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At least 379 records · Page 21

The scaling economics of small unit operations

We present a correlation that represents the capital costs of the components of even very small modular facilities. Conversion of distributed feedstocks (eg, associated natural gas, biomass, and carbonaceous wastes) could provide a small fraction of the liquid fuels now used for transportation in the U.S. (~6%),or nearly half of the chemical products now made from petroleum. However, those resources tend to be available at small geographically distributed sites, and they are difficult or expensive to transport to a distant processing center. Modular, and likely intensified, processes that can be numbered up promise to enable utilizing such distributed resources. Early stage economics evaluation of those processes requires cost estimates for the components, which are likely smaller in scale than can be accommodated by the 0.6 power law typically used in chemical engineering

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Review of historical monitoring data on Techa River contamination

The Mayak Production Association was the first Russian site for the production and separation of plutonium. The extensive increase in plutonium production during 1948-1955, as well as the absence of reliable waste-management technology, resulted in significant releases of liquid radioactive effluent into the rather small Techa River. This resulted in chronic external and internal exposure of about 30,000 residents of riverside communities; these residents form the cohort of an epidemiologic investigation. Analysis of the available historical monitoring data indicates that the following reliable data sets can be used for reconstruction of doses received during the early periods of operation of the Mayak Production Association: Temporal pattern of specific beta activity of river water for several sites in the upper Techa region since July 1951; average annual values of specific beta activity of river water and bottom sediments as a function of downstream distance for the whole river since 1951; external gamma-exposure rates near the shoreline as a function of downstream distance for the whole Techa River since 1952; and external gamma-exposure rate as a function of distance from the shoreline for several sites in the upper and middle Techa since 1951.

NASA Discipline Radiation Health↗

Site-Selective Polyolefin Hydrogenolysis on Atomic Ru for Methanation Suppression and Liquid Fuel Production

Catalytic hydrogenolysis of end-of-life polyolefins can produce value-added liquid fuels and therefore holds great promises in plastic waste reuse and environmental remediation. The major challenge limiting the recycling economic benefit is the severe methanation (usually >20%) induced by terminal C–C cleavage and fragmentation in polyolefin chains. Here, we overcome this challenge by demonstrating that Ru single-atom catalyst can effectively suppress methanation by inhibiting terminal C–C cleavage and preventing chain fragmentation that typically occurs on multi-Ru sites. The Ru single-atom catalyst supported on CeO 2 shows an ultralow CH 4 yield of 2.2% and a liquid fuel yield of over 94.5% with a production rate of 314.93 g fuels g Ru -1 h -1 at 250 °C for 6 h. Such remarkable catalytic activity and selectivity of Ru single-atom catalyst in polyolefin hydrogenolysis offer immense opportunities for plastic upcycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Biomass and Polymer Feedstock Variability Through Analytical Pyrolysis and Two Dimensional Gas Chromatography and Mass Spectrometry

Moving toward a circular carbon economy requires enabling reuse of carbon-based macromolecules like those in biomass and polymers. Meeting this goal requires increased upcycling of waste products into higher value products. For biomass waste such as corn stover, pine needles, or bark, one approach is using pyrolysis to convert these feedstocks into bio-oil that can be used for liquid fuel or transformed into other hydrocarbon based products, like bio-polymers. Waste plastics can be upcycled or recycled into new products, or alternatively converted into bio-oil by pyrolysis. Macromolecules from biomass and polymers are challenging to convert into liquid fuel or chemical feedstocks, due to large and sometimes heterogeneous networks of polymeric bonds. We work with the Idaho National Laboratory’s Biomass Feedstock National User Facility and Department of Energy’s Feedstock Conversion Interface Consortium to develop a molecular understanding of biomass variability that occurs naturally and as a result of storage or preprocessing techniques applied to feedstocks, to understand chemical reactions occurring during pyrolysis and other biomass or polymer conversion techniques. Using two dimensional gas chromatography mass spectrometry coupled to analytical pyrolysis provides insight into the molecular changes that occur during the pyrolysis event, and these insights can extend to bench or pilot scale pyrolysis conversions. Understanding pyrolysis of biomass and polymers at a molecular level contributes to development of new tools to predict and manipulate the optimum conditions and identify the best storage, preprocessing, and conversion techniques to maximize output of specific high-value chemical species in the conversion to fuels, or to characterize feedstocks for blending before pyrolysis. Identification and understanding of the molecular level changes resulting from novel preprocessing techniques that can be used to control and manipulate the chemical output of bench or pilot scale pyrolysis is another focus of investigation, including the use of gamma irradiation, acid, or enzyme pre-treatments. We also focus on the impacts of storage conditions and techniques, which can affect moisture levels, degradation, and impacts from naturally occurring microbes in the environment.

09 BIOMASS FUELS↗

Hydrothermal catalysis of waste greases into green gasoline, jet, and diesel biofuels in continuous flow supercritical water

Production of green gasoline, jet, and diesel biofuels from waste greases was achieved using a novel hydrothermal, continuous-flow catalytic process operating under supercritical water conditions, with recycled water the only added chemical. Thermally and chemically stable catalysts were explored to optimize yields of liquid biofuels and to minimize production of gases and acidic compounds. A 50:50 mixture of brown and yellow waste greases converted into 76.6 wt% liquid biocrude (BC); the remainder converted to water and gases. Less than 0.2% of the FS formed carbon char (mainly amongst catalyst particles). Various tubular reactors (Inconel, ® Hastelloy®, titanium, stainless) showed no interior defects, erosion, or mass loss after runs. Here, the titanium catalyst was fully recovered and regenerated back to its original potency. The BC was further refined into 28%, 48%, 20%, and 4 wt%, respectively for green gasoline, jet, diesel, and bunker. Biofuels were analyzed for compound class compositions and reaction mechanisms were proposed. The hundreds of identified fuel products (C3-C35) from processing oleic acid as a pure model compound were identified. The neat green gasoline and diesel biofuels along with a 50% green jet blend (with petroleum Jet A) were tested in appropriate spark ignition, turbine, and diesel engines at University of MN Engine Labs. Biofuels achieved 107.7%, 97.2%, and 101.3% engine power performance levels relative to petroleum fuels (91-Octane, Jet A, #2 Diesel) along with lower CO and pollutant emissions. Biofuels passed ASTM fuel specifications (D4814, D7566, D975) including mandated corrosion and low sulfur limits of all three biofuels.

09 BIOMASS FUELS↗

Vacuum Infusion Process Development for Conformal Ablative Thermal Protection System Materials

Conformal ablators are low density composite materials comprised of a flexible carbon felt based fibrous substrate and a high surface area phenolic matrix. These materials are fabricated to near net shape by molding the substrate, placing in a rigid matched mold and infusing with liquid resin through a vacuum assisted process. The open mold process, originally developed for older rigid substrate ablators, such as PICA, wastes a substantial amount of resin. In this work, a vacuum infusion process a type of liquid composite molding where resin is directly injected into a closed mold under vacuum is advanced for conformal ablators. The process reduces waste over the state-of-the-art technique. Small, flat samples of Conformal Phenolic Impregnated Carbon Ablator are infused using the new approach and subjected to a range of curing configurations and conditions. Resulting materials are inspected for quality and compared to material produced using the standard process. Lessons learned inform subsequent plans for process scale up.

TPS↗

Comparative Techno-economic Analysis and Life Cycle Assessment of Producing High-Value Chemicals and Fuels from Waste Plastic via Conventional Pyrolysis and Thermal Oxo-degradation

The rapid rise in global plastic production in recent decades has resulted in the massive generation of plastic waste. Over 75% of the plastic waste generated in the United States was sent to landfills, with a meager 8.7% recycled. Plastics are valuable feedstocks for platform chemicals and fuels. Chemical upcycling of waste high-density polyethylene (HDPE) is gaining more attention as a potentially feasible and environmentally friendly plastic waste management technology. Conventional pyrolysis (CPY) and thermal oxo-degradation (TOD) are two chemical upcycling technologies actively researched for decomposing waste HDPE into valuable chemicals and fuels. However, there are few studies on the techno-economic analysis (TEA) and life cycle assessment (LCA) of these technologies for converting waste HDPE to valuable products. This study conducts a comparative TEA and LCA study of the thermochemical decomposition of waste HDPE to produce gaseous (ethylene and propylene) and liquid (naphtha, diesel, and wax) products by CPY and TOD. The study elucidates and compares the impact of hydrocracking longer chain hydrocarbons to produce more valuable products on the TEA and LCA. The TEA showed that the fixed capital investment could range from $\$32.5$ million for TOD without hydrocracking to $\$244$ million for CPY with hydrocracking scenarios. Annual revenues range from $\$28.1$ million to $\$71.5$ million in favor of scenarios with hydrocracking. However, the net present value ranges from $\$1.4$ million to $\$265.8$ million in favor of scenarios without hydrocracking. Sensitivity analysis showed that fixed capital cost, facility capacity, and product prices have the biggest impact on the process economics of the facilities, while utilities and waste transportation to refineries have the biggest impact on environmental impacts. Here, the LCA showed that primary products from scenarios without hydrocracking can be more environmentally friendly than virgin products from petroleum processes. However, TOD and CPY with hydrocracking primary products have more emissions than those of virgin products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Magnesium Oxysulfate Formulation for SRPPF Aqueous Recovery Liquid Solidification

The liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery Processes will be solidified into a stable form that is acceptable by Waste Isolation Pilot Plant (WIPP) for disposal. The current Aqueous Recovery flow sheet proposes to solidify the liquid effluent using a grout formula that was developed and tested for the former Waste Solidification Building process. This Portland cement based mixture results in a high pH (~13) leachate from the solidified waste form which is not acceptable to WIPP in the large quantities expected from production at SRPPF. Various cementitious materials were previously evaluated as alternative grout formulations to Portland cement and a MgO-based mix was identified as a promising alternative. A magnesium oxysulfate (MOS) cement formulation comprised of reactive magnesium oxide (MgO), anhydrous magnesium sulfate (MgSO 4 ), and sand, as a non-reactive heat sink provided good mixability, similar density to the original Portland-cement based mix, and a leachate pH of 9.4, within the assumed WIPP brine pH range. However, the MOS formulation exhibited an appreciable amount of heat generation, which resulted in premature setting of a large-scale test.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Phosphonate functionalized magnetic mesoporous silica for rare earth element recovery from citrate assisted solid waste extracts

The growing high demand of rare earth elements (REEs) has prompted extensive research on REE recovery from waste streams. This study reports the synthesis and evaluation of phosphonate-functionalized magnetic mesoporous silica (MMS-PP) for REE recovery from the acidic extracts of solid wastes. MMS-PP was synthesized using surfactant template and post-synthesis methods, and tested using simulated and real extraction solutions from citrate-assisted REE extracts from municipal solid waste incineration (MSWI) ash. The organic-inorganic hybrid MMS-PP was evaluated for La recovery from 50 mM simulated citrate extract, with the adsorption capacity of 13.5 mg/g compared to ∼2.5 mg/g for non-functionalized MMS. The MMS-PP material exhibited fast adsorption within 10 min, good La selectivity against competing Na + and Ca 2+ , moderate selectivity against Al 3+ and Fe 3+ , high recyclability over multiple adsorption-desorption cycles, and equivalent efficiency for La, Ce, Nd, and Y recovery. Furthermore, the MMS-PP material also demonstrated 70–95% REE recovery from real citrate extracts of MSWI ash, and the spent MMS-PP material can be regenerated and reused for multiple cycles. Functionalized mesoporous materials in combination with organic-ligand assisted extraction can potentially provide a green, effective, and tunable solid-liquid separation platform for REE recovery from complex solid waste streams.

REE recovery↗

Nonwoven Fabric Uses and Prospects in Human Space Flight

The US space shuttle fleet has been flying for over 20 years. Although the shuttle operates in a unique exterior environment, the interior is intentionally made to be as close to the "normal" human environment as possible. The filtration needs of the shuttle are not substantially different from those of a large mobile home or camper, supporting the needs of a family of seven for up to two weeks. Therefore, most of the materials that are used to filter the air, water, and other fluids on the Shuttle are similar or identical to those employed in other sectors of the transportation industry. The only significantly different feature of the space environment is the unique "three-phase" nature of the air (with suspended liquids and solids ranging in size from aerosol droplets to binoculars). Such suspended debris contributes to the air filtration and waste management problem. Careful flow management and cleanliness practices help to mitigate the effect of debris, and liquid spills are rare, seldom making it to the filters. (It has been common on all spacecraft to look first for lost items on the air intake filters, since all objects ultimately migrate there in the flow. Liquids tend to seep rather than "spill", and so tend to aggregate in a ball near the source.) In addition to the basic fluids of the interior environment (water and water wastes, air, and its constituent supply gasses) the shuttle also has unfiltered fluid systems for Freon, hydrogen, helium, ammonia, hydraulic fluid, and propellants. Only the propellant system, owing to its uncommon chemistry, represents a fluid system that is not typical of household or medical applications. Careful external filtration prior to flight assures the cleanliness in these closed systems.

Bacon, Jack↗

Foam and Unreacted Material Reduction in Magnesium Oxysulfate for SRPPF Waste Solidification

A magnesium oxysulfate (MOS) grout formulation has been proposed to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). This formulation uses a combination of light-burnt MgO, anhydrous MgSO 4 , and dead-burnt MgO resulting in a grout with good mixability and acceptable density. The setting time for the grout is within the operational limits of the SRPPF facility and the leachate pH is ~9.4, which is within the assumed pH range of the brine from the Waste Isolation Pilot Plant (WIPP). When first tested at the 1-gallon small-scale and 55-gallon full-scale, there was a significant foam layer that raised concerns of a nonhomogeneous final form. A nonhomogeneous mixture could have variable density throughout the waste form and therefore allow for unequal shielding. To reduce the potential for unequal shielding in the final form, a series of foam reduction tests were carried out and a final formulation of 28 wt% light burnt MgO, 10 wt% MgSO 4 , and 62 wt% dead burnt MgO was used to remove the foam in under two hours while still maintaining a mix that has an acceptable density, mix time, peak temperature, and set time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Off-design performance of an organic Rankine-vapor compression cooling cycle using R1234ze(E)

In this study, a 264 kW th organic Rankine-vapor compression cycle (ORVC) was experimentally tested over a range of conditions to quantify the individual impact of off-design external conditions. The ORVC was designed to recover waste heat at 91 °C, reject heat to a liquid condenser stream at 30 °C, and produce chilled water at 7 °C. Here, the condenser heat rejection temperature was varied from 16.6 °C to 32.6 °C, the chilled water delivery temperature was varied between 2.1 °C and 13.1 °C, and the heat input temperature was varied from 91 °C to 120 °C. As the condenser heat rejection temperature decreased, the coefficient of performance (COP) of the ORVC improved from 0.558 at 30 °C to 0.682 at 16.6 °C, despite a reduction in compressor isentropic efficiency. Although the chilled water temperature variation had almost no impact on the organic Rankine cycle performance, the compressor efficiency decreased when the delivery temperature was below 7 °C. At the highest chilled water temperature, 13.1 °C, the COP of the ORVC was 0.643. Compressor stall was noted when the condenser heat rejection temperature was greater than 32.6 °C and the chilled water delivery temperature was below 2.1 °C. Increasing the driving heat source inlet temperature improved the COP of the ORVC and the thermal efficiency of the organic Rankine power cycle, while decreasing the efficiency of the compressor and the COP of vapor compression cycle. In addition, the integrated part load value of the system was determined through experimentation to be 0.682, which provides a realistic estimate of real-world performance.

30 DIRECT ENERGY CONVERSION↗

Optimal design of multi-stage vacuum membrane distillation and integration with supercritical water desalination for improved zero liquid discharge desalination

Herein this paper proposes a novel concept for the optimal design of multi-stage vacuum membrane distillation (VMD). Generally, a multi-stage VMD is designed with an equal temperature difference between each stage. However, such a design is energy inefficient and increases VMD area. An analytical methodology for calculating the optimal stage temperature is proposed. By selecting the optimal stage temperature, the energy efficiency and required membrane area can be potentially improved by 16% and 30%, respectively. The proposed concept applies to all heat sources, including latent, sensible, and waste heat. To illustrate the method, multi-stage VMD is integrated with the waste heat from a supercritical water desalination (SCWD) system to achieve zero liquid discharge. SCWD is an energy-intensive process, requires high-quality thermal heat (>450 °C), and exhibits high waste heat rejection. The integrated VMD-SCWD approach is approximately 50% more energy-efficient and 35% more cost-efficient than the standalone SCWD system. Compared to the commercially used brine concentrator and crystallizer, the multi-stage VMD-SCWD system is more energy efficient for feed concentrations >5%. VMD-SCWD system is 30% cheaper, due to less expensive membrane distillation modules compared to a brine concentrator. The proposed design concept can replace the brine concentrator and crystallizer as an improved alternative for a zero-liquid discharge desalination system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theory and Tests of Two-Phase Turbines

New turbines open possibility of new types of power cycles. Report describes theoretical analysis and experimental testing of two-phase impulse turbines. Such turbines open possibility of new types of power cycles operating with extremely wet mixtures of steam and water, organic fluids, or immiscible liquids and gases. Possible applications are geothermal power, waste-heat recovery, refrigerant expansion, solar conversion, transportation, and engine-bottoming cycles.

Elliott, D. G.↗

Integration, design, and construction of a CELSS breadboard facility for bioregenerative life support system research

Design criteria for the Biomass Production Chamber (BPC), preliminary operating procedures, and requirements for the future development of the Controlled Ecological Life Support System (CELSS) are discussed. CELSS, which uses a bioregenerative system, includes the following three major units: (1) a biomass production component to grow plants under controlled conditions; (2) food processing components to derive maximum edible content from all plant parts; and (3) waste management components to recover and recycle all solids, liquids, and gases necessary to support life. The current status of the CELSS breadboard facility is reviewed; a block diagram of a simplified version of CELSS and schematic diagrams of the BPS are included.

Prince, R.↗