The choice of an optimal composition and preparation method of non-promoted Pd/Al2O3 and promoted Pd-Co/Al2O3 catalysts for the selective hydrogenation of vinylacetylene

For the purpose of optimizing the chemical composition and technology of synthesis of the catalyst for the acetylene hydrocarbons hydrogenation in industrial streams of butadiene and ethyl-vinylacetylene fractions, the influence of the palladium initial compound nature, the active component concentration, the promotion by cobalt, the molar ratio of palladium to cobalt, the phase composition of the supporter on physical chemical properties, and the activity and selectivity to 1,3-butadiene of the catalysts was studied. The effect of acidic-base characteristics of the supporter on its ability to oligomerize unsaturated hydracarbons has been investigated. It has been established, than the δ-Al₂O₃ supporter is characterized by a low concentration of Bronsted and Lewis acidic sites, decreasing the quantity of oligomers formed on its surface. The optimal composition of the non-promoted KGV-07 catalyst, recommended for the raw butadiene fraction hydrogenation, is 0.5% of Pd deposited from palladium acetate on δ-Al₂O₃ with palladium particles of 16 nm in size, on which the vinylacetylene conversion of 100% and the selectivity to 1,3-butadiene of 69.9% are reached at a temperature of 20°C at the reactor input, hourly space velocity (HSV) of hydrocarbon raws of 700 h⁻¹, molar ratio of hydrogen to ethyl-vinylacetylenes of 4: 1, summary concentration of 49% of acetylene hydrocarbons, and 1.5% of 1,3-butadiene in hydrocarbon raws. The synthesis of the cobalt-promoted KGVP-07 catalyst with 0.5% of Pd deposited from palladium acetylacetonate on δ-Al₂O₃ and molar ratio of Pd: Co = 1: 1 has been developed for the hydrogenation of an ethyl-vinylacetylene fraction with a concentration of acetylene hydrocarbons to 6 wt %, with the vinylacetylene conversion of 100% and the selectivity to 1,3-butadiene of 61.3%, at HSV of the hydrocarbon stream of 700 h⁻¹, temperature of 6°C at the reactor input, and molar ratio of hydrogen to ethyl-vinylacetylene admixtures of 4: 1. Promotion by cobalt leads to the formation of palladium particles at the zero oxidation level and to an increase in their average size from 11 to 14 nm in comparison with the non-promoted Pd-catalyst. In the work, IR-spectroscopy, transmission electron microscopy (TEM), and physicochemical methods have been used to characterize the catalysts texture and supporter phase composition. Pilot tests of the KGV-07 and KGVP-07 catalysts on the Etilen plant unit have proven the correctness of the choice for the catalysts’ optimal chemical composition.     

原位红外光谱法研究Pd-Ag/Al2O3和Pd/ Al2O3乙炔加氢催化剂

以一氧化碳和乙炔为探针分子,采用原位红外光谱技术研究了Pd-Ag/ Al₂O₃和Pd/ Al₂O₃催化剂上乙炔加氢反应以及催化剂本身的表面形态,动态考察了乙炔加氢的气相反应行为、CO吸附以及催化剂表面吸附物种的变化。结果表明,在Pd-Ag/ Al₂O₃催化体系中,由于Ag的加入而受到几何效应和电子效应的共同影响,引起了催化剂表面形态的改变从而改变了催化剂的性能。另外,乙炔加氢反应会导致钯催化剂表面形成由长分子链的饱和烃组成的碳氢化合物层,该碳氢化合物层有可能是加氢反应形成的绿油。     

Performance of Ni-added Pd-Ag/Al2O3 catalysts in the selective hydrogenation of acetylene

Effects of Ni addition on the performance of Pd-Ag/Al₂O₃ catalysts in the selective hydrogenation of acetylene were investigated. Ni-added Pd-Ag catalysts showed higher conversions than Ni-free Pd-Ag catalyst under hydrogen-deficient reaction conditions, hydrogen/acetylene <2.0, due to the spillover of hydrogen from reduced Ni to Pd and the suppression of hydrogen penetration into the Pd bulk phase, which enriched the Pd surface with hydrogen. Ethylene selectivity was also increased by Ni addition because the amounts of surface hydrogen originating from the Pd bulk phase, which was responsible for the full hydrogenation of ethylene to ethane, were decreased due to the presence of Ni at the sub-surface of Pd-Ag particles. Added Ni also modified the geometric nature of the Pd surface by blocking large ensembles of Pd into isolated ones, which eventually improved ethylene selectivity.     

Pd‐Ag/α‐Al2O3 Catalyst Deactivation in Acetylene Selective Hydrogenation Process

The selective hydrogenation of acetylene to ethylene over Pd‐Ag/α‐Al₂O₃ catalysts prepared by different impregnation/reduction methods was studied. The best catalytic performance was achieved with the sample prepared by sequential impregnation. A kinetic model based on first order in acetylene and 0.5th order in hydrogen for the main reaction and second‐order independent decay law for catalyst deactivation was used to fit the conversion time data and to obtain quantitative assessment of catalyst performances. Fair fits were observed from which the reaction and deactivation rate constants were evaluated. Coke deposition amounts showed a good correlation with catalyst deactivation rate constants, indicating that coke formation should be the main cause of catalyst deactivation.     

Enhanced catalytic activity of Pt/Al2O3 on the CH4 SCR

In this study, we investigated the effect of mixing α-Al₂O₃ and γ-Al₂O₃ with a Pt catalyst on CH₄ selective catalytic reduction (SCR). Among the prepared catalysts, the Pt/α-Al₂O₃ catalyst was found to have the lowest catalytic activity, but the best adsorption characteristics for CH₄, which was used as the reductant. In contrast, the Pt/γ-Al₂O₃ catalyst was found to exhibit relatively high catalytic activity and moderate adsorption characteristics. To simultaneously enhance the catalytic activity and CH₄ adsorption characteristics, we developed a new catalyst, Pt/γ-Al₂O₃ + Pt/α-Al₂O₃, by mixing α-Al₂O₃ and γ-Al₂O₃ with a Pt catalyst. The catalytic activity test confirmed that mixing these catalysts led to enhanced catalytic activity.     

Preparation of Highly Active Nickel Catalysts Supported on Mesoporous Nanocrystalline γ‐Al2O3 for Methane Autothermal Reforming

Autothermal reforming (ATR) of methane was carried out over nanocrystalline Al₂O₃‐supported Ni catalysts with various Ni loadings. Mesoporous nanocrystalline γ‐Al₂O₃ powder with high specific surface area was prepared by the sol‐gel method and employed as support for the nickel catalysts. The prepared samples were characterized by X‐ray diffraction, Brunauer‐Emmett‐Teller, temperature‐programmed reduction, temperature‐programmed hydrogenation, and scanning electron microscopy techniques. It is demonstrated that the methane conversion increased with increasing in Ni content and that the catalyst with 25 wt % Ni exhibited the highest activity and a stable catalytic performance in the ATR process, with a low degree of carbon formation. Furthermore, the effects of the reaction temperature, the calcination temperature, the steam/CH₄ and O₂/CH₄ ratios, and the gas hourly space velocity on the catalytic performance of the 25 % Ni/Al₂O₃ catalyst were investigated.     

Advantage of carbon coverage over Al2O3 as support for Ni/C-Al2O3 catalyst in vapour phase hydrogenation of nitrobenzene to aniline

5wt% of Ni supported on activated carbon, Al₂O₃ and Carbon covered Al₂O₃ (C-Al₂O₃) prepared by impregnation technique have been subjected to nitrobenzene hydrogenation at atmospheric pressure in vapour phase conditions. The catalysts were characterized by XRD, BET surface area, TPR and H₂-Pulse chemisorption. Among the catalysts, Ni/C-Al₂O₃ catalyst exhibited excellent and steady activity in the nitrobenzene hydrogenation at 498 K which can be attributed to the presence of smaller Ni particles with proper metal support interaction.     

Methane-Propylene homologation and reactivity of surface carbon on modified Ni-Al2O3 catalysts

Modified Ni catalysts supported on alumina and reduced in CH₄ have been investigated for the synthesis of C₄ hydrocarbons from CH₄ and C₃H₆. Addition of K or P to the Ni/Al₂O₃ catalyst increased C₄ selectivity and C₃H₆ conversion. A maximum selectivity to the desired C₄ product of 9 mol % was obtained at 350°C and 101 kPa with a feed gas composition of 90 mol% CH₄/10 mol% C₃H₆, but the catalyst activity declined rapidly with time-on-stream. Large amounts of unreactive carbon were deposited on the catalyst surface following reduction in CH₄ and reaction in CH₄/C₃H₆. However, the relative amount of a much more reactive species identified from Temperature-Programmed-Surface-Reaction that was formed in the presence of CH₄ and C₃H₆, is shown to correlate with the catalyst C₄ yield. Both the C₄ yield and the relative amount of this low temperature carbonaceous species increased in the order Ni<Ni/P<Ni/K.     

Effect of promotion with cobalt or zinc on the hydrogenating and oligomerizing activities of the Pd/Al2O3 catalyst in the hydrogenation of the BTX fraction

The promoter nature and content effects on the catalytic activity and stability of Pd-Co/δ-Al₂O₃ and Pd-Zn/δ-Al₂O₃ bimetallic catalysts in the hydrogenation of dienic and vinyl aromatic hydrocarbons in the BTX fraction have been investigated by IR spectroscopy and temperature-programmed reduction. The Pd : Co (Zn) molar ratio in the catalysts prepared is 1.0 : 0.5, 1.0 : 1.0, or 1.0 : 1.5, and their Pd content is 0.5 wt %. The support is δ-Al₂O₃ doped with sodium (0.5 wt %). Promotion of the palladium catalyst with zinc and cobalt causes the disappearance of cationic palladium species, thereby reducing the oligomerizing capacity of the active component, and, as was demonstrated by 100-h-long catalytic tests, enhances the stability of the catalyst. The Pd-Co/δ-Al₂O₃(Na) catalyst with Pd : Co = 1.0 : 1.0 mol/mol is recommended for the hydrogenation of the BTX fraction under industrial conditions. The expected service life of this catalyst between regenerations is 16 months.     

Enhanced NOx Conversion with Decane Over Ag/Al2O3 and Metal Supported ZSM-5 Composite SCR Catalysts

A combination of Ag/Al₂O₃ and a partial oxidation catalyst M/ZSM-5, M being different metal cations, were evaluated for selective catalytic reduction of NO with decane. Physical mixture of Ag/Al₂O₃ and M/ZSM-5 catalysts showed significant increase in NOx conversion compared to single component Ag/Al₂O₃ catalyst. M/ZSM-5 as a second catalyst component was found to generate more reactive hydrocarbons, such as unsaturated small chain hydrocarbons and oxygenates in situ, and enhance the NOx conversion over Ag/Al₂O₃ HC-SCR catalyst.     

Comparative Study on CO2 Hydrogenation to Higher Hydrocarbons over Fe-Based Bimetallic Catalysts

This paper reports on notable promotion of C₂ ⁺ hydrocarbons formation from CO₂ hydrogenation induced by combining Fe and a small amount of selected transition metals. Al₂O₃-supported bimetallic Fe–M (M = Co, Ni, Cu, Pd) catalysts as well as the corresponding monometallic catalysts were prepared, and examined for CO₂ hydrogenation at 573 K and 1.1 MPa. Among the monometallic catalysts, C₂ ⁺ hydrocarbons were obtained only with Fe catalyst, while Co and Ni catalysts yielded higher CH₄ selectively than other catalysts. The combination of Fe and Cu or Pd led to significant bimetallic promotion of C₂ ⁺ hydrocarbons formation from CO₂ hydrogenation, in addition to Fe–Co formulation discovered in our previous work. CO₂ conversion on Ni catalyst nearly reached equilibrium for CO₂ methanation which makes this catalyst suitable for making synthetic natural gas. Fe–Ni bimetallic catalyst was also capable of catalyzing CO₂ hydrogenation to C₂ ⁺ hydrocarbons, but with much lower Ni/(Ni+Fe) atomic ratio compared to other bimetallic catalysts. The addition of a small amount of K to these bimetallic catalysts further enhanced CO₂ hydrogenation activity to C₂ ⁺ hydrocarbons. K-promoted Fe–Co and Fe–Cu catalysts showed better performance for synthesizing C₂ ⁺ hydrocarbons than Fe/K/Al₂O₃ catalyst which has been known as a promising catalyst so far.     

Role of the surface state of Ni/Al2O3 in partial oxidation of CH4

The effect of gas phase O₂ and reversibly adsorbed oxygen on the decomposition of CH₄ and the surface state of a Ni/Al₂O₃ catalyst during partial oxidation of CH₄ were studied using the transient response technique at atmospheric pressure and 700°C. The results show that, when the catalyst surface is completely oxidized under experimental conditions, only a small amount of CO and H₂ can be produced from non‐selective oxidation of CH₄ by reversibly adsorbed oxygen which is more active in oxidizing CH₄ completely than NiO via the Rideal–Eley mechanism and both the conversions of CH₄ and O₂ and the selectivities to CO and H₂ are very low. Therefore, keeping the catalyst surface in the reduced state is the precondition of high conversion of CH₄ and high selectivities to CO and H₂. The surface state of the catalyst decides the reaction mechanism and plays a very important role in the conversions and selectivities of partial oxidation of CH₄. During partial oxidation of CH₄, no oxygen species but a small amount of carbon exists on the catalyst surface, which is favorable for maintaining the catalyst in the reduced state and the selectivity of CO. The results also indicate that direct oxidation is the main route for partial oxidation of CH₄, and the indirect oxidation mechanism is not able to gain dominance in the reaction under the experimental conditions. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Partial Oxidation of CH3OH to CO2 and H2 Over a Cu/ZnO/Al2O3 Catalyst

The partial oxidation of CH₃OH to CO₂ and H₂ over a Cu/ZnO/Al₂O₃ catalyst has been studied by temperature-programmed oxidation (TPO) using N₂O and O₂ as the oxidant. Post-reaction analysis of the adsorbate composition of the surface of the catalyst was determined by temperature-programmed desorption (TPD). The temperature dependence of the composition of the mixture of products formed by TPO was shown to depend critically on the partial pressure of the oxidant, with the highest partial pressure of oxygen used (10% O₂ in He, 101 kPa—the CH₃OH partial pressure was 17% throughout), producing marked non-Arrhenius fluctuations on temperature programming. Unsurprisingly, therefore, the adsorbate composition of the catalyst revealed by post-reaction TPD was also found to be determined by the partial pressure of the oxidant. Using high partial pressures of oxidant (5% and 10% O₂ in He, 101 kPa), the only adsorbate detected was the bidentate formate species adsorbed on Cu. Lowering the oxygen partial pressure to 2% in He (101 kPa) revealed a catalyst surface on which the bidentate formate on Cu was the dominant intermediate with the formate on Al₂O₃ also being present. A further lowering of the partial pressure of the oxidant, obtained by using N₂O as the oxidant (2% N₂O in He, 101 kPa), resulted in a surface on which the formate adsorbed on ZnO was the dominant adsorbate with only a small coverage of the Cu by the bidentate formate.     

A core–shell structured Si–Al@Al2O3 as novel support of Pd catalyst

Core–shell structured support is an effective way in eliminating mass transfer limitation for multiphase hydrogenation reactions. In this study, a downy Al₂O₃ layer with a specific surface area of 213.7 m²/g was generated in situ on Si–Al alloy via facile hot water etching technique. The downy surface is conducive in achieving a satisfactory dispersion of Pd particles with an average size of 5.5 nm. The core–shell structure and the moderate dispersion of Pd on Si–Al@Al₂O₃ support lead to a higher activity and selectivity in hydrogenation of styrene and consecutive hydrogenation of phenylacetylene than that on commercial Al₂O₃.     

NO Adsorption on ZnAl2O4/Al2O3 Powder: A NEXAFS Study at the Nitrogen K Edge

In order to understand the mechanism of the selective catalysis of nitrogen oxide reduction by hydrocarbons on a ZnAl₂O₄/Al₂O₃ catalyst, the NO adsorption step has been studied as a function of the surface state of the catalyst by using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy at the nitrogen K edge. The role of oxygen, whose presence is essential for the reaction to occur, is examined. In absence of a preliminary surface oxidation, nitric oxide was found not to be adsorbed on the ZnAl₂O₄/Al₂O₃ surface. After this preliminary treatment, we observed that the nitrogen atom of the NO molecule was linked to a surface oxygen with an adsorption mode parallel or slightly tilted with respect to the catalyst surface. Through these experiments we clearly demonstrate the advantages of soft X-ray experiments in catalysis research even in the case of practical application to real materials.     

Selective hydrogenation of m-dinitrobenzene to m-nitroaniline catalyzed by PVP-Ru/Al2O3

Selective hydrogenation of m-dinitrobenzene to m-nitroaniline (m-NA) catalyzed by polylvinylpyrrolidone stabilized Ru/Al₂O₃ (PVP-Ru/Al₂O₃) was studied experimentally. The effects of solvents, metal cation additives and reaction conditions were examined. The highest total yield of m-NA was obtained with 97.9% selectivity at 100% conversion when Sn⁴⁺ used as modifier (the molar ratio of m-DNB to catalyst was 477:1, the molar ratio of Sn⁴⁺ to ruthenium was 1:4) under suitable conditions.     

A Pd/Al2O3/cordierite monolithic catalyst for hydrogenation of 2-ethylanthraquinone

A novel Pd/Al₂O₃/cordierite monolithic catalyst was prepared and investigated in hydrogenation of 2-ethylanthraquinone (eAQ) for H₂O₂ production. It was found that there was an optimal penetrating depth on the monolithic catalyst. By adjusting the loading on the Al₂O₃, the penetrating depth of Pd could be efficiently confined in the Al₂O₃ washcoat. When Pd distribution matched well with Pd content, the higher yields of H₂O₂ could be obtained. As a result, the average yield on monolithic catalyst was 1.3 times of that on pellet catalyst, and the products distribution confirmed the monolithic catalyst was the optimal for H₂O₂ production.     

Highly hydrogen-deficient hydrocarbon species for the CO2-reforming of CH4 on Co/Al2O3 catalyst

The dynamics of produced CO and H₂, measured by pulse surface reaction rate analysis (PSRA), revealed that the intermediate hydrocarbon species for the CO₂-reforming of CH₄ was highly hydrogen-deficient (CH_0.75) on supported Co/Al₂O₃ catalyst. It was also found that the species was more reactive than the less hydrogen-deficient one (CH_2.4) on Ni/Al₂O₃ catalyst.     

Pulse-MS study of the partial oxidation of methane over Ni/La2O3 catalyst

The CH₄ direct oxidation reaction was studied at 600°C by the pulse-MS transient method over the Ni/La₂O₃ catalyst. Over the freshly prepared catalyst (which contains NiO), the CO selectivity and CH₄ conversion increased and attained constant values as the number of CH₄/O₂ pulses increased. Over the reduced catalyst (containing Ni), as the number of CH₄/O₂ pulses increased, the CO selectivity and CH₄ conversion decreased before they reached the same constant values as over the fresh catalyst. The CO selectivity increased as the residence time of the reactants shortened, implying that CO was directly generated without the preformation of CO₂. The activation energies of CH₄ dehydrogenation in the presence and absence of oxygen have been calculated using the bond-order conservation Morse-potential approach. The results indicate (1) the direct dehydrogenation steps are more likely to occur; (2) the transient oxygen species adsorbed on-top of the metal atoms promote dehydrogenation; (3) the oxygen species adsorbed on bridge or hollow sites do not promote dehydrogenation.     

Partial Oxidation of Methane to Synthesis Gas Over Ru-Loaded Y2O3 Catalyst

Ru-loaded Y₂O₃ catalyst was investigated for the partial oxidation of methane to synthesis gas. Ru(0.5 wt%)/Y₂O₃ catalyst afforded a high CH₄ conversion of 27% at a CH₄:O₂ ratio of 5 to give nearly a 1:2 ratio of CO and H₂ with a selectivity of 75% at 873 K. Ru(0.5 wt%)/Y₂O₃ catalyst maintained high catalytic activity over 10 h in the partial oxidation of methane. Carbon deposition of the catalyst surface in the reaction of CH₄ was examined by thermogravimetric analyses, and it was found that no carbon deposition occurred on the Ru(0.5 wt%)/Y₂O₃ catalyst. The synthesis-gas production proceeded basically via a two-step reaction consisting of methane combustion to give H₂O and CO₂, followed by the reforming of methane from CO₂ and steam.