Effects of the preparation methods on the performance of the Cu–Cr–Fe/γ-Al2O3 catalysts for the synthesis of 2-methylpiperazine

Co-precipitation, impregnation and ultrasonic sol–gel (USG) methods have been used to prepare Cu–Cr–Fe/γ-Al₂O₃ catalysts, which were further used to synthesize 2-methylpiperazine. The catalysts were characterized by XRD, XPS, TG/DSC, BET, TPR, AAS and TEM. It is found that preparation method can greatly impact the catalytic performance of the catalysts, the Cu–Cr–Fe/γ-Al₂O₃ catalyst prepared by the ultrasonic sol–gel method proved to be the most active and stable for this reaction. The dispersion and stabilization of Cu⁰ in the reduced catalysts are attributed to the existence of CuCr₂O₄ and Fe₂O₃. A surprising copper migration was detected by XPS analysis for the Cu–Cr–Fe/γ-Al₂O₃-USG catalyst after the calcination process, which may be crucial to the high activity and stability of this catalyst.     

Preparation and characterization of sol–gel Al2O3/Ni–P composite coatings on carbon steel

Ceramic films have been applied to improve the resistance against high temperature oxidation of carbon steels. Alumina film was prepared on carbon steel surface by a dip coating technique. Electroless Ni–P plating film has been pre-deposited as an intermediate layer to improve the adherence of the film to carbon steel substrate. The oxidation kinetics of coated sample was investigated by measuring weight gain at 800 °C for 100 h. The surface and cross-section morphology of samples before and after oxidation were characterized by scanning electron microscopy (SEM). The composition and element distribution at the interface of the coated samples were analyzed by energy dispersive spectroscopy (EDS) and EMAX.The results show that the composite coating is uniform. The alumina coating adhesion strength to the substrate is up to 20 ± 2 N in scratch test because the alumina film presents interdiffusion of nickel and aluminum during heat treatment. The oxidation resistance test indicates higher oxidation resistance of as-coated carbon steel comparing to uncoated ones.     

Phase diagram of the Al2O3–ZrO2–Nd2O3 system

The phase diagram of the Al₂O₃–ZrO₂–Nd₂O₃ system was constructed in the temperature range 1250–2800 °C. The liquidus surface of the phase diagram reflects the preferentially eutectic interaction in the system. Two new ternary and one new binary eutectics were found. The minimum melting temperature is 1675 °C and it corresponds to the ternary eutectic Nd₂O₃·11Al₂O₃ + F-ZrO₂ + NdAlO₃. The solidus surface projection and the schematic of the alloy crystallization path confirm the preferentially congruent character of phase interaction in the ternary system. The polythermal sections present the complete phase diagram of the Al₂O₃–ZrO₂–Nd₂O₃ system. No ternary compounds or regions of remarkable solid solution were found in the components or binaries in this ternary system.     

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.     

Performance of Pd catalysts supported on nanocrystalline α-Al2O3 and Ni-modified α-Al2O3 in selective hydrogenation of acetylene

Nanocrystalline α-Al₂O₃ and Ni-modified α-Al₂O₃ have been prepared by sol–gel and solvothermal methods and employed as supports for Pd catalysts. Regardless of the preparation method used, NiAl₂O₄ spinel was formed on the Ni-modified α-Al₂O₃ after calcination at 1150 °C. However, an addition of NiO peaks was also observed by X-ray diffraction for the solvothermal-made Ni-modified α-Al₂O₃ powder. Catalytic performances of the Pd catalysts supported on these nanocrystalline α-Al₂O₃ and Ni-modified α-Al₂O₃ in selective hydrogenation of acetylene were found to be superior to those of the commercial α-Al₂O₃ supported one. Ethylene selectivities were improved in the order: Pd/Ni-modified α-Al₂O₃–sol–gel > Pd/Ni-modified α-Al₂O₃-solvothermal ≈ Pd/α-Al₂O₃–sol–gel > Pd/α-Al₂O₃-solvothermal  Pd/α-Al₂O₃-commerical. As revealed by NH₃ temperature program desorption studies, incorporation of Ni atoms in α-Al₂O₃ resulted in a significant decrease of acid sites on the alumina supports. Moreover, XPS revealed a shift of Pd 3d binding energy for Pd catalyst supported on Ni-modified α-Al₂O₃–sol–gel where only NiAl₂O₄ was formed, suggesting that the electronic properties of Pd may be modified.     

Atomic layer deposition of Al2O3 thin films on diamond

Atomic layer deposition (ALD) of aluminum oxide thin films on diamond was demonstrated for the first time, and the film properties as a gate insulator for diamond field effect transistor (FET) were examined. The interface between the aluminum oxide and the diamond was abrupt, and the ratio of aluminum to oxygen in the film was confirmed to be stoichiometric by Rutherford back scattering. Even a bumpy surface of polycrystalline diamond film was conformally covered by the Al₂O₃ films. To evaluate the feasibility of the film for FET gate insulator, the electrical characteristics of the Al₂O₃ films deposited by ALD on diamond were measured using metal–insulator–semiconductor structure. It was found that the Al₂O₃ films deposited by ALD were better than those deposited by conventional methods, which indicates that the ALD-Al₂O₃ films are feasible for gate insulators of diamond FETs.     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.     

Photo-Fenton degradation of 17β-estradiol in presence of α-FeOOHR and H2O2

A novel photocatalyst, α-FeOOH-coated resin (α-FeOOHR), was prepared and applied for the photodegradation of natural estrogen 17β-estradiol (E2) in presence of H₂O₂ under the relatively weak UV irradiation. The continuing loading of ferric oxide on resin was achieved by in situ hydrolysis of Fe³⁺ in alkaline solution. The effects of initial pH, catalyst loading, oxidant concentration and iron leaching on the photodegradation of E2 were investigated. The batch photodegradation experiment showed that high removal efficiency of E2 and fairly good mechanic stability could be obtained by the spherical photocatalyst α-FeOOHR in aqueous solutions. The photodegradation efficiencies slightly decreased with the increase of initial pH in the wide pH range of 3–11. Increase of oxidant and catalyst will enhance photodegradation efficiencies thus lead to increase the Ferric leaching. Neglected iron leaching showed the stability of the loaded α-FeOOH withstanding the oxidation. X-ray photoelectron spectrum (XPS) shed light on the surface activity change of photocatalyst and heterogeneous catalytic essence of this process.     

Effects of alumina incorporation in coprecipitated NiO–Al2O3 catalysts

The effect of Al₂O₃ levels on the properties of NiO in coprecipitated NiO–Al₂O₃ samples were investigated, using samples with up to 60.7 wt.% Al₂O₃ that had been calcined in the range 300–700°C. Characterization techniques included BET surface area of fresh and reduced catalysts, X-ray diffraction analysis of structure and crystallite size, magnetic susceptibility measurements, oxidizing power, and reducibility in H₂. Only NiO was detected in samples with up to 4.1 wt.% Al₂O₃ for all sample calcination temperatures. Surface areas were similar for all fresh samples but decreased rapidly after calcination at high temperatures. The surface area loss was less for the higher Al₂O₃-containing samples. Nickel oxide crystallite sizes increased at higher calcination temperatures, but remained approximately the same for each Al₂O₃ level.

The NiO was nonstoichiometric (NiO_1+x), with x decreasing at higher calcination temperatures and increasing with small amounts of added Al₂O₃ through a maximum at about 3 wt.% Al₂O₃. However, this did not correlate well with microstrain in the NiO crystallites nor with reducibility, which decreased with Al₂O₃ addition. At higher levels of Al₂O₃ (13.6 wt.% and above), surface areas increased with higher Al₂O₃ loadings, but NiO crystallite sizes remained approximately the same, independent of both Al₂O₃ content and calcination temperature. X-ray diffraction patterns were very diffuse, and it was not possible to rule out the presence of pseudo-spinel combinations of NiO and Al₂O₃. Reducibility was more difficult than with low Al₂O₃ levels, and nonstoichiometry was low and independent of Al₂O₃ content.

Reducibilities of all samples calcined at 300°C correlated well with the final BET surface area of the reduced samples, indicating that more dispersed NiO crystallites are more difficult to reduce, a conclusion that supports a model for reduction proposed previously.     

Deactivation patterns of Mo/Al2O3, Ni–Mo/Al2O3 and Ni–MoP/Al2O3 catalysts in atmospheric residue hydrodesulphurization

In the present work, a comparative study on the deactivation behavior of three types of industrial hydrotreating catalysts, namely, Mo/Al₂O₃, Ni–Mo/Al₂O₃ and Ni–MoP/Al₂O₃, that are used to promote primarily hydrodemetallization (HDM), hydrodesulphurization (HDS) and hydrodesulphurization + hydrodenitrogenation (HDS/HDN) reactions, respectively, in the first, second and third reactor of commercial atmospheric residue desulfurization (ARDS) units was carried out. The main objective of the study was to contribute to a better understanding of the relationship between catalyst type and catalyst deactivation patterns. The used catalysts from these experiments were fully characterized to determine the extent and the cause of deactivation. Special emphasis was paid to understanding the nature of the coke and metal deposition on the used catalysts by applying chemical analysis and various advanced analytical techniques, such as solid-state carbon-13 nuclear magnetic resonance spectroscopy (¹³C NMR), temperature-programmed oxidation (TPO), electron probe micro-analysis (EPMA), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The results are discussed scientifically based on the physico–chemical properties of the three catalysts.     

Performance and characterization of Ru/Al2O3 and Ru/SiO2 catalysts modified with Mn for Fischer–Tropsch synthesis

Mn effect and characterization on γ-Al₂O₃-, -Al₂O₃- and SiO₂-supported Ru catalysts were investigated for Fischer–Tropsch synthesis under pressurized conditions. In the slurry phase Fischer–Tropsch reaction, γ-Al₂O₃ catalysts showed higher performance on CO conversion and C₅⁺ selectivity than -Al₂O₃ and SiO₂ catalysts. Moreover, Ru/Mn/γ-Al₂O₃ exhibited high resistance to catalyst deactivation and other catalysts were deactivated during the reaction. From characterization results on XRD, TPR, TEM, XPS and pore distribution, Ru particles were clearly observed over the catalysts, and γ-Al₂O₃ catalysts showed a moderate pore and particle size such as 8 nm, where -Al₂O₃ and SiO₂ showed highly dispersed ruthenium particles. The addition of Mn to γ-Al₂O₃ enhanced the removal of chloride from RuCl₃, which can lead to the formation of metallic Ru with moderate particle size, which would be an active site for Fischer–Tropsch reaction. Concomitantly, manganese chloride is formed. These schemes can be assigned to the stable nature of Ru/Mn/γ-Al₂O₃ catalyst.     

The interaction of cobalt species with alumina on Co/Al2O3 catalysts prepared by atomic layer deposition

Alumina supported cobalt catalysts were prepared by atomic layer deposition (ALD) of cobalt acetylacetonate precursors (Co(acac)₂ and Co(acac)₃). The main modes of interaction between the acetylacetonate precursors and the support were found to be the exchange reaction between the alumina OH-groups and the acac-ligands of the precursor and dissociative adsorption on coordinatively unsaturated Al³⁺ sites. The amount of precursor that could adsorb on the support was determined by steric hindrance. Samples were prepared using 1–5 reaction cycles, i.e. subsequent precursor addition (Co(acac)₂) and calcination, resulting in catalysts containing ca. 3–10 wt.% Co. Samples were also prepared where the last calcination step was omitted, i.e. uncalcined catalysts. Calcination at 450 °C decreased the reducibility of the Co(acac)₂/Al₂O₃ catalysts due to formation of a cobalt oxide phase strongly interacting with the support and aluminate type surface species. The reducibility increased with metal loading on both calcined and uncalcined catalysts; however the reducibility of the calcined catalysts remained lower than of the uncalcined ones. The dispersion was found to be lower on the calcined catalysts. The cobalt particle sizes on the calcined samples was ca. 8 nm and on the uncalcined 4–5 nm, for cobalt loadings of ca. 6–10 wt.%. Catalytic activity was tested by gas phase hydrogenation of toluene in temperature programmed mode (30–150 °C).     

Physicochemical surface and catalytic properties of CuO–ZnO/Al2O3 system

A series of CuO–ZnO/Al₂O₃ solids were prepared by wet impregnation using Al(OH)₃ solid and zinc and copper nitrate solutions. The amounts of copper and zinc oxides were varied between 10.3 and 16.0 wt% CuO and between 0.83 and 7.71 wt% ZnO. The prepared solids were subjected to thermal treatment at 400–1000°C. The solid–solid interactions between the different constituents of the prepared solids were studied using XRD analysis of different calcined solids. The surface characteristics of various calcined adsorbents were investigated using nitrogen adsorption at −196°C and their catalytic activities were determined using CO-oxidation by O₂ at temperatures ranged between 125°C and 200°C.

The results showed that CuO interacts with Al₂O₃ to produce copper aluminate at ≥600°C and the completion of this reaction requires heating at 1000°C. ZnO hinders the formation of CuAl₂O₄ at 600°C while stimulates its production at 800°C. The treatment of CuO/Al₂O₃ solids with different amounts of ZnO increases their specific surface area and total pore volume and hinders their sintering (the activation energy of sintering increases from 30 to 58 kJ mol⁻¹ in presence of 7.71 wt% ZnO). This treatment resulted in a progressive decrease in the catalytic activities of the investigated solids but increased their catalytic durability. Zinc and copper oxides present did not modify the mechanism of the catalyzed reaction but changed the concentration of catalytically active constituents (surface CuO crystallites) without changing their energetic nature.     

Oxidation behaviour and catalytic properties of Pd/Al2O3 catalysts in the total oxidation of methane

A series of Pd/Al₂O₃ catalysts with a wide range of mean Pd particle sizes (ca. 2–30 nm in diameter) was prepared by using various precursors (H₂PdCl₄, Pd(NO₃)₂ and Pd(AcAc)₂) and pre-treatments. The mean particle size of reduced samples was determined by H₂ chemisorption. The catalytic activity in methane oxidation under lean burn conditions was measured. The oxidation of reduced samples was studied at 300 °C. The extent of oxidation was found to decrease with increasing mean particle size. While small particles (<5 nm) oxidised very rapidly, the oxidation of large particles (ca. >15 nm) proceeded via a two-step process, being first fast and then slow. The decomposition of oxide species was studied by temperature-programmed experiments under vacuum. Two distinct oxidised species with different stability were evidenced depending on the particle size. Oxidised species in larger particles were found of lower stability than in smaller ones. A correlation between the existence of distinct types of oxide species and catalytic properties in methane oxidation was discussed.     

The active phase of Au–Pd/Al2O3 for CO oxidation

Au–Pd/Al₂O₃ catalyst was prepared by modified impregnation method. It was found that the catalyst calcined in air at 473 K showed higher CO oxidation activity in comparison with the catalysts treated at other temperature. Nitrogen adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure spectroscopy (XANES) techniques were employed to study the relationship between the surface/bulk structures of these catalysts and their catalytic performance. The results indicated the higher activity was attributed to the smaller pore volume and co-existence of PdO and Au⁰ in their surface. The formation of Au_xPd_y alloy was unfavorable for the catalytic reaction.     

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.     

Hydrogenation of carvone on Pt–Sn/Al2O3 catalysts

The effect of Sn concentration in Pt–Sn/Al₂O₃ catalysts prepared by different procedures on the catalytic behavior in the carvone hydrogenation in liquid phase was studied. Results indicated that the increase of the Sn amount added to Pt modified the catalytic behavior, favoring the formation of unsaturated ketones and the simultaneous production of small quantities of unsaturated alcohols as reaction intermediaries. On the other hand, Pt/Al₂O₃ catalyst only produced carvomenthone as the main reaction intermediary.     

Influence of Ru segregation on the activity of Ru–Co/γ-Al2O3 during FT synthesis: A comparison with that of Ru–Co/SiO2 catalysts

γ-Al₂O₃ and SiO₂ supported Co catalysts, with varying amounts of Ru, were prepared and evaluated for Fischer–Tropsch synthesis (FTS). The composition of Ru for optimum activity was found to be support-dependent. The reducible Co₃O₄ was high in the region of 0–1.64 wt.% of Ru in Co/SiO₂ catalysts. Co/γ-Al₂O₃ displayed a maximum for reducible Co species at 0.42 wt.% Ru. Segregation of Ru occurred beyond this composition decreasing the extent of reduction. Co/γ-Al₂O₃ catalysts showed lower activity and olefin selectivity, in spite of higher Co dispersion, than Co/SiO₂ catalysts. The catalytic performance depends on the amount of reducible Co species, which again depends upon the optimum content of Ru.     

Abrasive wear of Al2O3–SiC and Al2O3–(SiC)–C composites with micrometer- and submicrometer-sized alumina matrix grains

The response of Al₂O₃, Al₂O₃–SiC–(C) and Al₂O₃–C nanocomposites to grinding was investigated in terms of changes of quality of ground surfaces and of the weight losses with time. The study used monolithic polycrystalline aluminas as references, and alumina-based composites with nanosized SiC and C inclusions and with alumina matrix grain size varying from submicrometer to approximately 4 μm. The studied materials can be roughly divided into two groups. Materials with submicrometer alumina matrix grains (Group 1) wear predominantly by plastic deformation and grooving. Coarse-grained materials (Group 2) wear by mixed wear mechanism involving crack initiation and interlinking accompanied by grain pull-out, plastic deformation and grooving. The wear rate of composites increases with increasing volume fraction of SiC. The Group 2 materials wear much faster then those with submicron microstructure. In all cases (with one exception) the wear resistance of composites was higher than that of pure aluminas of comparable grain sizes used as reference materials.