Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P

TiO₂- and CeO₂-promoted bulk Ni₂P catalysts were prepared by impregnation and in-situ H₂ temperature-programmed reduction method. The prepared catalysts were characterized by XRD and XPS. The hydrogenation activities of the catalysts were studied using 1.5 wt.% 1-heptene in toluene and 1.0 wt.% phenylacetylene in ethanol as the model feeds. The results indicate that bulk Ni₂P possesses low hydrogenation activity but is tunable by simply controlling the content of the additives (TiO₂ or CeO₂), suggesting that TiO₂ and CeO₂ are effective promoters to enhance the hydrogenation activity of Ni₂P.     

Co-decorated carbon nanotube-supported Co–Mo–K sulfide catalyst for higher alcohol synthesis

Using chemical reduction-deposition method, a type of metallic cobalt-decorated multi-walled carbon nanotubes, noted as y%(mass percentage)Co/MWCNTs, was prepared. TEM, SEM and XRD measurements demonstrated that the metallic cobalt was evenly coated on the MWCNT substrate, with granule-diameter of the Co _x ⁰ -crystallites of 5–8 nm. Using the y%Co/MWCNTs as support, a type of supported Co–Mo–K sulfide catalysts, noted as x%(Co _i Mo _j K _k )/(y%Co/MWCNTs), for higher alcohol synthesis (HAS) was developed. It was experimentally shown that using the Co-modified MWCNTs in place of simple MWCNTs or activated carbon (AC) as the catalyst support led to a significant increase in activity of CO hydrogenation conversion and improvement in the selective formation of C₂₊-alcohols. Under the reaction condition of 5.0 MPa, 613 K, CO/H₂/N₂ = 45/45/10 (v/v) and GHSV = 3600 ml_STPh⁻¹ g _−cat. ⁻¹ , the observed STY of C_1–4-alcohols reached 154.1 mgh⁻¹g _−cat. ⁻¹ at 12.6% conversion of CO over the 11.6%(Co₁Mo₁K_0.6)/(6.4%Co/MWCNTs) catalyst, which was 1.76 and 2.33 times as high as that (87.7 and 66.1 mgh⁻¹g _−cat. ⁻¹ ) of the reference systems supported by simple MWCNTs and AC respectively. Ethanol became the predominant product of the CO hydrogenation, with carbon-based selectivity ratio of C_2–4-alcohols to CH₃OH reaching 3.6 in the products. It was experimentally found that using the Co-modified MWCNTs in place of simple MWCNTs or AC as the catalyst support caused little change in the apparent activation energy for the conversion of CO, but led to a slight increase in the molar percentage of catalytically active Mo-species (Mo⁴⁺) in the total Mo-amount at the surface of the functioning catalyst. Based upon the results of TPD investigation, it could be inferred that, under the reaction condition of HAS, there existed a considerably larger amount of adsorbed H-species and CO-species on the functioning catalyst, thus in favour of increasing the rate of a series of surface hydrogenation reactions in HAS.     

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.     

Performance of Ni catalyst supported on La-hexaaluminate in CO<Subscript>2</Subscript> reforming of CH<Subscript>4</Subscript>

CO₂ reforming of CH₄ was performed using Ni catalyst supported on La-hexaaluminate which has been an well-known material for high-temperature combustion. La-hexaaluminate was synthesized by sol-gel method at various conditions where different amount of Ni (5–20 wt%) was loaded. Ni/La-hexaaluminate experienced 72 h reaction and its catalytic activity was compared with that of Ni/Al₂O₃, Ni/La-hexaaluminate shows higher reforming activity and resistance to coke deposition compared to the Ni/Al₂O₃ model catalyst. Coke deposition increases proportionally to Ni content. Consequently, Ni(5)/La-hexaaluminate(700) is the most efficient catalyst among various Ni/La-hexaaluminate catalysts regarding the cost of Ni in Ni(X)/La-hexaaluminate catalysts. BET surface area, XRD, EA, TGA and TPO were performed for surface characterization. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Catalytic Production of Carbon Nanotubes by Decomposition of CH4 over the Pre-reduced Catalysts LaNiO3, La4Ni3O10, La3Ni2O7 and La2NiO4

A large amount of more graphitic carbon nanotubes with a narrow size distribution was produced from catalytic decomposition of CH₄ over pre-reduced LaNiO₃, La₄Ni₃O₁₀, La₃Ni₂O₇ and La₂NiO₄. The structure and component of fresh and reduced LaNiO₃, La₄Ni₃O₁₀, La₃Ni₂O₇ and La₂NiO₄ were determined by X-ray diffraction (XRD). The carbon nanotubes obtained were characterized by means of transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Thermal oxidation of carbon nanotubes in air was made by thermogravimetric experiments (TG). The results revealed that the value of La/Ni in different catalyst precursors influences the diameter distribution and graphitic degree of carbon nanotubes. Lower La/Ni leads to wider diameter and higher graphitic degree of carbon nanotubes.     

Catalytic hydrotreating of indole,benzothiophene, and benzofuran over Mo2N

The activity of -Mo₂N for heteroatom removal from benzofuran, benzothiophene, and indole has been investigated. -Mo₂N is found to be an effective catalyst in all three cases. The distribution of products observed as a function of temperature suggests that the reaction mechanism is similar for all three reactants. Rapid hydrogenation of the heterocyclic ring is followed by hydrogenolysis of the X-C bond in the saturated ring and release of the heteroatom as XH _n (X = O, S, N). The product formed in the last step of the sequence is ethylbenzene. Hydrogenation of the benzene ring in ethylbenzene is not observed, but evidence is found for hydrogenolysis and dealkylation of the alkyl group.     

Characterization of aerogel Ni/Al2O3 catalysts and investigation on their stability for CH4-CO2 reforming in a fluidized bed

The CH₄-CO₂ reforming was investigated in a fluidized bed reactor using nano-sized aerogel Ni/Al₂O₃ catalysts, which were prepared via a sol–gel method combined with a supercritical drying process. The catalysts were characterized with BET, XRD, H₂-TPR and H₂-TPD techniques. Compared with the impregnation catalyst, aerogel catalysts exhibited higher specific surface areas, lower bulk density, smaller Ni particle sizes, stronger metal-support interaction and higher Ni dispersion degrees. All tested aerogel catalysts showed better catalytic activities and stability than the impregnation catalyst. Their catalytic stability tested during 48 h reforming was dependent on their Ni loadings. Characterizations of spent catalysts indicated that only limited graphitic carbon formed on the aerogel catalyst, while massive graphitic carbon with filamentous morphology was observed for the impregnation catalyst, leading to significant catalytic activity degradation. An aerogel catalyst containing 10% Ni showed the best catalytic stability and the lowest rate of carbon deposition among the aerogel catalysts due to its small Ni particle size and strong metal-support interaction.     

Development of iso-octane fuel processor system for fuel cell applications

An iso-octane fuel processor system with three different reaction stages, autothermal reforming (ATR) reaction of iso-octane, high temperature shift (HTS) and low temperature shift (LTS) reactions, was developed for applications in a fuel cell system. Catalytic properties of the prepared Ni/Fe/MgO/Al₂O₃ and Pt–Ni/CeO₂ or molybdenum carbide catalysts were compared to those of commercial NiO/CaO/Al₂O₃ and Cu/Zn/Al₂O₃ catalysts for ATR and LTS reaction, respectively. It was found that the prepared catalysts formulations in the fuel processor system were more active than those of the commercial catalysts. As the exit gas of iso-octane ATR over the Ni/Fe/MgO/Al₂O₃ catalyst was passed through Fe₃O₄–Cr₂O₃ catalyst for HTS and Mo₂C or Pt–Ni/CeO₂ catalyst for LTS reaction, the concentration of CO in hydrogen-rich stream was reduced to less than 2400 ppm. The results suggest that the iso-octane fuel processor system with prepared catalysts can be applied to PEMFC system when a preferential partial oxidation reaction is added to KIST iso-octane reformer system.     

Aromatization of n-Butane Over Supported Mo2C Catalysts

Similarly to the case of methane, ethane and propane, Mo₂C deposited on ZSM-5 significantly enhanced the aromatization of n-butane observed on ZSM-5 (SiO₂/Al₂O₃ ratio of 80) alone. The catalytic performance of Mo₂C/ZSM-5 sensitively depended on its preparation and pretreatment. The selectivity of aromatics measured for pure ZSM-5 increased from 11-13% to 28-34% at the conversion level of 60-65%. The formation of aromatics was also observed over Mo₂C/SiO₂.     

Ru/γ-Fe2O3-Al2O3催化剂在磁稳定床中 苯选择性加氢性能

设计建造了磁稳定床加氢实验装置,以磁性氧化铝为载体,通过浸渍法制备了蛋壳型钌基磁性Ru/γ-Fe₂O₃-γ-Al₂O₃微球催化剂,详细考察了磁性催化剂的制备参数、磁稳定床的操作参数对苯选择性加氢的影响。结果表明磁稳定床的链式操作状态提高了环己烯的选择性,证实了所研制的蛋壳型钌基磁性微球催化剂适用于磁稳定床中苯的选择性加氢工艺,具有较好的应用前景。     

Carbon dioxide hydrogenation over nickel-, ruthenium-, and copper-based catalysts: Review of kinetics and mechanism

This study critically reviews the mechanism of CO₂ hydrogenation over Ni, Ru, and Cu, and the effect of catalyst properties and operating conditions on reaction kinetics. Most studies have reported the presence of CO and formate species on Ni-, Ru-, and Cu-based catalysts, where subsequent conversion of these species depends on the type of catalyst and the physicochemical properties of the catalyst support. Methane is the major product that forms during CO₂ hydrogenation over Ni and Ru catalysts, while methanol and CO are mainly produced on Cu catalysts. A different approach for catalyst formulations and/or process development is required where long chain hydrocarbons are desired.     

The role of nickel in pyridine hydrodenitrogenation over NiMo/Al2O3

Al₂O₃ supported Mo, Ni, and NiMo/Al₂O₃ catalysts with various Ni contents were prepared to investigate the role of Ni as a promoter in a NiMo bimetallic catalyst system. The hydrodenitrogenation (HDN) reaction of pyridine as a catalytic probe was conducted over these catalysts under the same reaction conditions and the catalysts were characterized using BET surface area measurement, infrared spectroscopy, temperature programmed reduction, DRS and ESR. According to the results of reaction experiments, the NiMo/Al₂O₃ catalyst showed higher activity than Mo/Al₂O₃ catalyst in the HDN reaction and particularly the one with atomic ratio [Ni/(Ni+Mo)]=0.3 showed the best activity for the HDN of pyridine. The findings of this study lead us to suggest that the enhancement in the HDN activity with nickel addition could be attributed to the improvement in the reducibility of molybdenum and the formation of Ni-Mo-O phase.     

Methane reforming reaction with carbon dioxide over SBA-15 supported Ni-Mo bimetallic catalysts

A series of mesoporous molecular sieves SBA-15 supported Ni-Mo bimetallic catalysts (xMo1Ni, Ni = 12 wt.%, Mo/Ni atomic ratio = x, x = 0, 0.3, 0.5, 0.7) were prepared using co-impregnation method for carbon dioxide reforming of methane. The catalytic performance of these catalysts was investigated at 800 °C, atmospheric pressure, GHSV of 4000 ml·g_cat^− 1·h^− 1 and a V(CH₄)/(CO₂) ratio of 1 without dilute gas. The result indicated that the Ni-Mo bimetallic catalysts had a little lower initial activity compared with Ni monometallic catalyst, but it kept very stable performance under the reaction conditions. In addition, the Ni-Mo bimetallic catalyst with Mo/Ni atomic ratio of 0.5 showed high activity, superior stability and the lowest carbon deposition rate (0.00073g_c·g_cat^− 1·h^− 1) in 600-h time on stream. The catalysts were characterized by power X-ray diffraction, N₂-physisorption, H₂-TPR, CO₂-TPD, TG and TEM. The results indicate that the Ni-Mo bimetallic catalysts have smaller metal particle, higher metal dispersion, stronger basicity, metal-support interaction and Mo₂C species. It is concluded that Mo species in the Ni-Mo bimetallic catalysts play important roles in reducing effectively the amount of carbon deposition, especially the amount of shell-like carbon deposition.     

On the LiCo2/3Ni1/6Mn1/6O2 positive electrode material

LiCo_2/3Ni_1/6Mn_1/6O₂ layered oxide was synthesized by the combustion method that led to a crystalline phase with good homogeneity and low particles size. The structural properties of the prepared positive electrode material were investigated by performing XRD Rietveld refinement. Practically no Li/Ni mixing was detected evidencing that the studied compound adopts almost an ideal α-NaFeO₂ type structure. The Li||LiCo_2/3Ni_1/6Mn_1/6O₂ cell showed a discharge capacity of 199 mAh g⁻¹ when cycled in the 2.7–4.6 V potential range while the best cycling performances were recorded when the upper cut off is fixed at 4.5 V. Structural changes in Li_xCo_2/3Ni_1/6Mn_1/6O₂ with lithium electrochemical de-intercalation were studied using X-ray diffraction. This study clearly shows the existence of a solid solution domain in the 0.1 < x < 1.0 composition range while for x = 0.1, a new phase appears explaining the decrease of the electrochemical performance when the cell is cycled at high upper cut off voltage.     

Remarkable support effect of ZrO2 upon the CO2 reforming of CH4 over supported molybdenum carbide catalysts

In reforming of CH₄ with CO₂ over molybdenum carbide catalysts, the catalytic performance of unsupported hexagonal Mo₂C prepared by direct carburization of MoO₃ was considerably different from a similar composition, cubic MoC_1−x (x≈0.5), prepared through nitriding before carburization. The conversion levels over MoC_1−x were substantially higher than those over Mo₂C, although the turnover frequencies were lower. X‐ray diffraction analysis indicated that Mo₂C deactivated by conversion to MoO₂ during the reaction, but the MoC_1−x was transformed to the hexagonal Mo₂C and remained stable. The activity of Mo₂C dispersed on various supports for the CH₄–CO₂ reaction was also investigated. The performance depended strongly on the property of supports, with the ZrO₂‐supported Mo₂C catalyst exhibiting the highest activity and durability for this reaction. Moreover, deactivation of Mo₂C/ZrO₂ at ambient pressure was suppressed by decreasing the loading amount of Mo₂C. This revised version was published online in August 2006 with corrections to the Cover Date.     

One step synthesis of mibk (methyl isobutyl ketone) from acetone over CaO-supported Ni catalyst

One step synthesis of MIBK from acetone over Ni/CaO catalysts was studied. 10 wt% Ni/CaO catalysts were prepared by conventional impregnation method (catalyst I), and liquid phase oxidation method using NaOCl as an oxidant (catalyst L). Catalyst L showed much higher activity than catalyst I because of recovered CaO pore structure and high BET surface area. Catalyst C, prepared by coprecipitation method, showed 60% of MIBK selectivity with a fairly high overall acetone conversion. Catalysts L and C had two CO₂ desorption states (α, Β). Incorporated Ni enabled support precursor [Ca(CO)₃] to decompose easily into CaO andCO₂even at low temperature and generated weakCO₂desorption state (α) which was from active state.     

Selective transfer of cations between two electrolytes using the intercalation properties of Chevrel phases

A device based on an electrochemical transfer junction (constituted by M_xMo₆S₈ or M_xMo₆Se₈) placed between two tanks allows the transfer of cations by application of current density controlled between electrodes placed in tanks. The transfer protocol was tested on different mixed electrolytes containing cations directly engaged in the batteries industry (M²⁺ = Co²⁺, Ni²⁺, Cd²⁺, Zn²⁺, Mn²⁺, Cu²⁺). Good performances of the process are provided until 1.6 mA cm⁻². The electrolysis through an electrochemical transfer junction made of Chevrel phases represents a suitable method for the selective extraction of cations with appreciable selectivity rates with an appropriate choice of the host lattice (sulfide or selenide). Remarkable separations between Co/Ni, Zn/Mn with Mo₆S₈ and Cd/Zn, Cd/Ni, Cd/Co and Zn/Ni, with Mo₆Se₈ were observed.     

Gas phase hydrogenation of maleic anhydride to tetrahydrofuran by Cu/ZnO/TiO2 catalysts in the presence of n-butanol

Cu/ZnO/TiO₂ catalysts were prepared via the coprecipitation method. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectrometry, temperature programmed reduction, and N₂ adsorption. The catalytic activity of Cu/ZnO/TiO₂ catalyst in gas phase hydrogenation of maleic anhydride in the presence of n-butanol was studied at 235–280 °C and 1 MPa. The conversion of maleic anhydride was more than 95.7% and the selectivity of tetrahydrofuran was up to 92.7%. At the same time, n-butanol was converted to butyraldehyde and butyl butyrate via reactions, namely, dehydrogenation, disproportionation, and esterification. There were two kinds of CuO species present in the calcined Cu/ZnO/TiO₂ catalysts. At a lower copper content, the CuO species strongly interacted with ZnO and TiO₂; at a higher copper content, both the surface-anchored and bulk CuO species were present. The metallic copper (CuO) produced by the reduction of the surface-anchored CuO species favored the deep hydrogenation of maleic anhydride to tetrahydrofuran. The deep hydrogenation activity of Cu/ZnO/TiO₂ catalyst increased with the decrease of crystallite sizes of CuO and the increase of microstrain values. Compensations of reaction heat and H₂ in the coupling reaction of maleic anhydride hydrogenation and n-butanol dehydrogenation were distinct.     

Production of hydrogen by steam reforming of bio-oil over Ni/Al2O3 catalysts: Effect of addition of promoter and preparation procedure

Catalytic steam reforming of bio-oil was investigated in a fixed bed tubular reactor for production of hydrogen. Two series of nickel/alumina (Ni/Al₂O₃) supported catalysts promoted with ruthenium (Ru) and magnesium (Mg) were prepared. Each catalyst of the first series (Ru–Ni/Al₂O₃) was prepared by co-impregnation of nickel and ruthenium on alumina. They were examined to investigate the effect of adding ruthenium on the performance of the catalysts for hydrogen production. The effect of the temperature, the most effective parameter in the steam reforming of bio-oil, on the activity of the catalysts was also investigated. Each catalyst of the second series (Ni–MgO/Al₂O₃) was prepared by consecutive impregnation using various preparation procedures. They were tested to determine the effect of adding magnesium as well as the effect of the preparation procedure on the outlet gas concentrations. It was shown that in both series, the catalysts were more efficient in hydrogen production as well as carbon conversion than Ni/Al₂O₃ catalysts. The highest hydrogen yield was 85% which was achieved over Ru–Ni/Al₂O₃ at 950 °C. It was also found that the effect of adding a small amount of ruthenium was superior to that of nickel on the yield of hydrogen when the nickel content was equal to or greater than 10.7%.     

Hydrogen Production by Steam Reforming of Commercially Available LPG in UAE

Steam reforming of commercially available LPG using Ru/Al₂O₃ and Ni/Al₂O₃ catalysts has been studied at temperatures between 573 and 773 K. Ru/Al₂O₃ catalyst showed higher rates of reaction and lower activation energies of the three main components of LPG, compared with Ni/Al₂O₃. However, Ni/Al₂O₃ catalyst showed a better H₂:CH₄ selectivity. The activation energy of n-butane was the lowest over Ru/Al₂O₃, whereas over Ni/Al₂O₃, propane had the lowest activation energy. The activation energy of i-butane was always the highest over both catalysts, which suggests that both catalysts performed better with unbranched molecules. A slight increase in activation energy was observed, when each component of the LPG mixture was studied separately as a pure gas, compared with being mixed in LPG. At a constant temperature of 773 K, hydrogen production yield and H₂:CH₄ selectivity were determined using Ru/Al₂O₃ at different steam:carbon (S:C) ratios and LPG flow rates. It was found that the yield and selectivity increased with the increase in S:C ratio and the decrease in the flow rate. The highest yield of 0.64 was achieved using S:C ratio of 6.5 and a LPG flow rate of 50 mL min^?1. The work provides valuable information on steam reforming of pure components of LPG, compared with when they are in the mixture. The comparison is done using conventional steam reforming catalyst, Ni/Al₂O₃, and compared with Ru/Al₂O₃. The observed trends and variations in reaction rates, in pure and mixed gases, indicated that the mechanism of steam reforming of a hydrocarbon mixture depends on its composition.