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At least 325 records · Page 18

Model of Inclusion Evolution During Calcium Treatment in the Ladle Furnace

Calcium treatment of steel is typically employed to modify alumina inclusions to liquid calcium aluminates. However, injected calcium also reacts with the dissolved sulfur to form calcium sulfide. The current work aims to develop a kinetic model for the evolution of oxide and sulfide inclusions in Al-killed alloyed steel during Ca treatment in the ladle refining process. The model considers dissolution of the calcium from the calcium bubbles into the steel and reduction of calcium oxide in the slag to dissolved calcium. A steel–inclusion kinetic model is used for mass transfer to the inclusion interface and diffusion within the calcium aluminate phases formed on the inclusion. The inclusion–steel kinetic model is then coupled with a previously developed steel–slag kinetic model. The coupled inclusion–steel–slag kinetic model is applied to the chemical composition changes in molten steel, slag, and evolution of inclusions in the ladle. The result of calculations is found to agree well with an industrial heat for species in the steel as well as inclusions during Ca treatment.

36 MATERIALS SCIENCE↗

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Manganese Removal

In the earlier study, a dynamic model for the BOF process based on the multizone reaction kinetics has been developed. In the preceding part, the mechanism of manganese transfer in three reactive zones of the converter has been analyzed. The study predicts that temperature at the slag–metal reaction interface plays a major role in the Mn reaction kinetics. Further, mathematical treatments to simulate the transient rate parameters associated with each reaction interface have been developed. The model calculations of Mn removal rate obtained from different zones of the converter predicts that the first stage of the blow is dominated by the oxidation of Mn at the jet impact zone, albeit some additional Mn refining has been observed as a result of the oxidation of metal droplets in emulsion phase. The simulation result shows that the reversion of Mn from slag to metal primarily takes place at the metal droplet in the emulsion due to an increase in slag–metal interface temperature during the middle stage of blowing. In the final stage of the blow, the competition between simultaneous reactions in jet impact and emulsion zone controls the direction of mass flow of manganese. Further, the model prediction shows that the Mn refining in the emulsion is a strong function of droplet diameter and the residence time. Smaller sized droplets approach equilibrium quickly and thus contribute to a significant Mn conversion between slag and metal compared to the larger sized ones. The overall model prediction for Mn in the hot metal has been found to be in good agreement with two data sets obtained from different size converters reported in the literature.

36 MATERIALS SCIENCE↗

Element Distribution in the Silicomanganese Production Process

A pilot scale, silicomanganese alloy production campaign was performed in a 440 kVA, single phase electric furnace in order to establish an overview of the minor- and trace element contents in process input raw materials and their distribution in the resulting primary and secondary products. Samples of the in-going raw materials (manganese ore, coke, quartzite, and high carbon ferromanganese slag) and the out-going products (silicomanganese alloy, silicomanganese slag, and dust) were analyzed by inductively coupled plasma mass spectrometry. The distribution of 51 elements between the product phases was discussed in terms of their boiling temperatures, Gibbs energies of oxidation and activity coefficients of elements in the metal. A thermochemical simulation using the thermochemical software FactSage 7.1 was also carried out in order to model element phase distribution between the alloy, slag, and dust/gas. The correlation between the model and experimental element concentrations in the silicomanganese slag and dust is fair for most elements. However, in the metal phase, fewer elements show good correlation between modeled results and measured experimental concentrations. The discrepancy could be explained by a lack of accurate thermodynamic descriptions for several minor species in the database.

36 MATERIALS SCIENCE↗

Mathematical Modeling on the Influence of Casting Parameters on Initial Solidification at the Meniscus of Slab Continuous Casting

In the current study, the two-dimensional mold model was applied to investigate the influence of different casting parameters on the initial solidification at the meniscus of the continuous casting mold. The profile of the meniscus and the slag rim, and the heat flux on the hot face of the copper plate, were compared with different locations of the mold and different casting parameters. The depth of the oscillation marks and solidified meniscus through simulation was measured with different casting parameters. With the mold oscillating downward from the peak to the valley, the maximum heat flux on the hot face of the copper plate near the meniscus increased from 4.3 to 5.5 MW/m{sup 2}, the thickness of the slag rim decreased from 4.7 to 4.2 mm, and the height of the curved meniscus also decreased. With the increase of casting speed from 1.2 to 1.45 m/min, the maximum speed of the upper backflow increased from 0.6 to 0.8 m/s, and the lowest location of the meniscus at approximately 310 mm from the copper plate decreased from 22 to 12 mm below the meniscus near the nozzle, where the slag entrapment easily occurred. With the increase of the casting speed, casting superheat, and oscillation frequency, and the decrease of the water flow rate in the mold and oscillation amplitude, the thickness of the slag rim decreased. With the increase of casting speed and superheat, and the decrease of the water flow rate in the mold, oscillation frequency, and oscillation amplitude, the depth of the solidified meniscus decreased. The regression equation was fitted to estimate the depth of hooks at the subsurface of slabs.

36 MATERIALS SCIENCE↗

Development of a hybrid shrinking‐core shrinking‐particle model for entrained‐flow gasifiers

Slagging entrained‐flow gasifiers operate above the melting temperature of the ash. As slag is highly nonwetting on the surface of char (carbon) particles, it is likely that it will agglomerate into one or several slag droplets and some of these droplets can detach from the char particles. If the slag exists in the form of droplets on the char surface rather than as a solid shell around the unreacted char particle, a shrinking particle model would be more physically realistic representation in comparison to the widely used shrinking core model (SCM). In the early section of the gasifier, the temperature remains below the ash melting temperature and, therefore, the SCM is more appropriate in this region. With this motivation, a novel hybrid shrinking‐core shrinking‐particle model has been developed. The model provides spatial profile of a number of important variables that are not available from the traditional SCM. © 2015 American Institute of Chemical Engineers AIChE J , 62: 659–669, 2016

Pednekar, Pratik↗

Dissolution zone model of the oxide structure in additively manufactured dispersion-strengthened alloys

The structural evolution of oxides in dispersion-strengthened superalloys during laser-powder bed fusion is considered in detail. Alloy chemistry and process parameter effects on oxide structure are assessed through a parameter study on the model alloy Ni-20Cr, doped with varying concentrations of Y 2 O 3 and Al. Small angle neutron scattering measurements of the dispersoid size distribution show the dispersoid size increases with higher laser power, slower scan speed, and increasing Y 2 O 3 and Al content. Complementary electron microscopy measurements reveal reactions between Y 2 O 3 and Al, even in nanoscale dispersoids, and the presence of micron-scale oxide slag inclusions in select specimens. A scaling analysis of mass and momentum transport within the melt pool, presented here, establishes that diffusional structural evolution mechanisms dominate for nanoscale dispersoids, while fluid forces and advection become significant for larger slag inclusions. These findings are developed into a theory of dispersoid structural evolution, integrating quantitative models of diffusional processes – dispersoid dissolution, nucleation, growth, coarsening – with a reduced order model of time-temperature trajectories of fluid parcels within the melt pool. Calculations of the dispersoid size in single-pass melting reveal a zone in the center of the melt track in which the oxide feedstock fully dissolves. Within this zone the final Y 2 O 3 size is independent of feedstock size and determined by nucleation and growth kinetics. If the dissolution zones of adjacent melt tracks overlap sufficiently with each other to dissolve large oxides, formed during printing or present in the powder feedstock, then the dispersoid structure throughout the build volume is homogeneous and matches that from a single pass within the dissolution zone. Gaps between adjacent dissolution zones result in oxide accumulation into larger slag inclusions. Predictions of final dispersoid size and slag formation using this dissolution zone model match the present experimental data and explain process-structure linkages speculated in the open literature.

36 MATERIALS SCIENCE↗

The composition and performance of alite-ye'elimite clinker produced at 1300 °C

Alite-ye'elimite clinker is a high cementing clinker prepared by introducing calcium sulfoaluminate, a non-silicate mineral, into the cement clinker. The mineral composition and mechanics of tricalcium silicate-rich sulfur aluminate prepared at 1300 °C are reported. The effects of copper slag and phosphorus slag on the phase composition, heat release and compressive strength were investigated. The phase composition was analysed by X-ray powder diffraction. The results show that the copper slag and phosphorus slag can lower the burn temperature of the clinker and promote the coexistence of C{sub 3}S and C{sub 4}A{sub 3} S-bar . The quality of clinker produced at 1300 °C is satisfactory. The compressive strength of mortar curing at 28 d is higher than that of P·II 52.5.

36 MATERIALS SCIENCE↗

Performance assessment of dilute-acid leaching to improve corn stover quality for thermochemical conversion

Lignocellulosic biomass is a sustainable energy source that can help meet the increasing demand for biofuels in the United States. However, the quality and availability of such feedstocks greatly affects their suitability for downstream conversion. This work reports the effects of dilute-acid leaching at various solid loadings, temperatures and acid loadings on the quality of a traditional biochemical feedstock, corn stover, as a potential feedstock for thermochemical conversions. At 5 wt% solids, dilute-acid leaching was observed to effectively remove 97.3% of the alkali metals and alkaline earth metals that can negatively affect degradation pathways during pyrolysis and result in greater yield of non-condensable gases. In addition, up to 98.4% of the chlorine and 88.8% of the phosphorus, which can cause equipment corrosion and foul upgrading catalysts, respectively, were removed. At 25°C in the absence of acid, only 6.8% of the alkali metals and alkaline earth metals were removed; however 88.0% of chloride was still removed. The ratio of alkaline/acidic ash species has been suggested to proportionately relate to slagging in biopower applications. The initial alkali/acid ratio of the ash species present in the untreated corn stover was 0.38 (significant slagging risk). At 5 wt% solids, this ratio was decreased to 0.18 (moderate slagging risk) at 0 wt% acid and 90°C, and was decreased to 0.07, 0.08 and 0.06 at 0.5 wt% acid at 25°C, 50°C and 90°C, respectively (little or no slagging risk). Increasing the acid loading to 1.0% only slightly decreased the measured alkali/acid ratio of remaining ash species. Lastly, the results presented here show that a water wash or dilute-acid preprocessing step can improve corn stover quality for pyrolysis, hydrothermal liquefaction and biopower.

09 BIOMASS FUELS↗

Cast Stone Formulation At Higher Sodium Concentrations

A low temperature waste form known as Cast Stone is being considered to provide supplemental Low Activity Waste (LAW) immobilization capacity for the Hanford site. Formulation of Cast Stone at high sodium concentrations is of interest since a significant reduction in the necessary volume of Cast Stone and subsequent disposal costs could be achieved if an acceptable waste form can be produced with a high sodium molarity salt solution combined with a high water to premix (or dry blend) ratio. The objectives of this study were to evaluate the factors involved with increasing the sodium concentration in Cast Stone, including production and performance properties and the retention and release of specific components of interest. Three factors were identified for the experimental matrix: the concentration of sodium in the simulated salt solution, the water to premix ratio, and the blast furnace slag portion of the premix. The salt solution simulants used in this study were formulated to represent the overall average waste composition. The cement, blast furnace slag, and fly ash were sourced from a supplier in the Hanford area in order to be representative. The test mixes were prepared in the laboratory and fresh properties were measured. Fresh density increased with increasing sodium molarity and with decreasing water to premix ratio, as expected given the individual densities of these components. Rheology measurements showed that all of the test mixes produced very fluid slurries. The fresh density and rheology data are of potential value in designing a future Cast Stone production facility. Standing water and density gradient testing showed that settling is not of particular concern for the high sodium compositions studied. Heat of hydration measurements may provide some insight into the reactions that occur within the test mixes, which may in turn be related to the properties and performance of the waste form. These measurements showed that increased sodium concentration in the salt solution reduced the time to peak heat flow, and reducing the amount of slag in the premix increased the time to peak heat flow. These observations may help to describe some of the cured properties of the samples, in particular the differences in compressive strength observed after 28 and 90 days of curing. Samples were cured for at least 28 days at ambient temperature in the laboratory prior to cured properties analyses. The low activity waste form for disposal at the Hanford Site is required to have a compressive strength of at least 500 psi. After 28 days of curing, several of the test mixes had mean compressive strengths that were below the 500 psi requirement. Higher sodium concentrations and higher water to premix ratios led to reduced compressive strength. Higher fly ash concentrations decreased the compressive strength after 28 days of curing. This may be explained in that the cementitious phases matured more quickly in the mixes with higher concentrations of slag, as evidenced by the data for the time to peak heat generation. All of the test mixes exhibited higher mean compressive strengths after 90 days of curing, with only one composition having a mean compressive strength of less than 500 psi. Leach indices were determined for the test mixes for contaminants of interest. The leaching performance of the mixes evaluated in this study was not particularly sensitive to the factors used in the experimental design. This may be beneficial in demonstrating that the performance of the waste form is robust with respect to changes in the mix composition. The results of this study demonstrate the potential to achieve significantly higher waste loadings in Cast Stone and other low temperature, cementitious waste forms. Additional work is needed to elucidate the hydration mechanisms occurring in Cast Stone formulated with highly concentrated salt solutions since these reactions are responsible for determining the performance of the cured waste form. The thermal analyses completed in this study provide some preliminary insight, although the limited range of the factors in the test matrix hindered the identification of individual component effects. Future work should involve broader factor ranges to identify the roles played by each of the components in the mix via thermal analyses, analytical microscopy, and characterization of phase formation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Cast Stone Formulation At Higher Sodium Concentrations

A low temperature waste form known as Cast Stone is being considered to provide supplemental Low Activity Waste (LAW) immobilization capacity for the Hanford site. Formulation of Cast Stone at high sodium concentrations is of interest since a significant reduction in the necessary volume of Cast Stone and subsequent disposal costs could be achieved if an acceptable waste form can be produced with a high sodium molarity salt solution combined with a high water to premix (or dry blend) ratio. The objectives of this study were to evaluate the factors involved with increasing the sodium concentration in Cast Stone, including production and performance properties and the retention and release of specific components of interest. Three factors were identified for the experimental matrix: the concentration of sodium in the simulated salt solution, the water to premix ratio, and the blast furnace slag portion of the premix. The salt solution simulants used in this study were formulated to represent the overall average waste composition. The cement, blast furnace slag, and fly ash were sourced from a supplier in the Hanford area in order to be representative. The test mixes were prepared in the laboratory and fresh properties were measured. Fresh density increased with increasing sodium molarity and with decreasing water to premix ratio, as expected given the individual densities of these components. Rheology measurements showed that all of the test mixes produced very fluid slurries. The fresh density and rheology data are of potential value in designing a future Cast Stone production facility. Standing water and density gradient testing showed that settling is not of particular concern for the high sodium compositions studied. Heat of hydration measurements may provide some insight into the reactions that occur within the test mixes, which may in turn be related to the properties and performance of the waste form. These measurements showed that increased sodium concentration in the salt solution reduced the time to peak heat flow, and reducing the amount of slag in the premix increased the time to peak heat flow. These observations may help to describe some of the cured properties of the samples, in particular the differences in compressive strength observed after 28 and 90 days of curing. Samples were cured for at least 28 days at ambient temperature in the laboratory prior to cured properties analyses. The low activity waste form for disposal at the Hanford Site is required to have a compressive strength of at least 500 psi. After 28 days of curing, several of the test mixes had mean compressive strengths that were below the 500 psi requirement. Higher sodium concentrations and higher water to premix ratios led to reduced compressive strength. Higher fly ash concentrations decreased the compressive strength after 28 days of curing. This may be explained in that the cementitious phases matured more quickly in the mixes with higher concentrations of slag, as evidenced by the data for the time to peak heat generation. All of the test mixes exhibited higher mean compressive strengths after 90 days of curing, with only one composition having a mean compressive strength of less than 500 psi. Leach indices were determined for the test mixes for contaminants of interest. The leaching performance of the mixes evaluated in this study was not particularly sensitive to the factors used in the experimental design. This may be beneficial in demonstrating that the performance of the waste form is robust with respect to changes in the mix composition. The results of this study demonstrate the potential to achieve significantly higher waste loadings in Cast Stone and other low temperature, cementitious waste forms. Additional work is needed to elucidate the hydration mechanisms occurring in Cast Stone formulated with highly concentrated salt solutions since these reactions are responsible for determining the performance of the cured waste form. The thermal analyses completed in this study provide some preliminary insight, although the limited range of the factors in the test matrix hindered the identification of individual component effects. Future work should involve broader factor ranges to identify the roles played by each of the components in the mix via thermal analyses, analytical microscopy, and characterization of phase formation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of Oxy-combustion Impacts in Existing Coal-fired Boilers

Reaction Engineering International (REI) managed a team of experts from University of Utah, Siemens Energy, Praxair, Vattenfall AB, Sandia National Laboratories, Brigham Young University (BYU) and Corrosion Management Ltd. to perform multi-scale experiments, coupled with mechanism development, process modeling and CFD modeling, for both applied and fundamental investigations. The primary objective of this program was to acquire data and develop tools to characterize and predict impacts of CO{sub 2} flue gas recycle and burner feed design on flame characteristics (burnout, NO{sub x}, SO{sub x}, mercury and fine particle emissions, heat transfer) and operational concerns (fouling, slagging and corrosion) inherent in the retrofit of existing coal-fired boilers for oxy-coal combustion. Experimental work was conducted at Sandia National Laboratories’ Entrained Flow Reactor, the University of Utah Industrial Combustion Research Facility, and Brigham Young University. Process modeling and computational fluid dynamics (CFD) modeling was performed at REI. Successful completion of the project objectives resulted in the following key deliverables: 1) Multi-scale test data from 0.1 kW bench-scale, 100 kW and 200 kW laboratory-scale, and 1 MW semi-industrial scale combustors that describe differences in flame characteristics, fouling, slagging and corrosion for coal combustion under air-firing and oxygen-firing conditions, including sensitivity to oxy-burner design and flue gas recycle composition. 2) Validated mechanisms developed from test data that describe fouling, slagging, waterwall corrosion, heat transfer, char burnout and sooting under coal oxy-combustion conditions. The mechanisms were presented in a form suitable for inclusion in CFD models or process models. 3) Principles to guide design of pilot-scale and full-scale coal oxy-firing systems and flue gas recycle configurations, such that boiler operational impacts from oxy-combustion retrofits are minimized. 4) Assessment of oxy-combustion impacts in two full-scale coal-fired utility boiler retrofits based on computational fluid dynamics (CFD) modeling of air-fired and oxygen-fired operation. This research determined that it is technically feasible to retrofit the combustion system in an air-fired boiler for oxy-fired operation. The impacts of CO{sub 2} flue gas recycle and burner design on flame characteristics (burnout, NO{sub x}, SO{sub x}, mercury and fine particle emissions, heat transfer) and operational concerns (fouling, slagging and corrosion) were minimal, with the exception of high sulfur levels resulting from untreated flue gas recycle with medium and high-sulfur coals. This work focused on combustion in the radiant and convective sections of the boiler and did not address boiler system integration issues, plant efficiencies, impacts on downstream air pollution control devices, or CO{sub 2} capture and compression. The experimental data, oxy-firing system principles and oxy-combustion process mechanisms provided by this work can be used by electric utilities, boiler OEMs, equipment suppliers, design firms, software vendors, consultants and government agencies to assess retrofit applications of oxy-combustion technologies to existing boilers and to guide development of new designs.

20 FOSSIL-FUELED POWER PLANTS↗

Cast Stone Formulation At Higher Sodium Concentrations

A low temperature waste form known as Cast Stone is being considered to provide supplemental Low Activity Waste (LAW) immobilization capacity for the Hanford site. Formulation of Cast Stone at high sodium concentrations is of interest since a significant reduction in the necessary volume of Cast Stone and subsequent disposal costs could be achieved if an acceptable waste form can be produced with a high sodium molarity salt solution combined with a high water to premix (or dry blend) ratio. The objectives of this study were to evaluate the factors involved with increasing the sodium concentration in Cast Stone, including production and performance properties and the retention and release of specific components of interest. Three factors were identified for the experimental matrix: the concentration of sodium in the simulated salt solution, the water to premix ratio, and the blast furnace slag portion of the premix. The salt solution simulants used in this study were formulated to represent the overall average waste composition. The cement, blast furnace slag, and fly ash were sourced from a supplier in the Hanford area in order to be representative. The test mixes were prepared in the laboratory and fresh properties were measured. Fresh density increased with increasing sodium molarity and with decreasing water to premix ratio, as expected given the individual densities of these components. Rheology measurements showed that all of the test mixes produced very fluid slurries. The fresh density and rheology data are of potential value in designing a future Cast Stone production facility. Standing water and density gradient testing showed that settling is not of particular concern for the high sodium compositions studied. Heat of hydration measurements may provide some insight into the reactions that occur within the test mixes, which may in turn be related to the properties and performance of the waste form. These measurements showed that increased sodium concentration in the salt solution reduced the time to peak heat flow, and reducing the amount of slag in the premix increased the time to peak heat flow. These observations may help to describe some of the cured properties of the samples, in particular the differences in compressive strength observed after 28 and 90 days of curing. Samples were cured for at least 28 days at ambient temperature in the laboratory prior to cured properties analyses. The low activity waste form for disposal at the Hanford Site is required to have a compressive strength of at least 500 psi. After 28 days of curing, several of the test mixes had mean compressive strengths that were below the 500 psi requirement. Higher sodium concentrations and higher water to premix ratios led to reduced compressive strength. Higher fly ash concentrations decreased the compressive strength after 28 days of curing. This may be explained in that the cementitious phases matured more quickly in the mixes with higher concentrations of slag, as evidenced by the data for the time to peak heat generation. All of the test mixes exhibited higher mean compressive strengths after 90 days of curing, with only one composition having a mean compressive strength of less than 500 psi. Leachability indices were determined for the test mixes for contaminants of interest. The leaching performance of the mixes evaluated in this study was not particularly sensitive to the factors used in the experimental design. This may be beneficial in demonstrating that the performance of the waste form is robust with respect to changes in the mix composition. The results of this study demonstrate the potential to achieve significantly higher waste loadings in Cast Stone and other low temperature, cementitious waste forms. Additional work is needed to elucidate the hydration mechanisms occurring in Cast Stone formulated with highly concentrated salt solutions since these reactions are responsible for determining the performance of the cured waste form. The thermal analyses completed in this study provide some preliminary insight, although the limited range of the factors in the test matrix hindered the identification of individual component effects. Future work should involve broader factor ranges to identify the roles played by each of the components in the mix via thermal analyses, analytical microscopy, and characterization of phase formation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Conversion of Coal Wastes and Coal Plus Other Opportunity Fuel Mixtures, Such as Coal Plus Municipal Solids, to Produce Electricity and/or Liquid Fuels

For the foreseeable future, the Nation’s energy demand will continue to come largely from indigenous fossil energy resources and hydrocarbon fuels. Specifically waste coal plus other opportunity fuels need to be utilized as a feedstock to eliminate a waste stream and optimized to maximize energy yield and cleanly minimize pollutant emissions. Modular equipment is needed for installation in coal preparation locations, military installations, and research park facilities. Thermal decomposition of coal, biomass, and mixed solid waste (MSW) have been shown to reduce a waste stream while providing liquid and gaseous fuel products with low pollutant emissions. However, thermal decomposition processes have several challenges associated with preprocessing biomass and MSW, feeding and conveying material into the reactor, and post processing of syngas to remove undesirable products while upgrading to increase yield of high value products. Increasing total energy output from power plants by utilizing biomass and mixed wastes ultimately lowers energy costs, harmful environmental impacts of emissions, and has significant impacts on the energy security and sustainability of the U.S. economy. Entrained flow gasifiers (EFGs) produce very little CH4 and a wide range of H2/CO ratios (0.5–2.0) but are limited in their ability to effectively feed large biomass or MSW particles into the reactor. A solution to the feeding problems is to use pyrolysis torrefaction (PT) for conversion of waste materials to create a feedstock similar to coal and capable of grinding down and mixing with the coal feed. Mainstream experimentally explored reaction pathways for the conversion of coal waste plus municipal solids (CWPMS) and demonstrated a bench-scale reactor used for torrefaction of the municipal solid waste (MSW) to create a coal-like feed for blending with the coal waste. The material was processed in a pilot-scale EFG to determine product yield and emissions with CWPMS fuels, as well as the ash content and slagging properties of these feedstocks. The PT-EFG system was experimentally validated, where emissions and yield data were used to develop a high-fidelity process model and economic analysis. The following was accomplished in the Phase I: Determined optimal torrefaction process conditions for MSW and biomass through TGA; maximized heating value of fuel while maximizing final mass of torrefied product Demonstrated torrefaction of MSW and biomass feedstocks at 334°C, pulverized to uniform 74 µm particle size, and processed into coal-like feedstocks Demonstrated 8 lb/h pilot-scale EFG using MSW and biomass blends with waste coal; demonstrated 100% biomass in EFG Determined major effects of MSW torrefaction and co-gasifying high-ash coal waste-MSW blends have on pilot-scale EFG Demonstrated blending low-ash, low-sulfur torrefied biomass with high-ash waste bituminous and anthracite refuse coals generates a higher quality syngas compared to syngas from high-ash waste coals Demonstrated a high carbon conversion (> 99.5%) and syngas with 29.47% H2 content, and 0% CH4 content; greater water–gas shift occurs in EFG than predicted by equilibrium ASPEN Plus model Blended lower-ash, high-alkali biomass MSW to lower slag viscosities of the high-ash coal refuse sufficiently for better slag flow compared to feeding the high-ash coal Used low-sulfur biomass to greatly reduce the EFG syngas H2S concentrations and produce non-leachable slag and quench water with very little organic and trace metal contamination Developed a process model and TEA showing the modular PT EFG is cost competitive to existing power plants with the advantage of using low- or negative-value feedstocks such as waste coal stockpiles and non-landfilled MSW; providing a large incentive to implement an economical PT-EFG process

30 DIRECT ENERGY CONVERSION↗

Time Dependence of Methane Generation Rates from Saltstone

This report documents the tests performed to address the requirements listed in the Technical Request, which resulted in a Task Technical & Quality Assurance Plan (TTQAP) and a Run Plan to obtain the required information. The research expands previous scoping work to better understand methane generation in the Saltstone Disposal Facility (SDF). That scoping work demonstrated that methane is produced when sulfide-containing material is added to methylmercury (MeHg), which is found in the SDF Tank 50 feed waste. When Tank 50 waste is combined with grout premix solids dry feed ingredients of cement, slag cement, and fly ash, sulfides are released from the slag cement component of the premix. The prior testing results showed that while the concentration of total mercury was not affected in the pH 14 waste, the MeHg likely reacted with the sulfide contained in the slag. The scoping tests were performed in sealed reactors and thus, methane generation was not measured continuously; rather, it was measured after one hour and after 24 hours. After 24 hours, a large percentage of the MeHg was converted to methane, but after 1 hour only a small percentage of methane was released. It is noteworthy that the methane generation rate (MGR) was greater at the one-hour measurement. The data compiled from the scoping work needed to be expanded to better understand the generation of methane released from grout mixed with Tank 50 waste. This expanded study developed a more extensive knowledge of how and when methane is generated to inform the Documented Safety Analysis (DSA) of the SDF. As such, employing 8 sealed reactors, the methane generation time periods were extended to 2, 4, 6, 18, 30, 48, 72, and 96 hours (4 days). Results are documented herein to determine the capacity for MeHg, contained within Tank 50 salt solution (T50SS) simulant, to produce methane when mixed with saltstone dry feed ingredients, i.e., individual components (cement, slag, and fly ash) or a combination of those components.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of Saltstone Grout Line Samples

During a prestart recirculation operation in the Saltstone Processing Facility (SPF), operations staff noticed hardened scaling falling into the hopper. As a result, SPF operators and Saltstone Engineering decided to postpone operation and conduct a process room hopper cleanout. During the cleanout effort personnel noted greater than normal buildup of damp solid material in the transfer line. A borescope investigation was conducted and confirmed buildup was present throughout the transfer line to the downstream valves. Savannah River National Laboratory personnel were asked to characterize the scale material and samples collected from the saltstone grout line and provide recommendations and/or further guidance as to whether additional corrosion testing is needed for useful equipment operating life information. Based on the samples characterized results, the plug material contained only the 60:40 slag:fly ash saltstone. Portland cement in the original 10:45:45 Portland cement:slag:fly ash mix may result in a less abrasive slurry compared to the 60:40 slag:fly ash mix because the slag is > 95 % crushed angular, sharp edged glass. Saltstone grout erosion and corrosion testing of A36 carbon steel is needed to determine if the 60:40 mix is more abrasive and corrosive for A36 carbon steel than the 10:45:45 mix.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Plume diagnostics of SRM static firings for pressure perturbation studies

During the shuttle launches, the solid rocket motors (SRM) occasionally experience pressure perturbations (8-13 psi) between 65 and 75 seconds into the motor burn time. The magnitudes of these perturbations are very small in comparison with the operating motor chamber pressure, which is over 600 psi during this time frame. These SRM pressure perturbations are believed to be caused primarily by the expulsion of slag (aluminum oxide). Two SRM static tests, TEM-11 and FSM-4, were instrumented extensive]y for the study of the phenomenon associated with pressure perturbations. The test instrumentation used included nonintrusive optical and infrared diagnostics of the plume, such as high-speed photography, radiometers, and thermal image cameras. Results from all these nonintrusive observations strongly support the scenario that the pressure perturbation event in the shuttle SRM is caused primarily by the expulsion of molten slag. The slag was also expelled preferentially near the bottom of the nozzle due to slag accumulation at the bottom of the aft end of the horizontally oriented motor.

Sambamurthi, J. K.↗

Plume Diagnostics of the RSRM Static Firings for the Pressure Perturbation Studies

During the STS-54 launch (RSRM-29), the right hand solid rocket motor experienced a 13.9 psi chamber pressure perturbation at 67 seconds into the motor operation. This pressure augmentation equated to a thrust change of 51 klb. Concerns were raised regarding the adverse effects of this thrust imbalance on the shuttle system and the overall thrust into the external tank structural elements. Pressure perturbations have been observed in solid rocket motors due to expulsion of igniter or insulation materials; the motor thrust during such events drop abruptly before rising. However, the RSRM motors do not exhibit such behavior during the large chamber pressure perturbation events. Several scenarios were investigated to explain these pressure perturbations in the RSRM motors based on a fault tree developed after STS-54. Of these, the expulsion of the slag accumulated in the submerged nozzle region appeared to be the most plausible scenario to explain the observations. Slag is a natural combustion product of aluminized solid rocket motors. The RSRM propellant contains 16% by weight of aluminum. Any ejection of this slag mass during nozzle vectoring or other side loads on the motor will result in the chamber pressure perturbation. Two RSRM static firings were instrumented extensively to further understand the slag expulsion phenomenon in the RSRM and the associated pressure perturbations.

Mathias, Edward C.↗

Formation Mechanism of Oxide-Sulfide Complex Inclusions in High-Sulfur-Containing Steel Melts

The [S] content in resulfurized steel is controlled in the range of 200 to 800 ppm to ensure good machinability and workability. It is well known that “MgAl{sub 2}O{sub 4}(spinel)+CaS” complex inclusions are formed in molten steel during the ladle refining process, and these cause nozzle clogging during continuous casting. Thus, in the present study, the “Refractory-Slag-Metal-Inclusions (ReSMI)” multiphase reaction model was employed in conjunction with experiments to investigate the influence of slag composition and [S] content in the steel on the formation of oxide-sulfide complex inclusions. The critical [S] and [Al] contents necessary for the precipitation of CaS in the CaO-Al{sub 2}O{sub 3}-MgO-SiO{sub 2} (CAMS) oxide inclusions were predicted from the composition of the liquid inclusions, as observed by scanning electron microscopy–electron dispersive spectrometry (SEM-EDS) and calculated using the ReSMI multiphase reaction model. The critical [S] content increases with increasing content of SiO{sub 2} in the slag at a given [Al] content. Formation mechanisms for spinel+CaS and spinel+MnS complex inclusions were also proposed.

36 MATERIALS SCIENCE↗