Task 6.5 - Gas Separation and Hot-Gas Cleanup. Semi-annual report, July 1- December 31, 1996.

The objective of Subtask 6.5 is to develop and test superior gas separation membranes. Several methods are to be tested to prepare new membrane materials, including physical vapor deposition via electron beam evaporation. The selectivity of these membrane materials for separating undesired gases was to be determined. Selectivity will be measured by feeding the gases to the membrane and sampling the inlet, permeate, and raffinate streams for gas composition and volumetric flow rate

Task 3.0: Advanced power systems. Semi-annual report, April 1--June 30, 1993

A variety of activities are incorporated into the Advanced Power Systems program. Tasks included are (1) fuel utilization properties, (2) pressurized combustion, (3) catalytic gasification, and (4) hot-gas cleanup. ATRAN is stochastic and combines initial coal inorganics in a random manner in order to predict the resulting fly ash particle size and composition. ASHPERT, is an expert system yielding a first-order estimate of fly ash size and composition. Both models are designed to emulate pulverized-coal combustion. Input data required include identity, chemistry, size, quantity, and mineral-to-coal associations. The pressurized combustion task has focused on the construction of a versatile reactor system to simulate pressurized fluidized-bed combustion. Both castable and monolithic refractories have been investigated in determining slag prevention under a variety of conditions. Catalytic gasification coupled with a molten carbonate fuel cell offers an extremely efficient and environmentally sound power generating system using coal. Work with an Illinois No. 6 bituminous coal has not been successful. Continued efforts will focus on using the more reactive low-rank coals to try to achieve this goal. Hot-gas cleanup is the critical issue in many of the proposed advanced power system operations on coal. The key to successful ash removal is an understanding of the properties of the ash to be collected as well as the interactions of this material with the barrier itself. The knowledge base under development will assist in assessing many of these barrier material issues for a variety of coal ashes

JV 58-Effects of Biomass Combustion on SCR Catalyst

A portable slipstream selective catalytic reduction (SCR) reactor was installed at a biomass cofired utility boiler to examine the rates and mechanisms of catalyst deactivation when exposed to biomass combustion products. The catalyst was found to deactivate at a much faster rate than typically found in a coal-fired boiler, although this may have been the result of high ash loading rather than a general property of biomass combustion. Deactivation was mainly the result of alkali and alkaline-earth sulfate formation and growth in catalyst pores, apparently caused by alkaline-earth ash deposition on or near the pore sites. The high proportion of biomass in the fuel contributed to elevated levels of alkali and alkaline-earth material in the ash when compared to coal ash, and these higher levels provided more opportunity for sulfate formation. Based on laboratory tests, neither catalyst material nor ammonia contributed measurably to ash mass gains via sulfation. A model constructed using both field and laboratory data was able to predict catalyst deactivation of catalysts under subbituminous coal firing but performed poorly at predicting catalyst deactivation under cofiring conditions. Because of the typically higher-than coal levels of alkali and alkaline-earth elements present in biomass fuels that are available for sulfation at typical SCR temperatures, the use of SCR technology and biomass cofiring needs to be carefully evaluated prior to implementation

COAL SLAGGING AND REACTIVITY TESTING

Union Fenosa's La Robla I Power Station is a 270-MW Foster Wheeler arch-fired system. The unit is located at the mine that provides a portion of the semianthracitic coal. The remaining coals used are from South Africa, Russia, Australia, and China. The challenges at the La Robla I Station stem from the various fuels used, the characteristics of which differ from the design coal. The University of North Dakota Energy & Environmental Research Center (EERC) and the Lehigh University Energy Research Center (LUERC) undertook a program to assess problematic slagging and unburned carbon issues occurring at the plant. Full-scale combustion tests were performed under baseline conditions, with elevated oxygen level and with redistribution of air during a site visit at the plant. During these tests, operating information, observations and temperature measurements, and coal, slag deposit, and fly ash samples were obtained to assess slagging and unburned carbon. The slagging in almost all cases appeared due to elevated temperatures rather than fuel chemistry. The most severe slagging occurred when the temperature at the sampling port was in excess of 1500 C, with problematic slagging where first-observed temperatures exceeded 1350 C. The presence of anorthite crystals in the bulk of the deposits analyzed indicates that the temperatures were in excess of 1350 C, consistent with temperature measurements during the sampling period. Elevated temperatures and ''hot spots'' are probably the result of poor mill performance, and a poor distribution of the coal from the mills to the specific burners causes elevated temperatures in the regions where the slag samples were extracted. A contributing cause appeared to be poor combustion air mixing and heating, resulting in oxygen stratification and increased temperatures in certain areas. Air preheater plugging was observed and reduces the temperature of the air in the windbox, which leads to poor combustion conditions, resulting in unburned carbon as well as slagging. A second phase of the project involved advanced analysis of the baseline coal along with an Australian coal fired at the plant. These analysis results were used in equilibrium thermodynamic modeling along with a coal quality model developed by the EERC to assess slagging, fouling, and opacity for the coals. Bench-scale carbon conversion testing was performed in a drop-tube furnace to assess the reactivity of the coals. The Australian coal had a higher mineral content with significantly more clay minerals present than the baseline coal. The presence of these clay minerals, which tend to melt at relatively low temperatures, indicated a higher potential for problematic slagging than the baseline coal. However, the pyritic minerals, comprising over 25% of the baseline mineral content, may form sticky iron sulfides, leading to severe slagging in the burner region if local areas with reducing conditions exist. Modeling results indicated that neither would present significant fouling problems. The Australian coal was expected to show slagging behavior much more severe than the baseline coal except at very high furnace temperatures. However, the baseline coal was predicted to exhibit opacity problems, as well as have a higher potential for problematic calcium sulfate-based low-temperature fouling. The baseline coal had a somewhat higher reactivity than the Australian coal, which was consistent with both the lower average activation energy for the baseline coal and the greater carbon conversion at a given temperature and residence time. The activation energy of the baseline coal showed some effect of oxygen on the activation energy, with E{sub a} increasing at the lower oxygen concentration, but may be due to the scatter in the baseline coal kinetic values at the higher oxygen level tested

Fly ash from Texas lignite and western subbituminous coal: a comparative characterization

As examples, we use two Jackson group lignites from Atascosa and Fayette Counties, Texas, and a Green River Region subbituminous coal from Routt County, Colorado. The composition of individual fly ash particles was determined using scanning electron microscopy and electron microprobe, with support from x-ray diffraction of bulk ash. Using particle sample populations large enough to permit statistical treatment, we describe the relationship of composition to particle size and the correlation between elemental concentrations, as well as particle size and composition distributions. Correlations are displayed as data maps which show the complete range of observed variation among these parameters, emphasizing the importance of coal variability. We next use this data to produce a population distribution of ash particle resistivities calculated with Bickelhaupt's model. The relationship between calculated resistivity and particle size is also displayed, and the results are compared with measured values. 7 figures

Task 3.0 -- Advanced power systems: Subtask 3.18 -- Ash behavior in power systems. Semi-annual report, June 1--December 31, 1997

Advanced power systems such as integrated gasifier combined cycle systems and fluidized bed systems are at the forefront of power industry research because of the need for increased efficiency and the reduction of greenhouse gases. Ash behavior in power systems can have a significant impact on the design and performance of these systems. The Energy and Environmental Research Center (EERC) has developed a focused research initiative aimed at filling gaps in the understanding of fundamental mechanisms of ash behavior, which has relevance to commercial application and marketable products associated with advanced power systems. This program develops methods and means to better understand and mitigate adverse coal ash behavior in advanced power systems and can act to relieve the US reliance on diminishing recoverable oil resources and other greenhouse-producing fossil fuels. Subtask 3.18 is structured as three tasks. Task 1 pertains to summarizing the critical issues in ash behavior, especially for advanced power systems. Task 2 focuses on fundamental ash sintering and viscosity-ash composition relationships that are critical for developing a better mechanistic understanding of ash deposit formation and for predicting ash behavior. Task 3 is aimed primarily at determining the role of the ash chemistry and phase relationships for specific ash interactions in advanced power systems. The role of sulfides in the formation of ash deposits in gasification systems and the factors that influence alloy corrosion in supercritical boilers will be specifically analyzed. Task results to date are presented

Low-rank coal research: Volume 2, Advanced research and technology development: Final report

Volume II contains articles on advanced combustion phenomena, combustion inorganic transformation; coal/char reactivity; liquefaction reactivity of low-rank coals, gasification ash and slag characterization, and fine particulate emissions. These articles have been entered individually into EDB and ERA. (LTN

TASK 3.4--IMPACTS OF COFIRING BIOMASS WITH FOSSIL FUELS

With a major worldwide effort now ongoing to reduce greenhouse gas emissions, cofiring of renewable biomass fuels at conventional coal-fired utilities is seen as one of the lower-cost options to achieve such reductions. The Energy & Environmental Research Center has undertaken a fundamental study to address the viability of cofiring biomass with coal in a pulverized coal (pc)-fired boiler for power production. Wheat straw, alfalfa stems, and hybrid poplar were selected as candidate biomass materials for blending at a 20 wt% level with an Illinois bituminous coal and an Absaloka subbituminous coal. The biomass materials were found to be easily processed by shredding and pulverizing to a size suitable for cofiring with pc in a bench-scale downfired furnace. A literature investigation was undertaken on mineral uptake and storage by plants considered for biomass cofiring in order to understand the modes of occurrence of inorganic elements in plant matter. Sixteen essential elements, C, H, O, N, P, K, Ca, Mg, S, Zn, Cu, Fe, Mn, B, Mo, and Cl, are found throughout plants. The predominant inorganic elements are K and Ca, which are essential to the function of all plant cells and will, therefore, be evenly distributed throughout the nonreproductive, aerial portions of herbaceous biomass. Some inorganic constituents, e.g., N, P, Ca, and Cl, are organically associated and incorporated into the structure of the plant. Cell vacuoles are the repository for excess ions in the plant. Minerals deposited in these ubiquitous organelles are expected to be most easily leached from dry material. Other elements may not have specific functions within the plant, but are nevertheless absorbed and fill a need, such as silica. Other elements, such as Na, are nonessential, but are deposited throughout the plant. Their concentration will depend entirely on extrinsic factors regulating their availability in the soil solution, i.e., moisture and soil content. Similarly, Cl content is determined less by the needs of the plant than by the availability in the soil solution; in addition to occurring naturally, Cl is present in excess as the anion complement in K fertilizer applications. An analysis was performed on existing data for switchgrass samples from ten different farms in the south-central portion of Iowa, with the goal of determining correlations between switchgrass elemental composition and geographical and seasonal changes so as to identify factors that influence the elemental composition of biomass. The most important factors in determining levels of various chemical compounds were found to be seasonal and geographical differences related to soil conditions. Combustion testing was performed to obtain deposits typical of boiler fouling and slagging conditions as well as fly ash. Analysis methods using computer-controlled scanning electron microscopy and chemical fractionation were applied to determine the composition and association of inorganic materials in the biomass samples. Modified sample preparation techniques and mineral quantification procedures using cluster analysis were developed to characterize the inorganic material in these samples. Each of the biomass types exhibited different inorganic associations in the fuel as well as in the deposits and fly ash. Morphological analyses of the wheat straw show elongated 10-30-{micro}m amorphous silica particles or phytoliths in the wheat straw structure. Alkali such as potassium, calcium, and sodium is organically bound and dispersed in the organic structure of the biomass materials. Combustion test results showed that the blends fed quite evenly, with good burnout. Significant slag deposit formation was observed for the 100% wheat straw, compared to bituminous and subbituminous coals burned under similar conditions. Although growing rapidly, the fouling deposits of the biomass and coal-biomass blends were significantly weaker than those of the coals. Fouling was only slightly worse for the 100% wheat straw fuel compared to the coals. The wheat straw ash was found to show the greatest similarity from the fuel to the ash analyzed. A high percentage of particles from both fuel and ash samples contained both Si and K. While Cl was a significant component in the fuel, very little was detected in the ash sample