Iron-based Chemical Looping Gasification Technologies for Flexible Syngas Production from Fossil Fuels with Carbon-di-oxide Capture


Book Description

The following study entails process simulations and techno-economic analysis based investigations of novel chemical looping partial oxidation processes. The moving bed reactor system analyzed in this dissertation provides chemical looping technologies several intrinsic advantages over conventional energy processing schemes. Chapter 2 focusses on optimizing the counter-current moving bed chemical looping system for H2 production from natural gas. The chemical looping process for H2 production from natural gas is optimized based on isothermal thermodynamic limits of an iron-based counter-current moving bed reactor system. The iso-thermal analysis is followed by a parametric sensitivity for energy balance for satisfying the auto-thermal heat balance. This is completed by computing temperature swings based on a net heat duty calculation for individual chemical looping reactors. Overall the chemical looping process is shown to have a cold gas efficiency of 77.6% (HHV basis) and an effective thermal efficiency of 75.1% (HHV basis), both of which are significantly higher than the baseline case. Chapter 3 discusses the Shale gas to Syngas process for integration into a Gas to Liquid fuel (GTL) plant. Following the methodology for an isothermal and an adiabatic analysis from Chapter 2, Chapter 3 identifies a suitable auto-thermal operating condition for the chemical looping reactors. The process simulation model is used to derive cost estimates based on standard engineering assumptions and completes a sensitivity analysis for several important economic parameters. The STS process is shown to require significantly lower natural gas feedstock than the conventional process baseline for producing the same amount of liquid fuels. The STS process lowers the capital cost investment for the syngas production section of a GTL plant by over 50% and if commercialized can be disruptive to liquid fuel production markets. Chapter 4 discusses the Coal to syngas (CTS) process for its technical and economic performance when integrated into a 10,000 tpd methanol plant. This chapter details the equipment sizing philosophy and cost methodology used in this dissertation for calculating economic performance of the novel processes developed. Further, sensitivity studies which analyze effect of economic parameters like the capital charge factor, natural gas price are considered to identify the critical technology parameters necessary to be de-risked for pilot scale and commercial scale operation of the CTS technology. The CTS process reduced the coal consumption by 14% for the same amount of methanol production. The CTS process also reduced the methanol required selling price by 21% over the corresponding baseline case with greater than 90% carbon capture. Chapter 5 discusses the two reducer chemical looping configurations and the fixed bed chemical looping configurations. The two reducer chemical looping configurations provide the flexibility for designing two different reducer reactors, each optimized to a specific fuel feedstock. The two reducer chemical looping configurations can improve over thermodynamic performance of a single reducer chemical looping configuration by providing the flexibility to get high solids conversion with high fuel conversions. The fixed bed operating strategy opens up ways to operate iron-based chemical looping system without solids circulation for high-efficiency production of syngas.




Concepts in Syngas Manufacture


Book Description

1. Routes to syngas. 1.1. General trends. 1.2. Manufacture by steam reforming of hydrocarbons. 1.3. Other manufacture routes. 1.4. Other feedstocks. 1.5. Gas treatment -- 2. Syngas applications. 2.1. Thermodynamic framework for syngas processes. 2.2. Hydrogen. 2.3. Fuel cells. 2.4. CO rich gases. 2.5. Ammonia. 2.6. Methanol and synfuels. 2.7. Chemical recuperation -- 3. Technology of steam reforming. 3.1. Early developments. 3.2. Steam reforming reactors. 3.3. Modelling of steam reforming reactors. 3.4. Modelling of the catalyst particle. 3.5. Reaction kinetics -- 4. Catalyst properties and activity. 4.1. Catalyst structure and stability. 4.2. Nickel surface area. 4.3. Catalyst activity -- 5. Carbon and sulphur. 5.1. Secondary phenomena. 5.2. Carbon formation. 5.3. Steam reforming of higher hydrocarbons. 5.4. Sulphur poisoning of reforming reactions. 5.5. Sulphur passivated reforming. 5.6. Other poisons -- 6. Catalysis of steam reforming. 6.1. Historical perspective. 6.2. The role of step sites. 6.3. Geometric or electronic effects. 6.4. Metal activity. Micro-kinetics. 6.5. The parallel approach




High-pressure Natural Gas to Syngas Chemical Looping


Book Description

Chemical looping technologies can be used as an advanced reforming technology, capable of efficiently generating syngas to serve as a feedstock in a variety of important chemical industries. The pressure of the syngas feedstock to downstream chemical synthesis reactors is an important characteristic that can dictate the products and overall plant economics. While most chemical synthesis reactors, such as Fischer-Tropsch and methanol synthesis reactors, operate at high pressures, most chemical looping reforming studies have been conducted under atmospheric conditions. The high thermodynamic yields from the atmospheric chemical looping reformer run counter to the high conversion of the pressurized downstream reactors. Therefore, this study seeks to quantify the impact of the operating conditions of the chemical looping reformer on the overall system yields. Specifically, The Ohio State University methane to syngas process is analyzed, which uses a cocurrent moving bed fuel/reducer reactor and a fluidized bed air/combustor reactor. The syngas generation results are compared under a variety of operating conditions with the pressure varied between 1 and 30 atm. Initial studies are compared in an isothermal analysis to study the effect of variables, independent of operating temperature. The resulting isothermal analysis is used to guide an adiabatic reactor configuration in an attempt to develop an autothermal chemical looping system. The gas feedstocks, solid feedstocks, operating temperature, feedstock preheating conditions, and system pressure are all analyzed. The results of the autothermal chemical looping system are then integrated into a ~5000 MWth natural gas to liquid fuels plant, in which a chemical looping reformer replaces an autothermal reformer reactor. The study shows that operation of the chemical looping process allows for equivalent syngas yield compared to the autothermal reformer with a 7-13% reduction in natural gas feedstock. Lastly, a novel operating strategy is described in which the chemical looping reducer operates at higher pressure and the chemical looping combustor operates at atmospheric conditions. Such an operating strategy takes advantage of the air and natural gas feedstock pressures to the chemical looping system and is able to eliminate a significant amount of compression energy and equipment. Using the differential operating strategy allows equivalent syngas production to the baseline with a 7% decrease in natural gas usage and ~200 MWe increase in electricity production. A capital cost comparison of the equivalent pressure and differential pressure chemical looping systems indicate a 29% reduction in capital costs when using the differential pressure chemical looping system.




HIGH EFFICIENCY SYNGAS GENERATION.


Book Description

This project investigated an efficient and low cost method of auto-thermally reforming natural gas to hydrogen and carbon monoxide. Reforming is the highest cost step in producing products such as methanol and Fisher Tropsch liquids (i.e., gas to liquids); and reducing the cost of reforming is the key to reducing the cost of these products. Steam reforming is expensive because of the high cost of the high nickel alloy reforming tubes (i.e., indirectly fired reforming tubes). Conventional auto-thermal or Partial Oxidation (POX) reforming minimizes the size and cost of the reformers and provides a near optimum mixture of CO and hydrogen. However POX requires pure oxygen, which consumes power and significantly increases the cost to reforming. Our high efficiency process extracts oxygen from low-pressure air with novel oxygen sorbent and transfers the oxygen to a nickel-catalyzed reformer. The syngas is generated at process pressure (typically 20 to 40 bar) without nitrogen dilution and has a 1CO to 2H2 ratio that is near optimum for the subsequent production of Fisher-Tropsch liquid to liquids and other chemicals (i.e., Gas to Liquids, GTL). Our high process efficiency comes from the way we transfer the oxygen into the reformer. All of the components of the process, except for the oxygen sorbent, are commonly used in commercial practice. A process based on a longlived, regenerable, oxygen transfer sorbent could substantially reduce the cost of natural gas reforming to syngas. Lower cost syngas (CO + 2H2) that is the feedstock for GTL would reduce the cost of GTL and for other commercial applications (e.g., methanol, other organic chemicals). The vast gas resources of Alaska's North Slope (ANS) offer more than 22 Tcf of gas and GTL production in this application alone, and could account for as much as 300,000 to 700,000 bpd for 20 to 30+ years. We developed a new sorbent, which is an essential part of the High Efficiency Oxygen Process (HOP). We tested the sorbent and observed that it has both a good oxygen capacity and operates as a highly effective reforming catalyst. We conducted a long duration tests of the sorbent (1,500 hours of continuous operation in the HOP cycle). Although the sorbent lost some oxygen capacity with cycling, the sorbent oxygen capacity stabilized after 1,000 hours and remained constant to the end of the test, 1,500 hour. The activity of the catalyst to reform methane to a hydrogen and carbon monoxide mixture was unchanged through the oxidation/reduction cycling. Our cost and performance analyses indicated a significant reduction in the cost of GTL production when using the HOP process integrated into a GTL plant.




Greener Fischer-Tropsch Processes


Book Description

Greener Fischer-Tropsch Processes How can we use our carbon-based resources in the most responsible manner? How can we most efficiently transform natural gas, coal, or biomass into diesel, jet fuel or gasoline to drive our machines? The Big Questions today are energy-related, and the Fischer-Tropsch process provides industrially tested solutions. This book offers a comprehensive and up-to-date overview of the Fischer-Tropsch process, from the basic science and engineering to commercial issues. It covers industrial, economic, environmental, and fundamental aspects, with a specific focus on “green” concepts such as sustainability, process improvement, waste-reduction, and environmental care. The result is a practical reference for researchers, engineers, and financial analysts working in the energy sector, who are interested in carbon conversion, fuel processing or synthetic fuel technologies. It is also an ideal introductory book on the Fischer-Tropsch process for graduate courses in chemistry and chemical engineering.




Fischer-Tropsch Technology


Book Description

Fischer-Tropsch Technology is a unique book for its state-of-the-art approach to Fischer Tropsch (FT) technology. This book provides an explanation of the basic principles and terminology that are required to understand the application of FT technology. It also contains comprehensive references to patents and previous publications. As the first publication to focus on theory and application, it is a contemporary reference source for students studying chemistry and chemical engineering. Researchers and engineers active in the development of FT technology will also find this book an invaluable source of information. * Is the first publication to cover the theory and application for modern Fischer Tropsch technology * Contains comprehensive knowledge on all aspects relevant to the application of Fischer Tropsch technology* No other publication looks at past, present and future applications




Production of Liquid Fuels from Natural Gas


Book Description

Gas to Liquid (GTL) processes chemically convert natural gas to valuable liquid hydrocarbon products. The GTL process considered in this research is comprised of three phases: 1) syngas production, 2) Fischer-Tropsch synthesis (FTS), and 3) product separation. This study focuses on the simulation and optimization of a GTL process to convert natural gas to more valuable liquid fuels. In syngas production, steam methane reforming (SMR) is typically used although it requires an external heat source due to the endothermic nature of the reaction. In addition, the SMR approach produces syngas with a hydrogen to carbon monoxide ratio that is not ideal for the FTS reaction. An alternative approach that combines partial oxidation of methane (POX) and SMR in series is considered in this work. The heat released in the exothermic POX stage drives the endothermic SMR stage resulting in an auto-thermal reforming reaction (ATR) that is net exothermic. The resulting syngas product has the ideal hydrogen to carbon monoxide ratio for FTS. The aim of this work is to establish numerical models for the ATR and FTS reactor components of a GTL plant and study the impact of various input parameters on the output of the overall system. Kinetic models were developed based on laboratory data collected from a GTL pilot plant operating at UTA. A multiphysics finite element model was developed to simulate a multi tubular packed bed reactor for FTS. The impact of coolant flow rate and syngas space velocity on oil productivity and syngas conversion was studied.




Hydrogen Production Technologies


Book Description

Provides a comprehensive practical review of the new technologies used to obtain hydrogen more efficiently via catalytic, electrochemical, bio- and photohydrogen production. Hydrogen has been gaining more attention in both transportation and stationary power applications. Fuel cell-powered cars are on the roads and the automotive industry is demanding feasible and efficient technologies to produce hydrogen. The principles and methods described herein lead to reasonable mitigation of the great majority of problems associated with hydrogen production technologies. The chapters in this book are written by distinguished authors who have extensive experience in their fields, and readers will have a chance to compare the fundamental production techniques and learn about the pros and cons of these technologies. The book is organized into three parts. Part I shows the catalytic and electrochemical principles involved in hydrogen production technologies. Part II addresses hydrogen production from electrochemically active bacteria (EAB) by decomposing organic compound into hydrogen in microbial electrolysis cells (MECs). The final part of the book is concerned with photohydrogen generation. Recent developments in the area of semiconductor-based nanomaterials, specifically semiconductor oxides, nitrides and metal free semiconductor-based nanomaterials for photocatalytic hydrogen production are extensively discussed.




The Hydrogen Economy


Book Description

The announcement of a hydrogen fuel initiative in the President's 2003 State of the Union speech substantially increased interest in the potential for hydrogen to play a major role in the nation's long-term energy future. Prior to that event, DOE asked the National Research Council to examine key technical issues about the hydrogen economy to assist in the development of its hydrogen R&D program. Included in the assessment were the current state of technology; future cost estimates; CO2 emissions; distribution, storage, and end use considerations; and the DOE RD&D program. The report provides an assessment of hydrogen as a fuel in the nation's future energy economy and describes a number of important challenges that must be overcome if it is to make a major energy contribution. Topics covered include the hydrogen end-use technologies, transportation, hydrogen production technologies, and transition issues for hydrogen in vehicles.