporous catalysts was confirmed; the highest selectivity to allyl alcohol of about 40 % was obtained over the beta support whereas the mesoporous MCM‐41‐supported catalyst was unselective. The highest activity was obtained over the Pt/mordenite catalyst. In order to clarify the performance of catalysts, several characterization methods (XRD, XRF, FTIR, surface measurements) were employed.     

Adsorption behavior of NO and CO and their reaction over cobalt on zeolite beta

Adsorption behavior of NO and CO as well as their reaction was investigated on cobalt supported zeolite beta (Co/BEA) prepared by solid-state ion exchange (SSIE) and by impregnation (IMP). By temperature programmed desorption (TPD), two NO desorption peaks at 100 and 260‡C were observed over both SSIE and IMP catalysts with complete desorption after 450‡C. CO desorbed from SSIE catalyst between 50 and 200‡C. In the same temperature interval negligible CO₂ desorption was observed, most likely due to reaction of CO with trace of cobalt oxides. Over IMP catalysts, desorption of CO₂ was found mainly at 500‡C. By comparing CO TPD profiles from physical mixtures of cobalt oxides and HBEA, SSIE catalysts most likely contained cobalt cations in zeolite exchange position while IMP catalysts had cobalt in oxidic forms. The SSIE catalysts were active for NO reduction at 400 and 500‡C with a maximum conversion at 500‡C. However, the activity in the presence of water and oxygen was low. Water might inhibit the reaction by blocking active sites for NO and CO, while oxygen reacted with CO to form carbon dioxide. The activity of SSIE was better than IMP catalyst.     

Hydrogenation active sites of unsupported molybdenum sulfide catalysts for hydroprocessing heavy oils

The purpose of the present study was to elucidate the nature of the hydrogenation active sites on unsupported molybdenum sulfide catalysts, aimed at the improvement of the catalysts for the slurry processes. The number of hydrogenation active sites was found to relate to the “inflection” on the basal plane of the catalyst particles. The comparison of the catalytic activity to that of an oil-soluble catalyst in the hydroprocessing of heavy oils suggests that the performance of the oil-soluble catalyst was near the maximum, unless another component such as Ni or Co was incorporated.