Identifier: TDX:347
Authors: Torres Rivero, José Antonio
Abstract:
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.<br/>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.<br/>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.<br/>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.<br/>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.<br/>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.
Repositori URV