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At least 1,657 records · Page 92

Core-Cutoff Tool

A tool makes a cut perpendicular to the cylindrical axis of a core hole at a predetermined depth to free the core at that depth. The tool does not damage the surrounding material from which the core was cut, and it operates within the core-hole kerf. Coring usually begins with use of a hole saw or a hollow cylindrical abrasive cutting tool to make an annular hole that leaves the core (sometimes called the plug ) in place. In this approach to coring as practiced heretofore, the core is removed forcibly in a manner chosen to shear the core, preferably at or near the greatest depth of the core hole. Unfortunately, such forcible removal often damages both the core and the surrounding material (see Figure 1). In an alternative prior approach, especially applicable to toxic or fragile material, a core is formed and freed by means of milling operations that generate much material waste. In contrast, the present tool eliminates the damage associated with the hole-saw approach and reduces the extent of milling operations (and, hence, reduces the waste) associated with the milling approach. The present tool (see Figure 2) includes an inner sleeve and an outer sleeve and resembles the hollow cylindrical tool used to cut the core hole. The sleeves are thin enough that this tool fits within the kerf of the core hole. The inner sleeve is attached to a shaft that, in turn, can be attached to a drill motor or handle for turning the tool. This tool also includes a cutting wire attached to the distal ends of both sleeves. The cutting wire is long enough that with sufficient relative rotation of the inner and outer sleeves, the wire can cut all the way to the center of the core. The tool is inserted in the kerf until its distal end is seated at the full depth. The inner sleeve is then turned. During turning, frictional drag on the outer core pulls the cutting wire into contact with the core. The cutting force of the wire against the core increases with the tension in the wire and, hence, with the frictional drag acting on the outer sleeve. As the wire cuts toward the center of the core, the inner sleeve rotates farther with respect to the outer sleeve. Once the wire has cut to the center of the core, the tool and the core can be removed from the hole. The proper choice of cutting wire depends on the properties of the core material. For a sufficiently soft core material, a nonmetallic monofilament can be used. For a rubber-like core material, a metal wire can be used. For a harder core material, it is necessary to use an abrasive wire, and the efficiency of the tool can be increased greatly by vacuuming away the particles generated during cutting. For a core material that can readily be melted or otherwise cut by use of heat, it could be preferable to use an electrically heated cutting wire. In such a case, electric current can be supplied to the cutting wire, from an electrically isolated source, via rotating contact rings mounted on the sleeves.

Gheen, Darrell↗

Rankine cycle waste heat recovery system

A waste heat recovery (WHR) system connects a working fluid to fluid passages formed in an engine block and/or a cylinder head of an internal combustion engine, forming an engine heat exchanger. The fluid passages are formed near high temperature areas of the engine, subjecting the working fluid to sufficient heat energy to vaporize the working fluid while the working fluid advantageously cools the engine block and/or cylinder head, improving fuel efficiency. The location of the engine heat exchanger downstream from an EGR boiler and upstream from an exhaust heat exchanger provides an optimal position of the engine heat exchanger with respect to the thermodynamic cycle of the WHR system, giving priority to cooling of EGR gas. The configuration of valves in the WHR system provides the ability to select a plurality of parallel flow paths for optimal operation.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electrolytically Assisted Surface Decontamination (EASD{sup TM}) for POCO Operations - 20282

NNL in collaboration with C-Tech Innovation Ltd and Sellafield Ltd has been exploring innovative technologies to enable a significant reduction of radiological hazards within facilities during the Post Operational Clean Out (POCO) phase of a nuclear plant's life cycle. Reducing the hazard by effectively decontaminating plants in-situ during POCO delivers huge cost reductions for future decommissioning operations. These cost reduction benefits are realized by reducing the number and complexity of remote operations as well as lowering the long-term waste disposal costs. Whilst chemical decontamination can achieve the desired level of decontamination, applying aggressive chemical reagents is hazardous, potentially difficult to control and requires there to be complimentary effluent treatment and waste routes. This work has aimed to develop flexible and controllable decontamination processes which could be operated without the additional complexity and issues associated with chemical decontamination. The processes needed to be relatively fast and effective to minimize the time operators would spend in an active area. In addition, there was a driver to produce decontamination methodologies which generated a secondary waste compatible with current routes and which takes advantage of current waste capacity. The strategy therefore was to come up with a solution that works with, rather than against, the science and engineering behind process plants at Sellafield. Electrolytically Assisted Surface Decontamination (EASD{sup TM}) is an innovative electrochemical decontamination process (developed by NNL and C-Tech Innovation Ltd) that can remove activity from contaminated metal in very short time periods. Application of the patented electric waveform to the surface when treating contaminated metal with nitric acid has been shown to significantly enhance the decontamination performance. When compared to proposed baseline washout procedures at Sellafield, the only change to the process is the applied electrical waveform which is temporary and controllable. The current causes dissolution of the metal surface being decontaminated which leads to activity transferring from the plant item into the nitric acid effluent stream. This innovation has the potential to transform the POCO process and allow a nitric acid based washout approach to deliver POCO quickly and cost effectively within the existing infrastructure. Several devices have now been designed that incorporate this EASD{sup TM} technology and enable the decontamination process to be applied to a range items commonly identified as being contaminated during nuclear decommissioning programmes such as pipework, tanks and hotspots of walls/floors. Inactive and active laboratory-scale testing has been completed using both simulated and 'real-life' contaminated (low level waste) metallic items retrieved from different nuclear sites. Active trials demonstrated that contaminated items could be treated to free release levels within minutes. Engineering scale tests are currently being performed, with guidance from Sellafield's system engineers and plant managers, to provide the necessary re-assurance the designed devices could be successfully deployed in an on-plant scenario. The final stage of this development work is to carry out an active demonstration of the decontamination technology on Thorp at Sellafield. This paper aims to highlight progress made to date with the EASD{sup TM} technology and, more specifically, the development of an in-situ decontamination device for deployment within radioactive pipework. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Volatile species of technetium and rhenium during waste vitrification

Volatile loss of technetium (Tc) during vitrification of low-activity wastes is a technical challenge for treating and immobilizing the large volumes of radioactive and hazardous wastes stored at the U.S. Department of Energy's Hanford Site. There are various research efforts being pursued to develop technologies that can be implemented for cost effective management of Tc, including studies to understand the behavior of Tc during vitrification, with the goal of eventually increasing Tc retention in glass. Furthermore, one of these studies has focused on identifying the form or species of Tc and Re (surrogate for Tc) that evolve during the waste-to-glass conversion process. This information is important for understanding the mechanism of Tc volatilization. In this paper, available information collected from the literature is critically evaluated to clarify the volatile species of Tc and Re and, more specifically, whether they volatilize as alkali pertechnetate and perrhenate or as technetium and rhenium oxides after decomposition of alkali pertechnetate and perrhenate. The evaluated data ranged from mass spectrometric identification of species volatilized from pure and binary alkali pertechnetate and perrhenate salts to structural and chemical analyses of volatilized materials during crucible melting and scaled melter processing of simulated wastes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Non-equilibrium radiation nuclear reactor

An externally moderated thermal nuclear reactor is disclosed which is designed to provide output power in the form of electromagnetic radiation. The reactor is a gaseous fueled nuclear cavity reactor device which can operate over wide ranges of temperature and pressure, and which includes the capability of processing and recycling waste products such as long-lived transuranium actinides. The primary output of the device may be in the form of coherent radiation, so that the reactor may be utilized as a self-critical nuclear pumped laser.

Thom, K.↗

Effect of Feeding Rate on the Cold Cap Configuration in a Laboratory-Scale Melter

High level waste melter feed is converted into glass in a joule heated melter, where it forms a floating layer of reacting feed, called the cold cap. After the glass-forming phase becomes connected, evolving gases produce bubbles that form a foam layer under the cold cap. The bubbles coalesce into cavities that escape around the edges of the cold cap. The foam layer insulates the cold cap from the heat transferred from the molten glass below. More information is needed about the formation and behavior of the foam layer to control, limit and possibly avoid foaming, thus allowing for a higher rate of melting. The cold cap behavior was investigated in a laboratory scale assembly with a sealed silica-glass crucible. A high alumina waste simulant was fed into the crucible and the feed charging rate was varied from 3 to 7 mL min-1. After a fixed amount of time (35 min), feed charging was stopped and the crucible was removed from the furnace and quenched on a copper block to preserve the structure of the cold cap and foam during cooling. During the rapid quenching, thermal cracking of the glass and cold cap allowed it to be broken up into sections for analysis. The effect of the charging rate on the height, area and volume of the cold cap was determined. The size of the bubbles collected in the foam layer under the cold cap increased as the cold cap expanded. Under the cold cap, the bubbles coalesced into oblong cavities. These cavities allowed the evolved gases to escape around the edges of the cold cap through the molten glass into the melter plenum.

Dixon, Derek R.↗

Migration Rates of Some Cations in Unsaturated Layer around the Near-Surface Disposal Facilities of Radioactive Wastes - 16116

In the porous layer around the near-surface underground, the intermittent recharge process of rainwater forms a layer perfectly not saturated with liquid phase. Here, such a layer is simply called 'unsaturated layer'. In this study, the retardation effects of radionuclide migration were examined under an unsaturated condition by using a column packed with silica sand particles. As tracer ions, sodium (Na), europium (Eu) and cesium (Cs) were selected for estimating the retardation effects under both the saturated and unsaturated condition. Particularly, Cs is one of the key elements included in the contaminated soil due to Fukushima Daiichi Nuclear Power Plant Accident. These tracer ions were injected into column with the condition of constant flow rate or constant pressure flow. To quantify the influence of the unsaturated condition on the migration of radionuclides, retardation coefficient (R{sub d}) and Peclet number (P{sub e}) were estimated by applying advection diffusion equation to the experimental results. As a result, the conflicting effects on the retardation effect in the unsaturated layer were suggested; one is the decrease in the retardation effect by interrupting the sorption of ions with gas phase, the other is the increase in the retardation effect by the clogging with gas phase in flow paths. For the assessment of the radionuclide migration in the unsaturated layer, it is important to clarify such complicated behaviors with considering key parameters related to the migration of ions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Environmental Geochemistry and Acid Mine Drainage Evaluation of an Abandoned Coal Waste Pile at the Alborz-Sharghi Coal Washing Plant, NE Iran

In this paper, an abandoned waste coal pile, which is resulted from Alborz-Sharghi coal washing plant, NE of Iran was mineralogically and geochemically characterized to evaluate pyrite oxidation, acid mine drainage (AMD) generation, and trace element mobility. After digging ten trenches and vertical sampling, a quantitative method including the atomic absorption test, and the quality-based methods including optical study were carried out for determination of pyrite fractions in the waste pile. The geochemical results revealed that the fraction of remaining pyrite increased with depth, indicating that pyrite oxidation is limited to the shallower depths of the pile which were confirmed by variations of sulfate, pH, EC, and carbonate with depth of the pile. To evaluate the trend of trace elements and mineralogical constituents of the waste particles, the samples were analyzed by using XRD, ICP-MS, and ICP-OES methods. The results showed the secondary and neutralizing minerals comprising gypsum have been formed below the oxidation zone. Besides, positive values of net neutralization potential indicated that AMD generation has not taken in the waste pile. In addition, variations of trace elements with depth reveal that Pb and Zn exhibited increasing trends from pile surface toward the bottom sampling trenches while another of them such as Cu and Ni had decreasing trends with increasing depth of the waste pile.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion-Exchange Modeling of Crystalline Silicotitanate for Cesium Removal - 20283

The Tank Closure Cesium Removal (TCCR) system is a Savannah River Site (SRS) demonstration 'at-tank' process designed to remove {sup 137}Cs from the high-level aqueous tank waste so that the decontaminated solution can be disposed as low-level waste. Cesium is removed by ion exchange (IX) columns using engineered IONSIV{sup TM} R9120-B form of the Crystalline Silicotitanate (CST) media. The TCCR system is deployed at Tanks 10 and Tank 11 in the SRS H Tank Farm. Water is added to the salt-cake in Tank 10 H to dissolve it. The dissolved salt solution waste is pumped out of Tank 10H (feed tank), through filters and IX columns. The decontaminated salt solution is transferred to Tank 11 (receipt tank), and on to Tank 50H for final disposal in the Saltstone Production Facility. The current TCCR can accommodate lead-lag (two-column) or lead-lag-guard (three-column) configurations to optimize media utilization and achieve the target decontamination. To assist the TCCR operations, a parametric study was conducted to evaluate the impact of different parameters (e.g., column configurations (single column, two columns or three columns in series), waste characteristics, operating temperature, process flow rate, CST average particle size) on the IX column performance including CST bed utilization. The initial results indicate that the IX column performance is improved at slower process flow rate, at lower operating temperature, and with smaller CST average particle size. Multi-column configurations are recommended, because the single-column configuration does not utilize CST bed effectively. This paper demonstrates the versatility of the ion exchange modeling to evaluate the effects of CST characteristics and operational parameters on IX column performances. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modified Isotherm Modeling to Predict Cs Exchange with Crystalline Silicotitanate in Tank Waste Simulants

The U.S. Department of Energy is working to expedite processing of Hanford tank waste supernate at the Hanford Waste Treatment and Immobilization Plant. To support this goal, Washington River Protection Solutions is designing a Tank Side Cesium Removal (TSCR) system for suspended solids and cesium (Cs/ 137 Cs) removal from Hanford tank waste supernate. The ion exchange media selected for Cs removal at TSCR is crystalline silicotitanate (CST) that is manufactured in a nearly spherical form by Honeywell UOP LLC (UOP; Des Plaines, IL) as product IONSIV® R9140-B (Na form). The Zheng Anthony Miller (ZAM) isotherm model (Zheng et al. 1997) is a multicomponent ion exchange model used to predict the exchange of Group I metals onto CST. The ZAM isotherm has historically been used to predict Cs distribution values from Hanford and Savannah River Site (SRS) tank waste simulants. Figure S.1 summarizes model predictions from the ZAM isotherm that indicate poor prediction of Cs distribution values for simple and complex simulants with the engineered form of CST, IONSIV® R9140-B, and IONSIV® R9120-B where the solid line indicates a perfect fit by the model. The dotted lines indicate ±20% error. Batch contact testing with Hanford tank waste complex and simple simulants was used in conjunction with SRS simulants to experimentally determine Cs distribution values using a modification to the original isotherm model. The experimentally determined maximum Cs capacity for IONSIV® R9140-B CST in both the simple and complex matrices was found to be 0.53±0.3 mmoles Cs/g of CST. This value is not drastically different from the maximum Cs capacity of 0.58 mmoles Cs/g TAM-5 reported by Zheng et al. (1997). However, it is important to note that TAM-5 (commercially IONSIV® IE-910) is a powder. Hamm et al. (2002) determined that a dilution factor was needed to account for the Zr(OH)2 binder in the engineered form of CST. Hamm et al. determined that a dilution factor of 0.68 was appropriate to account for binder contribution and correct overprediction of Cs exchange on the engineered form of CST in ZAM calculations. This reduced the total capacity from 0.58 mmol/g with TAM-5 to 0.39 mmol/g for the engineered form of CST (Hamm et al. 2002). Despite substituting the experimentally determined maximum Cs capacity of 0.55 mmoles Cs/g for the literature-reported capacity of 0.39 mmoles Cs/g, it was determined that additional modifications to the model’s equilibrium rate constants were necessary in refining the isotherm model. The modified model overpredicted K+ uptake by the CST when compared to digested CST results described by Campbell et al. (2019). The modified model was further revised to omit three of the five K+ exchange equilibrium reactions described by ZAM to reduce the additional K+ loading seen by the model. Figure S.2 summarizes the revised model isotherm predictions plotted against measured Kd values.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Understanding the influence of iron on crystallization kinetics of nepheline based glasses - 15472

Hanford site in Washington is home to 55 million US gallons of high level radioactive waste rich in sodium, alumina and iron. The strategy is to vitrify this waste in borosilicate glasses. Crystallization of nepheline/carnegeite (NaAlSiO{sub 4}) in glass melts during vitrification and canister cooling is a big challenge as it severely deteriorates the chemical durability of the glass. As the HLW borosilicate glasses are similar to basalt glass on a borate-free basis and as no borate phase crystallize on the liquidus, the crystallization chemistry of waste glasses can be described by the known phase relations of the geochemical basalt quaternary Na{sub 2}O-Al{sub 2}O{sub 3}-Fe{sub 2}O{sub 3}-SiO{sub 2} system. The objective of this study is to understand the influence of iron on the thermal stability and crystallization kinetics of model sodium- and alumina- rich simplified silicate glasses in the Na{sub 2}O-Al{sub 2}O{sub 3}-Fe{sub 2}O{sub 3}-SiO{sub 2} system designed in the primary crystallization field of nepheline. The results obtained from this study will form the baseline for understanding the nucleation and crystallization kinetics of multicomponent complex nuclear waste glasses in future. A series of glasses with compositions 25Na{sub 2}O-(25-z) Al{sub 2}O{sub 3}-zFe{sub 2}O{sub 3} -50SiO{sub 2} (mol.%) where z varies between 0 -5% has been prepared by melt-quench technique. Glasses have been labelled in reference to their Fe{sub 2}O{sub 3} content, i.e. Fe-z. We could not obtain amorphous glasses with Fe{sub 2}O{sub 3} > 5 mol.% . Glass batches comprising oxides and carbonates were melted at 1650 deg. C in Pt-Rh crucibles for 2 h. The melts were quenched in cold water to yield ∼90 g of glass. Thermal stability and crystallization kinetics of glasses was studied using differential thermal analysis (DTA). Thermal scans (30-1580 deg. C) were collected on glass particles (particle size: 0.5 mm-1 mm) at four different heating rates: 5, 10, 15 and 20 K min{sup -1} in air and inert (N{sub 2}) atmosphere. Non-isothermal crystallization kinetics of the glasses was studied using the Augis-Bennett method and Ozawa method. In accordance with the crystallization data obtained from DTA, glasses were heated in the crystallization temperature range and air quenched. Glasses were also heated from 30 deg. C to 800, 900 and 1000 deg. C for 1 h, respectively, in air and inert (N{sub 2}) atmospheres, at heating rate of 10 K min{sup -1}. Resulting glass-ceramics were characterized for their crystalline phase evolution by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Conversion of melt -to glass-ceramic during cooling DTA data was also collected for all the glasses during their conversion from melt -to -glass-ceramic during cooling at different cooling rates, in air and inert (N{sub 2}) atmosphere. In accordance with the DTA data, conversion of melt to glass-ceramic during cooling was studied by re-melting the glass frit in Pt-Rh crucibles at 1650 deg. C. The melt was allowed to cool at 10 K min{sup -1} and was air quenched at different temperatures (as per DTA data). The as obtained glass-ceramics were characterized by XRD and SEM Incorporation of Fe{sub 2}O{sub 3} in glasses decreases their crystallization temperature and increases their crystallization tendency. Parent glass (stoichiometric nepheline composition) is prone to surface crystallization. Incorporating 5 mol.% Fe{sub 2}O{sub 3} in these glasses transforms the crystallization kinetics from surface to volume nucleation. Crystallization kinetics of glass Fe-2.5 is affected by the environment (N{sub 2} vs. Air) while no significant impact of environment could be seen for glass Fe-5. Devitrification in all the glasses begins with the crystallization of carnegeite (NaAlSiO{sub 4}, orthorhombic) (∼1200 deg. C). Prolonged heat treatments leads to the crystallization of nepheline (NaAlSiO{sub 4}, hexagonal) (∼1200 deg. C) as a secondary phase. Fe{sub 2}O{sub 3} promotes the crystallization of nepheline over carnegeite via formation of magnetite as nucleation site. Iron incorporation pre-nucleates the glasses which upon heat treatment result in the formation of magnetite phase as nucleation sites, thus, shifting the mechanism of crystallization from surface to volume. Unlike carnegeite, the crystal structure of nepheline allows partial substitution of Fe{sup 3+}/Al{sup 3+}. This promotes the crystallization of nepheline over carnegeite in iron-containing glasses. Iron incorporation in nepheline-based sodium aluminosilicate glasses shifts crystallization mechanism from surface to bulk. Our results indicate that atmosphere does affect the crystallization kinetics of iron-containing aluminosilicate glasses but only when Fe{sub 2}O{sub 3} concentration is low. Since nepheline crystal structure can easily accommodate iron in comparison to carnegeite, iron seems to promote nepheline formation in these glasses at the expense of carnegeite through formation of Fe{sub 3}O{sub 4} phase as nucleation site. Future work will be focused on adding compositional complexity to these glasses and studying them further for their nucleation and crystallization behavior.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Study on the Strategy for Final Disposal and Reuse of Decontamination Wastes after the Fukushima Daiichi NPP Accident - 20426

After the Fukushima Daiichi NPP accident, a large area of East Japan was contaminated by radio-Cs. To discuss the final disposal of the contaminated wastes off-site and the required development of related technologies, it is important to understand the volume and radiation concentration of the wastes after various treatments. For a scientific investigation purpose, a research committee has been formed by the Society for the Remediation of Radioactive Contamination in the Environment, which is independent from the Ministry of Environment. This committee's work is focused on discussing various scenarios for the final disposal considering a mass balance evaluation of the entire process, economic evaluations, and stakeholder consultation for final consensus. The current discussions of this committee are herein reported. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

ZAM Modeling Study to Support the Tank Closure Cesium Removal (TCCR) 1A Unit

Currently at the Savannah River Site (SRS), the Tank Closure Cesium Removal (TCCR) is an “at-tank” process designed to remove cesium from aqueous tank waste. Cesium will be removed by ion exchange using the engineered IONSIV® R9120 form of Crystalline Silicotitanate (CST) media. The current TCCR design has two columns online in a lead-lag configuration to optimize media usage and achieve the target decontamination. Once the lead column is saturated with cesium, it will be removed from service, the lag column will rotate into the lead position, and a new column with fresh ion-exchange media will be placed into the lag position. The TCCR process for cesium removal from Tank 10H is detailed in X-SOW-H- 00002. Demonstration of the system began in early calendar year 2019 with two batches of salt solution generated by dissolving saltcake in Tank 10H, followed by processing of these batches through the TCCR system. A third TCCR Tank 10H dissolved saltcake batch is scheduled for processing soon. Upon completion of the demonstration with Tank 10H dissolved saltcake, Tank 9H salt solution will be transferred to Tank 10H and subsequently processed through the TCCR unit with new CST media (referred to as R9120-B 30x60) added to new IX columns. The TCCR processing campaign of Tank 9H salt solution is referred to as TCCR-1A .

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Energy recovery from solid waste

A recent group study on the problem of solid waste disposal provided a decision making model for a community to use in determining the future for its solid waste. The model is a combination of the following factors: technology, legal, social, political, economic and environmental. An assessment of local or community needs determines what form of energy recovery is desirable. A market for low pressure steam or hot water would direct a community to recover energy from solid waste by incineration to generate steam. A fuel gas could be produced by a process known as pyrolysis if there is a local market for a low heating value gaseous fuel. Solid waste can also be used directly as a fuel supplemental to coal in a steam generator. An evaluation of these various processes is made.

Dalton, C.↗

Effect of Feeding Rate on the Cold Cap Configuration in a Laboratory-Scale Melter - 13362

High-level-waste melter feed is converted into glass in a joule-heated melter, where it forms a floating layer of reacting feed, called the cold cap. After the glass-forming phase becomes connected, evolving gases produce bubbles that form a foam layer under the feed. The bubbles coalesce into cavities, from which most of the gases are released around the edges of the cold cap while gases also escape through small shafts in the reacting feed. The foam layer insulates the cold cap from the heat transferred from the molten glass below. The cold cap behavior was investigated in a laboratory-scale assembly with a fused silica crucible. A high-alumina waste simulant was fed into the crucible and the feed charging rate was varied from 3 to 7 mL min{sup -1}. After a fixed amount of time (35 min), feed charging was stopped and the crucible was removed from the furnace and quenched on a copper block to preserve the structure of the cold cap during cooling. During the rapid quenching, thermal cracking of the glass and cold cap allowed it to be broken up into sections for analysis. The effect of the charging rate on the height, area and volume of the cold cap was determined. The size of the bubbles collected in the foam layer under the feed increased as the cold cap expanded and the relationship between these bubbles and temperature will be determined for input into a mathematical model. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of a Sulfur Tolerant CHG Process (CRADA 442) (Final Report)

The Pacific Northwest Laboratory (PNNL) has developed the Catalytic Hydrothermal Gasification (CHG) technology, which can convert low-value organics dispersed in aqueous streams, such as the aqueous phase byproduct from hydrothermal liquefaction (HTL) of wet wastes, to a mixture of methane, H 2 , and CO 2 . The current CHG catalyst, ruthenium (Ru) on a graphite substrate, was selected for its effectiveness as a reducing catalyst. However, the target waste aqueous feedstock, the HTL aqueous phase from wet wastes, such as sewage sludge, contains a fair amount of sulfur in both organic and inorganic forms. Like many other reduced metal catalysts, Ru is deactivated or poisoned by exposure to sulfur, among other contaminants. In general, a deactivated Ru catalyst cannot be reactivated or restored except by removing and returning it for remanufacturing. Therefore, there is an urgent need for a sulfur-resistant catalyst to enable CHG processing of the HTL aqueous waste stream. PNNL, with support from SoCalGas CRADA, has developed a sulfur resistant CHG catalyst and demonstrated a stable CHG process for converting HTL aqueous phases from wet wastes. Here, we report the major accomplishments of the project: • We have demonstrated that sulfided Ru based catalysts is stable during CHG of HTL aqueous waste stream, with a requirement of activity improvement. • We have developed a new catalyst, with 0.5-2 wt.% Ru loading, showing better activity compared to the baseline 6.7 wt.% RuSx/C catalyst. • With the new catalysts, the single-pass COD reduction is approximately 60% and two-pass COD reduction can reach approximately 85%. • The process is robust in terms of being effective across a wide range of organic species in the feedstock. • Techno-economic analysis was conducted to evaluate the economic impact of catalyst advancement and identify further improvement requirements. This type of catalyst shows great potential to be efficient and robust for CHG with low catalyst cost.

03 NATURAL GAS↗

Supercritical Water Oxidation (SCWO) for the treatment of spacecraft waste.

Supercritical water oxidation (SCWO) is a powerful waste treatment that has been considered as a substitute or complement to other potential spacecraft waste handling methods including jettisoning, compacted sealed storage, drying, and others. Combustible trash and garbage is mixed with water and then heated and pressurized above the critical point of water (705 °F and 218 atmospheres). The waste is nearly all oxidized to produce carbon dioxide, water and nitrogen. NOx is not formed. The combustion energy can be used to heat the input stream. SCWO is relatively complex, expensive, and hazardous compared to other methods. Oxidation of compounds containing chlorine and sulfur produces hydrochloric and sulfuric acid which can cause corrosion in the reactor. Neutralizing these acids produces salts which can precipitate and cause clogging. The major engineering challenges to implementing SCWO are chemical corrosion and fouling due to the deposition of salts. SCWO was first proposed for general waste treatment and for spacecraft in the 1980’s and extensive research has been carried out.

Harry W Jones↗

X-ray micro-tomography investigation of the foaming process in the system of waste glass–silica mud–MnO{sub 2}

In case of foamed lightweight aggregates (LWAs), porosity is introduced by the addition of a foaming agent to the glassy matrix, which degasses at an elevated temperature, so that the resulting gases remain trapped inside the glassy structure. The efficiency of action of MnO{sub 2} as a foaming agent in waste glass and waste glass/silica mud systems was studied. Samples were fired at different temperatures and with different dwelling times at a certain temperature, and the development of porosity was investigated by means of X-ray micro-tomography. It was found that, with the prolongation in dwelling times, the number of pores decreased, while, on the other hand, the volume of these pores increased, and that the addition of silica mud increases the foaming temperature and slows down the foaming process. - Highlights: • Preparation of lightweight aggregate from waste glass, silica sludge, and MnO{sub 2} • DTA/TG investigation of MnO{sub 2} • Characterization of pore-forming process by means of X-ray micro-tomography (μcT)

36 MATERIALS SCIENCE↗