Evaluation of amines for the selective catalytic reduction (SCR) of NOx from diesel engine exhaust

With a view to developing onboard generation of selective reductants for NO_x removal from diesel engine exhaust we compared the performance of a primary, secondary and tertiary amine to NH₃ using a typical mini core NH₃-SCR catalyst. Primary amines with short hydrocarbon chains, e.g. CH₃NH₂ (maximum NO_x conversion, 50%) approached the NO_x conversion obtained using NH₃ (maximum NO_x conversion, 70%). Increasing the amine to NO_x ratio greater than 1 results in NO_x conversions closer to those of NH₃ (maximum NO_x conversion increased to 60%). Secondary and tertiary amines had smaller NO_x conversions as a function of temperature and the drop in NO and NO_x conversion decreased with increasing amine hydrogen substitution. Also, the maximum NO_x conversion for each reductant tends to move to a lower temperature as the degree of substitution increases.Unlike NH₃, the amines can react in the gas phase at temperatures within the range of diesel engine exhaust. Due to this gas phase reactivity the NO_x conversions measured using the mini core SCR catalyst also contain a gas phase conversion component. Gas phase conversions were investigated by replacing the mini core SCR catalyst with an equivalent length of quartz beads. Subtraction of the two results highlighted the differences between the mini core catalytic and gas phase conversions measured in this manner over the temperature range investigated. These differential NO_x conversions for the three amines had maxima at about 375 °C.     

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.     

Exceptional Activity for NOx Reduction at Low Temperatures Using Combinations of Hydrogen and Higher Hydrocarbons on Ag/Al2O3 Catalysts

The effect of the addition of hydrogen on the SCR of NO _x with a hydrocarbon reaction was investigated. It was found that hydrogen had a remarkable effect on the temperature range over which NO _x could be reduced during the SCR reaction with octane. Reduction of NO _x was initiated at as low a temperature as 100 °C and >95% NO _x conversion was achieved over a temperature range of 200–450 °C. Hydrogen has the effect of activating octane at lower temperatures and also promotes the oxidation of NO to NO₂ in the absence of hydrocarbon. Transient kinetic and in situ DRIFTS measurements indicated that hydrogen has a direct role in the reaction mechanism by either promoting the formation and storage of an organic C = N species which can then readily reduce NO _x and/or removing a species which acts as a poison to the SCR reaction at low temperatures.     

Experimental investigation of nitrogen species release from different solid biomass fuels as a basis for release models

Experimental data on the release of NO_x precursors from solid biomass fuels during thermal conversion are necessary to study N release in general and to supply reliable data for the purpose of packed bed and gas phase conversion model development and validation. In this work the release of NO_x precursors was studied at a lab-scale pot furnace (batch reactor) by taking measurements during the conversion process of solid biomass in a packed bed. The investigations were carried out with relevant woody biomass fuels, which cover a broad range of fuel N contents: sawdust, bark, waste wood and MDF board. The most important NO_x precursor detected above the fuel bed under fuel rich conditions was NH₃, while HCN was almost insignificant with the exception of sawdust. NO was detected mainly under air rich conditions. Furthermore, the experimental data were utilised to derive release functions for the relevant NO_x precursors NO, NH₃ and HCN. The release functions were implemented in an in-house empirical packed bed combustion model, which serves as a basis for a subsequent CFD N species gas phase calculation.     

A reduced NOx reaction model for pulverized coal combustion under fuel-rich conditions

A reduced NO_x reaction model was developed for analysis of industrial pulverized coal firing boilers. The model was developed from experiments of laminar premixed combustion under a variety of stoichiometric ratios, burning temperatures, coal ranks (from sub-bituminous coal to anthracite) and particle diameters. Calculations agreed with experimental results for NO_x and nitrogen species (NH₃ and HCN), if the model assumed that the hydrocarbon radicals were formed not only from pyrolysis of volatile matter, but also from char oxidation and gasification. The presence of hydrogen in char at the final burnout stage supported this assumption. NO_x reduction by hydrocarbon radicals was the most important reaction in high temperature (>1500 K), fuel-rich, char combustion regions. NO_x reduction from nitrogen species was sensitive to peak NO_x concentration in volatile combustion regions, but NO_x emission downstream had little influence from the peak NO_x concentration. The heterogeneous reaction between char and NO_x was important for fuel-lean or low-temperature conditions.     

Dynamics and selectivity of NOx reduction in NOx storage catalytic monolith

Several nitrogen compounds can be produced during the regeneration phase in periodically operated NO_x storage and reduction catalyst (NSRC) for conversion of automobile exhaust gases. Besides the main product N₂, also NO, N₂O, and NH₃ can be formed, depending on the regeneration phase length, temperature, and gas composition. This contribution focuses on experimental evaluation of the NO_x reduction dynamics and selectivity towards the main products (NO, N₂ and NH₃) within the short rich phase, and consequent development of the corresponding global reaction-kinetic model. An industrial NSRC monolith sample of PtRh/Ba/CeO₂/ -Al₂O₃ type is employed in nearly isothermal laboratory micro-reactor. The oxygen and NO_x storage/reduction experiments are performed in the temperature range 100–500 °C in the presence of CO₂ and H₂O, using H₂, CO and C₃H₆ as the reducing agents.The spatially distributed NSRC model developed earlier is extended by the following reactions: NH₃ is formed by the reaction of H₂ with NO_x and it can further react with oxygen and NO_x deposited on the catalyst surface, producing N₂. Considering this scheme with ammonia as an active intermediate of the NO_x reduction, a good agreement with experiments is obtained in terms of the NO_x reduction dynamics and selectivity. A reduction front travelling in the flow direction along the reactor is predicted, with the NH₃ maximum on the moving boundary. When the front reaches the reactor outlet, the NH₃ peak is observed in the exhaust gas. It is assumed that the ammonia formation during the NO_x reduction by CO and HCs at higher temperatures proceed via the water gas shift and steam reforming reactions producing hydrogen. It is further demonstrated that oxygen storage effects influence the dynamics of the stored NO_x reduction. The temperature dependences of the outlet ammonia peak delay and the selectivity towards NH₃ are correlated with the effective oxygen and NO_x storage capacity.     

Formation of NOx precursors during the pyrolysis of coal and biomass. Part V. Pyrolysis of a sewage sludge

A sewage sludge sample from a wastewater treatment plant in China was pyrolysed in a fluidised-bed/fixed-bed reactor and in a fluidised-bed/tubular reactor. HCN was found to be the main NO_x precursor, representing up to about 80% of the nitrogen present in the sludge. The thermal cracking of volatiles is the main route of HCN formation. NH₃ was also an important NO_x precursor formed during the pyrolysis of the sewage sludge. The experimental results indicate that there are at least two distinctive stages of NH₃ formation during the pyrolysis of the sewage sludge at a fast heating rate. The formation of NH₃ at temperatures lower than 400-500 °C is at least partly due to the amino structures in the sludge. The reactions of volatiles in the gas phase make negligible contributions to the observed NH₃ yield.     

Experimental investigation of NOx emissions in oxycoal combustion

This work presents the results of an experimental investigation on NO_x emissions from coal combustion in a pilot scale test facility. Three oxidiser atmospheres have been compared, namely air, CO₂/O₂, and O₂ enriched recirculated flue gas. NO_x emissions from two different combustion modes have been studied, swirl flame and flameless combustion. The influence of the burner oxygen ratio and the oxidiser O₂ concentration on NO_x formation and reduction have been analysed. With increasing burner oxygen ratio, an increase of NO_x emissions has been obtained for air and CO₂/O₂ in both, swirl flame and flameless combustion. In case of the swirl flame, flue gas recirculation leads to a reduction of NO_x emissions up to 50%, whereas in case of flameless combustion this reduction is around 40% compared to CO₂/O₂. No significant impact of the oxidiser O₂ concentration in the CO₂/O₂ mixture on NO_x emissions is observed in the range between 18 and 27 vol.% in swirl flames. An analysis of NO_x formation and reduction mechanisms showed, that the observed reduction of NO_x emissions by flue gas recirculation cannot be attributed to the reduction of recirculated NO_x alone, but also to a reduced conversion of fuel-N to NO.     

Removal of NOx with radical injection caused by corona discharge

Removal of NO_x (namely DeNO_x) from simulated flue gas with direct current (d.c.) corona radical shower system was investigated. Steady streamer coronas occur when the flow rates of the fed gases are adjusted properly. The experimental results show that both the composition and the flow rate of the gas fed into the nozzles influence the V-I characteristic of corona discharge. The vapor in the flue gas restrains the discharge, reduces the discharge current, but enhances the DeNO_x efficiency. Furthermore, removal of NO_x from flue gas by radical injection associated with alkali solution (26% by weight of NaOH in water) scrubbing was carried out. Oxygen together with water vapor is fed into the nozzle electrode and the oxygen and water molecules are decomposed in the corona zone. It is found that NO and NO₂ can be converted into HNO₂ and HNO₃, respectively, by radicals formed during the discharge process and the conversion efficiency of NO_x in the plasma reactor is more than 60%. The overall DeNO_x efficiency of the system reaches 81.7% after the flue gas was scrubbed by the NaOH solution.     

Modelling of NOx adsorption over NOx adsorbers

Modelling of the phenomena involved during the adsorption of NO_x on NO_x trap catalysts was developed. The aim of the model is the prediction of the quantity of stocked barium nitrate as well as the emissions of NO and NO₂, as a function of time and temperature. The mechanism of the process is sounded on the adsorption of gas species (NO, NO₂, O₂) on platinum sites, equilibrium reaction between adsorbed species followed by the formation of Ba(NO₃)₂. This formation of barium nitrate is limited by the thermal decomposition reaction which liberates NO in the gas phase. The kinetic constant of decomposition of barium nitrate was determined by temperature programmed thermogravimetry on pure Ba(NO₃)₂, using the method of Freeman and Carroll. Other kinetic constants bound to the mechanism were estimated by fitting the results of the model to experimental results.The mechanism was validated for various values of the molar fraction of O₂, the molar fraction of NO and various values of the NO/NO₂ ratio in the gas entering the reactor. It was also tested with different catalyst compositions (variation of the platinum and BaO concentrations). The importance of oxygen in the process was clearly demonstrated as well as the promoting role of NO₂.     

NOx Abatement by Catalytic Traps: On the Mechanism of NOx Trapping Under Automotive Conditions

NO _x adsorption was measured with a barium based NO_x storage catalyst at an engine bench equipped with a lean burn gasoline direct injection engine (GDI). In order to study the influence of gas phase NO₂ on the NO_x storage efficiency two different pre-catalysts were used: One with excellent NO oxidation activity to produce a high NO₂ concentration and another pre-catalyst without NO oxidation activity and therefore high NO concentration at the NO _x storage catalyst inlet. Both pre-catalyst had excellent HC and CO conversion efficiency and therefore the CO and HC concentration at the NO _x storage catalyst inlet was practically zero. No lean NO _x reduction was observed. Under that conditions, experiments with NO _x storage catalysts of different length show that a high NO₂ inlet concentration did not enhance the NO _x storage efficiency. Moreover, we observed reduction of NO₂ to NO over the NO_x storage catalyst. However, in presence of a high NO inlet concentration NO₂ formation was observed which may proceed parallel to NO _x storage.     

Evaluation of the use of coal volatiles as reburning fuel for NOx reduction

In this study, computational fluid dynamic (CFD) and kinetic models were used to investigate the relative performances of coal volatiles and natural gas reburning. This modeling approach considers fluid dynamic and non-isothermal effects, which were not considered in past laboratory flow reactor studies. The commercial CFD code FLUENT 6.1 was used to predict the residence times and temperatures for reburning tests in the down-fired combustor (DFC), a 0.5 MMBTU/h research combustor at The Pennsylvania State University. To predict NO_x concentrations within the combustor, this data was then applied to an advanced reburning kinetic model used in past studies. For equal firing rates and stoichiometric ratios, reburning using methane yielded lower concentrations of NO_x (and, therefore, better NO_x reduction performance) than reburning using coal volatiles. The coal volatiles give increased flame temperature over natural gas, which apparently offsets the increased reburn zone hydrocarbon radical yield of coal volatiles over natural gas.     

Influence of burner-port geometry in hydrocarbon oxidation and NOx formation mechanisms in methane/air flames

The influence of burner-port geometry in the mechanisms of hydrocarbon oxidation and NO_x formation from a 50 kW industrial-type methane-fired burner was investigated experimentally. Imaging and tomographic reconstruction techniques were used to assess the effects of port geometry upon flame visible length and C₂ chemiluminescence distribution in the recirculation zone. C₂ emission of methane flames depicts that low fuel jet velocities allow very rich conditions at recirculation zone and lead methane oxidation through O₂-scarcity mechanism. Higher velocities imply that methane oxidises via a path including dissociation into free radicals. In-furnace measurements were performed from a refractory-lined vertical furnace. NO_x concentration results revealed that NO formation is closely connected with the dissociation process, suggesting that prompt-NO_x mechanism is more important than hitherto supposed.     

Selective Catalytic Reduction of NOx over H-ZSM-5 Under Lean Conditions Using Transient NH3 Supply

The selective catalytic reduction (SCR) of NO _x over zeolite H-ZSM-5 with ammonia was investigated using in situ FTIR spectroscopy and flow reactor measurements. The adsorption of ammonia and the reaction between NO _x , O₂ and either pre-adsorbed ammonia or transiently supplied ammonia were investigated for either NO or equimolar amounts of NO and NO₂. With transient ammonia supply the total NO reduction increased and the selectivity to N₂O formation decreased compared to continuous supply. The FTIR experiments revealed that NO _x reacts with ammonia adsorbed on Brønsted acid sites as NH₄ ⁺ ions. These experiments further indicated that adsorbed -NO₂ ^– is formed during the SCR reaction over H-ZSM-5.     

Sequence of monolithic converters DOC–CDPF–NSRC for lean exhaust gas detoxification: A simulation study

With increasingly strict automotive emission regulations the exhaust gas aftertreatment becomes more complex and expensive. Mathematical modelling and simulations play an important role in design of the aftertreatment systems consisting of multiple catalytic devices, reducing the time and cost demands of the system design. In this paper a combined exhaust gas aftertreatment system for diesel engines is studied. It consists of a diesel oxidation catalyst (DOC) for CO and hydrocarbons oxidation, a catalyzed diesel particulate filter (CDPF) for soot filtration, and an NO_x storage and reduction catalyst (NSRC, also called lean NO_x trap, LNT) for NO_x abatement. Effective mathematical models of the individual converters are presented and used first to demonstrate the functionalities of the system, and then to conduct a parametric simulation study. The aim of this study is to map the influence of the individual components on the performance of the entire system in standard test driving cycle. The sizes of the DOC, CDPF, and NSRC converters are varied while the overall volume of the combined system is kept constant. The resulting maps of pressure drop, CO, HC, particulate matter, and NO_x conversions show non-linear dependences on the sizes of individual converters. Co-operative and competitive effects occurring in the combined system are discussed. Suitable reactors sizes are found that enable high conversions of all controlled exhaust gas components.     

Mitigation of NOx emissions from a jatropha biodiesel fuelled DI diesel engine using antioxidant additives

Biodiesel offers cleaner combustion over conventional diesel fuel including reduced particulate matter, carbon monoxide and unburned hydrocarbon emissions. However, several studies point to slight increase in NO_x emissions (about 10%) for biodiesel fuel compared with conventional diesel fuel. Use of antioxidant additives is one of the most cost-effective ways to mitigate the formation of prompt NO_x. In this study, the effect of antioxidant additives on NO_x emissions in a jatropha methyl ester fuelled direct injection diesel engine have been investigated experimentally and compared. A survey of literature regarding the causes of biodiesel NO_x effect and control strategies is presented. The antioxidant additives L-ascorbic acid, α tocopherol acetate, butylated hydroxytoluene, p-phenylenediamine and ethylenediamine were tested on computerised Kirloskar-make 4 stroke water cooled single cylinder diesel engine of 4.4 kW rated power. Results showed that antioxidants considered in the present study are effective in controlling the NO_x emissions of biodiesel fuelled diesel engines. A 0.025%-m concentration of p-phenylenediamine additive was optimal as NO_x levels were substantially reduced in the whole load range in comparison with neat biodiesel. However, hydrocarbon and CO emissions were found to have increased by the addition of antioxidants.     

Transient TPSR, DRIFTS-MS and TGA studies of a Pd/ceria-zirconia catalyst in CH4 and NO2 atmospheres

In this study, the parameters governing the activity of Pd/ceria-zirconia catalysts in the selective catalytic reduction (SCR) of NO_x assisted by methane are investigated using a combination of temperature-programmed spectroscopic and thermogravimetric techniques and transient SCR conditions. By DRIFTS of adsorbed CO, it is established that Pd species on Ce_0.2Zr_0.8O₂ are mainly present in cationic form but exhibit high reducibility. As found by temperature-programmed surface reaction (TPSR) in CH₄ + NO₂ atmosphere, the CH₄-SCR reaction is initiated at 280 °C on Pd/Ce_0.2Zr_0.8O₂ and yields almost 100% N₂ above 500 °C. DRIFTS-MS and TGA experiments performed under transient SCR conditions show that DeNO_x activity is due to a surface reaction between some methane oxidation products on reduced Pd sites with ad-N_xO_y species presumably located on the support. The detrimental effect of O₂ on DeNO_x is explained by the promotion of the total combustion of methane assisted by the ceria-zirconia component at the expense of the SCR reaction above 320 °C.     

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.     

Diesel Soot Catalyzes the Selective Catalytic Reduction of NOx with NH3

The catalytic activity of soot samples for the selective catalytic reduction (SCR) of NO_x with NH₃ was investigated in dependence of the NO₂, NO and NH₃ concentration in the temperature range between 200 and 350 °C. The highest NO_x reduction of up to 25 % was measured in the presence of both NO₂ and NO at a GHSV of 35,000 h^?1. Decreasing space velocities resulted in an increase of the SCR activity. In the absence of NO₂, NO_x reduction was not observed. Carbon oxidation and SCR reaction occurred in parallel due to the presence of NO₂ and O₂, but hardly influenced each other, which suggested that in the NO_x reduction on soot most probably physisorbed species were involved. The observed stoichiometries indicated the action of the fast SCR reaction in the presence of NO and the NO ₂ SCR reaction in the absence of NO, while the observed gas phase and surface species pointed at reaction steps similar to those on classical SCR catalysts.