A study on the catalytic performance of Pd/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, prepared by microwave calcination,in the direct synthesis of dimethylether

A series of Pd/γ-Al₂O₃ hybrid catalysts were prepared by impregnation and subsequent calcination under microwave irradiation. The catalysts were used for direct synthesis of dimethylether (DME) from syngas. The results show that calcination under microwave irradiation improved both the activity and selectivity of the catalysts for DME synthesis. The optimum power of the microwave was determined to be 420 W. Under such optimum conditions, CO conversion, DME selectivity and time space yield of DME were 60.1%, 67.0%, and 21.5 mmol·mL^?1·h^?1, respectively. Based on various characterizations such as nitrogen physisorption, X-ray diffraction, CO-temperature- programmed desorption, and Fourier transform infrared spectral analysis, the promotional effect of the microwave irradiation on the catalytic property was mainly attributed to both the higher dispersion of Pd and the significant increase in the adsorption on the CO-bridge of Pd. Microwave irradiation with very high power led to the increase in CO-bridge adsorption and thereby decreased the catalytic activity, whereas the coverage by metallic Pd of the active sites on acidic γ-Al₂O₃ significantly occurred under microwave irradiation with very low power, resulting in a decrease in the selectivity to DME.     

Effect of magnesium addition on catalytic performance of PtSnK/γ-Al2O3 catalyst for isobutane dehydrogenation

The effect of magnesium addition on the catalytic properties of PtSnK/γ-Al₂O₃ catalyst for isobutane dehydrogenation has been investigated by reaction tests and some physicochemical characterizations such as nitrogen adsorption, TEM, H₂ chemisorption, TPR, H₂-TPD, and TPO. It was found that with the suitable addition of magnesium (0.2 and 0.4 wt.%), the platinum dispersion increased, while the carbon depositions decreased. The presence of Mg in the PtSnMgK/γ-Al₂O₃ catalysts could not only strengthen the Sn-Al₂O₃ interaction, but also stabilize the oxidation states of Sn species, which resulted in the increased reaction activity and stability. However, when the content of magnesium was excessive (0.6 and 0.8 wt.%), the character of platinum and the interfacial properties between the metal and the support changed evidently, which was disadvantageous to the reaction. In our experiments, addition of 0.4 wt.% Mg to PtSnK/Al₂O₃ catalyst showed the best catalytic performance. After reaction for 6 h, selectivity toward isobutene of higher than 94% was achieved with the corresponding conversion value of about 29.0%.     

Agglomeration of α-Al2O3 powders prepared by gel combustion

Ultrafine α-Al₂O₃ powders were prepared by a gel combustion method and the agglomeration characteristic of the resultant powders was studied. A variety of fine crystallite α-Al₂O₃ powders with different agglomeration structures could be obtained by altering the citrate-to-nitrate ratio γ and calcining the precursors at 1050 °C for 2 h. All the powders were of nearly equivalent crystallite size (60–80 nm) except for the P1 powder (113 nm) from the gel with γ = 0.033. The primary crystallites of the obtained α-Al₂O₃ powders were formed into large secondary particles with different degree of agglomeration. Except for the powder P1, the mean particle sizes from specific surface area and particle size distribution measurement increase with increasing citrate-to-nitrate ratio in the fuel-lean condition and decrease in the fuel-rich condition. Densities of alumina ceramics from powders P4 and P5 sintered at different temperatures were relatively low due to the wide particle size distribution.     

Pd/γ-Al2O3催化降解苯的研究

针对苯在Pd/γ-Al2O3催化剂上的催化降解过程,研究了预处理方式对Pd/γ-Al2O3催化活性的影响,考察了其稳定性,并与Pd-Pt/γ-Al2O3催化剂进行了比较。通过BET和XPS对不同预处理方式下的Pd/γ-Al2O3催化剂进行了表征。研究结果表明:预处理方式对于催化剂活性有明显影响,相比H2,反应气预处理也可以提高催化剂的催化性能,并使操作过程简化;与Pd-Pt/γ-Al2O3相比,Pd/γ-Al2O3同样具有良好的催化稳定性。当空速为3 000 h-1,催化降解反应持续120 h后,苯降解率仍维持在99.6%以上。     

Morphology control of α-Al2O3 platelets by molten salt synthesis

It is of great importance to control the morphology of α-Al₂O₃ plate-like powders since α-Al₂O₃ platelets with different shapes are needed in various applications. This paper was focused on how to control the morphology of α-Al₂O₃ platelets by molten salt synthesis. Results show that the morphology of α-Al₂O₃ platelets is affected by the heating temperature, heating time, the molten salts species, the weight ratio of salt to powders, additives and the addition of nano-sized seeds. Especially, it is very effective to control the morphology of α-Al₂O₃ platelets by adjusting the addition of additives such as Na₃PO₄·12H₂O and TiOSO₄. α-Al₂O₃ flakes with irregular shape are obtained by the addition of Na₃PO₄·12H₂O, while thick α-Al₂O₃ particles with hexagonal shape are obtained by the addition of TiOSO₄. The combination addition of Na₃PO₄·12H₂O and TiOSO₄ makes it possible to obtain thin α-Al₂O₃ platelets with discal shape. A small amount of nano-sized seeds addition also has a strong effect on the size of α-Al₂O₃ platelets. However, if the seeds are added too much, the overlapping and abnormal crystal growth of α-Al₂O₃ platelets occur, and the size distribution becomes nonuniform. The effect mechanism of additives and seeds on the morphology of α-Al₂O₃ platelets was also discussed in this paper.     

Performance of Pd–Ag/Al2O3 catalysts prepared by the selective deposition of Ag onto Pd in acetylene hydrogenation

The performance of Ag-promoted Pd/Al₂O₃ catalysts, which were prepared by the selective deposition of Ag onto Pd using a surface redox (SR) method, during acetylene hydrogenation was compared with that of catalysts prepared by impregnation. The Pd surface was more effectively modified with Ag added by SR, even when small amounts of Ag were added. The catalyst prepared by SR showed a higher ethylene selectivity than the one prepared by impregnation, because SR allowed both the preferential deposition of Ag on the low-coordination sites of Pd and a greater electronic modification of Pd by Ag.     

Catalytic performance of Co-Mo-Ce-K/γ-Al2O3 catalyst for the shift reaction of CO in coke oven gas

The catalytic performance of Co-Mo-Ce-K/γ-Al₂O₃ catalyst for the shift reaction of CO in coke oven gas is investigated using X-ray diffraction (XRD) and temperature-programmed reduction (TPR). The results indicate that Ce and K have a synergistic effect on promoting the catalytic activity, and the Co-Mo-Ce-K/γ-Al₂O₃ catalyst with 3.0 wt-% CeO₂ and 6.0 wt-% K₂O exhibits the highest activity. CeO₂ favors Co dispersion and mainly produces an electronic effect. TPR characterization results indicate that the addition of CeO₂-K₂O in the Co-Mo-Ce-K/γ-Al₂O₃ catalyst decreases the reduction temperature of active components, and part of octahedrally coordinated Mo⁶⁺ transforms into tetrahedrally coordinated Mo⁶⁺, which has a close relationship with the catalytic activity.     

Hydrotreating of heavy gas oil using CoMo/γ-Al2O3 catalyst prepared by equilibrium deposition filtration

CoMo/γ-Al₂O₃ catalyst containing 16.0 wt% MoO₃ and 3.2 wt% CoO was prepared by equilibrium deposition filtration method (EDF). The CoMo oxidic catalyst was characterized by elemental analysis, N₂ adsorption, XRD, and TPR. The sulfided catalyst was characterized by FTIR of adsorbed CO at 30 °C. Hydrodesulfurization (HDS) and hydrodearomatization activities were evaluated for heavy gas oil (HGO) in a trickle bed reaction system using the following conditions: reaction temperatures of 340, 360, 380 and 400 °C, a reaction pressure of 20, 35, 50 and 65 bar, a liquid hourly space velocity (LHSV) of 1.0, 1.5, 2.0, 2.5 and 3 h⁻¹ and a H₂/feed ratio of 400 L L⁻¹. The experimental results were used to determine apparent reaction orders and activation energies. The dispersion, nature of active sites and hydrotreating activity of this catalyst were compared with the conventionally prepared CoMo/γ-Al₂O₃ catalyst containing similar wt% of MoO₃ and CoO. The CoMo catalyst prepared by equilibrium deposition filtration method has higher HDS and HDA rate constants than the conventional catalyst due to an improved dispersion of MoS₂.     

Effects of pretreatment atmospheres on the catalytic performance of Pd/γ-Al2O3 catalyst in benzene degradation

In the current paper, a strategy for catalytic degradation of benzene over Pd/γ-Al₂O₃ catalysts via different atmospheres (H₂, N₂, He and air) pretreatment was carried out in a fixed bed reactor. The experimental results indicated that H₂, N₂, and He pretreatments have a significant positive effect on the initial activity of the catalyst compared to air. We have also investigated the effects of pretreatment atmospheres on the catalytic performance for benzene degradation through the information on the chemical state and crystal structure of the catalysts using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and CO chemisorption measurements techniques. The chemical state of Pd species decreased via H₂ pretreatment, leading to the increase of the initial catalytic activity, while chemical state increased accompanying with a decrease in degradation benzene via air pretreatment. There is no change in the chemical state of Pd species using inert atmosphere (N₂ and/or He) pretreatment, but the initial activity of the catalyst improved significantly due to the modified crystal structure of Pd species in the catalysts, with the crystalline PdO being transformed to amorphous state.     

Preparation of alumina ceramic by κ-Al2O3

This work aims to use κ-Al₂O₃ transition alumina to prepare alumina ceramics without cracks. It is found that the major reason for the cracking of κ-Al₂O₃ sintered bodies formed by traditional wet molding process is the inner stress in green bodies rather than the volume reduction during the κ-Al₂O₃ – α-Al₂O₃ phase transformation. The cold isostatic pressing can be used to eliminate the inner stress generated in the green bodies, the sintered bodies have no cracks and possess the microstructure which is close to that of the α-Al₂O₃ ceramic products formed by wet molding process. Due to the fact that the calcining temperature of κ-Al₂O₃ is much lower than that of α-Al₂O₃ (1050?°C in comparison with 1400?°C), the application of κ-Al₂O₃ can lower the production cost significantly.     

Pd-Fe/α-Al2O3/cordierite monolithic catalysts for the synthesis of dimethyl oxalate: effects of calcination and structure

Cordierite monoliths coated with Pd-Fe/α-Al₂O₃ catalysts were prepared at various calcination temperatures and characterized by thermogravimetry, temperature-programmed reduction, transmission electron microscopy, diffuse reflectance infrared Fourier transformation spectroscopy and X-ray diffraction. The performance of the catalytic monoliths for the synthesis of dimethyl oxalate (DMO) through a CO coupling reaction was evaluated. Monolithic catalysts with calcination temperatures ranging from 473 K to 673 K exhibited excellent dispersion of Pd, good CO adsorption properties, and excellent performance for the coupling reaction. The optimized monolithic catalyst exhibited a much higher Pd efficiency (denoted as DMO (g)·Pd (g)^-1·h^-1) (733 h^-1) than that of the granular catalyst (60.2 h^-1), which can be attributed to its honeycomb structure and the large pore sizes in the α-Al₂O₃ washcoat which was accompanied with an even distribution of the active component in the coating layer along the monoliths channels.     

Synthesis of mesoporous TiO2/γ-Al2O3 composite granules with different sol composition and calcination temperature

Mesoporous TiO₂/γ-Al₂O₃ composite granules were prepared by combining sol-gel method and oil-drop method. After calcination at 450 °C, the composite granules showed anatase and γ-Al₂O₃ phases with the specific surface area of 240-310 m²/g. The phase composition and pore structure of the granules can be controlled by calcination temperature and the mixing ratio of boehmite sol and titania sol. The product granules can be used as a photocatalyst or adsorbent in moving or fluidized bed reactors.     

A continuous process for the production of 2,2,6,6-tetramethylpiperidin-4-ol catalyzed by Cu-Cr/γ-Al2O3

A continuous process was established for the production of 2,2,6,6-tetramethylpiperidin-4-ol over Cu-Cr/γ-Al₂O₃ in a fixed-bed reactor. The catalyst was characterized by X-ray diffraction, X-ray photoelectron spectroscopy and temperature-programmed reduction. Cu⁰ was believed to be the active site for the hydrogenation, and the doped chromium was supposed to exert a positive impact on the dispersion of active species. The catalyst and parameters of hydrogenation were optimized. Thus, 2,2,6,6-tetramethylpiperidin-4-ol was obtained in the yield of 90% from 2,2,6,6-tetramethylpiperidin-4-one (purity, 95%) under the optimum reaction conditions.     

气氛预处理对Pd/γ-Al2O3催化降解苯的影响

研究了不同气氛(惰性、还原性及氧化性气氛)预处理对Pd/γ-Al2O3催化降解苯的影响,采用XPS、XRD和TEM等分析手段对预处理前后的催化剂进行了表征,探索了预处理方式对催化剂活性的影响机制。研究结果表明,预处理方式对于催化剂活性的影响显著,还原性及惰性气氛预处理均可以明显提高催化剂的活性;除Pd活性组分的化学态以外,晶体结构是影响催化剂活性的另一个重要因素,惰性气氛预处理过程中活性组分PdO由结晶态向无定形态转变,这种晶体结构的转变有利于Pd/γ-Al2O3催化降解苯性能的提高。     

Weakly agglomerated α-Al2O3 nanopowders prepared by a novel spray precipitation method

In this paper, weakly agglomerated and well dispersed α-Al₂O₃ powders were synthesized by a novel spray precipitation method. It was demonstrated that the as-prepared powders exhibited better dispersity than powders from conventional precipitation due to the increased phase contact and reaction area during the precipitation process. The effects of different titration ways, calcination temperature and holding time on the morphology, phase composition and sintering behaviour of Al₂O₃ powders were systematically investigated. Weakly agglomerated and well crystallized α-Al₂O₃ powders were obtained when the as-prepared precursors were calcined at 1150?°C for 2?h in air. The average particle size of α-Al₂O₃ powders with higher sintering activity was approximately 68.6?nm, and the specific surface area was above 22.4?m² g^?1.     

Synthesis of ultrafine α-Al2O3 powder by two-step hydrolysis

The ultrafine α-Al₂O₃ powder has been successfully synthesized via two-step hydrolysis of aluminum isopropoxide. The effects of synthesis parameters on the α-Al₂O₃ were investigated. The experimental results indicated that the concentration of aluminum isopropoxide, water bath temperature, the molar ratio of aluminum isopropoxide to isopropanol and aluminum isopropoxide to deionized water greatly affect the amount of nuclei and the microstructure of α-Al₂O₃. Additionally, the water bath temperature affects the rate of nucleation and growth of crystals. Transmission electron microscopy (TEM) images display that the well-dispersed α-Al₂O₃ powder with particle size about 100 nm was obtained via the method after calcination at 1200 °C for 1 h. The coalescence of crystal particles led to the formation of vermicular α-Al₂O₃ particles. The X-ray diffraction (XRD) and Fourier transform infrared spectra (FTIR) analysis demonstrated the possible phase transition process of α-Al₂O₃. The scanning electron microscopy (SEM) images of samples calcined at various temperatures showed the microstructure transformation. Brunauer-Emmett-Teller (BET) surface area and mean pore size of the samples varied with the calcination temperature. The addition of cetylrimethylammonium bromide (CTAB) has impacts on the phase transformation of α-Al₂O₃.     

Coke deposition mechanism on the pores of a commercial Pt-Re/γ-Al2O3 naphtha reforming catalyst

Coke deposition mechanism on a commercial Pt-Re/γ-Al₂O₃ naphtha reforming catalyst was studied. A used catalyst that was in industrial reforming operation for 28 months, as well as the fresh catalyst of the unit were characterized using XRD, XRF, and nitrogen adsorption/desorption analyses. Carbon and sulfur contents of the fresh and the used catalysts were determined using Leco combustion analyzer. The pore size distributions (PSD) of the fresh and the used reforming catalysts were determined using BJH and Comparison Plot methods. The Comparison Plot method produced the most reasonable PSDs for the catalysts. Through comparison of the PSDs of the fresh and the used catalysts, it was revealed that coke deposited on both micropores and mesopores of the catalyst at a constant thickness of 1.0 nm. The constant coke thickness on the catalyst pore walls in the naphtha reforming process (temp. ∼ 500 °C) implies that coke deposition reaction is the slow controlling step in comparison to the fast mass transfer rate of coke ingredients into the pores. The bulk density of the deposited coke on the used catalyst was calculated as 0.966 g/cm³.     

Selective CO oxidation over promoted Au/γ-Al2O3 catalysts in the presence of CO2 and H2O in the feed

In this work, the effect of promoter type (Mg, Mn, Ce, Co, Fe and Ni) on selective CO oxidation performance of Au/γ-Al₂O₃ was studied with the realistic feed stream containing CO₂ and H₂O. The effects of Au loading, promoter loading, reaction temperature and the feed composition were also investigated. It was found that MgO was the best promoter in the presence of CO₂ and H₂O, and 1.25 wt.% Mg was sufficient for promotion. The CO conversion decreased with the addition of CO₂ while the presence of H₂O had some positive effects.     

Preparation of micrometer-sized α-Al2O3 platelets by thermal decomposition of AACH

Micrometer-sized α-Al₂O₃ platelets with hexagonal shape were prepared by thermal decomposition of ammonium aluminum carbonate hydroxide (AACH) using AlF₃ as an additive. The precursor and the calcined product were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and differential scanning calorimetry. The α-Al₂O₃ platelets with the size of 2-3 μm were obtained by calcining AACH at 1200 °C with 5 wt.% AlF₃. The morphology modification is attributed to the various growth rates along different crystal orientations due to the adsorption and uneven distribution of AlF₃. A step growth mode is responsible for the formation of the platelets.     

Promotional effect of Ca on the Pd/Ce–Zr/Al2O3 catalyst for low-temperature catalytic combustion of methane

Promotional effect of Ca on the catalytic property of Pd/Ce–Zr/Al₂O₃ catalyst towards methane combustion is examined. The surface properties and the oxidation/reduction behavior of these catalysts are investigated by BET, TEM, XPS, TPR, TPO and TPSR techniques. Activity tests in methane combustion show that addition of Ca to Pd/Ce–Zr/Al₂O₃ can promote remarkably its low-temperature activity. The thermal stability of the Pd/Ce–Zr/Al₂O₃ catalyst to the exposure at high temperature is also enhanced by Ca loading. XPS and TEM results show that the addition of Ca to Pd/Ce–Zr/Al₂O₃ catalyst generates well-dispersed PdO particles on support. H₂–TPR, O₂–TPO and CH₄/O₂–TPSR experiments show that the addition of Ca improves the reduction/reoxidation properties and thermal stability of the active PdO species, which increases the catalytic activity and thermal stability of the Pd/Ce–Zr/Al₂O₃ catalyst.