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At least 631 records · Page 35

Detailed characterization of particulate matter emitted by lean-burn gasoline direct injection engine

This study presents detailed characterization of the chemical and physical properties of PM emitted by a 2.0L BMW lean-burn turbocharged GDI engine operated under a number of combustion strategies that include lean homogeneous, lean stratified, stoichiometric, and fuel rich conditions. We characterized PM number concentrations, size distributions, and the size, mass, compositions, and effective density of fractal and compact individual exhaust particles. For the fractal particles, these measurements yielded fractal dimension, average diameter of primary spherules, and number of spherules, void fraction, and dynamic shape factors as function of particle size. Overall, the PM properties were shown to vary significantly with engine operation condition. Lean stratified operation yielded the most diesel-like size distribution and the largest PM number and mass concentrations, with nearly all particles being fractal agglomerates composed of elemental carbon with small amounts of ash and organics. In contrast, stoichiometric operation yielded a larger fraction of ash particles, especially at low speed and low load. Three distinct forms of ash particles were observed, with their fractions strongly dependent on engine operating conditions: sub-50 nm ash particles, abundant at low speed and low load, ash-containing fractal particles, and large compact ash particles that significantly contribute to PM mass loadings

Environmental Molecular Sciences Laboratory↗

Differences in urban plant community compositions across an urban-rural gradient in Knoxville, TN

Urban forests, or vegetation in areas under heavy human influence, provide many ecosystem services to urban residents such as localized cooling via evapotranspiration, shade, filtering of air pollution, and the associated health benefits of natural spaces. In order to quantify the magnitude of localized cooling by trees growing in varying levels of urbanization (based on % impervious surfaces, e.g., buildings, pavement), urban forest species composition, tree size, and tree density must be characterized. As a part of Oak Ridge National Laboratory’s (ORNL) urban forest temperature study, we conducted tree censuses in five Knoxville city parks where ORNL meteorological stations are deployed. Moreover, we measured every woody plant ≥ 5 cm diameter at breast height (DBH) within a 50 m radius of each site’s meteorological station for its DBH and species identification. When possible, individuals were identified down to species. Certain genera (Quercus spp., Carya spp., Pinus spp.) were identified down to genera in interest of time. Individual and total site basal area were calculated from measured DBH data. Results show notable differences in urban plant community compositions and total woody plant basal area across sites, with more urban sites closer to downtown (West View and SEEED) having lower tree basal area than the more suburban sites (West Hills, Cumberland Estates, and Victor Ashe). We identified 54 species across all sites, with West Hills and Victor Ashe having the highest species diversity. Our results show differences in forest compositions and sizes across Knoxville, which are currently informing ORNL’s evapotranspiration estimates for each site. Data Summary: Census data for West Hills (WH), Cumberland Estates (CE), Victor Ashe (VA), West View (WV), and Socially Equal Energy Efficient Development or SEEED (SD) urban forests in Knoxville, TN, USA, including tree size based on diameter at breast height (DBH; 1.3 m), species identification (Latin and common names), and basal area per stem (BA=π×[.5*DBH]^2). Field data are summarized in this file: “Community_Composition_Data.CSV”. Site-specific data detailing each site’s coordinates, number of stems measured at DBH, average tree DBH, α-diversity (number of species present), and total site basal area (sum of individual basal areas per site) are in this file: “Site_Comparisons.CSV”.

Warren, Jeffrey [ORNL] (ORCID:0000000206804697)↗

Thermal Shock-resistant Cement

We studied the effectiveness of sodium silicate-activated Class F fly ash in improving the thermal shock resistance and in extending the onset of hydration of Secar #80 refractory cement. When the dry mix cement, consisting of Secar #80, Class F fly ash, and sodium silicate, came in contact with water, NaOH derived from the dissolution of sodium silicate preferentially reacted with Class F fly ash, rather than the #80, to dissociate silicate anions from Class F fly ash. Then, these dissociated silicate ions delayed significantly the hydration of #80 possessing a rapid setting behavior. We undertook a multiple heating -water cooling quenching-cycle test to evaluate the cement’s resistance to thermal shock. In one cycle, we heated the 200°C-autoclaved cement at 500°C for 24 hours, and then the heated cement was rapidly immersed in water at 25°C. This cycle was repeated five times. The phase composition of the autoclaved #80/Class F fly ash blend cements comprised four crystalline hydration products, boehmite, katoite, hydrogrossular, and hydroxysodalite, responsible for strengthening cement. After a test of 5- cycle heat-water quenching, we observed three crystalline phase-transformations in this autoclaved cement: boehmite → γ-Al 2 O 3 , katoite → calcite, and hydroxysodalite → carbonated sodalite. Among those, the hydroxysodalite → carbonated sodalite transformation not only played a pivotal role in densifying the cementitious structure and in sustaining the original compressive strength developed after autoclaving, but also offered an improved resistance of the #80 cement to thermal shock. In contrast, autoclaved Class G well cement with and without Class F fly ash and quartz flour failed this cycle test, generating multiple cracks in the cement. The major reason for such impairment was the hydration of lime derived from the dehydroxylation of portlandite formed in the autoclaved cement, causing its volume to expand.

15 GEOTHERMAL ENERGY↗

Radioactive Demonstration Of Mineralized Waste Forms Made From Hanford Low Activity Waste (Tank Farm Blend) By Fluidized Bed Steam Reformation (FBSR)

The U.S. Department of Energy’s Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford’s tank waste. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in the time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Supplemental Treatment is likely to be required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP’s LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750°C) continuous method by which LAW can be processed irrespective of whether the waste contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology can process these wastes into a crystalline ceramic (mineral) waste form. The mineral waste form that is produced by co-processing waste with kaolin clay in an FBSR process has been shown to be comparable to LAW glass, i.e. leaches Tc-99, Re and Na at <2g/m 2 during ASTM C1285 (Product Consistency) durability testing. Monolithing of the granular FBSR product was investigated to prevent dispersion during transport or burial/storage. Monolithing in an inorganic geopolymer binder, which is amorphous, macro-encapsulates the granules, and the monoliths pass ANSI/ANS 16.1 and ASTM C1308 durability testing with Re achieving a Leach Index (LI) of 9 (the Hanford Integrated Disposal Facility, IDF, criteria for Tc-99) after a few days and Na achieving an LI of >6 (the Hanford IDF criteria for Na) in the first few hours. The granular and monolithic waste forms also pass the EPA Toxicity Characteristic Leaching Procedure (TCLP) for all Resource Conservation and Recovery Act (RCRA) components at the Universal Treatment Standards (UTS). Two identical Benchscale Steam Reformers (BSR) were designed and constructed at SRNL, one to treat non-radioactive simulants and the other to treat actual radioactive wastes. The results from the non-radioactive BSR were used to determine the parameters needed to operate the radioactive BSR in order to confirm the findings of non-radioactive FBSR pilot scale and engineering scale tests and to qualify an FBSR LAW waste form for applications at Hanford. Radioactive testing commenced using SRS LAW from Tank 50 chemically trimmed to look like Hanford’s blended LAW known as the Rassat simulant as this simulant composition had been tested in the non-radioactive BSR, the non-radioactive pilot scale FBSR at the Science Applications International Corporation-Science and Technology Applications Research (SAIC-STAR) facility in Idaho Falls, ID and in the TTT Engineering Scale Technology Demonstration (ESTD) at Hazen Research Inc. (HRI) in Denver, CO. This provided a “tie back” between radioactive BSR testing and non-radioactive BSR, pilot scale, and engineering scale testing. Approximately six hundred grams of non-radioactive and radioactive BSR product were made for extensive testing and comparison to the non-radioactive pilot scale tests performed in 2004 at SAIC-STAR and the engineering scale test performed in 2008 at HRI with the Rassat simulant. The same mineral phases and off-gas species were found in the radioactive and non-radioactive testing. The granular ESTD and BSR products (radioactive and non-radioactive) were analyzed for total constituents and durability tested as a granular waste form. A subset of the granular material was stabilized in a clay based geopolymer matrix at 42% and 65% FBSR loadings and durability tested as a monolith waste form. The 65 wt% FBSR loaded monolith made with clay (radioactive) was more durable than the 67-68 wt% FBSR loaded monoliths made from fly ash (non-radioactive) based on short term PCT testing. Long term, 90 to 107 day, ASTM C1308 testing (similar to ANSI/ANS 16.1 testing) was only performed on two fly ash geopolymer monoliths at 67-68 wt% FBSR loading and three clay geopolymer monoliths at 42 wt% FBSR loading. More clay geopolymers need to be made and tested at longer times at higher FBSR loadings for comparison to the fly ash monoliths. Monoliths made with metakaolin (heat treated) clay are of a more constant composition and are very reactive as the heat treated clay is amorphous and alkali activated. The monoliths made with fly ash are subject to the inherent compositional variation found in fly ash as it is a waste product from burning coal and it contains unreactive components such as mullite. However, both the fly ash and the clay based monoliths perform well in long term ASTM C1308 testing.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High Tonnage Forest Biomass Production Systems from Southern Pine Energy Plantations

In this study, a high-tonnage harvesting system designed specifically to operate efficiently in the expected stand types of a bioenergy scenario was built, deployed, and evaluated in a production setting. Stands on which the system was evaluated exhibited the heavy stocking levels (> 600 stems per acre) and tree size distributions with significant volume in small stems (down to 2” DBH) that were expected in the modified energy plantation silvicultural approach. The harvest system also was designed to be functional in the traditional plantation stands dominating the commercial forestry landscape in the region. The Tigercat 845D feller buncher, which was a prototype machine designed for the high tonnage harvest system, used a boom-mounted prototype DT1802 shear felling head and incorporated a number of options intended to maximize its small-stem productivity, including: a high-speed shear severing system that was cheaper to operate than a saw; a large-pocket felling head that allowed larger accumulations of small stems to be built before expending the time to drop them for the skidder; efficient, low ground pressure, tracked carrier system to decrease the amount of maneuvering, saving time and minimizing soil disturbance; and various energy-saving devices to lower fuel costs and minimize air quality impacts. Overall, the feller buncher represented a quantum advance in small-stem harvesting technology. Extensive testing showed the machine’s production rate to be relatively insensitive to piece size, much less so than comparable traditional equipment. In plantation stands, the feller buncher was able to produce approximately 100 green tons of biomass per productive machine hour (PMH), and in natural stands, it produced nearly 120 green tons per PMH. The ability of the high tonnage feller buncher to maintain high productivity in stands with smaller diameter stems is something that has not been achieved in previous feller buncher designs. The Tigercat 845D feller buncher is now a production machine for Tigercat and is being sold in their current product line. The high-speed felling system was paired with a Tigercat 630D skidder and high-capacity grapple; one that could match the felling productivity when pulling small stems. The harvesting system minimized hourly costs using a single, high-capacity skidder (with a single operator), rather than two smaller ones, which is the traditional practice. The skidder itself can be considered a mid-range size and had an engine no larger than other machines in its class, but it incorporated a very large capacity 25 ft2 grapple. The large grapple is well suited to grabbing and hauling a large bunch of small-diameter trees, as produced by the high tonnage feller buncher. The grapple worked effectively in larger stems as well, but its ability to carry large numbers of small stems meant the average payload did not drop as stand DBH decreased. Tests with the machine indicated its travel speeds were nearly the same as, or perhaps slightly better than, conventionally equipped skidders, but grapple capacity was 75% larger. Productivity and cost per ton of the new skidder were better than conventional skidders for average skid distances of any length greater than 100 feet. Measured skidder productivity was as high as 143 gt/PMH. Its productivity exceeded that of the high-capacity feller buncher for skid distances out to nearly 700 feet, so system productivity could be expected to remain high for stands of a size typical in the southern U.S. The Tigercat 630D skidder is a production machine for Tigercat and the large grapple can now be ordered by customers using it for small diameter trees. When the feller buncher and skidder are analyzed as a two-machine system, overall productivity is fixed at the level of the least productive machine. Results from a set of side-by-side tests in the same density stand with conventional feller bunchers and skidders showed that the high tonnage system produced 97 gt/PMH versus 68 gt/PMH for a comparable conventional system. Machine rate costs for felling and skidding were $2.31/gt and $3.72/gt for the high tonnage, and conventional systems, respectively. However, the most significant result of the project is that the high tonnage system was shown to be relatively insensitive to tree size. This ability to maintain felling and skidding productivity and cost as tree size decreases is a breakthrough in harvesting systems for southern pine plantations. The concept of transpirational drying of woody biomass was tested at an industrial scale at multiple locations during this project. Felled trees were allowed to dry in two scenarios: 1) in bunches where they were felled, and 2) in roadside piles. Although the wood piled in large piles at roadside did experience drying, the wood left in bunches experienced a greater moisture reduction. Drying times of 72 days in the late summer resulted in mean wood moisture content of 26% for skidder bunches and 39% for the large pile at roadside as compared to moisture contents of 55% to 58% for freshly cut trees. An existing whole-tree chipper, Precision 2675, was modified to allow production of chips smaller than the traditional pulp size chip (i.e. “microchips”). Feed rates and knife placements were retained in the new design, while additional pockets were incorporated in the chipper disk to allow the attachment of either four knives for pulp chips or eight knives for microchips. This design facilitated switching between the energy and pulp chip product options at relatively low expense (about ½ day downtime). Chipping of whole-trees into pulp chips and microchips with the Precision 2675 disk chipper resulted in average productivities of 79.5 gt/PMH and 70.7 gt/PMH, respectively. Production rates of the chipper were lower when producing microchips by about 10% relative to producing pulp chips, but rates were similar to those achievable when making clean pulp chips. Particle size analysis for clean pine microchips revealed 26.6% retention on a 13 mm (slightly less than 3/8-inch) round hole screen and 25.9% retention for whole-tree pine microchips. For comparison, clean pine pulp chips had 52.2% retained. Ash content (% dry basis) was 0.54% for clean pine microchips and 0.62% for whole-tree pine microchips. Ash content for clean pine pulp chips was 0.39%. For transpirationally-dried material there was 38.1% retention for whole-tree microchips on a 13mm screen compared to 70.1% for dried clean pulp chips. Ash content was 0.78% and 0.44% respectively for these two chip types. Clean pine microchips stored at roadside had 25.2% retention on a 13 mm screen and 0.50% ash content. For mixed species (pine and hardwood), whole-tree microchips had 25.1% retention on a 13 mm screen compared to 50.6% for whole-tree pulp chips. Ash content was 2.12% and 2.74% respectively for these two chip types. Clean hardwood microchips stored at roadside had 35.0% retention on a 13 mm screen and an ash content of 1.24%. There are two significant advantages to using transpirational drying: reduced transportation costs, and reduced drying costs (capital and operating costs) for the biorefinery. This project evaluated the potential to reduce transportation costs through transpirational drying, and it included a component that tested higher capacity chip trailers (23% larger volume) to be able to transport dry wood with a lower bulk density. For transpirationally-dried chips at 35% MC, the high-capacity trailers achieved loads with a mean payload of 24 tons with maximum payloads of 29 tons. The typical legal payload on this trailer is 28.5 tons. Therefore, the project demonstrated that it is possible to achieve maximum legal payloads on chip trailers with transpirationally dried wood. Assuming that the truck is loaded to the legal payload limit, the transportation costs of chips can be reduced from $15.91/dry ton (dt) for 56% MC wood to $10.77/dt for transpirationally dried wood at 35% MC (for an example 50-mile haul distance at $0.14 per one-way ton-mile). For longer haul distances, these savings in trucking costs become even more significant. These results have demonstrated how significant savings in transportation costs can be achieved through transpirational drying. Also, these results show that it may be possible to increase the procurement radius for a biorefinery by using transpirational drying. Further cost reductions can be realized by the biorefinery when drying costs are reduced. The goal of this study was development of a timber harvesting system as productive in stands optimized for biomass production as it was in stands grown for roundwood markets. If that goal is achieved, a logger can invest in a single suite of equipment and operate efficiently in any future silvicultural regime that might include energy feedstocks as an output. It was the premise of the study that a future biomass market would shift the age distribution and stem size in stands grown for energy downward, and the key strategy in developing a harvest system for that scenario would be creating one with logging costs relatively insensitive to tree size. Our vision for such a system included a felling machine with a large capacity head to minimize time spent building bunches, plus a skidder capable of moving large volumes of small trees. The study proposed building the system and testing it against existing equipment in stands similar to those envisioned as resulting from biomass-optimized silviculture. As stated previously, the new feller buncher and skidder evaluated on their own merits showed their designs were clearly a step in the right direction - their productivity was indeed high and less sensitive to reductions in stem size. Cost projections based on extensive time and production studies of the high tonnage and benchmark operations showed modest advantages in FOB costs of the new system in both ‘average’ and simulated ‘energy’ stands (7.7% and 9.5%, respectively). But it was clear, when coupled into a traditional logging system, the in-woods productivity advantage of the modified equipment was easily overwhelmed by inefficiencies in chipping or trucking. Some additional savings can be achieved by spreading the cost of the feller buncher over multiple chipping operations (another 7.5%), but generally, in stands with average DBH above 6 inches, the in-woods equipment was not limiting productivity, and costs were driven by chipping and transport. Our results were a positive step in lowering delivered cost of trees grown for energy purposes, but they also argue strongly for a more comprehensive approach in solving this issue. The procurement system in its entirety has to be optimized to take full advantage of the productivity gains achieved with the machines and transpirational drying techniques developed in this project. We have to understand the true costs of all logistical options, particularly those of the choice in chipping strategy and in truck allocation, both of which seemed, in this study, to be the greatest source of variability in cost, and often the most expensive operations as well.

09 BIOMASS FUELS↗

Slag Management of Carbon Feedstock Used in Gasification FY17 TCF between Eastman Chemical and NETL (Final Report)

NETL, in collaboration with Eastman Chemical Corp (Kingsport, TN), targeted the joint evaluation and refinement of a slag management program developed by NETL (NETL IP, patent applied for) to control gasifier slag properties formed from ash in individual or combinations of different coal-based carbon feedstock materials and specific slag modifiers used in gasification. Slag forms from mineral or organic-metallic impurities in the carbon feedstock that melt at the high temperatures of gasification, coalescing to form a liquid (slag) that must flow from the gasifier. Slag additives, also known as slag modifiers, are often added to the carbon feedstock to modify the ash chemistry and achieve desired slag flow properties at target temperatures used in gasification. If slag does not flow from a gasifier, its buildup within the gasification chamber will cause either gasifier shutdown to physically remove the slag (consuming time and damaging the protective refractory lining), or the gasification temperature must be increased to lower slag viscosity so it can flow from the gasifier, leading to greater refractory wear/corrosion, along with increased fouling and downstream component wear. Because of these issues, gasification is typically targeted at the lowest temperature possible where slag will flow in a controlled manner (a temperature range called T100 for the lowest temperature, with T250 being the highest temperature where the slag has achieved the desired fluidity). That temperature range also needs to yield a desired syngas composition, highlighting the importance of knowing and being able to control carbon feedstock slag viscosity and the temperature of thermal breakdown of the carbon feedstock. Slag viscosity varies with changes in the gasification chamber temperature, oxygen partial pressure, and slag chemistry. The slag model work with Eastman Chemical targeted predicting and controlling molten coal ash slag behavior at specific gasification conditions. The final goal of the refined model was to develop/refine the NETL slag model so a gasifier operator would be able to predict slag behavior prior to purchasing or using a carbon feedstock and control slag properties once a carbon feedstock is being gasified, allowing a gasifier user to determine what mineral additives or blends of different carbon materials would be needed to achieve desired slag properties at targeted gasification conditions. For a given carbon feedstock and desired gasification condition, the actual gasification cost and slag behavior would be able to be predicted using the slag management program in advance of purchasing or using the carbon feedstock – allowing accurate control of slag ash behavior in real time. As part of the TCF project work with Eastman Chemical, the viscosity of several ash compositions of interest to them would be measured and used to populate the slag model, along with a large database of historical slag temperature, chemistry, and viscosity information they possess – information that would in-crease the predictive accuracy of the slag management model with slag ash chemistry of interest to them. As part of the model evaluation and refinement, the predictive model and its database will be installed on computers at Eastman Chemical and used to manage slag properties in a gasifier during real-time operation of their gasifier. In summary, success of the slag management program at Eastman Chemical would support its use by other gasifier operators to manage slag chemistry and properties over other desired gasification temperature ranges, allowing greater process control and efficiency of their carbon feedstock conversion during gasification.

01 COAL, LIGNITE, AND PEAT↗

Optimal N Application Rates on Switchgrass for Producers and a Biorefinery

This study analyzes the effects of N fertilizer application rates on profitability of growing switchgrass and using the feedstock in a pyrolysis biorefinery facility to create a source of sustainable aviation fuel (SAF) supply in Tennessee. Switchgrass (Panicum virgatum L.) is a perennial bunchgrass native to North America with traits suitable for biofuel and co-product production. Previous chemical analysis has shown that ash content in switchgrass is related to the amount of nitrogen applied to the field, while at the biorefinery level, the percentage ash content reduces the biorefinery fuel output. To obtain optimal nitrogen (N) application rates for the switchgrass producers and the biorefinery, a two-part analysis is employed. First, a partial budgeting profitability analysis is conducted for this cropping enterprise at the farm-gate level without considering downstream implications of biomass quality, i.e., ash content. Second, the effects of higher ash content as a percentage of the feedstock on biorefinery output are analyzed. Results show farm-gate profit is maximized when N fertilizer is applied at 111 kg/ha, while as a result of increased production levels and decreased percentage ash content, biorefinery profit is maximized when N is applied at 157 kg/ha. Lower ash could lead to premium prices paid to switchgrass producers if higher quality feedstock were to be demanded as part of an integrated biofuel industry.

Robertson, Keven Alan↗

Incineration as a Method for Resource Recovery from Inedible Biomass in a Controlled Ecological Life Support System

Resource recovery from waste streams in a space habitat is essential to minimize the resupply burden and achieve self-sufficiency. In a Controlled Ecological Life Support System (CELSS) human wastes and inedible biomass will represent significant sources of secondary raw materials necessary for support of crop plant production (carbon, water, and inorganic plant nutrients). Incineration, pyrolysis, and water extraction have been investigated as candidate processes for recovery of these important resources from inedible biomass in a CELSS. During incineration CO2 is produced by oxidation of the organic components and this product can be directly utilized by plants. Water is concomitantly produced, requiring only a phase change for recovery. Recovery of inorganics is more difficult, requiring solubilization of the incinerator ash. The process of incineration followed by water solubilization of ash resulted in loss of 35% of the inorganics originally present in the biomass. Losses were attributed to volatilization (8%) and non-water-soluble ash (27%). All of the ash remaining following incineration could be solubilized with acid, with losses resulting from volatilization only. The recovery for individual elements varied. Elemental retention in the ash ranged from 100% of that present in the biomass for Ca, P, Mg, Na, and Si to 10% for Zn. The greatest water solubility was observed for potassium with recovery of approximately 77% of that present in the straw. Potassium represented 80% of the inorganic constituents in the wheat straw, and because of slightly greater solubility made up 86% of the water-soluble ash. Following incineration of inedible biomass from wheat, 65% of the inorganics originally present in the straw were recovered by water solubilization and 92% recovered by acid solubilization. Recovery of resources is more complex for pyrolysis and water extraction. Recovery of carbon, a resource of greater mass than the inorganic component of biomass, is more difficult following pyrolysis and water extraction of biomass. In both cases, additional processors would be required to provide products equivalent to those resulting from incineration alone. The carbon, water, and organic resources of inedible biomass are effectively separated and output in usable forms through incineration.

Bubenheim, David L.↗

Impacts of feedstock properties on the process economics of fast-pyrolysis biorefineries

Feedstock properties are an important factor affecting process yields and economics of fast pyrolysis biorefineries. Here, this study develops a fast pyrolysis process model sensitive to feedstock properties based on the experimental results. 64 simulations are run to evaluate the impacts of carbon, ash and moisture content in biomass feedstocks on process yields and energy consumptions. An economic analysis is conducted for each run to quantify process economics under different feedstock properties. With biomass feedstocks of 48% carbon and 15% moisture, Minimum Fuel Selling Price (MFSP) increases from 0.97/L to 1.06/L when ash content increases from 1% to 7%, due to reduced hydrocarbon yields. With biomass feedstocks of 48% carbon and 3% ash content, MFSP increases from 1.03/L to 1.08/L when feedstock moisture increases from 15% to 45% as a consequence of increased energy demand for feedstock drying. Finally, the impact of feedstock ash content decreases gradually as ash content increases. Feedstock carbon content has less significant impacts on process economics in this study.

09 BIOMASS FUELS↗

Manganese Oxidation during Vegetation Burning

Redox recycling of manganese (Mn) plays a key role in organic matter decomposition and nutrient cycling in terrestrial vegetated ecosystems, and it is expected to be changed by fires. This study revealed how Mn is oxidized during vegetation burning, by characterizing the chemical speciation of Mn in fire ash from wildland fires and laboratory burning and evaluating the factors governing its average oxidation state (AOS) and speciation. Manganese in wildland fire ash from different ecosystems showed variable AOS that ranges from 2.5 to 3.3. Laboratory burning experiments showed that Mn oxidation was primarily controlled by fire thermal intensity (temperature × duration) and burning completeness. As heating time increased from 5 min to 5 h at 550 and 700 °C, Mn AOS in the lab-burned vegetation ash increased from 2.7 to 4.0 and the oxidation rate was faster at higher temperature. Diverse Mn species can present in wildland fire ash and differ structurally from biogenic Mn oxides. The oxidized Mn species enable fire ash to mediate oxidative degradation of catechol, demonstrating its potential in mediating organic matter decomposition. This study revealed a new paradigm of Mn redox recycling, as compared to the microbe-mediated Mn redox cycling in the absence of fires.

36 MATERIALS SCIENCE↗

THE DETONATION MECHANISM OF THE PULSATIONALLY ASSISTED GRAVITATIONALLY CONFINED DETONATION MODEL OF Type Ia SUPERNOVAE

We describe the detonation mechanism composing the 'pulsationally assisted' gravitationally confined detonation (GCD) model of Type Ia supernovae. This model is analogous to the previous GCD model reported in Jordan et al.; however, the chosen initial conditions produce a substantively different detonation mechanism, resulting from a larger energy release during the deflagration phase. The resulting final kinetic energy and {sup 56}Ni yields conform better to observational values than is the case for the 'classical' GCD models. In the present class of models, the ignition of a deflagration phase leads to a rising, burning plume of ash. The ash breaks out of the surface of the white dwarf, flows laterally around the star, and converges on the collision region at the antipodal point from where it broke out. The amount of energy released during the deflagration phase is enough to cause the star to rapidly expand, so that when the ash reaches the antipodal point, the surface density is too low to initiate a detonation. Instead, as the ash flows into the collision region (while mixing with surface fuel), the star reaches its maximally expanded state and then contracts. The stellar contraction acts to increase the density of the star, including the density in the collision region. This both raises the temperature and density of the fuel-ash mixture in the collision region and ultimately leads to thermodynamic conditions that are necessary for the Zel'dovich gradient mechanism to produce a detonation. We demonstrate feasibility of this scenario with three three-dimensional (3D), full star simulations of this model using the FLASH code. We characterized the simulations by the energy released during the deflagration phase, which ranged from 38% to 78% of the white dwarf's binding energy. We show that the necessary conditions for detonation are achieved in all three of the models.

79 ASTRONOMY AND ASTROPHYSICS↗

In Situ Observations and Sampling of Volcanic Emissions with Unmanned Aircraft: A NASA/UCR Case Study at Turrialba Volcano, Costa Rica

Burgeoning new technology in the design and development of robotic aircraft-unmanned aerial vehicles (UAVs)-presents unprecedented opportunities for the volcanology community to observe, measure, and sample eruption plumes and drifting volcanic clouds in situ. While manned aircraft can sample dilute parts of such emissions, demonstrated hazards to air breathing, and most particularly turbine, engines preclude penetration of the zones of highest ash concentrations. Such areas within plumes are often of highest interest with respect to boundary conditions of applicable mass-loading retrieval models, as well as Lagrangian, Eulerian, and hybrid transport models used by hazard responders to predict plume trajectories, particularly in the context of airborne hazards. Before the 2010 Ejyafyallajokull eruption in Iceland, ICAO zero-ash-tolerance rules were typically followed, particularly for relatively uncrowded Pacific Rim airspace, and over North and South America, where often diversion of aircraft around ash plumes and clouds was practical. The 2010 eruption in Iceland radically changed the paradigm, in that critical airspace over continental Europe and the United Kingdom were summarily shut by local civil aviation authorities and EURO CONTROL. A strong desire emerged for better real-time knowledge of ash cloud characteristics, particularly ash concentrations, and especially for validation of orbital multispectral imaging. UAV platforms appear to provide a viable adjunct, if not a primary source, of such in situ data for volcanic plumes and drifting volcanic clouds from explosive eruptions, with prompt and comprehensive application to aviation safety and to the basic science of volcanology. Current work is underway in Costa Rica at Turrialba volcano by the authors, with the goal of developing and testing new small, economical UAV platforms, with miniaturized instrument payloads, within a volcanic plume. We are underway with bi-monthly deployments of tethered SO2-sondes and are in the planning stages for the deployment of the SIERRA UAV to our site in March 2013. We will be conducting in situ observations simultaneously with ASTER orbital multispectral TIR data acquisitions, in order to compare in situ measurements with estimates of SO2 mass loading and dispersion derived from ASTER data. Though small UAVs are now being considered for use in active volcanic areas for in situ sampling of emissions (e.g., efforts by our group, and by our colleagues at the INGV in Italy and the Applied Science University in Dusseldorf, Germany, and others in the United Kingdom and Iceland), and also for remote sensing, much more needs to be done in the way of instrument development, and in developing small UAVs for both low altitude (tropospheric) and high altitude (stratospheric) applications. In particular, the development of all weather and day/night operational flight capabilities in close proximity to hazardous topography is crucial to a truly responsive volcano in situ measurement system. Finally, it is imperative that national civil aviation authorities recognize the unique benefits of such platforms. It is important that authorities understand that severely restricting or not deploying such tools in airspace over restless volcanoes or within eruption plumes, ostensibly because of the perceived (small) risk that such unmanned aircraft pose to manned air operations, itself poses a bigger transcendental risk to proximal populations and particularly to the aviation community, itself.

Volcanic Ash Advisory Centers (VAACs)↗

Kinetic modeling of the formation and growth of inorganic nano-particles during pulverized coal char combustion in O 2 /N 2 and O 2 /CO 2 atmospheres

In this formation of nano-particles during coal char combustion, the vaporization of inorganic components in char and the subsequent homogeneous particle nucleation, heterogeneous condensation, coagulation, and coalescence play decisive roles. Furthermore, conventional measurements cannot provide detailed information on the dynamics of nano-particle formation and evolution, In this study, a sophisticated intrinsic char kinetics model that considers ash effects (including ash film formation, ash dilution, and ash vaporization acting in tandem), both oxidation and gasification by CO 2 and H 2 O, homogeneous particle nucleation, heterogeneous vapor condensation, coagulation, and and coalescence mechanisms is developed and used to compare the temporal evolution of the number and size of nano-particles during coal char particle combustion as a function of char particle size, ash content, and oxygen content in O 2 /N 2 and O 2 /CO 2 atmospheres .

01 COAL, LIGNITE, AND PEAT↗

Liberation and release of rare earth minerals from Middle Kittanning, Fire Clay, and West Kentucky No. 13 coal sources

Here, a laboratory REE release test procedure was designed to better understand the association and liberation characteristics of rare earth elements (REEs) from coal-based material, such as coal middlings and refuse. For this particular study, three samples of mixed-phase, middling material was collected from three coal preparation plants operating in three different coal basins and coal seams, namely Fire Clay, Middle Kittanning, and West Kentucky #13. In these release tests, the mixed-phase material was first ground in a laboratory ball mill for a designated amount of time and subsequently decarbonized using staged flotation. The REE content of the high ash tailings and low ash concentrate was determined, and the process was repeated for various target grind sizes down to the micron range. The results indicate that smaller grind sizes produce increased REE concentrations in the high ash tailings, and this result is predominantly driven by the increased ash content in the decarbonized tailings. The grinding characteristics of the Fire Clay coal source showed that more energy is needed to achieve the desired particle size reduction; however further size reduction of this sample resulted in a significantly higher ash and REE content in the tailings material due to improved liberation. For the Middle Kittanning and West Kentucky #13 sources, the grinding and release data indicates that the mineral matter is liberated at a coarser particle size, and micronizing the coals only produces marginal improvements in rare earth mineral liberation and recovery.

01 COAL, LIGNITE, AND PEAT↗

Burn Intensity Drives the Alteration of Phenolic Lignin to (Poly) Aromatic Hydrocarbons as Revealed by Pyrolysis Gas Chromatography–Mass Spectrometry (Py-GC/MS)

High-intensity wildfires alter the chemical composition of organic matter, which is expected to be distinctly different from low-intensity prescribed fires. In this study, we used pyrolysis gas chromatography/mass spectrometry (Py-GC/MS), in conjunction with solid-state 13 C nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectroscopy, to assess chemical alterations from three wildfires and a long-term frequent prescribed fire site. Our results showed that black ash formed under moderate intensity burns contained less aromatic (ArH), polyaromatic hydrocarbon (PAH), and nitrogen-containing compounds (Ntg) but more lignin (LgC) and phenol compounds (PhC), compared to white ash formed under high intensity burns. Both 13 C NMR and FT-IR confirmed a higher relative percentage of carboxyl carbon in white ash, indicating the potential for higher water solubility and more mobile carbon, relative to black ash. Compared to wildfires, ash from low-intensity prescribed fire contained less ArH, PAH, and Ntg and more LgC and PhC. Controlled laboratory burning trials indicated that organic matter alteration was sensitive to the burn temperature, but not related to the fuel type (pine vs fir) nor oxygen absence/presence at high burn temperatures. This study concludes that higher burn temperatures resulted in higher (poly)aromatic carbon/nitrogen and lower lignin/phenol compounds.

54 ENVIRONMENTAL SCIENCES↗

In-situ biogas upgrading during anaerobic digestion of food waste amended with walnut shell biochar at bench scale

Here, a modified version of an in-situ CO 2 removal process was applied during AD of food waste with two types of walnut shell biochar (WSB) at bench-scale under batch operating mode. Compared to the coarse WSB, the fine WSB has a higher ash content (43 vs. 36 wt%) and higher concentrations of calcium (31 vs. 19 wt% of ash), magnesium (8.4 vs. 5.6 wt% of ash) and sodium (23.4 vs. 0.3 wt% of ash), but a lower potassium concentration (0.2 vs. 40% wt% of ash). The 0.96 - 3.83 g biochar (g VS added ) -1 fine WSB amended digesters produced biogas with 77.5-98.1% CH 4 content by removing 40-96% of the CO 2 compared to the control digesters at mesophilic and thermophilic temperature conditions. In a direct comparison at 1.83 g biochar (g VS added ) -1 , the fine WSB amended digesters (85.7% CH 4 content and 61% CO 2 removal) outperformed the coarse WSB amended digesters (78.9% CH 4 content and 51% CO 2 removal). Biochar addition also increased alkalinity as CaCO3 from 2,800 mg L -1 in the control digesters to 4,800-6,800 mg L -1 providing process stability for food waste AD.

09 BIOMASS FUELS↗

Characterization of Advanced Preprocessed Materials (Hydrothermal)

The initial hydrothermal treatment parameters did not achieve the proposed objective of this effort; the reduction of intrinsic ash in the corn stover. However, liquid fractions from the 170°C treatments was indicative that some of the elements routinely found in the ash that negatively impact the biochemical conversion processes had been removed. After reviewing other options for facilitating ash removal, sodium-citrate (chelating agent) was included in the hydrothermal treatment process, resulting in a 69% reduction in the physiological ash. These results indicated that chelation –hydrothermal treatment is one possible approach that can be utilized to reduce the overall ash content of feedstock materials and having a positive impact on conversion performance.

09 BIOMASS FUELS↗