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At least 307 records · Page 17

R&D of Novel Materials for Animal Litters Using High Carbon Fly Ash Final Progress Report

This research program performed by Ceramatec may significantly increase the beneficial utilization of fly ash, and improve the overall performance of high quality animal litter products. Ceramatec has developed a novel high surface area material, which is capable of ammonia adsorption. High surface area zeolites when combined with agglomerated fly ash can significantly reduce the use of naturally mined materials (i.e. clay bentonite) for animal litter manufacture. This not only preserves natural resources and the natural environment, but it also will reduce CO 2 emissions, via the reduced need for heavy mining equipment. This novel animal litter is made with over 85% of recycled materials, thus preventing their disposition to landfills. The novel litter material is similar to traditional clay-like litters, and it is clumpable and has superior odor control properties.

20 FOSSIL-FUELED POWER PLANTS↗

488-1D Ash Basin closure cap help modeling- Microdrain® liner option

At the request of Area Completion Engineering and in support of the 488-1D Ash Basin closure, the Savannah River National Laboratory (SRNL) performed hydrologic simulations of the revised 488-1D Ash Basin closure cap design using the Hydrologic Evaluation of Landfill Performance (HELP) model. The revised design substitutes a MicroDrain Liner®—60-mil low-density polyethylene geomembrane structurally integrated with 130-mil drainage layer—for the previously planned drainage/barrier system—300-mil geosynthetic drainage layer (GDL), 300-mil geosynthetic clay liner (GCL), and 6-inch common fill soil layer. For a 25-year, 24-hour storm event, HELP model v3.07 was employed to (1) predict the peak maximum daily hydraulic head for the geomembrane layer, and (2) ensure that South Carolina Department of Health and Environmental Control (SCDHEC) requirements for the barrier layer (i.e., ≤ 12 inches hydraulic head on top of a barrier having a saturated hydraulic conductivity ≤ 1.0E-05 cm/s) will not be exceeded. A 25-year, 24-hour storm event at the Savannah River Site (SRS) is 6.1 inches rainfall (Weber 1998). HELP model v3.07 results based upon the new planned cap design suggest that the peak maximum daily hydraulic head on the geomembrane barrier layer will be 0.15 inches for a minimum slope equal to 3%, which is two orders of magnitude below the SCDHEC upper limit of 12 inches.

58 GEOSCIENCES↗

488-1D Ash basin closure cap help modeling-Microdrain® liner option

At the request of Area Completion Engineering and in support of the 488-1D Ash Basin closure, the Savannah River National Laboratory (SRNL) performed hydrologic simulations of the revised 488-1D Ash Basin closure cap design using the Hydrologic Evaluation of Landfill Performance (HELP) model. The revised design substitutes a MicroDrain Liner®—50-mil linear low-density polyethylene geomembrane structurally integrated with 130-mil drainage layer—for the previously planned drainage/barrier system—300-mil geosynthetic drainage layer (GDL), 300-mil geosynthetic clay liner (GCL), and 6-inch common fill soil layer. For a 25-year, 24-hour storm event, HELP model v3.07 was employed to (1) predict the peak maximum daily hydraulic head for the geomembrane layer, and (2) ensure that South Carolina Department of Health and Environmental Control (SCDHEC) requirements for the barrier layer (i.e., ≤ 12 inches hydraulic head on top of a barrier having a saturated hydraulic conductivity ≤ 1.0E-05 cm/s) will not be exceeded. A 25-year, 24-hour storm event at the Savannah River Site (SRS) is 6.1 inches rainfall (Weber 1998). HELP model v3.07 results based upon the new planned cap design suggest that the peak maximum daily hydraulic head on the geomembrane barrier layer will be 0.179 inches for a minimum slope equal to 3%, which is approximately two orders of magnitude below the SCDHEC upper limit of 12 inches.

54 ENVIRONMENTAL SCIENCES↗

High-Resolution Transmission Electron Microscopy Study of a Powder River Basin Coal-Derived Fly Ash

Examination of a fly ash derived from the combustion of a low-S, subbituminous Powder River Basin coal by Scanning Electron Microscopy (SEM) and High-resolution Transmission Electron Microscopy (HRTEM), both supplemented by Energy-dispersive X-ray spectroscopy (EDS), showed that the fly ashes were dominated by amorphous phases, Ca-rich plagioclase feldspars, Mg-rich phases, complex Ca-Mg-Al-Si-Ti-Fe grains, and trace amounts of REE-rich particles. Many of the particles were rimmed by a Ca-S, possibly a sulfate. HRTEM-EDS examination of a REE-rich particle proved it to be a mix of light- and heavy-rare earth minerals mixed with amorphous phases.

58 GEOSCIENCES↗

Techno-economic analysis of bioplastic and biofuel production from a high-ash microalgae biofilm cultivated in effluent from a municipal anaerobic digester

Rotating Algae Biofilm Reactors (RABRs) are a promising technology for efficient treatment of wastewater and production of algae-based bioproducts. However, RABR-grown algae can contain a high content of ash (30–60 wt%, dry basis), which influences the technical and economic feasibility of bioproduct conversion processes. In this report, experimental studies and economic analysis were conducted to compare different processes for bioproduct conversion of a high-ash microalgae biofilm grown using a RABR treating 0.6 million gallons per day of anaerobic digestion centrate at the Central Valley Water Reclamation Facility in Salt Lake City, UT. Process and economic models were developed and compared for three conversion processes: 1) the production of bioplastics, 2) the production of bioplastics with a lipid-extraction pretreatment, and 3) the production of biocrude via hydrothermal liquefaction. Techno-economic analysis was performed for each conversion process, including three cases for algae productivity: 231, 391, and 577 metric tons per year (dry basis). The calculated value for the minimum plastic selling price (MPSP) of bioplastics produced from algae ranges from $\$4050$ to $\$3520$ per metric ton based on the baseline and final productivity cases of the RABR, respectively. The extraction of lipids in addition to bioplastic production results in an MPSP of $\$4570$ to $\$4000$ per metric ton for the same productivity cases. The relatively small production scale and complex processing for hydrothermal liquefaction results in a minimum fuel selling price of the biocrude of $\$5.32$ per gallon of gasoline equivalent. In conclusion, the conversion process for bioplastic production from whole algae has the highest income:expense ratio and the most cost-competitive pricing of the three modeled processes.

09 BIOMASS FUELS↗

Charge fingerprint in relation to mineralogical composition of Quaternary volcanic ash along a climatic gradient on Java Island, Indonesia

We studied the relationship between the mineralogical composition and surface charge properties of representative Quaternary volcanic ash soils, classified as Andosols, along an East-West sequence on Java Island in Indonesia. Most of the studied soils have a limited ability to retain cations under their forest or grass vegetation. The surface charge properties of these soils are mainly controlled by the relative amounts of nanocrystalline minerals, mainly allophane and to a lesser extent ferrihydrite, in addition to organic matter (especially Al- and Fe-humus complexes), crystalline Fe oxides, gibbsite, and layer silicates (e.g., halloysite, smectite, kaolinite). Based on the composition of their clay fraction, the studied soils can be grouped in two categories: (i) allophane-poor Andosols of East Java, which contain a considerable amount of either halloysite or a mixture of 2:1 and 1:1 layer silicates; and (ii) allophane-rich Andosols dominated either by kaolinitic clays, gibbsitic material or a mixture of 1:1 and 2:1 layer silicate clays, which are more prominent in West and also occur in Central Java. Differences between both groups are attributed mainly to more pronounced seasonality in East Java, with variations in parent ash composition, becoming more acidic from east to west, as subordinate factor. The more severely leaching environment in West Java results in a higher degree of desilication , which led to a higher point of zero net charge (PZNC) and pHo in the allophane-rich soils. The soils belonging to this group exhibit extreme variable charge characteristics, and a net ‘positive’ variable surface charge at soil pH.

Utami, S. R.↗

Application of nanofiltration for Rare Earth Elements recovery from coal fly ash leachate: Performance and cost evaluation

Here this work evaluated nanofiltration (NF) as a potential step in the recovery process of Rare Earth Elements (REEs) from leachates of coal combustion fly ashes. A pre-treatment step, by pH adjustment and microfiltration (MF), has been studied to separate REEs by major elements. The individual and combined effects of applied pressure (12–24 bar) and NF feed acidity (pH 1.5–3.5) on rejection of six critical REEs and permeate flux have been investigated via response surface methodology (RSM). The resulting model equations were used to develop a cost model for the recovery chain, in order to select the optimum NF operating conditions. The optimization of the REE recovery chain, including pre-treatment and NF, was done with respect to the objective of maximizing the difference between NF concentrate economic value and treatment cost. NF with an appropriate MF pre-treatment has been effective in concentrating REEs from fly ash leachate, reaching the maximum potential gain at the optimum operating conditions of 12 bar and pH 3.5.

42 ENGINEERING↗

Thermal and mechanical performance of gypsum composites containing fly ash cenosphere encapsulated phase change materials

Utilizing phase change materials (PCMs) within construction materials improves the thermal energy storage capabilities in the built environment. Notably, integrating PCMs into drywalls presents a promising avenue to reduce building energy use. However, incorporating PCMs into drywalls poses challenges, particularly reduced mechanical properties and workability limitations as it can adversely affect the hardening and cohesiveness of gypsum composites. To address these challenges, this study explores a novel strategy to incorporate PCMs into gypsum composites through fly ash cenosphere-encapsulated PCM, namely CenoPCM, aiming to enhance the mechanical properties and thermal conductivity over existing commercial counterparts. An experimental program was conducted to study the impact of the inclusion of CenoPCM on the mechanical and thermal performance of gypsum composites, and the results were compared to those of commercially available polymerencapsulated PCM benchmark (Micronal). The findings highlighted that PCM-charged samples exhibited up to 95.90 J/g (CenoPCM) of latent heat with 70 % CenoPCM loading. The results of mechanical tests also showed that CenoPCM outperformed its polymer-encapsulated counterpart, achieving 55 % higher mechanical strength on average. Here, this improvement is attributed to the rigid shell of fly ash cenosphere (FAC) serving as a PCM carrier, providing a skeleton-like structure to gypsum composites for higher load-bearing capacity. Additionally, hotbox tests demonstrated that the CenoPCM-charged wall panels yielded a 20 % higher thermal conductivity and a 22 % increased time lag compared to Micronal PCM-charged panels, indicating its potential to shift the peak load in buildings.

Ceno PCM↗

Conventional and autothermal pyrolysis of corn stover: Overcoming the processing challenges of high-ash agricultural residues

The high ash content of agricultural residues and other kinds of herbaceous biomass makes it a challenging feedstock for fast pyrolysis to bio-oil. Using corn stover as a representative feedstock, this study investigates fast pyrolysis of high ash, herbaceous biomass in a pilot-scale fluidized bed reactor using both conventional, nitrogen-blown and autothermal, air-blown operation. Initial efforts to pyrolyze corn stover were challenged by bed fouling, which prevented steady reactor operation. Substitution of coarser bed material allowed operation at higher superficial velocities, which promoted attrition and elutriation of recalcitrant biochar particles from the reactor. This resulted in dramatic improvement in stable reactor operation for both conventional and autothermal pyrolysis with bio-oil yields among the highest reported for pyrolysis of corn stover. The oxygen-to-biomass equivalence ratio required for autothermal operation was 6.8%. Autothermal operation also resulted in significant process intensification, increasing corn stover throughput from 7.8 kg hr –1 to 21.9 kg hr –1 for this 8.9 cm diameter reactor. Air-blown, autothermal operation did not significantly reduce bio-oil yield despite the presence of partial oxidation reactions. In conclusion, carbon balances indicate carbon yields of biochar and aqueous, bio-oil light ends decreased by 18.5% and 4.7%, respectively, during autothermal pyrolysis compared to conventional pyrolysis while the more valuable, organic-rich heavy ends of the bio-oil were essentially preserved.

09 BIOMASS FUELS↗

Integrated modeling methodology for ash agglomeration in poly-disperse fluidized beds using particle population framework

This article discusses a unique agglomeration modeling methodology developed based on binary collisions to combine the effects of heterogeneity in ash chemistry and granular physics. A simple population balance is defined to find changes in the particle size distribution (PSD) of a fluidized bed. Thermodynamic equilibrium calculations and a computational fluid dynamics (CFD) code, are used to obtain hydrodynamic parameters. A method to calculate and use a distribution of collision frequencies in fluidized beds, corresponding to a poly-disperse particle size distribution, was developed in order to incorporate the particle level heterogeneities. A distribution of collision frequencies obtained for poly-dispersed particles showed a three orders of magnitude higher collision frequency amongst the smaller particles than the coarser ones, at the initiation of agglomeration. Ash agglomeration occurred when the slag amount (binder) was less than 10 wt% at temperatures <850 °C for Pittsburgh No. 8 coal.

42 ENGINEERING↗

Selective Recovery of Rare Earth Elements from Coal Fly Ash Leachates Using Liquid Membrane Processes

Coal combustion residues and other geological waste materials have been proposed as a resource for rare earth elements (REEs, herein defined as the 14 stable lanthanides, yttrium, and scandium). The extraction of REEs from residues often generate acidified leachates that require highly selective separation methods to recover the REEs from other major soluble ions in the leachates. We studied two liquid membrane processes (liquid emulsion membranes, LEM, and supported liquid membranes, SLM) and compared them to standard solvent extraction techniques for selective recovery and concentration of REEs from a leachate of coal fly ash. All separation methods involved an organic solution of di(2-ethylhexyl)phosphoric acid dissolved in kerosene or mineral oil and an acid strippant solution of 5 M nitric acid for the liquid-based separations. The LEM configuration, which separated REEs by immersing an acid-in-oil emulsion in the ash leachate, resulted in similar recovery percentages of individual REEs as the conventional solvent extraction approach. The recovery of REEs in the SLM configuration, which involved the impregnation of the solvent in a hydrophobic membrane, was slower than the LEM process. However, the SLM process was notably more selective for the heavy (and higher value) REEs, while the conventional extraction and LEM processes were more selective for the light REEs. A flux-based model of the extraction processes suggested that recovery rates were limited by REE affinity for the solvent chelator in the SLM, while the rates of REEs separation via LEM were limited by diffusive mass transfer across the liquid membrane. Altogether, these results help to identify specific steps in the recovery process that future work should target in the development of scalable liquid membrane separations for REE recovery.

42 ENGINEERING↗

Systematic characterization of selenium speciation in coal fly ash

Millions of tons of coal fly ashes (CFAs) are produced annually during coal combustion in the U.S., which are commonly beneficially used in the concrete industry or disposed of in ash ponds. CFAs contain trace amounts of a range of toxic heavy metals including selenium (Se). Because the toxicity of Se is dependent on its speciation, investigating Se speciation in CFAs as affected by coal source and combustion conditions can help understand the related environmental and human health impacts during disposal or beneficial reuse. In this study, a set of representative CFA samples were characterized for Se speciation using synchrotron X-ray absorption spectroscopy (XAS) and micro-X-ray fluorescence spectromicroscopy (μ-XRF/XAS). Se-containing particles were highly heterogeneous, and individual particles might contain multiple oxidation states including Se(0), Se(IV), and Se(VI). Principal component analysis was performed for sample characteristics including Al 2 O 3 , SiO 2 , CaO, FeO, loss on ignition, average particle size, Se concentration, and Se oxidation state. Selective catalytic reduction (SCR), which is used to limit nitrogen oxide (NO x ) emissions during coal combustion, was found to be associated with the presence of reduced Se oxidation states, with up to 90% Se(0) observed in samples with SCR. Alongside SCR, FeO content may also influence Se speciation.

01 COAL, LIGNITE, AND PEAT↗

AsH{sub 3} ultraviolet photochemistry: An ab initio view

Multireference configuration interaction calculations have been carried out for low-lying electronic states of AsH{sub 3}. Bending potentials for the nine lowest states of AsH{sub 3} are obtained in C{sub 3v} symmetry for As-H distances fixed at the ground state equilibrium value of 2.850 a{sub 0}, as well as for the minimum energy path constrained to R{sub 1}=R{sub 2}=R{sub 3}. The calculated equilibrium geometry and bond energy for the X-tilde {sup 1}A{sub 1} ground state agree very well with the previous experimental and theoretical data. It is shown that the lowest excited singlet state belongs to the {sup 1}A{sub 1} symmetry (in C{sub 3v}), in contradiction to the previous calculations. This state is characterized by a planar equilibrium geometry. Asymmetric stretch potential energy surface (PES) cuts along the H{sub 2}As-H recoil coordinate (at R{sub 1}=R{sub 2}= 2.850 a{sub 0}, {theta}= 123.9 deg. and 90 deg.) for numerous excited states and two-dimensional PESs for the X-tilde and A-tilde states up to the dissociation limits are obtained for the first time. The A-tilde {sup 1}A{sub 1},B-tilde {sup 1}E-X-tilde {sup 1}A{sub 1} transition moments are calculated as well and used together with the PES data for the analysis of possible photodecay channels of arsine in its first absorption band.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Resistance of fly ash-Portland cement blends to thermal shock

Thermal-shock resistance of high-content fly ash-Portland cement blends was tested in the following ways. Activated and non-activated blends with 80-90 % fly ash F (FAF) were left to set at room temperature, then hydrated for 24 hours at 85°C and 24-more hours at 300°C and tested in five thermal-shock cycles (600°C heat - 25°C water quenching). XRD, and thermal gravimetric analyses, along with calorimetric measurements and SEM-EDX tests demonstrated that the activated blends form more hydrates after 24 hours at 300°C, and achieve a higher short-term compressive strength than do non-activated ones. Sodium meta-silicate and sodaash engendered the concomitant hydration of OPC and FAF, with the formation of mixed crystalline FAF-OPC hydrates and FAF hydrates, such as garranite, analcime, and wairakite, along with the amorphous FAF hydration products. In SS-activated and non-activated blends separate OPC (tobermorite) and FAF (amorphous gel) hydrates with no mixed crystalline products formed. The compressive strength of all tested blends decreased by nearly 50% after 5 thermal-shock test cycles. These changes in the compressive strength were accompanied by a marked decrease in the intensities of XRD patterns of the crystalline hydrates after the thermalshock. As a result, there was no significant difference in the performance of the blends with different activators

15 GEOTHERMAL ENERGY↗

AmeriFlux FLUXNET-1F US-ASH USSL San Joaquin Valley Almond High Salinity

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-ASH USSL San Joaquin Valley Almond High Salinity. This is the FLUXNET version of the carbon flux data for the site US-ASH USSL San Joaquin Valley Almond High Salinity produced by applying the standard ONEFlux (1F) software.

Anderson, Ray G.↗

Alkali-activated Class F Fly Ash-rich Portland Cement Blends as Alternative Thermal Shock Resistant Cements

This study focused on evaluating the resistance of 300°C-autocalved alkali-activing Class F fly ash (FAF)-rich Type II Ordinary Portland Cement (OPC) blends with 80/20 and 90/10 FAF/OPC ratios to five thermal-shock (TS) fatigue cycles (one cycle, 600°C heat – 25°C water quenching). The factors to be evaluated included the hydration behaviors, crystalline/ amorphous phaseidentifications, -compositions and -transformations, and microstructural-developments andalterations for blended cements assembled by three different alkaline activators, sodium metasilicate (SMS), soda ash (SA), and sodium sulfate (SS). All factors were related directory to the changes in compressive strength after TS testing. The setting time of cement slurries at 25° and 85°C depended on the alkaline activators; SMS and SA contributing to a strong alkalinity hastened setting, while SS with moderate alkalinity extended the setting time. A more prolonged setting time was observed from non-activated cement. In this case, there were two separated hydration reactions: The first reaction was the hydration of OPC; the second one was associated with the dissolution and pozzolanic activity of FAF. In contrast, all alkali- activated cements engendered the concomitant hydration of OPC and FAF, thereby conferring a higher compressive strength on them than that of the non-activator one. The principal contributor to the development of strength of both the non-activated and activated cements at 300°C was the amorphous NaO 2 - or CaO-Al 2 O 3 - SiO 2 -H 2 O (N,C-A-S-H) phase formed by the interactions between alkaline activator, OPC, and FAF. This phase played an important role in minimizing the loss in strength after TS. On the other hand, adding SMS and SA introduced the mixed crystalline FAF-OPC hydrates, such as garranite and wairakite, as the major phases, into the autoclaved cement bodies. Also, these activators induced the formation of two FAF-related crystalline hydrates, analcime as the major phase and riversidelite (0.9 nm tobermorite) as the minor one. However, these identified phases were sensitive to TS, so converting the major phases into minor phases or vanishment. In contrast, three crystalline phases including calcite and anhydrous sodium sulfate as the major ones and 1.1 nm tobermorite as the minor one, that formed in non-activated and activated cements remained unchanged after TS. Additionally, SAactivated cement revealed porous microstructure created by the incorporation of copious amount of carbonate reaction products into the cement, raising concerns that cements might enhance the rate of water transportation and reduce compressive strength. Nevertheless, TS-insensitive amorphous N,C-A-S-H phase as the major cementitions structure coexisting with TS-insensitive crystalline products were responsible for sustaining the integrity of alkali-activated FAF-rich OPC cement systems in such harsh heat-cooling fatigue environments.

15 GEOTHERMAL ENERGY↗

Recovery of High Purity Rare Earth Elements (REE) from Coal Ash via a Novel Electrowinning Process (Final Report)

The goal of this project was to produce a high purity, separated (>90%) rare earth oxide (REO) product from coal-based sources. This product was achieved using the following three steps: 1. Battelle’s ADP: The ADP process involves pretreatment of ash (milling and caustic leaching), leaching of pretreated ash with nitric acid, roasting of loaded acid solution containing REE, and water leaching of residual from roasting step, resulting in a REE pregnant solution. 2. Solvent Extraction (SX) Upgrading: The SX involves the extraction of REE from a pregnant REE solution using an organic extractant (note after extraction, the aqueous phase was a residual solution and the organic phase contained REE), and stripping of REE from the organic phase product obtained from the extraction using an acid solution (the stripped solution was the final purified product containing REE, organic traces, and traces of other metals for further separation in the electrowinning process). 3. Rare Earth Salts’ (RES) Electrochemical Separation and Purification Process: The staged electrochemical process was separated REO products from the mixed REE solution. Testing by RES was also included in the investigation of options to minimize the solvent extraction steps. This report covers laboratory testing, production of a high purity coal-based REO, process design of the overall REE recovery and purification process, technoeconomic assessment (TEA), and a commercialization plan discussing the overall REE recovery and purification process.

01 COAL, LIGNITE, AND PEAT↗