CoAl2O4 spinel catalyst for soot combustion with NOx/O2

Mesoporous and nanosized cobalt aluminate spinel with high specific surface area was prepared using microwave assisted glycothermal method and used as soot combustion catalyst in a NO_x + O₂ stream. For comparison, zinc aluminate spinel and alumina supported platinum catalysts were prepared and tested. All samples were characterised using XRD, (HR)TEM, N₂ adsorption–desorption measurements. The CoAl₂O₄ spinel was able to oxidise soot as fast as the reference Pt/Al₂O₃ catalyst. Its catalytic activity can be attributed to a high NO_x chemisorption on the surface of this spinel, which leads to the fast oxidation of NO to NO₂.     

Investigation of flue-gas treatment with O3 injection using NO and NO2 planar laser-induced fluorescence

Direct ozone (O₃) injection is a promising flue-gas treatment technology based on oxidation of NO and Hg into soluble species like NO₂, NO₃, N₂O₅, oxidized mercury, etc. These product gases are then effectively removed from the flue gases with the wet flue gas desulfurization system for SO₂. The kinetics and mixing behaviors of the oxidation process are important phenomena in development of practical applications. In this work, planar laser-induced fluorescence (PLIF) of NO and NO₂ was utilized to investigate the reaction structures between a turbulent O₃ jet (dry air with 2000 ppm O₃) and a laminar co-flow of simulated flue gas (containing 200 ppm NO), prepared in co-axial tubes. The shape of the reaction zone and the NO conversion rate along with the downstream length were determined from the NO-PLIF measurements. About 62% of NO was oxidized at 15d (d, jet orifice diameter) by a 30 m/s O₃ jet with an influence width of about 6d in radius. The NO₂ PLIF results support the conclusions deduced from the NO-PLIF measurements.     

NO reduction with H2 in the presence of excess O2 over Pd/MFI catalyst

The NO SCR (selective catalytic reduction) activity with H₂ in the presence of excess O₂ was investigated over Pd/MFI catalyst prepared by sublimation method. With GHSV=90?000 h⁻¹, a very high steady-state conversion of NO to N₂ (70%) is achieved at 100 °C. Significant reorganizations take place inside the catalyst upon its first contact with all reactants and products at the reaction temperature. Pd⁰, which has a significant role in the NO-H₂-O₂ reaction, is possibly the active site for NO reduction. The formation of Pd-β hydride deactivates the catalyst for NO reduction. Throughout the entire NO-H₂-O₂ reaction, no N₂O or NO₂ is formed; N₂ is the only N-containing product. The presence of O₂ inhibits the formation of undesirable NH₃. The rate of the NO+H₂ reaction is fast or comparable to that of the H₂+O₂ reaction. The oxidation of Pd⁰ and subsequent agglomeration of PdO are responsible for the decreased NO reduction activity at high temperature.     

NO2 and N2 sorption in MFI films with varying Si/Al and Na/Al ratios

MFI crystals or films with controlled thicknesses and different Si/Al ratios were grown on seeded cordierite monoliths using a clear synthesis mixture with template or a template-free gel. The materials were analyzed by scanning electron microscopy, X-ray diffraction, inductively coupled plasma-atomic emission spectrometry, X-ray photoelectron spectroscopy, thermogravimetric analysis and sorption experiments using N₂ or NO₂ adsorbates. The films were uniformly distributed over the support surface. As expected, the specific monolayer N₂ adsorption capacity (mol/g_zeolite) was constant and independent of film thickness. The specific molar NO₂ adsorption capacity was significantly lower than the specific molar monolayer N₂ adsorption capacity, indicating that NO₂ is adsorbed at specific sites rather than evenly distributed in a monolayer. A number of NO₂ adsorption sites with varying strengths were observed by TPD experiments. At 30 °C, the amount of adsorbed NO₂ in the MFI films increased with increasing Al and Na content as opposed to the N₂ adsorption capacity, which was independent of these parameters. At 200 °C, the adsorbed amount of NO₂ was lower than at 30 °C and apparently independent on Al concentration in the Na-MFI films. These results indicate that different mechanisms are involved in NO₂ adsorption. NO₂ may adsorb weakly on Na⁺ cations and also react with silanol groups and residual water in the zeolite, the latter two results in more strongly bound species. Upon NO₂ adsorption, formation of NO was observed. This work represents the first systematic study of the effects of Al and Na content on NO₂ adsorption in MFI films.     

Pulverized coal combustion in air and in O2/CO2 mixtures with NOx recycle

This paper presents experimental results of a 20 kW vertical combustor equipped with a single pf-burner on pulverised coal combustion in air and O₂/CO₂ mixtures with NO_x recycle. Experimental results on combustion performance and NO_x emissions of seven international bituminous coals in air and in O₂/CO₂ mixtures confirm the previous findings of the authors that the O₂ concentration in the O₂/CO₂ mixture has to be 30% or higher to produce matching temperature profiles to those of coal-air combustion while coal combustion in 30% O₂/70% CO₂ leads to better coal burnout and less NO_x emissions than coal combustion in air. Experimental results with NO_x recycle reveal that the reduction of the recycled NO depends on the combustion media, combustion mode (staging or non-staging) and recycling location. Generally, more NO is reduced with coal combustion in 30% O₂/70% CO₂ than with coal combustion in air. Up to 88 and 92% reductions of the recycled NO can be achieved with coal combustion in air and in 30% O₂/70% CO₂ respectively. More NO is reduced with oxidant staging than without oxidant staging when NO is recycled through the burner. Much more NO is reduced when NO recycled through the burner (from 65 to 92%) than when NO is recycled through the staging tertiary oxidant ports (from 33 to 54%). The concentration of the recycled NO has little influence on the reduction efficiency of the recycled NO with both combustion media—air and 30% O₂/70% CO₂.     

DRIFTS study of the catalytic N2O reduction by SO2 on FeZSM-5

SO₂ has been recognized as an effective reducing agent for N₂O over iron-containing zeolite catalysts, lowering the operation temperature up to 100 K with respect to the direct N₂O decomposition. This unique behavior contrasts with the common poisoning effect of SO₂ over other active de-N₂O metals (e.g. Co, Cu, Rh, and Ru). The formation of surface sulfates has been generally posed as the main cause for catalyst deactivation by SO₂. Through the use of in situ infrared spectroscopy (DRIFTS), we show that steam-activated FeZSM-5 indeed builds up stable sulfate species during the N₂O + SO₂ reaction. Significant amounts of sulfur were detected in the used catalyst by elemental analysis and X-ray photoelectron spectroscopy. However, the enhanced N₂O conversion is remarkably stable, indicating that the reducing action by SO₂ and the sulfation of the surface are decoupled. The resulting sulfate species are thus spectators in the catalytic process and do not block or alter the structure of the active sites for N₂O reduction and decomposition.     

Application of the thermal DeNOx process to diesel engine DeNOx: an experimental and kinetic modelling study

Diesel DeNO_x experiments have been conducted using the selective noncatalytic ‘thermal DeNO_x’ process in a diesel fuelled combustion-driven flow reactor which simulated a single cylinder (966 cm³) and head equipped with a water-cooling jacket and an exhaust pipe. NH₃ was directly injected into the cylinder to reduce NO_x emissions. A wide range of air/fuel ratios (A/F=20-40) was selected for NO_x reduction where an initial NO_x of 530 ppm was usually maintained with a molar ratio (β=NH₃/NO_x) of 1.5.The results indicate that a 34% NO_x reduction can be achieved from the cylinder injection in the temperature range, 1100-1350 K. Most of the NO_x reduction occurs within the cylinder and head section (residence time<40 ms), since temperatures in the exhaust are too low for additional NO_x reduction. Under large gas quenching rates, increasing β values (e.g. 4.0) substantially increase the NO_x reduction up to 60%, which is comparable with those achieved under isothermal conditions. Experimental findings are analysed by chemical kinetics using the Miller and Bowman mechanism including both N/H/O species and CO/hydrocarbon reactions to account for CO/UHC oxidation effects, based on practical nonisothermal conditions. Comparisons of the kinetic calculations with the experimental data are given as regards temperature characteristics, residence time and molar ratio. In addition, the effects of CO/UHC and branching ratio (α=k₁/(k₁+k₂)) for the reaction NH₂+NO=products are discussed in terms of NO reduction features, together with practical implications.     

Heterogeneous reactions of NO2 and NO-O2 on the surface of carbons

The interactions of nitrogen oxides with carbons differing in the chemical structure of surface functional groups were studied using in situ FTIR combined with the measurements of catalytic activity. Microporous carbon samples with similar pore size distribution were prepared from cellulose. The structure and coverage of adsorbates during reactions at temperatures between 295 and 573 K are determined by FTIR. No significant changes in NO_x reaction with carbon surface were found by oxidation of the carbonized film. During the study of the reaction of NO/O₂ mixture with carbons, the infrared absorption bands for the surface species formed are similar to the IR bands observed after the reaction of carbon samples with NO₂. For both reactions, surface species, including C-NO₂, C-ONO, C-NCO and anhydride structures are formed. Catalytic NO_x reduction by carbons has been investigated in the temperature range 295-623 K in the flow reactor equipped with an FTIR gas analyzer. As the surface of carbon is exposed to NO₂ gaseous NO is formed. The reduction of NO₂ to N₂ without the use of an externally supplied reductant can be achieved with microporous carbons. Significant NO₂ conversion to N₂ occurred at 623 K on both oxidized and non-oxidized carbons.     

Low cost coal-based carbons for combined SO2 and NO removal from exhaust gas

The aim of this paper is to show how a cheap carbonaceous material such as low rank coal-based carbon (or char) can be used in the combined SO₂/NO removal from exhaust gas at the linear gas velocity used in commercial systems (0.12 m s⁻¹). Char is produced from carbonization and optionally activated with steam. This char is used in a first step to abate the SO₂ concentration at the following conditions: 100 °C, space velocity of 3600 h⁻¹, 6% O₂, 10% H₂O, 1000 ppmv SO₂, 1000 ppmv NO and N₂ as remainder. In a second step, when the SO₂ concentration in the flue gas is low, NO is reduced to N₂ and steam at the following experimental conditions: 150 °C, space velocity of 900 h⁻¹, 6% O₂, 10% H₂O, 0-500 ppmv SO₂, 1000 ppmv NO, 1000 ppmv NH₃ and N₂ as remainder.It has been shown that the presence of NO has no effect on SO₂ abatement during the first step of combined SO₂/NO removal system and that low SO₂ inlet concentration has a negligible effect on NO reduction in the second step. Moreover, this char can be thermally regenerated after use for various cycles without loss of activity. On the other hand, this regenerated char shows the highest NO removal activity (compared to parent chars, either carbonized or steam activated) which can be attributed to the activating effect of the sulfuric acid formed during the first step of the combined SO₂/NO removal system.     

XPS investigation of the reaction of carbon with NO, O2, N2 and H2O plasmas

The interaction of graphite with plasmas of pure gases (O₂, N₂ or H₂O), air or mixtures of gases containing NO has been studied by XPS “in situ” analysis. Depending on the type of plasma, different species of nitrogen, oxygen and carbon have been detected on the surface of graphite. The nitrogen containing species have been attributed to pyridinic, pyrrol, quartenary and oxidized groups adsorbed on the surface. The evolution with the treatment time of the relative intensity of the different nitrogen bands for Ar + NO, N₂ + NO, air or N₂ plasmas has served to propose a model accounting for the reactions of graphite with plasmas of NO containing gases. The model explains why carbon materials (in the form of graphite, soot particles, etc.) can be very effective for the removal of the NO present in exhaust combustion gases excited by a plasma. The analysis of the C1s and O1s photoemission peaks reveals the formation of C/O adsorbed species up to a maximum concentration on the surface of around 10% atomic oxygen. A general evolution is the progressive formation of C/O species where the carbon is sp³ hybridized. This tendency is enhanced when graphite is treated with the plasma of water.     

Transformations and destruction of nitrogen oxides—NO, NO2 and N2O—in a pulsed corona discharge reactor

There has been an increasing recent research interest in the removal of NO_x from combustion gases using electrical discharges, especially pulsed corona discharge reactors. The major issues in development of this technology are (a) the energy consumption required to achieve the desired pollutant reduction; and (b) the formation of undesirable byproducts. In this study, the transformations and destruction of nitrogen oxides—NO, NO₂ and N₂O—were investigated in a pulsed corona discharge reactor. Gas mixtures—NO in N₂, N₂O in N₂, NO₂ in N₂ and NO-N₂O-NO₂ in N₂—were allowed to flow through the reactor with initial concentrations, flow rates and energy input as operating variables. The reactor effluent gas stream was analyzed for N₂O, NO, NO₂, by means of an FTIR spectrometer. In some experiments, oxygen was measured using a gas chromatograph.Reaction mechanisms were proposed for the transformations and destruction of the different nitrogen oxides within a unified model structure. The corresponding reaction rates were integrated into a simple reactor model for the pulsed corona discharge reactor. The reactor model brings forth the coupling between reaction rates, electrical discharge parameters, and fluid flow within the reactor. It was recognized that the electron-impact dissociation of the background gas N₂ leads to both ionic and radical product species. In fact, ionic reactions were found responsible for N₂O destruction. Radical reactions were dominant in the transformation and destruction of NO and NO₂. However, decomposition of N₂⁺ ions also leads to indirect production of N radicals; this appears to be a less-power intensive route for NO destruction though longer residence times may be necessary. In addition, the decomposition of N₂⁺ ions limits the N₂O destruction that can be achieved. Comparison with our experimental data, as well as data in the literature, was very encouraging.     

Synthesis and characterization of ZnxMg1 − xGa2O4:Co fabricated by low-temperature burning method

A series of Zn_xMg_1 − xGa₂O₄:Co²⁺ spinels (x = 0, 0.25, 0.5, 0.75, and 1.0) was successfully produced through low-temperature burning method by using Mg(NO₃)₂·4H₂O, Zn(NO₃)₂·6H₂O, Ga(NO₃)₃·6H₂O, CO(NH₂)₂, NH₄NO₃, and Co(NO₃)₂·6H₂O as raw materials. The product was characterized by X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The product was not merely a simple mixture of MgGa₂O₄ and ZnGa₂O₄; rather, it formed a solid solution. The lattice constant of Zn_xMg_1 − xGa₂O₄:Co²⁺ (0 ≤ x ≤ 1.0) crystals has a good linear relationship with the doping density, x. The synthesized products have high crystallinities with neat arrays. Based on an analysis of the form and position of the emission spectrum, the strong emission peak around the visible region (670 nm) can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴A₂(⁴F)] of Co²⁺ in the tetrahedron. The weak emission peak in the near-infrared region can be attributed to the energy level transition [⁴T₁(⁴P) → ⁴T₂(⁴F)] of Co²⁺ in the tetrahedron.     

Investigations of the reduction of NO to N2 by reaction with Fe

The paper presents the results of the investigation of nitric oxide reduction by its reaction with metallic iron, within the temperature range of 750-1200 °C. Experiments were carried out in a one-dimensional tubular flow reactor externally heated in an electrical furnace. The spherical and cylindrical iron samples of well-defined and fixed surface area were placed in the center of the reactor. Mixtures NO/N₂, NO/O₂/N₂, NO/CO₂/N₂ of different molar compounds fractions were continuously fed into the reactor. The surfaces and cross-sections of partly oxidized iron samples were observed using a scanning microscope. The rate of nitric oxide reduction in the first stage of iron oxidization was measured. The obtained values lie between those presented in the literature and measured in the fluidized bed reactor and thermogravimetrically. A very strong influence of oxygen but a very weak one of carbon dioxide on the efficiency of NO reduction was observed within the investigated range of temperature.     

Soft template synthesis of mesoporous Co3O4/RuO2·xH2O composites for electrochemical capacitors

Co₃O₄/RuO₂·xH₂O composites with various Ru content (molar content of Ru = 5%, 10%, 20%, 50%) were synthesized by one-step co-precipitation method. The precursors were prepared via adjusting pH of the mixed aqueous solutions of Co(NO₃)₂·6H₂O and RuCl₃·0.5H₂O by using Pluronic123 as a soft template. For the composite with molar ratio of Co:Ru = 1:1 annealed at 200 °C, Brunauer-Emmet-Teller (BET) results indicated that the composite showed mesoporous structure, and the specific surface area of the composite was as high as 107 m² g⁻¹. The electrochemical performances of these composites were measured in 1 M KOH electrolyte. Compared with the composite prepared without template, the composite with P123 exhibited a higher specific capacitance. When the molar content of Ru was rising, the specific capacitance of the composites increased significantly. It was also observed that the crystalline structures as well as the electrochemical activities were strongly dependent on the annealing temperature. A capacitance of 642 F/g was obtained for the composite (Co:Ru = 1:1) annealed at 150 °C. Meanwhile, the composites also exhibited good cycle stability. Besides, the morphologies and textural characteristic of the samples were also investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM).     

Formation of LiNi0.5Co0.5VO4 nano-crystals by solvothermal reaction

LiNi_0.5Co_0.5VO₄ nano-crystals were solvothermally prepared using a mixture of LiOH·H₂O, Ni(NO₃)₂·6H₂O, Co(NO₃)₂·6H₂O and NH₄VO₃ in isopropanol at 150–200 °C followed by 300–600 °C calcination to form powders. TGA curves of the solvothermal products show weight losses due to evaporation and decomposition processes. The purified products seem to form at 500 °C and above. The products analyzed by XRD, selected area electron diffraction (SAED), energy dispersive X-ray (EDX) and atomic absorption spectrophotometer (AAS) correspond to LiNi_0.5Co_0.5VO₄. V–O stretching vibrations of VO₄ tetrahedrons analyzed using FTIR and Raman spectrometer are in the range of 620–900 cm⁻¹. A solvothermal reaction at 150 °C for 10 h followed by calcination at 600 °C for 6 h yields crystals with lattice parameter of 0.8252 ± 0.0008 nm. Transmission electron microscope (TEM) images clearly show that the solvothermal temperatures play a more important role in the size formation than the reaction times.     

FTIR study of NO, C3H6 and O2 adsorption and interaction on gold modified MCM-41 materials

This paper is devoted to the detailed FTIR study of the adsorption, co-adsorption, and interaction of all the reagents used in NO HC-SCR process addressed to lean-burn engines with the surface of new gold catalysts based on ordered mesoporous materials. Gold was introduced into silicate and niobiosilicate matrices by the impregnation (Au/MCM-41 and Au/NbMCM-41, respectively) and via co-precipitation with siliceous and niobium sources (AuNbMCM-41). The in situ FTIR study allowed the estimation of the possible chemisorption of the reagents and their interaction towards intermediates, depending on the chemical composition of the catalyst and the way of gold introduction. It has been found that propene is chemisorbed, but not, NO, on gold species at room temperature. Chemisorbed C₃H₆ interacts with NO only in the presence of oxygen excess. Oxygen oxidizes NO to NO₂, the latter interacts with chemisorbed propene towards carboxylates (1570 cm⁻¹) and NO₂ is reduced to N₂O. At higher temperatures carboxylates interact with gaseous NO to carbonate, N₂O, CO and CO₂. The presence of niobium in the NbMCM-41 matrix enhances the oxidative properties of the catalysts and as a consequence the interaction between intermediates in NO reduction with propene in the oxygen excess. The co-precipitated AuNbMCM-41 exhibits higher NOx storage properties than the impregnated one.     

Catalytic reduction of NH4NO3 by NO: Effects of solid acids and implications for low temperature DeNOx processes

Ammonium nitrate is thermally stable below 250 °C and could potentially deactivate low temperature NO_x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH₄NO₃ above its 170 °C melting point, while acidic solids catalyze this reaction even at temperatures below 100 °C. NO₂, a product of the reduction, can dimerize and then dissociate in molten NH₄NO₃ to NO⁺ + NO₃⁻, and may be stabilized within the melt as either an adduct or as HNO₂ formed from the hydrolysis of NO⁺ or N₂O₄. The other product of reduction, NH₄NO₂, readily decomposes at ≤100 °C to N₂ and H₂O, the desired end products of DeNO_x catalysis. A mechanism for the acid catalyzed reduction of NH₄NO₃ by NO is proposed, with HNO₃ as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO_x systems could help mitigate catalyst deactivation at low operating temperatures (<150 °C).     

Calcination and sintering characteristics of limestone under O2/CO2 combustion atmosphere

The O₂/CO₂ coal combustion technology is an innovative combustion technology that can control CO₂, SO₂ and NO_x emissions simultaneously. Calcination and sintering characteristics of limestone under O₂/CO₂ atmosphere were investigated in this paper. The pore size, the specific pore volume and the specific surface area of CaO calcined were measured by N₂ adsorption method. The grain size of CaO calcined was determined by XRD analysis. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere are less than that of CaO calcined in air at the same temperature. And the pore diameter of CaO calcined in O₂/CO₂ atmosphere is larger than that in air. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere increase initially with temperature, and then decline as temperature exceeds 1000 °C. The peaks of the specific pore volume and the specific surface area appear at 1000 °C. The specific surface area decreases with increase in the grain size of CaO calcined. The correlations of the grain size with the specific surface area and the specific pore volume can be expressed as L = 744.67 + 464.64 lg(1 / S) and L = − 608.5 + 1342.42 lg(1 / ε), respectively. Sintering has influence on the pore structure of CaO calcined by means of influencing the grain size of CaO.     

Synthesis and electrochemical performance of LiNi0.5Mn1.5O4 spinel compound

Spinel compound LiNi_0.5Mn_1.5O₄ was synthesized by a chemical wet method. Mn(NO₃)₂, Ni(NO₃)₂·6H₂O, NH₄HCO₃ and LiOH·H₂O were used as the starting materials. At first, Mn(NO₃)₂ and Ni(NO₃)₂·6H₂O reacted with NH₄HCO₃ to produce a precursor, then the precursor reacted with LiOH·H₂O to synthesize product LiNi_0.5Mn_1.5O₄. The product showed a single spinel phase under appropriate calcination conditions, and exhibited a high voltage plateau at about 4.6-4.8 V in the charge/discharge process. The LiNi_0.5Mn_1.5O₄ had a discharge specific capacity of 118 mAh/g at about 4.6 V and 126 mAh/g in total in the first cycle at a discharge current density of 2 mA/cm². After 50 cycles, the total discharge capacity was above 118 mAh/g.     

Phase diagram of the Al2O3-HfO2-Y2O3 system

The phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system was first constructed in the temperature range 1200-2800 °C. The phase transformations in the system are completed in eutectic reactions. No ternary compounds or regions of appreciable solid solution were found in the components or binaries in this system. Four new ternary and three new quasibinary eutectics were found. The minimum melting temperature is 1755 °C and it corresponds to the ternary eutectic Al₂O₃ + HfO₂ + Y₃Al₅O₁₂. The solidus surface projection, the schematic of the alloy crystallization path and the vertical sections present the complete phase diagram of the Al₂O₃-HfO₂-Y₂O₃ system.