Selective catalytic reduction of nitrogen oxides with ammonia in forced unsteady state reactors - Case based reasoning and mathematical model simulation reasoning

The application of forced unsteady-state reactors in case of selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3) is sustained by the fact that favorable temperature and composition distributions which cannot be achieved in any steady-state regime can be obtained by means of unsteady-state operations. In a normal way of operation the low exothermicity of the selective catalytic reduction (SCR) reaction (usually carried out in the range of 280-350°C) is not enough to maintain by itself the chemical reaction. A normal mode of operation usually requires supply of supplementary heat increasing in this way the overall process operation cost. Through forced unsteady-state operation, the main advantage that can be obtained when exothermic reactions take place is the possibility of trapping, beside the ammonia, the moving heat wave inside the catalytic bed. The unsteady state-operation enables the exploitation of the thermal storage capacity of the catalyticbed. The catalytic bed acts as a regenerative heat exchanger allowing auto-thermal behaviour when the adiabatic temperature rise is low. Finding the optimum reactor configuration, employing the most suitable operation model and identifying the reactor behavior are highly important steps in order to configure a proper device for industrial applications. The Reverse Flow Reactor (RFR) - a forced unsteady state reactor - corresponds to the above mentioned characteristics and may be employed as an efficient device for the treatment of dilute pollutant mixtures. As a main disadvantage, beside its advantages, the RFR presents the 'wash out' phenomena. This phenomenon represents emissions of unconverted reactants at every switch of the flow direction. As a consequence our attention was focused on finding an alternative reactor configuration for RFR which is not affected by the incontrollable emissions of unconverted reactants. In this respect the Reactor Network (RN) was investigated. Its configuration consists of several reactors connected in a closed sequence, simulating a moving bed by changing the reactants feeding position. In the RN the flow direction is maintained in the same way ensuring uniformcatalyst exploitation and in the same time the 'wash out' phenomena is annulated. The simulated moving bed (SMB) can operate in transient mode giving practically constant exit concentration and high conversion levels. The main advantage of the reactor network operation is emphasizedby the possibility to obtain auto-thermal behavior with nearly uniformcatalyst utilization. However, the reactor network presents only a small range of switching times which allow to reach and to maintain an ignited state. Even so a proper study of the complex behavior of the RN may give the necessary information to overcome all the difficulties that can appear in the RN operation. The unsteady-state reactors complexity arises from the fact that these reactor types are characterized by short contact times and complex interaction between heat and mass transportphenomena. Such complex interactions can give rise to a remarkable complex dynamic behavior characterized by a set of spatial-temporal patterns, chaotic changes in concentration and traveling waves of heat or chemical reactivity. The main efforts of the current research studies concern the improvement of contact modalities between reactants, the possibility of thermal wave storage inside the reactor and the improvement of the kinetic activity of the catalyst used. Paying attention to the above mentioned aspects is important when higher activity even at low feeding temperatures and low emissions of unconverted reactants are the main operation concerns. Also, the prediction of the reactor pseudo or steady-state performance (regarding the conversion, selectivity and thermal behavior) and the dynamicreactor response during exploitation are important aspects in finding the optimal control strategy for the forced unsteady state catalytic tubular reactors. The design of an adapted reactor requires knowledge about the influence of its operating conditions on the overall process performance and a precise evaluation of the operating parameters rage for which a sustained dynamic behavior is obtained. An apriori estimation of the system parameters result in diminution of the computational efforts. Usually the convergence of unsteady state reactor systems requires integration over hundreds of cycles depending on the initial guess of the parameter values. The investigation of various operation models and thermal transfer strategies give reliable means to obtain recuperative and regenerative devices which are capable to maintain an auto-thermal behavior in case of low exothermic reactions. In the present research work a gradual analysis of the SCR of NOx with ammonia process in forced unsteady-state reactors was realized. The investigation covers the presentationof the general problematic related to the effect of noxious emissions in the environment, the analysis of the suitable catalysts types for the process, the mathematical analysis approach for modeling and finding the system solutions and the experimental investigation of the device found to be more suitable for the present process. In order to gain information about the forced unsteady state reactor design, operation, important system parameters and their values, mathematical description, mathematicalmethod for solving systems of partial differential equations and other specific aspects, in a fast and easy way, and a case based reasoning (CBR) approach has been used. This approach, using the experience of past similarproblems and their adapted solutions, may provide a method for gaining informations and solutions for new problems related to the forced unsteady state reactors technology. As a consequence a CBR system was implemented and a corresponding tool was developed. Further on, grooving up the hypothesis of isothermal operation, the investigation by means of numerical simulation of the feasibility of the SCR of NOx with ammonia in the RFRand in the RN with variable feeding position was realized. The hypothesis of non-isothermal operation was taken into account because in our opinion ifa commercial catalyst is considered, is not possible to modify the chemical activity and its adsorptive capacity to improve the operation butis possible to change the operation regime. In order to identify the most suitable device for the unsteady state reduction of NOx with ammonia, considering the perspective of recuperative and regenerative devices, a comparative analysis of the above mentioned two devices performance was realized. The assumption of isothermal conditions in the beginningof the forced unsteadystate investigation allowed the simplification of the analysis enabling to focus on the impact of the conditions and mode of operation on the dynamic features caused by the trapping of one reactant in the reactor, without considering the impact of thermal effect on overall reactor performance. The non-isothermal system approach has been investigated in order to point out the important influence of the thermal effect on overall reactor performance, studying the possibility of RFR and RN utilization as recuperative and regenerative devices and the possibility of achieving a sustained auto-thermal behavior in case of lowexothermic reaction of SCR of NOx with ammonia and low temperature gasfeeding. Beside the influence of the thermal effect, the influence of the principal operating parameters, as switching time, inlet flow rate and initial catalyst temperature have been stressed. This analysis is important not only because it allows a comparison between the two devices and optimisation of the operation, but also the switching time is the main operating parameter. An appropriate choice of this parameter enables the fulfilment of the process constraints. The level of the conversions achieved, the more uniform temperature profiles, the uniformity ofcatalyst exploitation and the much simpler mode of operation imposed the RN as a much more suitable device for SCR of NOx with ammonia, in usual operation and also in the perspective of control strategy implementation. Theoretical simplified models have also been proposed in order to describe the forced unsteady state reactors performance and to estimate their internal temperature and concentration profiles. The general idea was to extend the study of catalytic reactor dynamics taking into account the perspectives that haven't been analyzed yet. The experimental investigation ofRN revealed a good agreement between the data obtained by model simulation and the ones obtained experimentally.

Understanding catalytic reactions over zeolites: A density functional theory study of selective catalytic reduction of NOX by NH3 over Cu-SAPO-34

Metal exchanged CHA-type (SAPO-34 and SSZ-13) zeolites are promising catalysts for selective catalytic reduction (SCR) of NOx by NH3. However, the understanding of the process at the molecular level is still limited, which hinders the identification of its mechanism and the design of more efficient zeolite catalysts. In this work, modelling the reaction over Cu-SAPO-34, a periodic density functional theory (DFT) study of NH3-SCR was performed using hybrid functional with the consideration of van der Waals (vdW) interactions. A mechanism with a low N–N coupling barrier is proposed to account for the activation of NO. The redox cycle of Cu2+ and Cu+, which is crucial for the SCR process, is identified with detailed analyses. Besides, the decomposition of NH2NO is shown to readily occur on the Brønsted acid site by a hydrogen push-pull mechanism, confirming the collective efforts of Brønsted acid and Lewis acid (Cu2+) sites. The special electronic and structural properties of Cu-SAPO-34 are demonstrated to play an essential role the reaction, which may have a general implication on the understanding of zeolite catalysis.

A new CuZ active form in the catalytic reduction of N2O by nitrous oxide reductase from Pseudomonas nautica

J Biol Inorg Chem (2010) 15:967–976 DOI 10.1007/s00775-010-0658-6

Reduction of nitrogen oxide emissions in lime kiln

Different nitrogen oxide removal technologies for rotary lime kiln are studied in this thesis, the main focus being in commercial technologies. Post-combustion methods are investigated in more detail as potential possible NOx removal with combustion methods in rotary lime kiln is more limited or primary methods are already in use. However, secondary methods as NOx scrubber, SNCR or SCR technologies are not listed as the Best Available Technologies defined by European Union. BAT technologies for NOx removal in lime kiln are (1) Optimised combustion and combustion control, (2) Good mixing of fuel and air, (3) Low-NOx burner and (4) Fuel selection/low-N fuel. SNCR method is the most suitable technique for NOx removal in lime kiln when NOx removal from 50 % to 70 % is required in case primary methods are already in use or cannot be applied. In higher removal cases ammonia slip is an issue in SNCR. By using SCR better NOx reduction can be achieved but issues with catalyst materials are expected to arise because of the dust and sulphur dioxide which leads to catalyst poison formation in lower flue gas temperatures. NOx scrubbing has potential when simultaneous NOx and SO2 removal is required. The challenge is that NO cannot be scrubbed directly, but once it is oxidized to NO2 or further scrubbing can be performed as the solubility of NO2 is higher. Commercial installations have not been made regarding SNCR, SCR or NOx scrubbing regarding rotary lime kiln. For SNCR and SCR the closest references come from cement industry.

Selective catalytic oxidation of alkylaromatic molecules by nanosize water droplets containing Co2+ species in supercritical carbon dioxide fluid

Stabilized nano-sized water droplet carrying water-soluble Co2+ species is employed as a new catalyst system for the oxidation of the alkyl aromatics in the presence of a fluorinated surfactant. This stable system contains no labile C-H structure and can facilitate excellent mixing of catalytic Co(II)/NaBr species, hydrocarbon substrates and oxygen in supercritical carbon dioxide fluid, which is demonstrated to be an excellent alternative solvent system to acetic acid or nitric acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions. As a result, potential advantages of this 'greener' catalytic method including safer operation, easier separation and purification, higher catalytic activity with selectivity and without using corrosive or oxidation unstable solvent are therefore envisaged.

Electrospinning of silica sub-microtubes mats with platinum nanoparticles for NO catalytic reduction

Silica sub-microtubes loaded with platinum nanoparticles have been prepared in flexible non-woven mats using co-axial electrospinning technique. A partially gelated sol made from tetraethyl orthosilicate was used as the silica precursor, and oil was used as the sacrificial template for the hollow channel generation. Platinum has been supported on the wall of the tubes just adding the metallic precursor to the sol–gel, thus obtaining the supported catalyst by one-pot method. The silica tubes have a high aspect ratio with external/internal diameters of 400/200 nm and well-dispersed platinum nanoparticles of around 2 nm. This catalyst showed a high NO conversion with very high selectivity to N2 at mild conditions in the presence of excess oxygen when using C3H6 as reducing agent. This relevant result reveals the potential of this technique to produce nanostructured catalysts onto easy to handle conformations.

Carbon nanotube-supported metal catalysts for NOx reduction using hydrocarbon reductants. Part 1:catalyst preparation, characterization and NOx reduction characteristics

A dual catalyst system for the Selective Catalytic Reduction of NOx with hydrocarbons (HC-SCR), including distinct low and high temperature formulations, is proposed as a means to abate NOx emissions from diesel engines. Given that satisfactory high temperature HC-SCR catalysts are already available, this work focuses on the development of an improved low temperature formulation. Pt supported on multiwalled carbon nantubes (MWCNTs) was found to exhibit superior NOx reduction activity in comparison with Pt/Al2O3, while the MWCNT support displayed a higher resistance to oxidation than activated carbon. Refluxing the MWCNT support in a 1:1 mixture of H2SO4 and HNO3 prior to the metal deposition step proved to be beneficial for the metal dispersion and the NOx reduction performance of the resulting catalysts. This support effect is ascribed to the increased Brønsted acidity of the acid-treated MWCNTs, which in turn enhances the partial oxidation of the hydrocarbon reductant. Further improvements in the HC-SCR performance of MWCNT-based formulations were achieved using a 3:1 Pt–Rh alloy as the supported phase.

Hierarchical mesoporous Pd/ZSM-5 for the selective catalytic hydrodeoxygenation of m-cresol to methylcyclohexane

Mesopore incorporation into ZSM-5 enhances the dispersion of Pd nanoparticles throughout the hierarchical framework, significantly accelerating m-cresol conversion relative to a conventional microporous ZSM-5, and dramatically increasing selectivity towards the desired methylcyclohexane deoxygenated product. Increasing the acid site density further promotes m-cresol conversion and methylcyclohexane selectivity through efficient dehydration of the intermediate methylcyclohexanol.

Catalytic reduction of organic pollutants using supported metal nanoparticles

Metal nanoparticle catalysts have in the last decades been extensively researched for their enhanced performance compared to their bulk counterpart. Properties of nanoparticles can be controlled by modifying their size and shape as well as adding a support and stabilizing agent. In this study, preformed colloidal gold nanoparticles supported on activated carbon were tested on the reduction of 4-nitrophenol by NaBH4, a model reaction for evaluating catalytic activity of metal nanoparticles and one with high significance in the remediation of industrial wastewaters. Methods of wastewater remediation are reviewed, with case studies from literature on two major reactions, ozonation and reduction, displaying the synergistic effects observed with bimetallic and trimetallic catalysts, as well as the effects of differences in metal and support. Several methods of preparation of nanoparticles are discussed, in particular, the sol immobilization technique, which was used to prepare the supported nanoparticles in this study. Different characterization techniques used in this study to evaluate the materials and spectroscopic techniques to analyze catalytic activities of the catalyst are reviewed: ultraviolet-visible (UV-Vis) spectroscopy, dynamic light scattering (DLS) analysis, X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM) imaging. Optimization of catalytic parameters was carried out through modifications in the reaction setup. The effects of the molar ratio of reactants, stirring, type and amount of stabilizing agent are explored. Another important factor of an effective catalyst is its reusability and long-term stability, which was examined with suggestions for further studies. Lastly, a biochar support was newly tested for its potential as a replacement for activated carbon.

Catalytic reduction of levulinic acid derivatives to bio-fuel components

Levulinic Acid and its esters are polyfunctional molecules obtained by biomass conversion. The most investigated strategy for the valorization of LA is its hydrogenation towards fuel additives, solvents and other added-value bio-based chemicals and, in this context, heterogeneous and homogeneous catalysts are widely used. Most commonly, it is typically performed with molecular hydrogen (H2) in batch systems, with high H2 pressures and noble metal catalysts. Several works reported the batch liquid-phase hydrogenation of LA and its esters by heterogenous catalysts which contained support with Brønsted acidity in order to obtain valeric acid and its esters. Furthermore, bimetallic and monometallic systems composed by both a metal for hydrogen activation and a promoter were demonstrated to be suitable catalysts for reduction of carboxylic group. However, there were no studies in the literature reporting the hydrogenation of alkyl levulinates to 1-pentanol (1-PAO). Therefore, bimetallic and monometallic catalysts were tested for one-pot hydrogenation of methyl levulinate to 1-PAO. Re-based catalysts were investigated, this way proving the crucial role of the support for promoting the ring-opening of GVL and its consecutive reduction to valeric compounds. All the reactions were performed in neat without the need of any additional solvents. In these conditions, bimetallic Re-Ru-O/HZSM-5 afforded methyl valerate and valeric acid (VA) with a productivity of 512 mmol gmetal-1 h-1, one of the highest reported in literature to date. Rhenium can also promote the reduction of valeric acid/esters to PV through the formation of 1-pentanol and its efficient esterification/transesterification with the starting material. However, it was proved that Re-based catalysts may undergo leaching of active phase in presence of carboxylic acids, especially by working in neat with VA. Furthermore, the over-reduction of rhenium affects catalytic performance, suggesting not only that a pre-reduction step is unnecessary but also that it could be detrimental for catalyst’s activity.

V(2)O(5) nanoparticles obtained from a synthetic bariandite-like vanadium oxide: Synthesis, characterization and electrochemical behavior in an ionic liquid

Highly stable and crystalline V(2)O(5) nanoparticles with an average diameter of 15 nm have been easily prepared by thermal treatment of a bariandite-like vanadium oxide, V(10)O(24)center dot 9H(2)O. Their characterization was carried out by powder X-ray diffractometry (XRD). Fourier transform infrared (FT-IR) and Raman spectroscopies, and transmission electron microscopy (TEM). The fibrous and nanostructured film obtained by electrophoretic deposition of the V(2)O(5) nanoparticles showed good electroactivity when submitted to cyclic voltammetry in an ionic liquid-based electrolyte. The use of this film for the preparation of a nanostructured electrode led to an improvement of about 50% in discharge capacity values when compared with similar electrodes obtained by casting of a V(2)O(5) xerogel. (C) 2009 Elsevier Inc. All rights reserved.

Automotive diesel engine transient operation: modeling, optimization and control

Traditionally, the study of internal combustion engines operation has focused on the steady-state performance. However, the daily driving schedule of automotive engines is inherently related to unsteady conditions. There are various operating conditions experienced by (diesel) engines that can be classified as transient. Besides the variation of the engine operating point, in terms of engine speed and torque, also the warm up phase can be considered as a transient condition. Chapter 2 has to do with this thermal transient condition; more precisely the main issue is the performance of a Selective Catalytic Reduction (SCR) system during cold start and warm up phases of the engine. The proposal of the underlying work is to investigate and identify optimal exhaust line heating strategies, to provide a fast activation of the catalytic reactions on SCR. Chapters 3 and 4 focus the attention on the dynamic behavior of the engine, when considering typical driving conditions. The common approach to dynamic optimization involves the solution of a single optimal-control problem. However, this approach requires the availability of models that are valid throughout the whole engine operating range and actuator ranges. In addition, the result of the optimization is meaningful only if the model is very accurate. Chapter 3 proposes a methodology to circumvent those demanding requirements: an iteration between transient measurements to refine a purpose-built model and a dynamic optimization which is constrained to the model validity region. Moreover all numerical methods required to implement this procedure are presented. Chapter 4 proposes an approach to derive a transient feedforward control system in an automated way. It relies on optimal control theory to solve a dynamic optimization problem for fast transients. From the optimal solutions, the relevant information is extracted and stored in maps spanned by the engine speed and the torque gradient.

Parameter identification of a copper-zeolite SCR catalyst model using reactor data

The selective catalytic reduction system is a well established technology for NOx emissions control in diesel engines. A one dimensional, single channel selective catalytic reduction (SCR) model was previously developed using Oak Ridge National Laboratory (ORNL) generated reactor data for an iron-zeolite catalyst system. Calibration of this model to fit the experimental reactor data collected at ORNL for a copper-zeolite SCR catalyst is presented. Initially a test protocol was developed in order to investigate the different phenomena responsible for the SCR system response. A SCR model with two distinct types of storage sites was used. The calibration process was started with storage capacity calculations for the catalyst sample. Then the chemical kinetics occurring at each segment of the protocol was investigated. The reactions included in this model were adsorption, desorption, standard SCR, fast SCR, slow SCR, NH3 Oxidation, NO oxidation and N2O formation. The reaction rates were identified for each temperature using a time domain optimization approach. Assuming an Arrhenius form of the reaction rates, activation energies and pre-exponential parameters were fit to the reaction rates. The results indicate that the Arrhenius form is appropriate and the reaction scheme used allows the model to fit to the experimental data and also for use in real world engine studies.

Adaptación de una central térmica de carbón a la Directiva de Emisiones Industriales

El proyecto que se presenta a continuación recoge la adaptación de una Central Térmica de carbón al cumplimiento de la DIRECTIVA 2010/75/UE DEL PARLAMENTO EUROPEO Y DEL CONSEJO de 24 de noviembre de 2010 sobre las emisiones industriales. La Central sobre la que se realiza el proyecto tiene un grupo térmico de carbón suscritico refrigerado por agua, con una potencia a plena carga de 350 MWe y de 190 MWe a mínimo técnico. Genera 1 090 t/h de vapor a 540 °C y 168 kg/cm2 funcionando a plena carga. Actualmente las emisiones de NOx son de 650 mg/m3, (condiciones normales, seco, 6 % O2). El objeto del proyecto es reducir estas emisiones a un valor máximo de 200 mg/m3 en las mismas condiciones. El proyecto analiza detalladamente las condiciones actuales de operación de la instalación en cuanto a combustible utilizado, horas de funcionamiento, condiciones climáticas y producción. Se analiza así mismo, todas las técnicas disponibles en mercado para la reducción del NOx, diferenciando entre medidas primarias (actúan sobre los efectos de formación) y secundarias (limpieza de gases). Las medidas primarias ya están implementadas en la central, por tanto, el proyecto plantea la reducción con medidas secundarias. De las medidas secundarias analizadas se ha seleccionado la instalación de un Reactor de Reducción Selectiva Catalítica (Reactor SCR). Tras un análisis de los diferentes reactores y catalizadores disponibles se ha seleccionado un reactor de configuración High-dust, una disposición de catalizador en 3 capas más 1, cuyos componentes están basados en óxidos metálicos (TiO2, V2O5, WO3) y estructura laminar. Se ha buscado la instalación del reactor para operar a una temperatura inferior a 450 °C. Como agente reductor se ha seleccionado NH3 a una dilución del 24,5 %. El proyecto recoge también el diseño de todo el sistema de almacenamiento, evaporación, dilución e inyección de amoniaco. El resultado del proyecto garantiza una concentración en los gases de salida por la chimenea inferior 180 mg/m3(n) de NOx. La reducción del NOx a los límites establecidos, tienen un coste por MWh neto generado para la central, trabajando 60 % a plena carga y 40 % a mínimo técnico y una amortización de 10 años, de 4,10 €/MWh. ABSTRACT The following project shows the compliance adjustment of a coal-fired power station to the 2010/75/EU Directive of the European Parliament and Council 24th November 2010 on industrial emissions. The project is based on a power station with a subcritical thermal coal unit, cooled with water, with a maximum power of 350 MWe and a technical minimum of 190 MWe. It produces 1 090 t/h of steam at 540 ° C and 168 kg/cm2 operating under full load. Currently, NOx emissions are 650 mg / m3 (normal conditions, dry, 6% O2). The project aims to reduce these emissions to a maximum value of 200 mg / m3 under the same conditions. The project analyses in detail the current operating conditions of the system in terms of fuel used, hours of operation, climatic conditions and production. In addition, it also analyses every available technique of NOx reduction on the market, distinguishing between primary (acting on the effects of formation) and secondary measures (gas cleaning). Primary measures are already implemented in the plant, thus proposing reduction with secondary measures. Among the secondary measures analyzed, it has been selected to install a Selective Catalytic Reduction Reactor (SCR Reactor). Having researched the different reactors and catalysts available, for the reactor has been selected High-dust configuration, an arrangement of catalyst in 3 layers plus 1, whose components are based on metal oxides (TiO2, V2O5, WO3) and laminar structure. The reactor has been sought facility to operate at a temperature below 450 ° C. NH3 diluted to 24,5 % has been selected as reducing agent. The project also includes the design of the entire storage system, evaporation, dilution and ammonia injection. The results of the project ensure a gas concentration in the lower chimney exit below 180 mg / m3(n) NOx. The reduction of NOx to the established limits has a cost per net MWh generated in the plant, working at 60% of full load and at 40% of technical minimum, with an amortization of 10 years, 4,10 € / MWh.