The structure of vanadium oxide species on γ-alumina; an in situ X-ray absorption study during catalytic oxidation

The mechanism of catalytic oxidation reactions was studied using in situ X-ray absorption spectroscopy (XAFS) over a 17.5 wt% V₂O⁵/Al₂O₃ catalyst, i.e., at reaction temperatures and in the presence of reactants. It was found that X-ray absorption near-edge structure (XANES) is a powerful tool to study changes in the local environment and the oxidation state of the vanadium centres during catalytic oxidation. At 623 K, the catalyst follows the associative mechanism in CO oxidation. XAFS revealed that the Mars–van Krevelen mechanism is operative at 723 K for CO oxidation. The extended X-ray absorption fine structure (EXAFS) results showed that the structure of the supported V₂O⁵ phase consists of monomeric tetrahedral (Al–O)₃–V=O units after dehydration in air at 623 K. However, the residuals of the EXAFS analysis indicate that an extra contribution has to be accounted for. This contribution probably consists of polymeric vanadate species. The structure remains unchanged during steady-state CO oxidation at 623 and 723 K. Furthermore, when oxygen was removed from the feed at 623 K, no changes in the spectra occurred. However, when oxygen is removed from the feed at 723 K, reduction of the vanadium species was observed, i.e., the vanadyl oxygen atom is removed. The V³⁺ ion subsequently migrates into the γ-Al₂O₃ lattice, where it is positioned at an Al³⁺ octahedral position. This migration process appears to be reversible; so the (Al–O)₃–V=O units are thus restored by re-oxidation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Ozonide ions on the surface of MgO nanocrystals

The adsorption properties of oxygen radicals on the surface of polycrystalline oxides can provide relevant information about the functionality of specific surface sites in oxidation catalysis. Using electron paramagnetic resonance spectroscopy, we investigated O₂ adsorption at MgO nanocrystal surfaces which were previously enriched with O⁻ radicals i.e. trapped hole centers. On dehydroxylated particle surfaces, two ozonide radical types O ₃ ⁻ were isolated as adsorbates and the related energies for O₂ adsorption were found to be 55 ± 5 kJ mol⁻¹ and 100 ± 5 kJ mol⁻¹. The respective adsorption sites are assigned to hole centers trapped on oxygen terminated corners and cation vancancies, respectively. In addition, O ₃ ⁻ ions were also employed as probes for electron trapping sites on partially hydroxylated sample surfaces. Five types of O⁻ radicals emerge from surface colour centre bleaching with N₂O, but only two of them adsorb O₂ at room temperature. A connection between the well-characterized (H⁺)(e^-) defect – an electron trapped in close vicinity of a nearby proton [Chiesa et al. J. Phys. Chem. B 109 (2005) 7314] – and one ozonide type which exhibits significant magnetic coupling with an adjacent proton, was established on the basis of their production parameter dependence. Although the g tensor of an O₃ ⁻ species reflects the properties of the radical itself rather than the structure of the adsorption site, the related signatures are proposed to serve also as spectroscopic fingerprints for catalytically relevant surface anion environments.     

Gasification of an Indonesian subbituminous coal in a pilot-scale coal gasification system

Indonesian Roto Middle subbituminous coal was gasified in a pilot-scale dry-feeding gasification system and the produced syngas was purified with hot gas filtering and by low temperature desulfurization to the quality that can be utilized as a feedstock for chemical conversion. Roto middle coal produced syngas that has a typical composition of 36–38% CO, 14–16% H₂, and 5–8% CO₂. Particulates in syngas were 99.8% removed by metal filters at the operating temperature condition of 200–250°C. Sulfur containing compounds of H₂S and COS in syngas were also desulfurized in the Fe chelate system to yield less than 0.5 ppm level. The full stream gasification and syngas purifying system has been successfully operated and thus can provide clean syngas for the research on the conversion of syngas to chemicals like DME and on the future IGFC using fuel cells. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Comprehensive kinetic characterization of the oxidation and gasification of model and real diesel soot by nitrogen oxides and oxygen under engine exhaust conditions: Measurement, Langmuir-Hinshelwood, and Arrhenius parameters

The reaction kinetics of the oxidation and gasification of four types of model and real diesel soot (light and heavy duty vehicle engine soot, graphite spark discharge soot, hexabenzocoronene) by nitrogen oxides and oxygen have been characterized for a wide range of conditions relevant for modern diesel engine exhaust and continuously regenerating particle trapping or filter systems (0-20% O₂, 0-800 ppm NO₂, 0-250 ppm NO, 0-8% H₂O, 303-773 K, space velocities 1.3 × 10⁴-5 × 10⁵ h⁻¹). Soot oxidation and NO₂ adsorption experiments have been performed in a model catalytic system with temperature controlled flat bed reactors, novel aerosol particle deposition structures, and sensitive multicomponent gas analysis by FTIR spectroscopy. The experimental results have been analyzed and parameterized by means of a simple carbon mass-based pseudo-first-order rate equation, a shrinking core model, oxidant-specific rate coefficients, Langmuir-Hinshelwood formalisms (maximum rate coefficients and effective adsorption equilibrium constants), and Arrhenius equations (effective activation energies and pre-exponential factors), which allow to describe the rate of reaction as a function of carbon mass conversion, oxidant concentrations, and temperature. At temperatures up to 723 K the reaction was driven primarily by NO₂ and enhanced by O₂ and H₂O. Within the technically relevant concentration range the reaction rates were nearly independent of O₂ and H₂O variations, while the NO₂ concentration dependence followed a Langmuir-Hinshelwood mechanism (saturation above ∼200 ppm). Reaction stoichiometry (NO₂ consumption, CO and CO₂ formation) and rate coefficients indicate that the reactions of NO₂ and O₂ with soot proceed in parallel and are additive without significant non-linear interferences. The reactivity of the investigated diesel soot and model substances was positively correlated with their oxygen mass fraction and negatively correlated with their carbon mass fraction.     

Ethanol Steam Reforming for Hydrogen Production over Bimetallic Pt–Ni/Al2O3

Ethanol steam reforming was studied at 673–823 K over Pt–Ni/δ-Al₂O₃. Results indicate that bimetallic catalyst is resistant to coke deposition at steam-to-carbon ratios as low as 1.5 and higher ratios are beneficial for both ethanol conversion and hydrogen formation. About 773 K is the optimum since high H₂ production rates are accompanied by low CO and CH₄ production rates. A power-function rate expression obtained on the basis of intrinsic rates at 673 K gives reaction orders of 1.25 (±0.05) and −0.215 (±0.015) for ethanol and steam, respectively; the apparent activation energy is calculated as 39.3 (±2) kJ mol⁻¹ between 673 and 723 K.     

Experimental investigation of role of steam in entrained flow coal gasification

Experimental investigations of the influence of excess oxygen coefficient, H₂O/coal mass ratio using high-temperature steam, mean mass diameter of pulverized coal and coal size fraction on basic characteristics of coal gasification were performed. Experiments were carried out on a laboratory scale (0.09 m i.d. × 1.5 m high) coal gasification apparatus with lignite type of coal. Influence of steam was realized through comparison of results obtained from experiments with (H₂O/coal = 0.287 kg kg⁻¹) and without steam addition (H₂O/coal = 0.024 kg kg⁻¹). High values of carbon conversion, obtained both for finely ground and for coarse pulverized coal points to the easiness of lignite gasification, i.e. to its high suitability for gasification.     

The Effect of Sulfur on ZrO<Subscript>2</Subscript>-Based Biomass Gasification Gas Clean-Up Catalysts

The effect of sulfur on biomass gasification gas clean-up over ZrO₂, Y₂O₃–ZrO₂ and SiO₂–ZrO₂ catalysts was examined. Experiments were carried out at the temperature range of 600–900 °C with sulfur free and 100 ppm H₂S containing simulated gasification gas feeds. A mixture of toluene and naphthalene was used as a tar model compound. Results revealed that the sulfur addition affected positively on the catalyst properties mainly at 600 and 700 °C: over Y₂O₃–ZrO₂ and ZrO₂ sulfur addition improved naphthalene and ammonia conversion. However, over SiO₂–ZrO₂ no clear effect with H₂S addition was observed. The effect of sulfur addition on the catalyst properties was connected to the formation of SO₂ from H₂S when oxygen was available. The intensity of the sulfur effect increased with the Lewis basicity strength of the catalysts. This indicates that the sulfur adsorption has a role in generating new type of active sites and/or plays role in changing the redox properties of the zirconia. Since the biomass gasification gas contains usually significant amounts of H₂S the sulfur tolerance of the zirconia based catalysts is a remarkable benefit.     

Promotional effect of H2O on the activity of In2O3‐doped Ga2O3–Al2O3 for the selective reduction of nitrogen monoxide

Effect of metal oxide additives on the catalytic performance of Ga₂O₃–Al₂O₃ prepared by the sol–gel method for the selective reduction of NO with propene in the presence of oxygen was studied. Of several metal oxide additives, the addition of In₂O₃ enhanced drastically the activity of Ga₂O₃–Al₂O₃ for NO reduction by propene in the presence of H₂O. In addition, the activity of In₂O₃‐doped Ga₂O₃–Al₂O₃ catalyst was extremely intensified by the presence of H₂O below 350°C. The promotional effect of H₂O was interpreted by the suppression of undesirable propene oxidation and the removal of carbonaceous materials deposited on the catalyst surface. We also found that close interaction of In₂O₃ and Ga₂O₃ is necessary for the enhancement of activity by H₂O. A lot of hydrocarbons except methane and oxygenated compounds served as good reducing agents, among which propene and 2‐propanol were the most efficient ones. In₂O₃‐doped Ga₂O₃–Al₂O₃ catalyst was capable of reducing NO into N₂ quite efficiently in the presence of H₂O at a very high space velocity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation of brownmillerite type calcium ferrite (Ca2Fe2O5) and catalytic properties in propylene combustion

Several types of calcium ferrite base catalysts (Ca/Fe = 0.33–3) for propylene (C₃H₆) combustion were prepared. Calcium ferrite catalyst with brownmillerite crystal structure provided catalytic activity for C₃H₆ combustion in the temperature range of 250–450 °C. The brownmillerite phase (Ca₂Fe₂O₅) was responsible for the formation of oxygen adspecies (O ₂ ⁻ ) in the surface layer below 450 °C.     

Crystal Structure, Thermal and Magnetic Behavior of Inorganic–Organic Hybrid [VIV 4O10 VV 2O4] (C6H14N2)·H2O Polymeric Framework

Summary The inorganic–organic hybrid [V^IV ₄O₁₀V^V ₂O₄] (C₆H₁₄N₂)·H₂O polymeric framework was prepared under mild hydrothermal conditions from a mixture of DABCO and V₂O₅ in deionized water with a 1:1:450 mole ratio, at neutral pH. The reaction was carried out at 180 °C for 3 days under autogenous pressure yielding phase pure crystals product. The crystal structure was studied using both powder and single crystal X-ray crystallography, revealing the structure to be of the ({UuDd}:T*)α′ type in the SP+T class and Z-T subclass. The presence of the organic cation was confirmed by FT-IR spectrum and chemical composition analysis. The structure was thermally stable up to over 400 °C, and showed ferromagnetic character at room temperature with the maximum molar susceptibility of 8.26 × 10⁻³ emu/mol⁻¹ at zero applied field.     

Oxidation of propane over a diesel exhaust catalyst

The oxidation of propane, over a concentration range of 0.30 to 1.04 mole % in air was investigated over a commercial diesel exhaust catalyst consisting of CuO, Cr₂O₃ and Pd supported on Al₂O₃. The rate of reaction was correlated by a first order, irreversible rate function; the resulting pre-exponential factor and activation energy were 3.15 × 10⁷ cc/g-sec and 21.3 kcal/gmole, respectively. At high temperatures the reaction rate became influenced by pore diffusion. A temperature of 675°K was required to obtain 50% propane conversion. It was concluded that this catayst is unsuitable for catalytic mufflers on diesel buses since the measured value of diesel exhaust temperatures at the cataytic muffler inlet is significantly less than 675°K.     

Laboratory-scale coal reactivity testing for entrained gasification

A relatively simple and rapid micro-gasification test has been developed for measuring gasification reactivities of carbonaceous materials under conditions which are more or less representative of an entrained gasification process, such as the Shell coal gasification process. Coal particles of < 100 μm are heated within a few seconds to a predetermined temperature level of 1000–2000 °C, which is subsequently maintained. Gasification is carried out with either CO₂ or H₂O. It is shown that gasification reactivity increases with decreasing coal rank. The CO₂ and H₂O gasification reactions of lignite, bituminous coal and fluid petroleum coke are probably controlled by diffusion at temperatures 1300–1400 °C. Below these temperatures, the CO₂ gasification reaction has an activation energy of about 100 kJ mol^?1 for lignite and 220–230 kJ mol^?1 for bituminous coals and fluid petroleum coke. The activation energies for H₂O gasification are about 100 kJ mol^?1 for lignite, 290–360 kJ mol^?1 for bituminous coals and about 200 kJ mol^?1 for fluid petroleum coke. Relative ranking of feedstocks with the micro-gasification test is in general agreement with 6 t/d plant results.     

Flame propagation in mixtures of monogermane and oxygen. I. Limits, flame propagation characteristics, and gas-phase products

The concentration limits for flame propagation in GeH₄−O₂ (air) mixtures are determined over a wide range of initial pressures (0.7–100 kPa) at room temperature. Flame propagation is found to be of a chain-thermal character and excited intermediate particles are involved in the reactions which limit the branching rate. The gas-phase reaction products (H₂O₂, H₂O, and H₂) are determined and its is shown that the relative yields of these components and the stoichiometry, as a whole, vary with the composition of the initial gas mixture. Chemically induced decomposition of GeH₄ by a branching-chain oxidation process for oxidation of the hydride by oxygen is observed. Translated fromFizika Goreniya i Vzryva, Vol. 35, No. 1, pp. 72–76, January–February 1999.     

Development of a pilot-scale acid gas removal system for coal syngas

The Korean pilot-scale gasification facility consists of a coal gasifier, hot gas filtering system, and acid gas removal (AGR) system. The syngas stream from the coal gasification at the rate of 100–120 Nm³/hr included pollutants such as fly ash, H₂S, COS, etc. The acid gas, such as H₂S and COS, is removed in the AGR system before generating electricity by gas engine and producing chemicals like Di-methyl Ether (DME) in the catalytic reactor. A hydrolysis system was installed to hydrolyze COS into H₂S. The designed operation temperature and pressure of the COS hydrolysis system are 150 °C and 8 kg/cm². After the hydrolysis system, COS was reduced below 1 ppm at the normal operating condition. The normal designed operation temperature and pressure of the AGR system are below 40 °C and 8 kg/cm². Fe-chelate was used as an absorbent. H₂S was removed below 0.5 ppm in the AGR system when the maximum concentration of H₂S was 900 ppm. A small scale COS adsorber was also installed and tested to remove COS below 0.5 ppm. COS was removed below 0.1 ppm after the COS adsorbents such as the activated carbon and ion exchange resin. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Formation of brownmillerite type calcium ferrite (Ca2Fe2O5) and catalytic properties in propylene combustion

Several types of calcium ferrite base catalysts (Ca/Fe = 0.33–3) for propylene (C₃H₆) combustion were prepared. Calcium ferrite catalyst with brownmillerite crystal structure provided catalytic activity for C₃H₆ combustion in the temperature range of 250–450 °C. The brownmillerite phase (Ca₂Fe₂O₅) was responsible for the formation of oxygen adspecies (O ₂ ⁻ ) in the surface layer below 450 °C.     

Cobalt(II), Zinc(II) and Cadmium(II)-Squarate Complexes with N-Methylimidazole

Three M(II)-squarate complexes, [Co(sq)(H₂O)(Nmim)₄] (1), [Zn(μ_1,3-sq)(H₂O)₂ (Nmim)₂] _n (2) and [Cd(μ_1,3-sq)(H₂O)₂(Nmim)₂] _n (3) (sq = squarate, Nmim = N-methylimidazole) have been synthesized and characterized by elemental, spectral (IR and UV–Vis.) and thermal analyses. The molecular structures of the complexes have been investigated by single crystal X-ray diffraction technique. The squarate ligand acts as two different coordination modes as a monodentate (in 1) and bis(monodentate) (O ^1– O ³ ) bridging ligand (in 2, 3). The Co(II) atom has a distorted octahedral geometry with the basal plane comprised of three nitrogen atoms of Nmim ligands and a oxygen atom of squarate ligand. The axial position is occupied by a nitrogen atom of Nmim and one aqua ligand. The crystallographic analysis reveals that the crystal structures of 2 and 3 are one-dimensional linear chain polymers along the c and b axis, respectively. The configuration around each metal(II) ions are distorted octahedral geometry with two nitrogen atoms of trans-Nmim, two aqua ligands and two oxygen atoms of squarate-O¹,O³ ligand. These chains are held together by the C–H···π, π···π and hydrogen-bonding interactions, forming three-dimensional network.     

Experimental studies of 1 ton/day coal slurry feed type oxygen blown, entrained flow gasifier

Experimental Studies of a 1 Ton/Day coal slurry feed type oxygen blown, entrained flow gasifier have been performed with the slurry concentration and gasifier temperature at 65% and above 1,300 ‡C, respectively. The characteristics of ash fusion temperature with addition of CaO as a flux were investigated to maintain the proper slag tapping condition in the range of reaction temperature. As the flux addition increased, ash fusion temperature showed a eutectic effect with the eutectic at around 20–30% CaO. In order to analyze the gasification characteristics, the effects of O₂/coal feed ratio on the product gas composition, heating value, gasifier temperature and cold gas efficiency were evaluated. From the results, it was shown in the case of Kideco coal that the cold gas efficiency was 44–60% and the heating value was 1,700-2,200 kcal/Nm³, while Drayton coal showed a cold gas efficiency of 55–62% and a heating value of 1,800-2,200 kcal/Nm³. In the case of Datong coal, the cold gas efficiency was 38–65%, and the heating value was 2,000-2,300 kcal/Nm³. Also, the results showed that the optimal operating condition of O₂/coal ratio for the three different coals was 0.9. Presented at the Int’/Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Novel Au/TiO2/Al2O3 · xH2O catalysts for CO oxidation

Au/Al₂O₃ · xH₂O and Au/TiO₂/Al₂O₃ · xH₂O (x = 0–3) catalysts were prepared by assembling gold nanoparticles on neat and TiO₂-modified Al₂O₃, AlOOH, and Al(OH)₃ supports, and their catalytic activity in CO oxidation was tested either as synthesized or after on-line pretreatment in O₂–He at 500 °C. A promotional effect of TiO₂ on the activity of gold catalysts was observed upon 500 °C-pretreatment. The catalyst stability as a function of time on stream was tested in the absence or presence of H₂, and physiochemical characterization applying BET, ICP-OES, XRD, TEM, and ²⁷Al MAS NMR was conducted.     

Kinetics of hydrogen peroxide oxidation of alkyl dimethyl amines

We measured the absolute rate constants for the hydrogen peroxide oxidation of two different octyl dimethyl amines in isopropanol/water mixtures at 23°C. The amines were 1-octyl dimethyl amine (1) and 2-ethylhexyl dimethyl amine (2); their structures were analogous to those most often encountered in commercial alkyl dimethyl amine oxide production. The observed first-order rate constants for the disappearance of amine across a range of H₂O₂ concentrations (0.5–8 M) indicated that the overall rate was first-order in amine and 3/2-order in H₂O₂. Calculations showed k ₁=0.16 M⁻¹h⁻¹, k ₂=0.046 M⁻¹h⁻¹, and k ₁/k ₂=3.5. The rates appeared to decrease with increasing steric hindrance around the nitrogen atom. We also investigated the effect of water on the reaction rates. When [H₂O]<∼4.5 M in isopropanol, the rates increased with increasing [H₂O]; for [H₂O]>∼4.5 M, the rates were insensitive to [H₂O].     

Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.