Fast model predictive control for hydrogen outflow regulation in ethanol steam reformers

© 20xx IEEE. Personal use of this material is permitted. Permission from IEEE must be obtained for all other uses, in any current or future media, including reprinting/republishing this material for advertising or promotional purposes, creating new collective works, for resale or redistribution to servers or lists, or reuse of any copyrighted component of this work in other works.In the recent years, the presence of alternative power sources, such as solar panels, wind farms, hydropumps and hydrogen-based devices, has significantly increased. The reasons of this trend are clear: contributing to a reduction of gas emissions and dependency on fossil fuels. Hydrogen-based devices are of particular interest due to their significant efficiency and reliability. Reforming technologies are among the most economic and efficient ways of producing hydrogen. In this paper we consider the regulation of hydrogen outflow in an ethanol steam reformer (ESR). In particular, a fast model predictive control approach based on a finite step response model of the process is proposed. Simulations performed using a more realistic non-linear model show the effectiveness of the proposed approach in driving the ESR to different operating conditions while fulfilling input and output constraints.Peer ReviewedPostprint (author's final draft

Synthesis gas as a fuel for internal combustion engines in transportation

© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).The adverse environmental impact of fossil fuel combustion in engines has motivated research towards using alternative low-carbon fuels. In recent years, there has been an increased interest in studying the combustion of fuel mixtures consisting mainly of hydrogen and carbon monoxide, referred to as syngas, which can be considered as a promising fuel toward cleaner combustion technologies for power generation. This paper provides an extensive review of syngas production and application in internal combustion (IC) engines as the primary or secondary fuel. First, a brief overview of syngas as a fuel is presented, introducing the various methods for its production, focusing on its historical use and summarizing the merits and drawbacks of using syngas as a fuel. Then its physicochemical properties relevant to IC engines are reviewed, highlighting studies on the fundamental combustion characteristics, such as ignition delay time and laminar and turbulent flame speeds. The main body of the paper is devoted to reviewing the effect of syngas utilization on performance and emissions characteristics of spark ignition (SI), compression ignition (CI), homogeneous charge compression ignition (HCCI), and advanced dual-fuel engines such as reactivity-controlled compression ignition (RCCI) engines. Finally, various on-board fuel reforming techniques for syngas production and use in vehicles are reviewed as a potential route towards further increases in efficiency and decreases in emissions of IC engines. These are then related to the research reported on the behavior of syngas and its blends in IC engines. It was found that the selection of the syngas production method, choice of the base fuel for reforming, its physicochemical properties, combustion strategy, and engine combustion system and operating conditions play critical roles in dictating the potential advantages of syngas use in IC engines. The discussion of the present review paper provides valuable insights for future research on syngas as a possible fuel for IC engines for transport.Peer reviewe

Fuel Reforming for High Efficiency and Dilution Limit Extension of Spark-ignited Engines

Engine efficiency improvement can help combustion powertrains, which include conventional, hybrid, and plug-in hybrid systems, to meet the strict emissions standards and the increasing demand from customers for performance, drivability, and affordability of vehicles. Cooled exhaust gas recirculation (EGR) can reduce fuel consumption and NOx emissions of gasoline engine systems while keeping the capability of using a conventional three-way catalyst for effective emissions reduction. However, too much EGR would lead to combustion instability and misfire. This thesis identified opportunities to improve efficiency in internal combustion engines by high EGR dilution SI combustion by using thermodynamics-based approaches. This goal has been achieved by using fuel reforming in a thermodynamically-favorable way. Exhaust heat was used to drive endothermic reforming reactions to increase the chemical fuel energy to attain thermochemical recuperation (TCR), a form of waste heat recovery, with robust integrated systems and the regular gasoline. Three strategies for fuel reforming, along with the unique designs of corresponding integrated engine systems, a committed in-cylinder reformer, a catalytic EGR-loop reforming system, and fuel reforming by fuel injection during Negative Valve Overlap (NVO), have been proposed and investigated with unique engine system setups and corresponding experimental and simulation research. The concept and the system to use one cylinder to serve as a committed fuel reformer without spark ignition is first demonstrated. The committed in-cylinder reformer engine system achieves 8% brake thermal efficiency improvement through EGR and cylinder deactivation effects, even though there is low fuel conversion. The novel catalytic EGR-loop reforming integrated engine system was designed and tested. The experiments and thermodynamic equilibrium calculations reveal that the suppression of H2 and CO caused by the enthalpy limitation could be countered by adding small amounts of O2 by running one-cylinder lean. As much as 15 volume % H2 at the catalyst outlet is produced when the fuel and air equivalence ratio is between 4 and 7 under quasi-steady-state conditions. It is also found that this catalytic EGR reforming strategy makes it possible to sustain stable combustion with a volumetric equivalent of 45%–55% EGR, compared to a baseline EGR dilution limit which is under 25%. This catalytic EGR-loop reforming strategy results in a decrease of more than 8% in fuel consumption with significant potentials for even higher brake thermal efficiency. This novel design also opens up a new control method to control the amount of fuel reforming and the fraction of the partial oxidation reaction and steam reforming reaction by adjusting the lambda value of the cylinder which is running lean. Through this design, the engine is serving as an active system, which can also be adapted to respond to the needs of the passive catalyst system so that even better more significant benefit can be achieved. The results demonstrate fuel injection during NVO can extend the dilution limit, improve brake specific fuel consumption (BSFC), and reduce CO and NOx emissions on the engine modified with the capability of variable intake and exhaust valve timing and higher compression ratio. A comprehensive comparison of different reforming strategies for engine application and analysis of critical factors contributing to the performance of integrated fuel reforming engine systems is also provided. The research of this dissertation has demonstrated new pathways and scientific outcomes for technology development of internal combustion engine powertrain systems that can operate significantly more efficiently and cleanly.PHDMechanical EngineeringUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttps://deepblue.lib.umich.edu/bitstream/2027.42/144107/1/yanchang_1.pd

Plasma Catalytic Reforming of Biofuels

Vegetable oils and ethanol have been used in a plasmatron reformer to generate synthesis gas. Corn, canola, and soybean oils and ethanol have been reformed at different oxygen to carbon ratios and different power levels. Both homogeneous plasma reforming (uncatalyzed) and catalytic plasma reformer have been evaluated. I

Catalysts for steam reforming of Ethanol in a catalytic wall reactor

La energía se ha convertido en una necesidad vital para garantizar el desarrollo de las sociedades modernas. Entre las diferentes posibles alternativas para producir energía, el hidrogeno presenta varias características que lo convierten en un atractivo vector energético: primero, se trata de una tecnología más eficiente para transformar la energía química en electricidad -por ejemplo, utilizando pilas de-combustible, las cuales también reducen de manera significativa los niveles de emisión de CO2 -; en segundo lugar, el hidrogeno puede ser producido a partir de una amplia variedad de materias primas, incluyendo recursos renovables y no renovables. Sin embargo, las tecnologías para producir hidrogeno para applicaciones con pilas de combustible aun requieren de un esfuerzo en investigación y desarrollo.El objetivo principal de esta tesis fue de evaluar técnicamente las opciones para preparar y utilizar catalizadores en placas insertados en un reactor de pared catalítica para producir hidrogeno mediante el reformado por vapor de etanol bajo condiciones de alta eficiencia térmica. Para completar el objetivo general y los objetivos específicos, se diseño un plan experimental sistemático, compuesto de tres partes: documentación, experimentación y simulación numérica. La información utilizada se puede clasificar en tres ramas: primero, una revisión detallada de las características generales que presentan las técnicas de reformado, seguido por una revisión descriptiva del reformado por vapor de etanol, enfocado en los principales aspectos de la preparación de catalizadores y la realización de la reacción química. A continuación en segundo lugar, se presenta una descripción acerca de reactores estructurados y los métodos para preparar catalizadores. Por último, en tercer lugar, se expone una explicación centrada en los materiales, equipos y métodos empleados para explorar el rendimiento de los catalizadores. Esta parte incluye la descripción de: algunas de las técnicas analíticas más comunes para caracterizar y evaluar tanto catalizadores como compuestos químicos y la descripción de las herramientas utilizadas en la simulación numérica.El primer bloque de simulación numérica tiene como fin evaluar las posibles restricciones termodinámicas por medio de análisis específicos basados en el equilibrio termodinámico, tanto del reactor como del proceso integrado. Luego, se ejecuta un mapeo del conjunto de condiciones operacionales, compuesto por cuatro variables principales: (temperatura, relación vapor carbón, presión y factor de recobro de hidrogeno en el separador de membrana). Ello con el fin de garantizar una operación auto-térmica del procesador de combustible. Se compara la habilidad y la ventaja entre los diferentes tipos de catalizadores publicados en trabajos previos en base a las condiciones termodinámicas ideales determinadas en el análisis termodinámico.Para los catalizadores en polvo, se realizo experimentos de caracterización y reacción mediante el empleo de un reactor de lecho fijo. Se ha efectuado un estudio sistematico para comparar la actividad y la selectividad de dos tipos de catalizadores, bajo condiciones moderadas de temperatura y relación vapor carbón. Los catalizadores basados en níquel (Ni/La2O3-Al2O3) y cobalto (Co-Fe/ZnO y Co-Mn/ZnO) han sido preparados y probados a las siguientes condiciones: temperatura en el rango de 400-500°C, relación vapor carbono entre 2 y 4, tiempo de contacto desde 4.3 hasta 1100 min·gcat molEtOH-1, cubriendo un rango de conversión de etanol desde 20 hasta 100%. Se ha efectuado un diseño de análisis multifactorial para establecer la influencia de las variables (temperatura, relación vapor carbón, tiempo de contacto y formulación del catalizador) en términos de la conversión de etanol y la selectividad hacia los diferentes productos.Por último, se ha efectuado la caracterización, simulación y experimentación utilizando una configuración de reactor de pared catalítica. Primero, se emplea un modelo en 2D para analizar las características principales del reactor de pared catalítica diseñado y construido para realizar la reacción sobre las placas con catalizador previamente preparadas. En segundo lugar, se expone de manera detallada el método seguido para preparar dos tipos diferentes de placas catalíticas. Estas placas con catalizador son caracterizadas de manera similar al método empleado con los catalizadores en polvo. Luego, se ha realizado un estudio sistemático para comparar la actividad y la selectividad de los dos tipos de placas catalíticas. Por último, mediante un modelo 1D se revelan aspectos fundamentales de la configuración del reactor de pared catalítica utilizando una configuración con dos canales paralelos, en los cuales se ejecutan una reacción endotérmica y otra exotérmica respectivamente.La principal conclusión de este trabajo es que el reformado por vapor de etanol puede ser realizado bajo condiciones de alta eficiencia térmica si se emplea un diseño basado en un reactor de pared catalítica con recobro de calor integrado a una unidad de separación para la purificación del hidrogeno. Las placas catalíticas han demostrado ser un elemento fundamental en este tipo de reactor porque incrementan de manera significativa el transporte de calor que se requiere para sostener las reacciones endotérmicas.Energy has become a fundamental necessity to guarantee modern society development. Among different alternatives possible to produce energy, hydrogen presents several characteristics which make it an attractive energy vector: first, more efficient processes to transform chemical energy into electricity -such as Fuel Cells that, in addition, will help to reduce significantly CO2 emission levels-; and second, hydrogen can be produced from a large variety of feed stocks, including fossil and renewable resources. However, as hydrogen production technologies for Fuel Cell applications are not available commercially yet, it still requires additional R&D efforts.The principal objective of this thesis was to evaluate technical feasibility for preparing and using catalytic plates in a Catalytic Wall Reactor configuration to produce hydrogen by Steam Reforming of Ethanol under conditions of high thermal efficiency. To fulfill the overall and specific objectives, a systematic experimental plan was designed and executed. It was composed of three main parts: documentation, experimentation and numerical simulation. Background information is divided into three branches, first a detailed overview of technical features for reforming technology, followed by a descriptive review of Steam Reforming of Ethanol key aspects for catalysts preparation and reaction performance. Third is presented a comprehensive examination on structured reactor and catalyst preparation methods. In this part is exposed a detailed explanation of materials, equipments, and methods employed for screening catalyst and evaluating catalytic reactor performance. Also, is presented employed techniques for catalyst characterization and fluid analysis. Finally are described tools for numerical simulation.First component of numerical simulations evaluates possible thermodynamic constrains through specific analyses based on thermodynamic equilibrium of reactor and integrated fuel processor. Then, is performed a mapping for the set of four operational variables (temperature, steam to carbon ratio, pressure, and hydrogen recovery in the membrane separator), that allow an auto-thermal operation of the fuel processor. The suitability and advantages of the different catalysts preparations that are known from recent publications are discussed on the basis of the operation conditions determined on the thermodynamic analysis.Experimental work is performed for powder catalyst characterization and catalytic experimentation using a Packed Bed Reactor (PBR). It has conducted a systematic study to compare the activity and selectivity of two types of catalyst at moderate temperature and steam to carbon (SC) ratios. Nickel-based catalysts (Ni/La2O3-Al2O3) and novel Co-based catalysts (Co-Fe/ZnO and Co-Mn/ZnO) have been prepared and tested at temperatures of 400 and 500 °C, Steam to Carbon (SC) molar ratios of 2 and 4, and contact times from 4.3 to 1100 min·gcat molEtOH-1, covering a range of ethanol conversion from 20 to 100%. A multifactorial design analysis has been conducted to establish the significance of temperature, SC ratio, contact time and catalyst formulation on ethanol conversion and selectivity towards the different reaction products.At last, it is carried out the catalytic plate characterization, simulation and experimentation using a Catalytic Wall Reactor configuration. First, is used a 2D modeling to analyze main characteristics of the Catalytic Wall Reactor designed and constructed to perform reactions on the prepared catalytic plates. Prepared catalytic plates are characterize in a similar way to that employed for the powder catalysts. After that, it was conducted a systematic study to compare the activity and selectivity of two types of catalytic plates. 1D model reveals main aspects on thermal performance for a theoretical Catalytic Wall Reactor using two co-current channels with endothermic and exothermic reactions respectively.Main conclusion from this work is that Steam Reforming of Ethanol can be performed at high thermal efficiency if the design of the fuel processor is based on structured catalytic wall reactors with integrated heat recovery coupled to a separation unit for hydrogen purification. Catalytic plates have proven to be a key component on CWR because improves significantly the heat transfer which is required to sustain endothermic reactions

Analysis of Dry Reforming as direct route for gas phase CO2 conversion. The past, the present and future of catalytic DRM technologies

Transition to low carbon societies requires advanced catalysis and reaction engineering to pursue green routes for fuels and chemicals production as well as CO2 conversion. This comprehensive review provides a fresh perspective on the dry reforming of methane reaction (DRM) which constitutes a straightforward approach for effective CO2 conversion to added value syngas. The bottleneck for the implementation of this process at industrial scale is the development of highly active and robust heterogeneous catalysts able to overcome the CO2 activation barrier and deliver sufficient amount of the upgrading products at the desired operation conditions. Also, its high energy demand due to the endothermic nature of the reaction imposes extra difficulties. This review critically discusses the recent progresses on catalysts design ranging from traditional metal-supported catalysts to advanced structured and nanostructured systems with promising performance. The main advantages and culprits of the different catalytic systems are introduced aiming to inspire the catalysis community to further refine these formulations towards the development of “supercatalysts” for DRM. Besides the design of increasingly complex catalyst morphologies as well as other promising alternatives aiming at reducing the energy consumption of the process or tackle deactivation through reactor design are introduced

Exhaust gas fuel reforming to achieve fuel saving

As much as 70 to 75% of the energy in the fuel used by a car is turned into waste heat, with more than a third of this released through the exhaust pipe. Catalysis offers a way of recovering exhaust heat. By adding some of the fuel to a portion of the exhaust as it passes through a catalytic reactor, it is possible to produce a gas mixture with a higher heating value than the fuel. This strategy depends, however, on the catalytic reaction consuming heat, while generating readily-combustible products that can be fed back to the engine. An investigation into catalytic exhaust gas fuel reforming and its potential to improve engine emissions and efficiency when close-coupled to a spark ignition engine. Initial ethanol reforming reactions with simulated exhaust gas suggests that the desired reforming path, i.e. dry reforming, steam reforming and partial oxidation reforming reactions can raise the heating value of the input fuel (ethanol) by up to 120% providing exhaust gas temperatures are made available, with the highest being steam reforming > dry reforming > oxidative reforming. The undesired water gas shift reaction is inactive with this reforming catalyst, regardless of the reaction temperature and reactant ratios (e.g. O:C and H$_2$O:C). The characteristic of each reforming path is tentatively explained with deviations from the stoichiometry. Actual exhaust gas fuel reforming studies of gasoline is carried out at a range of exhaust gas temperatures. It was found that at exhaust gas temperature 600$^0$ to 950$^0$C, the overall process efficiency ranges from 107 to 119%. By replacing 23.9% of gasoline fuel with simulated reformate, improvements in engine specific fuel consumption (SFC) and emissions (e.g. NOx, HC, CO2, CO) was achieved