Mechanism of the hydrodenitrogenation of o-toluidine and methylcyclohexylamine over NiMo/γ-Al2O3

The hydrodenitrogenation (HDN) of o-toluidine and its reaction intermediates was studied over a NiMo/γ-Al₂O₃ catalyst. The kinetics of the HDN of methylcyclohexylamine and of the hydrogenation of cyclohexene were also studied. Hydrogenation of o-toluidine alone produces methylcyclohexene and methylcyclohexane. When a sufficient quantity of cyclohexene is added during the HDN of toluidine, methylcyclohexylamine, the first intermediate in the hydrogenation of toluidine, becomes detectable. Because of its strong adsorption constant and high rate constant for reacting further to methylcyclohexene and methylcyclohexane, methylcyclohexylamine is not observed in the HDN of toluidine. Adding cyclohexene decreases the adsorption of methylcyclohexylamine, thus enabling its detection. The rate and adsorption constants of methylcyclohexylamine and cyclohexene in the HDN of methylcyclohexylamine were calculated by fitting the kinetic data to a Langmuir–Hinshelwood equation. A two-site model was used to describe the surface reactions, with one site for the methylcyclohexylamine reactions and the other for the cyclohexene reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Steam reforming of liquid petroleum gas over Mn-promoted Ni/γ-Al2O3 catalysts

Three different Mn-promoted Ni/γ-Al₂O₃ catalysts, Mn/Ni/γ-Al₂O₃, Mn-Ni/γ-Al₂O₃ and Ni/Mn/γ-Al₂O₃, were prepared and applied to the steam reforming of liquid petroleum gas (LPG) mainly composed of propane and butane. For comparison, Ni/γ-Al₂O₃ catalysts containing different amount of Ni were also examined. In the case of the Ni/γ-Al₂O₃ catalysts, 4.1 wt% Ni/γ-Al₂O₃ showed the stable catalytic activity with the least amount of coke formation. Among the various Mn-promoted Ni/γ-Al₂O₃ catalysts, Mn/Ni/γ-Al₂O₃ showed the stable catalytic activity with the least amount of coke formation. It also exhibited a similar H₂ formation rate compared with Ni/γ-Al₂O₃. Several characterization techniques—N₂ adsorption/desorption, X-ray diffraction (XRD), CO chemisorptions, temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS) and CHNS analysis—were employed to characterize the catalysts. The catalytic activity increased with increasing amount of chemisorbed CO for the Mn-promoted Ni/γ-Al₂O₃ catalysts. The highest proportion of Mn⁴⁺ species was observed for the most stable catalyst.     

Preparation,characterization and hydrotreating performances of ZrO2–Al2O3-supported NiMo catalysts

A series of Al₂O₃–ZrO₂ composite supported NiMo catalysts with various ZrO₂ contents were prepared. Several techniques including XRD, SEM, N₂ physisorption, H₂-TPR, and UV–vis DRS were used for typical physico-chemical properties characterization of the ZrO₂–Al₂O₃ composite supports and their NiMo/ZrO₂–Al₂O₃ catalysts. The test results showed that the composite supports prepared by the chemical precipitation method existed as amorphous phase in the samples with insufficient contents of ZrO₂, and the incorporation of ZrO₂ into supports provided a better dispersion of NiMo species, which made their reductions become easier. The pyridine-adsorbed FT-IR results indicated that the Lewis acid sites of catalysts increased significantly by the introduction of ZrO₂ into the supports. The activities of these catalysts for diesel oil hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) were evaluated in a high pressure micro-reactor system. The results showed that the ZrO₂–Al₂O₃-supported NiMo catalysts with suitable ZrO₂ contents exhibited much higher catalytic activities than that of Al₂O₃-supported one, and when the ZrO₂ contents were 15% and 5%, the NiMo/Al₂O₃–ZrO₂ catalysts presented the highest HDS and HDN activities, respectively.     

Coking of a Ni–Mo/Al2O3 hydrotreatment catalyst: Simulated and experimental results

Coking due to possible cracking reactions in a Ni–Mo/Al₂O₃ hydrotreatment catalyst was studied independently of the sulfur present. A model has been tested to predict the carbon concentration profiles obtained during the reaction. Simulated and experimental results are compared and several kinetic equations are tested in the simulation. The model predicts well the average carbon level in the catalytic bed and gives a slightly higher maximum carbon concentration.     

Comparative investigations of the catalytic properties of an anodic Al2O3-coated catalyst and of α- and γ-Al2O3 bulk catalysts

The catalytic properties of an Al₂O₃-coated catalyst formed by anodic oxidation of aluminium were compared with those of α- and of γ-Al₂O₃- bulk catalysts in the dehydration of 2-propanol and in the isomerization of n-butenes. In the dehydration reaction both the Al₂O₃-coated catalyst and the γ-Al₂O₃ bulk catalyst show approx. the same activities and activation energies. However, the reaction rate based on the unit of the surface area for the Al₂O₃-coated catalyst is approx. 30 times larger than that for the γ-A1₂O₃ bulk catalyst. In the isomerization of the individual isomeric n-butenes the Al₂O₃-coated catalyst was more active than the γ-Al₂O₃, bulk catalyst and under otherwise equal conditions equilibrium was reached at approx. 80 K lower temperature.     

The effect of toluene-insoluble fraction of coal on catalytic activities of a Ni-Mo-γ-Al2O3 catalyst in the hydrotreating of coal liquids

Feedstocks prepared with 723 K⁺ distillation residues obtained from the Australian brown coalderived oil and hydrogenated creosote oil were hydrotreated to elucidate the effects of toluene-insoluble fractions of coal on the catalytic activities of a Ni-Mo-γ-Al₂O₃ catalyst. The toluene-insoluble fractions exerted harmful effects on the catalyst by deactivation due to carbonaceous deposits formed on the catalyst surfaces. The deactivation of the catalyst was more significant in hydroconverting of 623 K⁺ residues to 623 K⁻ oil fractions and hydrodenitrogenation reactions than in hydrodesulfurization reaction.The analyses of carbonaceous deposits on the spent catalyst surfaces by using an EPMA and a CP/MAS ¹³C-NMR indicated that the toluene-insoluble fractions were too refractory to be hydrogenated on the catalyst surfaces and hindered the reactant molecules from accessing to the active sites compared to asphaltenes.     

Activation and deactivation of the commercial-type CuO–Cr2O3–Fe2O3 high temperature shift catalyst

This work elucidates the structural evolution of a commercial-type iron oxide-based high temperature water–gas shift (HT-WGS) catalyst during activation and deactivation stages. The findings highlight the importance of Cu–FeO _x interfaces. Based on the new insights, future improvement of commercial iron-based catalysts should focus on stabilization of the active Cu–FeO _x interface. Much effort has been devoted to understanding the structure, mechanism, and promotion of the commercial-type CuO–Cr₂O₃–Fe₂O₃ catalyst for the high temperature water–gas shift (HT-WGS) reaction. However, structural evolution of the catalyst during the activation and deactivation stages was rarely reported. Herein, catalyst characterization, temperature-programmed studies, and kinetic analysis were conducted on iron oxide-based HT-WGS catalysts. Addition of Cu was found to accelerate both the bulk (Fe₂O₃ → Fe₃O₄) and surface (active FeO _x–Cu interface) transformations during the catalyst activation stage. During catalyst deactivation, Cu accelerated both sintering of the Fe₃O₄ bulk phase and unfavorable encapsulation of the metallic Cu particles with a substantial FeO _x overlayer. The loss of the initial active Cu–FeO _x interfacial sites reversed the promotional effect of Cu.     

Reactivity of surface isocyanate species with NO, O2 and NO+O2 in selective reduction of NOχ over Ag/Al2O3 and Al2O3 catalysts

Reactivity of surface isocyanate (NCO(a)) species with NO, O₂ and NO+O₂ in selective reduction of NOχ over Ag/Al₂O₃ and Al₂O₃ catalysts was studied by a pulse reaction technique and an in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The NCO(a) species on Ag/Al₂O₃ reacted with O₂ or NO+O₂ mixture gas to produce N₂ effectively above 200°C, while the reaction of NCO(a) with NO hardly produced N₂ even at 350°C. In the case of Al₂O₃ alone, less N₂ was detected in the reaction of NCO(a) with NO+O₂, indicating that silver plays an important role in the N₂ formation from NCO(a). These behaviors of the reactivity of NCO(a) species with reactant gases were in good agreement with the changes in NCO(a) bands shown by in situ DRIFT measurements. Based on these findings, the role of NCO(a) species in the selective reduction of NOχ on Ag/Al₂O₃ and Al₂O₃ catalysts is discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Effect of water on liquid phase DME synthesis from syngas over hybrid catalysts composed of Cu/ZnO/Al2O3 and γ-Al2O3

DME synthesis from syngas via methanol has been carried out in a single-stage liquid phase reactor. Cu/ ZnO/Al₂O₃ and γ-Al₂O₃ were used together as methanol synthesis catalyst and dehydration catalyst, respectively. The influence of water on the catalytic system was investigated mainly. Water affected the activity of methanol dehydration catalyst as well as methanol synthesis catalyst. Thus, removal of water from the reaction system, by adding a dehydrating agent or controlling methanol formation rate by the reaction parameters, was efficient in maintaining the high catalytic activity and stability. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8-10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Influence of the support composition on the hydrogenation of acrolein over Ag/SiO2–Al2O3 catalysts

The gas phase hydrogenation of acrolein over supported silver catalysts has been investigated with a focus on the influence of the support acidity. Acidity has been varied by preparing silver catalysts supported on silica/alumina supports with varying SiO₂/Al₂O₃ ratio. After the catalytic experiments the Ag catalysts exhibit similar particle sizes, as revealed with TEM (transmission electron microscopy). The acidity of the samples was estimated using TPD of adsorbed ammonia which gives the total acidity of the samples, furthermore by IR of adsorbed pyridine to identify the Brønsted and Lewis acidity. No Brønsted acidity was found, and the Lewis acidity showed a clear dependence on the support composition. It is shown that a high total acidity and a high amount of strong Lewis acid sites on the catalysts cause a low conversion of acrolein and low selectivity to allyl alcohol. The interaction of silver with the support or effects of the metal–support perimeter are discussed as possible reasons for this behaviour.     

Ru-Pt catalysts supported on Al2O3 and SiO2─Al2O3 for the selective ring opening of naphthenes

Alumina and silica-alumina supported Ru-Pt catalysts were evaluated for the ring opening of naphthenes. Pt, Ru, and Ru-Pt catalysts were prepared by the impregnation of inorganic precursors over γ-alumina and silica-alumina supports. The catalysts were evaluated by temperature programmed reduction (TPR), pyridine temperature programmed desorption (TPD), CO-FTIR, and by test reactions of 33DM1B isomerization, cyclohexane dehydrogenation, cyclopentane hydrogenolysis, and the ring opening of decalin. The strong interaction between the metals (Pt-Ru) was attributed to their reductions occurring simultaneously. The acidity and strength of the acid sites of the monometallic Ru catalyst were higher than those of the monometallic Pt catalyst. The total acidity (Lewis and Brønsted) and the strength of the acid sites were higher for the silica-alumina supported catalysts. The silica-alumina catalysts had 10 times more Brønsted acidity than the γ-alumina ones and an increased activity and selectivity to decalin ring opening products. Supported monometallic Ru had the best performance for the ring opening reaction.     

Gas-phase dehydration of glycerol over commercial Pt/γ-Al2O3 catalysts

Gas-phase dehydration of glycerol to produce acrolein was investigated over commercial catalysts based onγ-Al2O3, viz. A-64, A-56, I-62, AP-10, AP-56, AP-64 and KR-104. To understand the effect of Cl?anions, HCl-impregnated sup-ports have been investigated in the dehydration reaction of glycerol at 375 °C. For comparison, various H-zeolites were also examined. It was found that the glycerol conversion over the solid acid catalysts was strongly dependent on their acidity and surface area. And the relationship between the catalytic activity and the acidity of the catalysts was discussed. The outstanding properties of Pt/γ-Al2O3 catalyst systems for the dehydration of glycerol were revealed. Pt/γ-Al2O3 catalyst (AP-64) showed the highest catalytic activity after 50 h of reaction with an acrolein selectivity of 65%at a conversion of glycerol of 90%. Based on these results, catalysts based onγ-Al2O3 appear to be most promising for gas phase dehydration of glycerol.     

The nature of the deactivation of hydrothermally stable Ni/SiO2–Al2O3 catalyst in long-time aqueous phase hydrogenation of crude 1,4-butanediol

The deactivation of Ni/SiO₂–Al₂O₃ catalyst in hydrogenation of crude 1,4-butanediol was investigated. During the operation time of 2140 h, the catalyst showed slow activity decay. Characterization results, for four spent catalysts used at different time, indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst. The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet. Such carbonaceous species might be eliminated through either direct H₂ reduction or the combined oxidation–reduction methodologies.     

Role of support in CO2 reforming of CH4 over a Ni/γ-Al2O3 catalyst

A catalyst of 10% Ni/γ-Al₂O₃ for CO₂/CH₄ reforming was prepared and characterized by TPR, TPD, XPS, XRD and activity measurements. XPS and TPR showed that Ni mainly exists in the form of NiAl₂O₄ in the calcined catalyst and is hard to reduce below 650°C, indicating a strong interaction between metal and support. Reduction of the calcined catalyst results in fine particles of Ni⁰, with an average diameter of about 20 nm as determined by XRD. The uptake of H on the reduced catalyst measured by H₂-TPD is 4.2–4.6 mole per mole of Ni species and does not depend on the reduction degree of Ni species. This provides a convincing piece of evidence for the occurrence of hydrogen spillover in the reduced catalyst. Only reduced catalysts present good activity, but the degree of nickel reduction has almost no effect on the reforming activity. This seems to suggest that Ni⁰ is vital for the reforming activity, but γ-Al₂O₃ is also involved in CO₂/CH₄ reforming and contributes even more. Based on the mechanism proposed by Bradford et al. and on our observations, a mechanistic model has been proposed to elucidate the role of γ-Al₂O₃ in CO₂/CH₄ reforming.     

The effect of the Ce content on the oxidative dehydrogenation of propane over CrOy-CeO2/γ-Al2O3 catalysts

A series of CrO_y (17.5 wt%)-CeO₂ (X wt%)/γ-Al₂O₃ catalysts (X=0, 0.5, 2, 5, 8) with various Ce contents were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 550℃ and 0.1 MPa. The prepared catalysts were characterized by BET, H₂-TPR, O₂-TPD, XPS, XRD, SEM-EDS and Raman spectroscopy. Among the prepared catalysts, the 17.5Cr-2Ce/Al catalyst with the largest amount of lattice oxygen exhibited the best catalytic performance for the dehydrogenation of propane to propylene with lattice oxygen. The decreased presence of oxygen defects and reducibility were the factors responsible for the improved dehydrogenation activity of the catalysts. The CeO₂ layer could inhibit the evolution of lattice oxygen (O^2-) to electrophilic oxygen species (O₂^-), and the oxygen defects on the catalyst surface were reduced. The inhibited lattice oxygen evolution prevented the deep oxidation of propane or propylene, the average CO_x selectivity decreased from 24.41% (17.5Cr/Al) to 5.71% (17.5Cr-2Ce/Al), and the average propylene selectivity increased from 60.15% (17.5Cr/Al) to 85.05% (17.5Cr-2Ce/Al).     

The effect of the Ce content on the oxidative dehydrogenation of propane over CrOy-CeO2/γ-Al2O3 catalysts

A series of CrO_y (17.5 wt%)-CeO₂ (X wt%)/γ-Al₂O₃ catalysts (X = 0, 0.5, 2, 5, 8) with various Ce contents were prepared by a wetness impregnation method and were applied to the dehydrogenation of propane to propylene at 550 °C and 0.1 MPa. The prepared catalysts were characterized by BET, H₂-TPR, O₂-TPD, XPS, XRD, SEM-EDS and Raman spectroscopy. Among the prepared catalysts, the 17.5Cr-2Ce/Al catalyst with the largest amount of lattice oxygen exhibited the best catalytic performance for the dehydrogenation of propane to propylene with lattice oxygen. The decreased presence of oxygen defects and reducibility were the factors responsible for the improved dehydrogenation activity of the catalysts. The CeO₂ layer could inhibit the evolution of lattice oxygen (O²⁻) to electrophilic oxygen species (O₂⁻), and the oxygen defects on the catalyst surface were reduced. The inhibited lattice oxygen evolution prevented the deep oxidation of propane or propylene, the average CO_x selectivity decreased from 24.41% (17.5Cr/Al) to 5.71% (17.5Cr-2Ce/Al), and the average propylene selectivity increased from 60.15% (17.5Cr/Al) to 85.05% (17.5Cr-2Ce/Al).     

Dehydrogenation of ethylbenzene with CO2 over V2O5/Al2O3–ZrO2 catalyst

V-containing catalysts supported on Al₂O₃, modified with varying amounts of ZrO₂, were prepared by impregnation method. Dehydrogenation of ethylbenzene with CO₂ was run over these catalysts in a fixed-bed downflow stainless steel reactor. Compared with pure Al₂O₃ support, a small amount of ZrO₂ in the support led to a significant increase in catalytic activity. Partial reduction of vanadium oxides and carbon deposition were the main reasons for the decreased catalytic activity.