Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

Arquitectura de Comunicaciones para Sistemas Ciber-Físicos Basada en OPC UA

[ES]Los sistemas Ciber-Físicos (Cyber-Physical Systems – CPS) son dispositivos que integran computación, control y comunicaciones. Actualmente se puede encontrar este tipo de sistemas en áreas tan diversas como la industria aeroespacial, automotriz, procesos químicos, infraestructura civil, etc. Entre las arquitecturas de comunicación empleadas en estos dispositivos, OPC UA se consolida como la más adecuada. OPC Unified Architecture es la nueva generación de tecnología propuesta por OPC Foundation para transmitir datos en bruto e información pre procesada entre los niveles de producción y los sistemas de planificación de producto de la empresa. Mediante OPC UA se puede disponer de toda la información deseada para cualquier aplicación y usuario autorizados, en cualquier instante y en cualquier lugar. En este proyecto se pretende desarrollar una arquitectura basada en OPC UA sobre CPSs para el acceso a datos de producción. Para ello se partirá de arquitecturas basadas en PC empotrados y redes de comunicación industriales.

Estudo Comparativo de Controladores Fuzzy Aplicados a um Sistema Solar Fotovoltaico.

Neste trabalho apresenta-se o modelo de um controlador baseado em Lógica Fuzzy para um sistema de energia baseado em fonte renovável solar fotovoltaica (photovoltaic - PV) multi-string em operação isolada, para o aproveitamento da máxima potência desta fonte. O sistema é composto por painéis solares, conversor CC-CC tipo elevador de tensão (boost), armazenamento por banco de baterias, inversor trifásico e carga trifásica variável. O sistema fotovoltaico foi modelado no MATLAB/Simulink de forma a representar a curva característica V-I do módulo PV, e que é baseado nos dados disponíveis em data-sheets de painéis fotovoltaicos comerciais. Outros estudos de natureza elétrica tais como o cálculo dos valores eficazes das correntes no conversor CC-CC, para avaliação das perdas, indispensáveis para o dimensionamento de componentes eletrônicos, foram realizados. O método tradicional Perturb and Observe de rastreamento do ponto de máxima potência (Maximum Power Point Tracking MPPT) de painéis foi testado e comparado com métodos que usam a Lógica Fuzzy. Devido ao seu desempenho, foi adotado o método Fuzzy que realiza o MPPT por inferência do ciclo de trabalho de um modulador por largura de pulso (Pulse Width Modulation - PWM) através da variação da potência pela variação da corrente do painel solar. O modelo Fuzzy adotado neste trabalho foi testado com sucesso. Os resultados mostraram que ele pode ser robusto e atende à aplicação proposta. Segundo alguns testes realizados, este controlador pode realizar o MPPT de um sistema PV na configuração multi-string onde alguns arranjos fotovoltaicos são usados. Inclusive, este controle pode ser facilmente adaptado para realizar o MPPT de outras fontes de energia baseados no mesmo princípio de controle, como é o caso do aerogerador.

Proposta de um otimizador para rastreamento do ponto de máxima potência de um conjunto de painéis solares conectados em um sistema híbrido de energia.

Este trabalho apresenta o projeto e os algoritmos de controle, de um sistema de geração de energia híbrido. Este sistema é formado por conversores de potência conectados em Back-to-Back associados a um arranjo solar fotovoltaico, que por sua vez é conectado no lado CC dos conversores. Em relação ao sistema de geração fotovoltaico, a contribuição consiste no desenvolvimento de cinco algoritmos para determinar o ponto de máxima potência (MPP) do arranjo fotovoltaico. O primeiro algoritmo consiste em uma versão modificada do algoritmo de Perturbar e Observar (PeO); o segundo algoritmo proposto é baseado no método do gradiente (MG); e o terceiro é baseado na otimização do MG (MGO). Porém, são desenvolvidos algoritmos híbridos que combinam rede neural com o método PeO, e rede neural com o algoritmo MGO. O sistema foi desenvolvido e simulado utilizando o Matlab/Simulink, e os resultados de simulação são apresentados com objetivo da avaliar o comportamento do sistema e a resposta dos diferentes algoritmos. Esta resposta foi avaliada para condições transitórias e de regime permanente, considerando diferentes requisitos de consumo na carga, irradiância e temperatura.

船载综合信息显示系统半实物仿真设计与实现

针对船载综合信息显示系统在实体船舶内开发不方便的问题,提出了一种半实物仿真系统的设计与实现方法。结合"科学三号"海洋科学考察船的综合信息显示系统的设计和开发过程,从体系结构、信息流程和实现方法3个方面对半实物仿真系统的设计和实现过程进行了探索。实践结果表明,这种半实物仿真系统一方面可以为实际系统的体系结构、信息流程设计提供支持,另一方面可以为实际系统应用软件的开发提供较为真实的环境,有效的缩短开发时间和降低开发风险。

Enrichment of the hydrogen-producing microbial community from marine intertidal sludge by different pretreatment methods

To determine the effects of pretreatment on hydrogen production and the hydrogen-producing microbial community, we treated the sludge from the intertidal zone of a bathing beach in Tianjin with four different pretreatment methods, including acid treatment, heat-shock, base treatment as well as freezing and thawing. The results showed that acid pretreatment significantly promoted the hydrogen production by sludge and provided the highest efficiency of hydrogen production among the four methods. The efficiency of the hydrogen production of the acid-pretreated sludge was 0.86 +/- 0.07 mol H-2/mol glucose (mean +/- S.E.), whereas that of the sludge treated with heat-shock, freezing and thawing, base method and control was 0.41 +/- 0.03 mol H-2/mol glucose, 0.17 +/- 0.01 mol H-2/mol glucose, 0.11 +/- 0.01 mol H-2/mol glucose and 0.20 +/- 0.04 mol H-2/mol glucose, respectively. The result of denaturing gradient gel electrophoresis (DGGE) showed that pretreatment methods altered the composition of the microbial community that accounts for hydrogen production. Acid and heat pretreatments were favorable to enrich the dominant hydrogen-producing bacterium, i.e. Clostridium sp., Enterococcus sp. and Bacillus sp., However, besides hydrogen-producing bacteria, much non-hydrogen-producing Lactobacillus sp. was also found in the sludge pretreated with base, freezing and thawing methods. Therefore, based on our results, we concluded that, among the four pretreatment methods using acid, heat-shock, base or freezing and thawing, acid pretreatment was the most effective method for promoting hydrogen production of microbial community. (C) 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

Fermentative hydrogen production by the new marine Pantoea agglomerans isolated from the mangrove sludge

A new fermentative hydrogen-producing bacterium was isolated from mangrove sludge and identified as Pantoea agglomerans using light microscopic examination, Biolog test and 16S rRNA gene sequence analysis. The isolated bacterium, designated as P. agglomerans BH-18, is a new strain that has never been optimized as a potential hydrogen-producing bacterium. In this study, the culture conditions and the hydrogen-producing ability of P. agglomerans BH-18 were examined. The strain was a salt-tolerant facultative anaerobe with the initial optimum pH value at 8.0-9.0 and temperature at 30 degrees C on cell growth. During fermentation, hydrogen started to evolve when cell growth entered late-exponential phase and was mainly produced in the stationary phase. The strain was able to produce hydrogen over a wide range of initial pH from 5 to 10, with an optimum initial pH of 6. The level of hydrogen production was affected by the initial glucose concentration, and the optimum value was found to be 10 g glucose/l. The maximum hydrogen-producing yield (2246 ml/l) and overall hydrogen production rate (160 ml/l/h) were obtained at an initial glucose concentration of 10 g/l and an initial pH value of 7.2 in marine culture conditions. In particular, the level of hydrogen production was also affected by the salt concentration. Hydrogen production reached a higher level in fresh culture conditions than in marine ones. In marine conditions, hydrogen productivity was 108 ml/l/h at an initial glucose concentration of 20 g/l and pH value of 7.2, whereas, it increased by 27% in fresh conditions. In addition, this strain could produce hydrogen using glucose and many other carbon sources such as fructose, sucrose, sorbitol and so on. As a result, it is possible that P. agglomerans BH-18 is used for biohydrogen production and biological treatment of mariculture wastewater and marine organic waste. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

基于多种群遗传算法的波能装置的优化设计及分析

作为可再生能源,波浪能的吸收和利用一直是国内外热点研究内容之一。本文提出一种新的基于惯性摆结构的波浪能吸收转换方法,对这种结构在波浪力作用下的频域响应进行了分析,建立了其最优化能量获取模型,提出采用多种群遗传算法对其结构进行优化设计,并针对系统所受波浪力(矩)随载体半径改变而改变,且求取困难的问题,采用最小二乘法对波浪力(矩)与载体半径变化的关系进行了拟和。通过优化结果找出影响结构获取波浪能量的因素,仿真结果表明了方法的先进性,为进一步的应用研究和频域波能获取研究奠定了基础。

基于惯性摆的波能系统研究

提出了一种基于惯性摆结构的波浪能吸收转换方法,并对采用此结构构成的水中载体所受到的波浪力及水动力进行了理论分析,建立了实验模型,对其进行了运动学、动力学仿真实验,仿真结果证明了方案的可行性。

基于OpenGL的交会对接仿真系统

针对基于视觉的空间载体位姿测量很难进行真实实验的特点,提出了一种基于OpenG1的半物理仿真实验方法。该方法通过计算机图形学技术和计算机视觉技术的结合,能够直观、快速地模拟空间载体位姿测量过程。

虚拟数控车削物理仿真系统的研究与开发

面向数控车削 ,开发了一套动态车削物理仿真系统 ,提出了仿真系统的总体框架 ,建立了动态物理仿真模型及相关子模型 ,分析了动态车削过程的影响因素 ,阐述了系统开发过程中有关模型构成及工件数据描述等技术性问题。

Adapting Home Service Robot Behaviours by Experience Reuse and Interaction with Humans

Meng, Q., Lee, M. (2003). Adapting Home Service Robot Behaviours by Experience Reuse and Interaction with Humans. 673-678. Paper presented at IEEE/ASME International Conference on Advanced Intelligent Mechatronics (AIM 2003), Port Island, Kobe, Japan

Learning and Reuse of Experience in Behavior-Based Service Robots

M.H.Lee, Q. Meng and H. Holstein, ?Learning and Reuse of Experience in Behavior-Based Service Robots?, Seventh International Conference on Control, Automation, Robotics and Vision (ICARCV2002), pp1019-24, December 2002, Singapore

Participation by place-based community organisations in local development: case studies from East Cork

The past two decades have witnessed concerted efforts by theorists and policy-makers to place civil society at the centre of social, economic and environmental development processes. To this end, policies grounded in a Third Way approach have sought to forge stronger linkages between the state and voluntary community-based organisations. Concepts such as active citizenship, social capital, partnership and sustainability have underpinned this political philosophy, which reflects a movement in development theory and political science away from notions of state-led development and unfettered neo-liberalism. In the Irish context, a series of initiatives have given expression to this new policy agenda, the foremost amongst them the publication of a White Paper in 2000. New local governance structures and development schemes have multiplied since the early 1990s, while the physical planning system has also been modified. All this has taken place against the backdrop of unprecedented economic development and social change precipitated by the ‘Celtic Tiger’.This thesis examines the interaction between community organisations, state institutions and other actors in development processes in East Cork. It focuses upon place-based community organisations, who seek to represent the interests of their particular localities. A case study approach is employed to explore the realpolitik of local development and to gauge the extent to which grassroots community organisations wield influence in determining the development of their communities. The study concludes that the transfer of decision-making power to community organisations has been more illusory than real and that, in practical terms, such groups remain marginal in the circuits of power. However, the situation of community organisations operating in different geographical locales cannot be reduced to an overarching theoretical logic. The case studies show that the modus operandi of community groups varies considerably and can be influenced by specific local geographies, events and personalities.

Empirical analysis and improved modelling of natural gas demand in Ireland

Countries across the world are being challenged to decarbonise their energy systems in response to diminishing fossil fuel reserves, rising GHG emissions and the dangerous threat of climate change. There has been a renewed interest in energy efficiency, renewable energy and low carbon energy as policy‐makers seek to identify and put in place the most robust sustainable energy system that can address this challenge. This thesis seeks to improve the evidence base underpinning energy policy decisions in Ireland with a particular focus on natural gas, which in 2011 grew to have a 30% share of Ireland’s TPER. Natural gas is used in all sectors of the Irish economy and is seen by many as a transition fuel to a low-carbon energy system; it is also a uniquely excellent source of data for many aspects of energy consumption. A detailed decomposition analysis of natural gas consumption in the residential sector quantifies many of the structural drives of change, with activity (R2 = 0.97) and intensity (R2 = 0.69) being the best explainers of changing gas demand. The 2002 residential building regulations are subject to an ex-post evaluation, which using empirical data finds a 44 ±9.5% shortfall in expected energy savings as well as a 13±1.6% level of non-compliance. A detailed energy demand model of the entire Irish energy system is presented together with scenario analysis of a large number of energy efficiency policies, which show an aggregate reduction in TFC of 8.9% compared to a reference scenario. The role for natural gas as a transition fuel over a long time horizon (2005-2050) is analysed using an energy systems model and a decomposition analysis, which shows the contribution of fuel switching to natural gas to be worth 12 percentage points of an overall 80% reduction in CO2 emissions. Finally, an analysis of the potential for CCS in Ireland finds gas CCS to be more robust than coal CCS for changes in fuel prices, capital costs and emissions reduction and the cost optimal location for a gas CCS plant in Ireland is found to be in Cork with sequestration in the depleted gas field of Kinsale.