Download Free Redox Kinetics Study For Chemical Looping Combustion Water And Co2 Splitting Using Nickel And Cerium Based Oxygen Carrier Book in PDF and EPUB Free Download. You can read online Redox Kinetics Study For Chemical Looping Combustion Water And Co2 Splitting Using Nickel And Cerium Based Oxygen Carrier and write the review.

Chemical-looping (CL) is a novel and promising technology for several applications including oxy-combustion for carbon capture, hydrogen production and CO2 reuse. In this process, oxygen carriers are utilized to cyclically adsorb and release oxygen producing two separated exhaust streams with desirable products. A rotary reactor design with micro-channel structure was developed in the Reacting Gas Dynamics Lab (RGDL) at MIT, which exhibits superior performance over conversional designs. Preliminary simulation identified OC redox kinetics and material characteristics as keys to the success of CL technology. This thesis examines the fundamentals of the reduction and oxidation (redox) processes with the aim of achieving fast and reliable reaction kinetics for CL applications. Experiments are conducted in a button-cell fixed-bed reactor with an on-line mass spectrometer. The timeresolved kinetics are modeled with consideration of thermodynamics, surface chemistry, transport mechanism, and structural evolution. Our approach, combining well-controlled experiment and detailed kinetics modeling, enables a new methodology for identifying the rate-limiting mechanism, examining the defect electrochemistry, and designing alternative materials for chemical-looping technology. Redox study with nickel thin foils reveals that structural evolution is the determining factor. Nickel oxidation starts via nucleation of oxide grains, which overlap and annihilate the fast diffusion paths. The model shows that the reaction is limited by the decreasing ionic diffusivity. To achieve practical redox repeatability, NiO fine particles supported on YSZ nanopowder is tested, and superior kinetics and cyclic stability are observed. Fast oxygen exchange is achieved from 500 to 1000°C with sufficient utilization of the carrying capacity within 1 min. Improvement is attributed to the enhanced ionic diffusivity with YSZ. The use of ceria nanopowder exhibits an order of magnitude H2 production rate improvement as compared to the state-of-the-art. Ceria reduction is slow with a threshold temperature of 700°C. The model reveals that the charge transfer is the rate-determining step for H2 production. Improving H2 splitting requires: (i) reducing the defect formation enthalpy, and (ii) accelerating charge-transfer. The addition of Zr lowers the threshold temperature to 650°C with 60% improvement in the rates, resulting from 40% decrease in the defect formation enthalpy. Doping ceria with Pr 3+ further lowers the threshold temperature to 600°C while doubling the peak rate. The model reveals that the high concentration of surface defects achieved from either approach promotes adsorbate formation, thus accelerating the splitting steps. Similar conclusions are obtained for CO2 splitting. Using the derived kinetics, H2-syngas co-production with CH4 as fuel is examined. Two important stages are identified: the formation of the complete products on oxidized surface, and syngas on the reduced surface. CH4 reduction is found to be rate-limited by the slow fuel cracking reaction. To accelerate the kinetics, a novel perovskite-nickel composite OC is examined, in which nickel effectively catalyzes reduction, leading to an order of magnitude faster kinetics at 600-700°C. This project has clearly demonstrated that using novel materials, CL technology can provide an efficient solution to oxy-combustion based CO2 capture, and H2/syngas co-production. Specifically, the use of NiO/YSZ achieves fast kinetics, robust stability and sufficient OC utilization from 500 to 1000°C, enabling complete CO2 capture with minimum energy penalty. The ceria-, and perovskite-based OCs exhibit over an order-of-magnitude faster kinetics compared to the state-of-the-art, enabling improved H2 production/CO 2 reduction efficiency isothermally at 600-700°C. In-depth understanding gained on the redox fundamentals will shed light on the design and fabrication of new materials as well as optimization of the CL applications.
One of the most promising methods of capturing CO2 emitted by coal-fired power plants for subsequent sequestration is chemical looping combustion (CLC). A powdered metal oxide such as NiO transfers oxygen directly to a fuel in a fuel reactor at high temperatures with no air present. Heat, water, and CO2 are released, and after H2O condensation the CO2 (undiluted by N2) is ready for sequestration, whereas the nickel metal is ready for reoxidation in the air reactor. In principle, these processes can be repeated endlessly with the original nickel metal/nickel oxide participating in a loop that admits fuel and rejects ash, heat, and water. Our project accumulated kinetic rate data at high temperatures and elevated pressures for the metal oxide reduction step and for the metal reoxidation step. These data will be used in computational modeling of CLC on the laboratory scale and presumably later on the plant scale. The oxygen carrier on which the research at Utah is focused is CuO/Cu2O rather than nickel oxide because the copper system lends itself to use with solid fuels in an alternative to CLC called 'chemical looping with oxygen uncoupling' (CLOU).
This book focuses on the chemistry and processes for conversion and utilization of carbon dioxide. Topics include CO 2 utilization, its conversion to industrial chemicals and fuels, its coversion via synthesis gas, and new catalysts and chemical processes for conversion.
This book presents the current carbonaceous fuel conversion technologies based on chemical looping concepts in the context of traditional or conventional technologies. The key features of the chemical looping processes, their ability to generate a sequestration-ready CO2 stream, are thoroughly discussed. Chapter 2 is devoted entirely to the performance of particles in chemical looping technology and covers the subjects of solid particle design, synthesis, properties, and reactive characteristics. The looping processes can be applied for combustion and/or gasification of carbon-based material such as coal, natural gas, petroleum coke, and biomass directly or indirectly for steam, syngas, hydrogen, chemicals, electricity, and liquid fuels production. Details of the energy conversion efficiency and the economics of these looping processes for combustion and gasification applications in contrast to those of the conventional processes are given in Chapters 3, 4, and 5.Finally, Chapter 6 presents additional chemical looping applications that are potentially beneficial, including those for H2 storage and onboard H2 production, CO2 capture in combustion flue gas, power generation using fuel cell, steam-methane reforming, tar sand digestion, and chemicals and liquid fuel production. A CD is appended to this book that contains the chemical looping simulation files and the simulation results based on the ASPEN Plus software for such reactors as gasifier, reducer, oxidizer and combustor, and for such processes as conventional gasification processes, Syngas Chemical Looping Process, Calcium Looping Process, and Carbonation-Calcination Reaction (CCR) Process. Note: CD-ROM/DVD and other supplementary materials are not included as part of eBook file.
The school held at Villa Marigola, Lerici, Italy, in July 1997 was very much an educational experiment aimed not just at teaching a new generation of students the latest developments in computer simulation methods and theory, but also at bringing together researchers from the condensed matter computer simulation community, the biophysical chemistry community and the quantum dynamics community to confront the shared problem: the development of methods to treat the dynamics of quantum condensed phase systems.This volume collects the lectures delivered there. Due to the focus of the school, the contributions divide along natural lines into two broad groups: (1) the most sophisticated forms of the art of computer simulation, including biased phase space sampling schemes, methods which address the multiplicity of time scales in condensed phase problems, and static equilibrium methods for treating quantum systems; (2) the contributions on quantum dynamics, including methods for mixing quantum and classical dynamics in condensed phase simulations and methods capable of treating all degrees of freedom quantum-mechanically.
This comprehensive and up-to-date handbook on this highly topical field, covering everything from new process concepts to commercial applications. Describing novel developments as well as established methods, the authors start with the evaluation of different oxygen carriers and subsequently illuminate various technological concepts for the energy conversion process. They then go on to discuss the potential for commercial applications in gaseous, coal, and fuel combustion processes in industry. The result is an invaluable source for every scientist in the field, from inorganic chemists in academia to chemical engineers in industry.