Long Term Testing Of The Zinc Titanate For Desulfurization Of Hot Coal Gas In A Fluidized Bed Reactor

Research Triangle Institute (RTI) under contract to the US Department of Energy (DOE), Morgantown energy Technology Center has recently completed a long-term test consisting of 100 sulfidation-regeneration cycles on a zinc titanate material intended for use as a high-temperature, regenerable sorbent to desulfurize coal-derived gas. The primary motivation for this development is to generate a more economical, environmentally superior, and reliable process to purify the product gas of coal gasifiers for use in gas turbines and fuel cells. This zinc titanate formulation (designated as ZT-4 and containing Zn-to-Ti in a molar ratio of 1.5) exhibited the best overall performance in terms of chemical reactivity, sulfur capacity, regenerability, structural properties and, most importantly, the attrition resistance based on multicycle testing of a number of sorbent formulations in a bench scale fluidized-bed reactor. The conditions in the test were -- desulfurization temperature: 750C (1382F); pressure: 1.52 MPa (220 psia); coal gas: simulated Texaco entrained-bed oxygen-blown gasifier gas containing 12,000 ppmv of H2S; superficial gas velocity: 15 cm/s (0.49 ft/s). The ZT-4 sorbent used in this test was prepared using a granulation technique and 500 g of the sorbent in the 100 to 300 microns particle diameter range were used in a 5.1-cm (2-inch) i.d. stainless steel reactor.

Economic and environmental requirements for advanced power generating systems demand the removal of corrosive and other sulfurous compounds from hot coal gas. After a brief account of the world energy resources and an overview of clean coal technologies, a review of regenerable metal oxide sorbents for cleaning the hot gas is provided. Zinc oxide, copper oxide, calcium oxide, manganese oxide based as well as supported and mixed metal oxide sorbents are treated. Performance analysis of these sorbents, effects of various parameters on the desulfurization efficiency, kinetics of sulfidation and regeneration reactions, sulfiding and regeneration mechanisms are discussed. Two chapters present recent results in the direct production of elemental sulfur from regeneration or SO2-rich gases.

The following conclusions were made, based upon this study of T-2535 molybdenum-promoted zinc titanate: (1) Results of the half-cycle sulfidation experiments showed that sorbent efficiency and capacity of this formulation of zinc titanate were weak functions of operating-bed temperature. Evidence of diffusion limitations on the sulfidation reaction were observed, particularly at superficial velocities greater than 30 cm/s (1 ft/s). Sorbent performance appeared to be affected by the concentration of reducing gases and/or water content of the simulated coal gas mixtures. Sorbent capacity and efficiency deteriorated during the first three cycles, but stabilized thereafter. (2) Sorbent spalling was observed and appeared to increase with sulfur loading. Possible causes of spalling may be attributed to the induced crystal lattice stresses due to the formation of ZnS and especially ZnSO4, which have relative molar volumes that are approximately 1-1/2 and 3 times larger, respectively, than that of the original ZnO. (3) Based on these results, it is apparent that the molybdenum-promoted zinc titanate with Zn/Ti molar ratio of 1.91 may not be a suitable sorbent for hot gas desulfurization in the fixed bed reactor for the Pinon Pine project, due to problems with spalling and loss of reactivity during sulfidation/regeneration cycling.

Sections 1-2. Keyword Index.--Section 3. Personal author index.--Section 4. Corporate author index.-- Section 5. Contract/grant number index, NTIS order/report number index 1-E.--Section 6. NTIS order/report number index F-Z.

Fuel Cells: Technologies for Fuel Processing provides an overview of the most important aspects of fuel reforming to the generally interested reader, researcher, technologist, teacher, student, or engineer. The topics covered include all aspects of fuel reforming: fundamental chemistry, different modes of reforming, catalysts, catalyst deactivation, fuel desulfurization, reaction engineering, novel reforming concepts, thermodynamics, heat and mass transfer issues, system design, and recent research and development. While no attempt is made to describe the fuel cell itself, there is sufficient description of the fuel cell to show how it affects the fuel reformer. By focusing on the fundamentals, this book aims to be a source of information now and in the future. By avoiding time-sensitive information/analysis (e.g., economics) it serves as a single source of information for scientists and engineers in fuel processing technology. The material is presented in such a way that this book will serve as a reference for graduate level courses, fuel cell developers, and fuel cell researchers. Chapters written by experts in each area Extensive bibliography supporting each chapter Detailed index Up-to-date diagrams and full colour illustrations

The objectives of this project are to identify and demonstrate methods for enhancing long-term chemical reactivity and attrition resistance of zinc oxide-based mixed metal-oxide sorbents for desulfurization of hot coal-derived gases in a high-temperature, high-pressure (HTHP) fluidized-bed reactor. Specific objectives of this study are the following: {sm_bullet} Investigating various manufacturing methods to produce fluidizable zinc ferrite and zinc titanate sorbents in a particle size range of 50 to 400?m; Characterizating and screening the formulations for chemical reactivity, attrition resistance, and structural properties; Testing selected formulations in an HTHP bench-scale fluidized-bed reactor to obtain an unbiased ranking of the promising sorbents; Investigating the effect of various process variables, such as temperature, nature of coal gas, gas velocity, and chemical composition of the sorbent, on the performance of the sorbent; Life-cycle testing of the superior zinc ferrite and zinc titanate formulations under HTHP conditions to determine their long-term chemical reactivity and mechanical strength; Addressing various reactor design issues; Generating a database on sorbent properties and performance (e.g., rates of reaction, attrition rate) to be used in the design and scaleup of future commercial hot-gas desulfurization systems; Transferring sorbent manufacturing technology to the private sector; Producing large batches (in tonnage quantities) of the sorbent to demonstrate commercial feasibility of the preparation method; and Coordinate testing of superior formulations in pilot plants with real and/or simulated coal gas.