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At least 595 records · Page 33

Recycle of Inorganic Nutrients for Hydroponic Crop Production Following Incineration of Inedible Biomass

Recovery of resources from waste streams is essential for future implementation and reliance on a regenerative life support system. The major waste streams of concern are from human activities and plant wastes. Carbon, water and inorganics are the primary desired raw materials of interest. The goal of resource recovery is maintenance of product quality to insure support of reliable and predictable levels of life support function performance by the crop plant component. Further, these systems must be maintained over extended periods of time, requiring maintenance of nutrient solutions to avoid toxicity and deficiencies. Today, reagent grade nutrients are used to make nutrient solutions for hydroponic culture and these solutions are frequently changed during the life cycle or sometimes managed for only one crop life cycle. The focus of this study was to determine the suitability of the ash product following incineration of inedible biomass as a source of inorganic nutrients for hydroponic crop production. Inedible wheat biomass was incinerated and ash quality characterized. The incinerator ash was dissolved in adequate nitric acid to establish a consistent nitrogen concentration in all nutrient solution treatments. Four experimental nutrient treatments were included: control, ash only, ash supplemented to match control, and ash only quality formulated with reagent grade chemicals. When nutrient solutions are formulated using only ash following-incineration of inedible biomass, a balance in solution is established representing elemental retention following incineration and nutrient proportions present in the original biomass. The resulting solution is not identical to the control. This imbalance resulted in suppression of crop growth. When the ash is supplemented with nutrients to establish the same balance as in the control, growth is identical to the control. The ash appears to carry no phytotoxic materials. Growth in solution formulated with reagent grade chemicals but matching the quality of the ash only treatment resulted in growth similar to that of the ash only treatment. The ash product resulting from incineration of inedible biomass appears to be a suitable form for recycle of inorganic nutrients to crop production.

Bubenheim, David L.↗

CO.sub.2 utilization in electrochemical systems

A process for treating fly ash to render it highly usable as a concrete additive. A quantity of fly ash is obtained that contains carbon and which is considered unusable fly ash for concrete based upon foam index testing. The fly ash is mixed with a quantity of spray dryer ash (SDA) and water to initiate a geopolymerization reaction and form a geopolymerized fly ash. The geopolymerized fly ash is granulated. The geopolymerized fly ash is considered usable fly ash for concrete according to foam index testing. The geopolymerized fly ash may have a foam index less than 40%, and in some cases less than 20%, of the foam index of the untreated fly ash. An optional alkaline activator may be mixed with the fly ash and SDA to facilitate the geopolymerization reaction. The alkaline activator may contain an alkali metal hydroxide, carbonate, silicate, aluminate, or mixtures thereof.

36 MATERIALS SCIENCE↗

Advancing the Renewable Industry in Minnesota

This report deals with seven topics: 1. "Utilizing Ash Wastes as a Nutrient Source for Corn": As forms of gasification and combustion grow in the area of renewable energy in Minnesota the question arises regarding the utilization/application of the ash co product produced from these processes. Currently there are four facilities in Minnesota producing an ash co product (three ethanol facilities and one combusting biomass to produce energy). These ash wastes are generated from using ethanol by-products as a fuel or heating source for fermentation. Other ash wastes from agricultural sources include turkey litter ash. When applied to agricultural fields, ash wastes can be a source of nutrients for agricultural crops. Chemical analyses of ash wastes vary, but 200 to 300 lb of P 2 O 5 and K 2 O per ton of ash is typical. The value of ash wastes as a fertilizer has increased because commercial fertilizer prices have increased significantly over the last few years. Specifically: Compaction/Agglomeration research- Research included development of an appropriate product for use in current delivery systems by densifying the ash into the form of pellets or briquettes which may reduce fertilizer input cost to farmers. The initiative addresses the use of phosphorus and potassium from co-firing or gasification processes as a fertilizer source. 2. "Use of Glycerol as a Corn Replacement in Calf Starter Diets": Glycerol is a sugar alcohol by-product of bio-diesel production. About 1 gallon of glycerin is produced for every 10 gallons of bio-diesel of which the glycerol content may vary between 63 and almost 100%. There is some uncertainty of the exact energy value of glycerol as an ingredient for animal feed but it has been successfully used as a replacement for corn up to 10% of the diet dry matter for lactating dairy cows. There is a lack of information on incorporating glycerol into diets for pre- and post weaned dairy heifer calves which has the potential to expand the market for this by product. Preliminary work at SROC indicates that there are no palatability problems using glycerol up to 6% of the mix in post weaning pellets for group fed dairy heifers. 3. "Intervention Strategies for Reduction of Food-borne Pathogens in Cattle Fed Ethanol Byproducts": Ethanol plants and cattle producers create a symbiotic relationship: The use of wet and dry distiller’s grains in beef cattle rations provides significant improvement in overall feedlot performance for many producers in Minnesota and the Upper Midwest. Distiller’s grain is the coproduct that remains following the distillation of ethanol. It may be dehydrated to produce dried distiller’s grain (DDG) which is then commonly used as livestock feed. The use of distiller’s grains in livestock rations has been the subject of numerous research projects over the past ten years. Recently published research data conducted at Kansas State University (K-State) has created controversy over the feeding of distiller’s grains in beef cattle rations. The research indicates that cattle fed distiller’s grain may have an increased probability of Escherichia coli O157 in their hindgut. Specifically: This research assessment was a two part project consisting of feeding trials conducted at the University of Minnesota and an intervention study conducted at Kansas State University. This report is the Kansas State University portion. This report is a task-level final technical report. 4. "Impact of Distillers' Grains and Glycerin on Cattle Fecal Shedding of Escherichia coli O157:H7" 5. "Study Assessing the Opportunities and Potential of Soybean Based Products and Technologies": Based on demand/market potential, economic feasibility, stage of development and strength of institutional support, Informa Economics, Inc. ("Informa") narrowed down a list of more than 100 emerging soybean products and to 8 of the most promising for soybean, considered to have the greatest potential to add significant value to Minnesota's soybean commodity production. However, as with the potential of any biobased product or technology, the development of these emerging soybean products and technologies will be heavily reliant on future market price environments (especially for petroleum) and government policies. This report identifies what the contractor believes are the top 8 products and technologies for soybeans at the time of publishing. 6. "Study Assessing the Opportunities and Potential of Corn-Based Products and Technologies": Based on demand/market potential, economic feasibility, stage of development and strength of institutional support, Informa Economics, Inc. ("Informa") narrowed down a list of more than 100 emerging corn products and technologies to 8 of the most promising for corn, considered to have the greatest potential to add significant value to Minnesota's corn commodity production. However, as with the potential of any biobased product or technology, the development of these emerging corn products and technologies will be heavily reliant on future market price environments (especially for petroleum) and government policies. This report identifies what the contractor believes are the top 8 products and technologies for corn at the time of publishing. 7. "Distributed Power Generation Technology (Roseau Gasification)."

09 BIOMASS FUELS↗

Expectation vs. Reality: The Unexpected Abrasive Nature of Biomass Feedstocks

Early reports coming from stover-fed biorefineries have indicated that the feedstock is damaging equipment due to wear caused by the feedstock. It is suspected that biomass ash, both physiological and introduced ash, is responsible for the accelerated rates of wear being observed. Biomass ash can contain several different types of minerals, some of which are very hard. To simulate biomass wear on material handling equipment, a sandblaster was modified to shoot ground biomass at a metal coupon. The angle of impingement was set at 90°, 65.5°, or 45° by rotating the coupon. The coupon was weighed before and after shooting a known quantity of biomass to determine mass loss, and the surface characteristics of the blasted coupon were analyzed using laser microscopy. Coupon mass loss was positively correlated with ash content. Coupons blasted with loblolly pine (0.58% ash) lost 2.2mg±0.3mg per kg biomass shot, while high-ash stover (12.56% ash) coupons lost 104.7±2.1mg per kg biomass shot. Coupons blasted with NaOH leached low-ash stover (4.01% ash) lost 10.1±2.7mg per kg biomass shot. Decreasing the angle of impingement (90° to 45°) increased mass loss by about 17%. The concentrations of soil elements (silicon, aluminum, iron, titanium, sodium) were positively correlated with coupon mass loss, indicating that introduced ash is likely the primary source of wear to equipment. Future studies will identify mineral forms of ash present in biomass to further characterize biomass wear properties and to identify strategies to improve biomass quality.

09 BIOMASS FUELS↗

Constitution of Drop-Tube-Generated Coal Chars from Vitrinite- and Inertinite-Rich South African Coals

The structural transformations of coal and the resultant char morphologies are strongly dependent on the initial structure and degree of thermoplasticity achieved during coal-to-char transition. These are a function of petrographic composition, rank, particle size, and heating rate and strongly affect combustion behavior. This study compares the devolatilization and subsequent combustion behavior of an inertinite-rich (87.7% dmmf) and a vitrinite-rich (91.8% dmmf) South African coal, wet-screened to a narrow particle size distribution of 200 x 400 mesh. Pyrolysis chars were generated under rapid-heating conditions (104-105 °C/s) in a drop-tube reactor to closely resemble chars generated in pulverized combustion conditions. The inertinite-rich coal took ~ 400 ms to devolatilize in the drop-tube, compared to only ~ 240 ms for the vitrinite-rich sample. The chemical and physical structure (the constitution) of the chars were investigated through a range of chemical, physical, and optical characteristics including the maceral differences, and high ash yields. To evaluate the combustion reactivity non-isothermal burn-out profiles were obtained through thermogravimetrical analyses (TGA) in air. The vitrinite-rich char had on average 20% higher reaction rates than the inertinite-rich char under the various combustion conditions. The char samples were de-ashed with HCl and HF acid which resulted in an increase in combustion reactivity. The maximum reaction rate of the high-ash (36% ash yield) inertinite-rich char increased with 80% after de-ashing. While the vitrinite-rich char with an ash yield of 15%, had a 20% increase in reactivity after de-ashing. The ash acted as a barrier, and the removal of ash most likely increased the access to reactive surface area. The chemical and physical structures of the chars were characterized through a range of different analytical techniques to quantify the factors contributing to reactivity differences. The morphologies of the chars were characterized with SEM and optical microscopy, while quantitative information on the ordered nature of chars was obtained through XRD on de-ashed chars. The inertinite-rich coal experienced limited fluidity during heat-treatment, resulting in slower devolatilization, limited growth in crystallite height (11.8 to 12.6Å), only rounding of particle edges, and producing > 40% of mixed-dense type chars. The vitrinite-char showed more significant structural transformations; producing mostly (80%) extensively swollen crassisphere, tenuisphere, and network-type chars, and XRD showed a large increase in crystallite height (4.3 to 11.7Å). Nitrogen adsorption and small-angle X-ray scattering (SAXS) were utilized to compare the nitrogen surface areas and pore size distributions. Both chars were mostly mesoporous but the inertinite-rich char had double the average pore size, which also resulted in a larger nitrogen surface area since nitrogen can only access surface areas in larger pores. The BET surface area was 3.9 and 2.7 m2/g for the inertinite- and vitrinite-rich chars respectively. SAXS data showed that the vitrinite-rich char had 60% higher frequencies of pores in the micropore range. Helium porosimetry indicated that the inertinite-rich coal and resultant char had higher densities than the vitrinite coal and char; 1.6 and 2.0 g/cm3, compared to 1.3 and 1.9 g/cm3 (dry basis). Non-isothermal TGA burnout profiles showed the inertinite-rich char had a burnout temperature of 680°C, slightly higher than the vitrinite-rich char’s 650 °C. This, along with the peak shape and position in the burnout profiles indicate that the vitrinite-rich char has a higher reactivity. The higher reactivity is due to a combination of factors likely including less organization, grater porosity and access to the reactive site, less ash blocking, and char morphology differences.

Combustion↗

Co-gasification of municipal solid waste and material recovery in a large-scale gasification and melting system

Highlights: Black-Right-Pointing-Pointer This study evaluates the effects of co-gasification of MSW with MSW bottom ash. Black-Right-Pointing-Pointer No significant difference between MSW treatment with and without MSW bottom ash. Black-Right-Pointing-Pointer PCDD/DFs yields are significantly low because of the high carbon conversion ratio. Black-Right-Pointing-Pointer Slag quality is significantly stable and slag contains few hazardous heavy metals. Black-Right-Pointing-Pointer The final landfill amount is reduced and materials are recovered by DMS process. - Abstract: This study evaluates the effects of co-gasification of municipal solid waste with and without the municipal solid waste bottom ash using two large-scale commercial operation plants. From the viewpoint of operation data, there is no significant difference between municipal solid waste treatment with and without the bottom ash. The carbon conversion ratios are as high as 91.7% and 95.3%, respectively and this leads to significantly low PCDD/DFs yields via complete syngas combustion. The gross power generation efficiencies are 18.9% with the bottom ash and 23.0% without municipal solid waste bottom ash, respectively. The effects of the equivalence ratio are also evaluated. With the equivalence ratio increasing, carbon monoxide concentration is decreased, and carbon dioxide and the syngas temperature (top gas temperature) are increased. The carbon conversion ratio is also increased. These tendencies are seen in both modes. Co-gasification using the gasification and melting system (Direct Melting System) has a possibility to recover materials effectively. More than 90% of chlorine is distributed in fly ash. Low-boiling-point heavy metals, such as lead and zinc, are distributed in fly ash at rates of 95.2% and 92.0%, respectively. Most of high-boiling-point heavy metals, such as iron and copper, are distributed in metal. It is also clarified that slag is stable and contains few harmful heavy metals such as lead. Compared with the conventional waste management framework, 85% of the final landfill amount reduction is achieved by co-gasification of municipal solid waste with bottom ash and incombustible residues. These results indicate that the combined production of slag with co-gasification of municipal solid waste with the bottom ash constitutes an ideal approach to environmental conservation and resource recycling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Generation and distribution of PAHs in the process of medical waste incineration

Highlights: ► PAHs generation and distribution features of medical waste incineration are studied. ► More PAHs were found in fly ash than that in bottom ash. ► The highest proportion of PAHs consisted of the seven most carcinogenic ones. ► Increase of free oxygen molecule and burning temperature promote PAHs degradation. ► There is a moderate positive correlation between total PCDD/Fs and total PAHs. - Abstract: After the deadly earthquake on May 12, 2008 in Wenchuan county of China, several different incineration approaches were used for medical waste disposal. This paper investigates the generation properties of polycyclic aromatic hydrocarbons (PAHs) during the incineration. Samples were collected from the bottom ash in an open burning slash site, surface soil at the open burning site, bottom ash from a simple incinerator, bottom ash generated from the municipal solid waste (MSW) incinerator used for medical waste disposal, and bottom ash and fly ash from an incinerator exclusively used for medical waste. The species of PAHs were analyzed, and the toxicity equivalency quantities (TEQs) of samples calculated. Analysis results indicate that the content of total PAHs in fly ash was 1.8 × 10{sup 3} times higher than that in bottom ash, and that the strongly carcinogenic PAHs with four or more rings accumulated sensitively in fly ash. The test results of samples gathered from open burning site demonstrate that Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT) and other PAHs were inclined to migrate into surrounding environment along air and surface watershed corridors, while 4- to 6-ring PAHs accumulated more likely in soil. Being consistent with other studies, it has also been confirmed that increases in both free oxygen molecules and combustion temperatures could promote the decomposition of polycyclic PAHs. In addition, without the influence of combustion conditions, there is a positive correlation between total PCDD/Fs and total PAHs, although no such relationship has been found for TEQ.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of Rare Earth Element Minerals in Coal Utilization Byproducts

The United States currently produces over 100 million tons of coal utilization byproducts (CUB) per year in the form of fly ash, bottom ash, slag, and flue gas (American Coal Ash Association (ACCA), 2015). But this “waste material” also contains potentially useful levels of rare earth elements (REE). Rare earth elements are crucial for many existing and emerging technologies, but the U.S. lacks a domestic, sustainable REE source. Our project explored the possibility of developing a supply of REEs for U.S. technologies by extracting REEs from CUBs. This work offers the potential to reduce our dependence on other countries for supply of these critical elements (NETL, REE 2016 Project Portfolio). Geologic and diagenetic history, industrial preparation methods, and the specific combustion process all play major roles in the composition of CUB. During combustion, inorganic mineral phases of coal particles are fluidized at temperatures higher than 1400oC, so inorganic mineral materials are oxidized, fused, disintegrated, or agglomerated into larger spherical and amorphous (non-crystalline) particles. The original mineralogy of the coal-containing rock and heating/cooling of the material significantly affects the composition and morphology of the particles in the combustion byproduct (Kutchko and Kim, 2006). Thus, different types of coal/refuse/ash must be characterized to better understand mineral evolution during the combustion process. Our research focused on developing a working model to address how REE minerals behave during the combustion process: this research should help determine the most effective engineering methods for extracting REEs from CUBs. We used multimodal imaging and image processing techniques to characterize six rock and ash samples from different coal power plants with respect to morphology, grain size, presence of mineral phases, and elemental composition. The results of these characterization activities provided thresholds for realizing the occurrence of REE mineral phases in CUB and allowed us to calculate structural and volumetric estimates of REE. Collectively, the rock and coal ash samples contained minerals such as quartz, kaolinite, muscovite/illite, iron oxide (as hematite or magnetite), mullite, and clinochlore. Trace minerals included pyrite, zircon, siderite, rutile, diopside, foresterite, gypsum, and barite. We identified REE phosphate minerals monazite (Ce,La,Nd,Th)(PO 4 ,SiO 4 ), xenotime (YPO 4 ,SiO 4 ), and apatite (Ca 5 (PO 4 ) 3 (F,Cl,OH) via SEM and electron microprobe analysis: these materials generally occurred as 1-10 μm-long crystals in the rock and ash samples. As has been shown in other studies, amorphous material-aluminosilicate glass or iron oxyhydroxide-are the major components of coal fly and bottom ash. Trace amounts of amorphous calcium oxide and mixed element (e.g., Al-Si-Ca-Fe) slag are also present. Quartz, mullite, hematite, and magnetite are the crystalline phases present. We found that REEs are present as monomineralic grains dispersed within the ash, as well as fused to or encapsulated by amorphous aluminosilicate glass particles. Monazite and xenotime have relatively high melting points (>1800 °C) compared to typical combustion temperatures; our observations indicate that the REE-phosphates, which presumably contribute a large percentage of REE to the bulk ash REE pool, as measured by mass spectroscopy, are largely unaltered by the combustion. Our study shows that conventional coal combustion processes sequester REE minerals into aluminosilicate glass phases, which presents a new engineering challenge for extracting REE from coal ash. The characterization work summarized in this report provides a semi-quantitative assessments of REE in coal-containing rock and CUB. The data we obtained from 2- and 3-D imaging, elemental mapping, volumetric estimates, and advanced high-resolution pixel classification successfully identified the different mineral phases present in CUB. Further, our characterization results can guide techniques for extracting REEs from CUB, or other geologic and engineered materials. Whilst, interpretations will inform future REE separation and extraction techniques and technologies practical for commercial utilization of combustion byproducts generated by power plants.

01 COAL, LIGNITE, AND PEAT↗

Diesel Particulate Filter Durability Performance Comparison Using Metals Doped B20 vs. Conventional Diesel Part II: Chemical and Microscopic Characterization of Aged DPFs

This project's objective was to generate experimental data to evaluate the impact of metals doped B20 on diesel particle filter (DPF) ash loading and performance compared to that of conventional petrodiesel. The effect of metals doped B20 vs. conventional diesel on a DPF was quantified in a laboratory controlled accelerated ash loading study. The ash loading was conducted on two DPFs - one using ULSD fuel and the other on B20 containing metals dopants equivalent to 4 ppm B100 total metals. Engine oil consumption and B20 metals levels were accelerated by a factor of 5, with DPFs loaded to 30 g/L of ash. Details of the ash loading experiment and on-engine DPF performance evaluations are presented in the companion paper (Part I). The DPFs were cleaned, and ash samples were taken from the cleaned material. X-ray Fluorescence (XRF), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Diffraction (XRD) were conducted on the ash samples. Core samples were taken from the cleaned DPF and were subjected to scanning electron microscope energy dispersive x-ray spectroscopy (SEM-EDS) and XRF analysis. A comparison of the data from the two DPFs is presented. The XRD and XPS analysis showed that the compounds present in the ash from the two DPFs were nearly identical, though differing in concentrations. CaSO4 was the biggest component of the ash from both DPFs. The metals doped B20 fuel resulted in ash with similar characteristics to that deposited by the lube oil and did not appear to have any deleterious physical effects on the DPF substrate (did not penetrate the substrate).

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗

A Brief Review of Viscosity Models for Slag in Coal Gasification

Many researchers have defined the phenomenon of 'slagging' as the deposition of ash in the radiative section of a boiler, while 'fouling' refers to the deposition of ash in the convective-pass region. Among the important parameters affecting ash deposition that need to be studied are ash chemistry, its transport, deposit growth, and strength development; removability of the ash deposit; heat transfer mechanisms; and the mode of operation for boilers. The heat transfer at the walls of a combustor depends on many parameters including ash deposition. This depends on the processes or parameters controlling the impact efficiency and the sticking efficiency. For a slagging combustor or furnace, however, the temperatures are so high that much of the coal particles are melted and the molten layer, in turn, captures more particles as it flows. The main problems with ash deposition are reduced heat transfer in the boiler and corrosion of the tubes. Common ways of dealing with these issues are soot blowing and wall blowing on a routine basis; however, unexpected or uncontrolled depositions can also complicate the situation, and there are always locations inaccessible to the use of such techniques. Studies have indicated that slag viscosity must be within a certain range of temperatures for tapping and the membrane wall to be accessible, for example, between 1300 C and 1500 C, the viscosity is approximately 25 Pa {center_dot} s. As the operating temperature decreases, the slag cools and solid crystals begin to form. In such cases the slag should be regarded as a non-Newtonian suspension, consisting of liquid silicate and crystals. A better understanding of the rheological properties of the slag, such as yield stress and shear-thinning, are critical in determining the optimum operating conditions. To develop an accurate heat transfer model in any type of coal combustion or gasification process, the heat transfer and to some extent the rheological properties of ash and slag, especially in high-temperature environments need to be understood and properly modeled. The viscosity of slag and the thermal conductivity of ash deposits are among two of the most important constitutive parameters that need to be studied. The accurate formulation or representations of the (transport) properties of coal (and biomass for co-firing cases) present a special challenge of modeling efforts in computational fluid dynamics applications. In this report, we first provide a brief review of the various approaches taken by different researchers in formulating or obtaining a slag viscosity model. In general, these models are based on experiments. Since slag behaves as a non-linear fluid, we discuss the constitutive modeling of slag and the important parameters that must be studied.

01 COAL, LIGNITE, AND PEAT↗

Degradation of Thermal Barrier Coatings from Deposits and Its Mitigation

Ceramic thermal barrier coatings (TBCs) used in gas-turbine engines afford higher operating temperatures, resulting in enhanced efficiencies and performance. However, in the case of syngas-fired engines, fly ash particulate impurities that may be present in syngas can melt on the hotter TBC surfaces and form glassy deposits. These deposits can penetrate the TBCs leading to their failure. In experiments using lignite fly ash to simulate these conditions we show that conventional TBCs of composition 93wt% ZrO 2 + 7wt% Y 2 O 3 (7YSZ) fabricated using the air plasma spray (APS) process are completely destroyed by the molten fly ash. The molten fly ash is found to penetrate the full thickness of the TBC. The mechanisms by which this occurs appear to be similar to those observed in degradation of 7YSZ TBCs by molten calcium-magnesium-aluminosilicate (CMAS) sand and by molten volcanic ash in aircraft engines. In contrast, APS TBCs of Gd 2 Zr 2 O 7 composition are highly resistant to attack by molten lignite fly ash under identical conditions, where the molten ash penetrates ~25% of TBC thickness. This damage mitigation appears to be due to the formation of an impervious, stable crystalline layer at the fly ash/Gd 2 Zr 2 O 7 TBC interface arresting the penetrating molten-fly-ash front. Additionally, these TBCs were tested using a rig with thermal gradient and simultaneous accumulation of ash. Modeling using an established mechanics model has been performed to illustrate the modes of delamination, as well as further opportunities to optimize coating microstructure. Transfer of the technology was developed in this program to all interested parties.

20 FOSSIL-FUELED POWER PLANTS↗

Air gasification of biogas-derived digestate in a downdraft fixed bed gasifier

Highlights: • Air gasification of digestate with high ash content was studied in detail. • Compared to original biomass, less tar was observed in digestate gasification process. • Improved molar ratio of H{sub 2}/CO potential for chemical synthesis was gained at 800 °C. • The by-products (biochar and ash) can be land applied as fertilizer. - Abstract: Digestate is a byproduct from biomass anaerobic digestion process. Gasification of dried digestate to produce gasesous product might be a promising route. In this work, air gasification of digestate with high ash content was performed in a downdraft fixed bed gasifier at temperature varying from 600 °C to 800 °C and air equivalence ratio (ER) ranging from 0.25 to 0.30. The ash melting properties were firstly detected by the Intelligent Ash Melting Point Test, and the by-products (biochar and ash) were analyzed. The results showed that no ash slagging was observed and therefore it is feasible to operate digestate gasification under 800 °C and ER ranging from 0.25 to 0.30. High temperature favored gas production, 800 °C is proposed for digestate gasification in the present study. ER with a medium value improved gas quality and cold gas efficiency (CGE), and the optimal LHV of 4.78 MJ/N m{sup 3} and CGE of 67.01% were obtained with ER of 0.28. High ER favored the increase of gas yield and decrease of tar concentration, and the optimal gas yield of 2.15 N m{sup 3}/kg and tar concentration of 1.61 g/N m{sup 3} were achieved with ER of 0.30. Improved molar ratio of H{sub 2}/CO varying from 1.03 to 1.08 was obtained at 800 °C, indicating gaseous product has the potential for chemical synthesis processes (1 < H{sub 2}/CO < 2). The byproducts biochar and ash could be applied on land as fertilizer.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermal treatment of solid residues from WtE units: A review

Highlights: • We review the thermal treatment methods for ashes and residues from WtE plants. • We review the results from extensive laboratory work on vitrification, melting and vaporization of ash. • We analyze the results from the extensive patent literature on thermal treatment. • We review industrial concepts for thermal treatment of ash. - Abstract: Thermal treatment methods of bottom ash, fly ash and various types of APC (air pollution control) residues from waste-to-energy plants can be used to obtain environmentally stable material. The thermal treatment processes are meant to reduce the leachability of harmful residue constituents, destroy toxic organic compounds, reduce residue volume, and produce material suitable for utilization. Fly ash and APC residues often have high levels of soluble salts, particularly chlorides, metals such as cadmium, lead, copper and zinc, and trace levels of organic pollutants such as dioxins and furans. Different thermal treatment methods can be used to either decompose or stabilize harmful elements and compounds in the ash, or separate them from the ash to get a material that can be safely stored or used as products or raw materials. In the present paper, thermal treatment methods, such as sintering, vitrification, and melting have been reviewed. In addition to a review of the scientific literature, a survey has been made of the extensive patent literature in the field.

54 ENVIRONMENTAL SCIENCES↗

The cost of improved quality feedstocks: How good is "good enough"?

Not all biomass is created equal, and the low quality of many sources of biomass precludes their use in many conversion processes. As we work to achieve the Billion Ton vision, more of these low quality biomass sources will need to be integrated into the feedstock supply chain and their quality issues must be dealt with to make them usable. Many of these feedstocks suffer from elevated concentrations of ash, which can interfere with thermochemical conversion reactions, catalysts, and conversion products. In this study, the cost of incremental reductions in ash concentrations was investigated in three potential biomass feedstocks: logging residues, corn stover, and construction and demolition waste. Air classification (AC) is a mechanical separations method that has been shown to concentrate ash into the lighter fractions, and ash content can be decreased by discarding these fractions. However, the cost of disposal and replacement of the discarded fraction make this strategy unaffordable (= $11.04 ton-1). Alternatively, the lightest AC fraction can be acid-leached to remove ash and recombined with the remainder of the sample. Using this approach, ash content can be decreased in logging residues from 1.1% to 0.83% for $1.95 ton-1. Ash concentrations could be further decreased with the combined strategy to 0.67% (a 40% reduction) for $3.88 per ton. This approach costs between $0.07 and $0.10 percent-1 ton-1 for the removal of up to 40% of the ash in the feedstock. This separate-treat-recombine method is an effective way to introduce lower quality feedstocks into the biomass feedstock supply chain.

09 BIOMASS FUELS↗

Radioactive Cs behavioral analysis in the incinerator at garbage incineration - 15031

About 4.7 kg cesium 137 (Cs{sup 137}) and about 0.3 kg cesium 134 (Cs{sup 134}) were released to the atmosphere around Fukushima Prefecture by the accident of the Tokyo Electric Power Company Fukushima Daiichi nuclear power plant accompanying the Great Earthquake in East Japan, which occurred on March 11, 2011. In the general incineration system which a local government owns, the garbage to which radioactive cesium (Cs) adhered (less than 8000 Bq/kg) is incinerate usual time. Before incinerating the garbage to which radioactive Cs has adhered, we did the preliminary test. As a result, if a very special case is removed, it is checked by measurement that radioactive Cs is not released from an exhaust stack of general incineration system. Our research is the elucidation of the mechanism by which radioactive Cs contained in garbage is not again released to the atmosphere with combustion gas. Concretely, we focus on the agglomeration of Cs molecular and deposition of radioactive Cs particles to the ash particle that occurs at the time of refuse incineration. And we formulated the simulation model for analyzing this phenomenon. It is presumed from an analysis result that radioactive Cs is not re-releasing by the following reasons. First, radioactive cesium hydroxide (Cs(OH)) adhering to garbage changes to radioactive cesium oxide (CsO{sub 2}) by an incineration process. Furthermore, it changes to radioactive cesium chloride (CsCl) via Cs. CsCl and Cs(OH) molecules deposit to the surrounding incineration ashes (main ashes and fly ash), in form of agglomerations. About fly ash, agglomeration and deposition are occurrence from a combustion chamber to bag filter via flue and temperature reducing tower. All radioactive Cs deposits to fly ash and main ash particles in this process. Therefore, radioactive Cs is not re-released to the atmosphere with combustion gas. Also about the main ashes, the same phenomenon occurs. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Rare earth minerals in a "no tonstein" section of the Dean (Fire Clay) coal, Knox County, Kentucky

The Dean (Fire Clay) coal in Knox County, Kentucky, does not contain the megascopically-visible ash-fall tonstein present in most other sections of the coal bed. Like the Fire Clay tonstein, a low-ash portion of the coal is enriched in rare earth elements (>2400ppm, on ash basis). In addition to kaolinite produced in the diagenesis of volcanic glass, transmission electron microscopy studies indicate the coal contains primary kaolinite, La Ce Nd Th monazite, barium niobate, native gold, and Fe Ni Cr spinels. The mineral assemblages, particularly the kaolinite-monazite association and its similarity to the tonsteins in coal to the east, demonstrate the coal was subject to the REE-enriched volcanic ash fall, apparently just at a more dilute level than at locations where the tonstein is present.

coal, rare earth, tonstein↗

Pilot plant reliability metrics for grinding and fast pyrolysis of woody residues

Here we report on the effects of loblolly pine residue variability on material throughput, pilot plant uptime, operator intervention, product yield, and product quality for grinding, fast pyrolysis, and hydrotreating operations. Preprocessing throughput using a hammer mill varied between 31-48% of nameplate capacity (5 tons/hr). Grinder overloads in the size reduction step were more prevalent for lower ash and higher moisture materials. Fast pyrolysis throughput varied between 57-72% of nameplate capacity (20 kg/hr) and bio-oil yields varied between 46-53% (feedstock carbon to oil, dry basis). During fast pyrolysis operations, downtime was caused by bridging in the feed and char removal systems and plugging in the condensation system. Cohesion of feedstock and char leading to system plugging was less frequent for higher ash feedstocks, and differences in condenser plugging behavior between high and low ash feedstocks were observed. The catalyst stability of the bio-oil stabilization step was strongly dependent on the sulfur content in the bio-oil, which was higher for the high-ash residue oils. Lower moisture content in the starting biomass was consistent with lower sulfur content in bio-oil. Yields and properties of hydrotreated fuel products showed minimal deference among the bio-oils.

Klinger, Jordan↗

Aragonite saturation horizon variability along North Pacific seamounts and implications for deep-sea coral reefs

The 2014 discovery of living deep-sea coral reefs along the Northwest Hawaiian Islands (NWHI) and lower Emperor Seamount Chain (ESC), despite the North Pacific’s shallow aragonite saturation horizon (ASH) and high CaCO3 dissolution rates, underscores the need to understand the local seawater chemistry that allows these reefs to persist. We investigated seawater carbonate chemistry using discrete samples along the NWHI and ESC from two cruises ~1 year apart (08/26/21 – 09/26/21, 09/09/22 – 10/24/22). Across the two cruises, ASH depth difference ranged from 15 to 77 m. Since the Pacific ASH shoals by 1–2 m yr?¹, this long-term trend cannot explain the magnitude of ASH change observed between cruises. Temperature-salinity plots similarly indicate no major shifts in intermediate water masses that could account for these changes. Instead, ASH depth variability was primarily governed by localized biogeochemical processes, namely changes in intermediate water respiration and CaCO3 dissolution. Indicators for dissolution (TA*) and respiration (AOU) suggest changes in ASH depth were driven by changes in dissolution at the northern- and southern-most sites, whereas respiration exerted stronger control at central sites. Combining 2021 and 2022 data with data from 2014 – 2019 (excluding 2018) revealed high interannual ASH variability, by as much as >200 m at one site. Deep-sea coral reefs across the NWHI and ESC currently reside close to the ASH depth and likely experience seasonal and interannual shifts between under- and supersaturation. As ocean acidification progresses however, persistent exposure to undersaturated seawater could further threaten these critical deep-sea ecosystems.

coral reefs↗