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At least 91 records · Page 5

Improving Volatile Fatty Acid Productivity of Anaerobic Digestion

Typical anaerobic digestion (AD) focusses on complete conversion of waste to biogas (primarily carbon dioxide and methane). However, the intermediate metabolites of the AD process, which includes short- and long-chain volatile fatty acids (VFAs), that could serve as the precursors for useful industrial applications are typically ignored. The goal of this project is to eliminate production of biogas while enhancing the production of the intermediate VFAs. Using a mixed microbial consortium (from rumen sources and waste-water sludge), we have determined the optimal carbon loading (chemical oxygen demand, "COD") and optimal pH, that results in high VFA concentrations from food waste. The best VFA yields were obtained using 15 g COD/L and a pH of 9.0 for this substrate. pH 9 produced over 200% higher VFA titers than the controlled conditions (i.e., ph 7.0) after 35 d of digestion, in comparison to pH 5 that showed - 88% higher titers than the control digestion. As expected, the cumulative biogas production was highest in the pH 7.0 condition, in comparison to pH 5.0 or pH 9.0. We further observed that removal of VFAs using solid-liquid separation technique reduce the inhibitory effects of VFAs, thereby leading to overall improvement in conversion efficiency. 16s rRNA analysis is being carried out to explain and identify the biocatalysts that enable VFA production in these AD cultures. Additional efforts to improve VFA yields via increasing the total solid content, temperature optimizations, VFA removal via electrodialysis, and improving hydrolysis via microaeration will be presented.

anaerobic digestion↗

Aqueous-phase product treatment and monetization options of wet waste hydrothermal liquefaction: Comprehensive techno-economic and life-cycle GHG emission assessment unveiling research opportunities

While wet waste hydrothermal liquefaction technology has a high biofuel yield, a significant amount of the carbon and nitrogen in the feedstock reports to the aqueous-phase product. Pretreatment of this stream before sending to a conventional wastewater plant is essential or at the very least, advisable. In this work, techno-economic and life-cycle assessments were conducted for the state-of-technology baseline and four aqueous-phase product treatment and monetization options based on experimental data. Further, these options can cut minimum fuel selling prices by up to 13 % and life-cycle greenhouse gas emissions by up to 39 % compared to the baseline. These findings highlight the substantial influence of aqueous produce treatment strategies on the entire wet waste hydrothermal liquefaction process, demonstrating the potential for optimizing economic viability and environmental impact through further research and development of milder treatment methods and diversified by-product valorization pathways.

09 BIOMASS FUELS↗

Catalytic Conversion of Biogenic and Synthetic Polymers into Carbon-Negative and -Neutral Chemicals and Fuels

We investigated a technology that enables the distributed decomposition of biogenic (lignin, cellulose) and synthetic (plastic) polymers into renewable or low-carbon-emission chemicals and fuel intermediates that can substitute fossil hydrocarbons for energy, chemical, and fuel production. The specific goal of this project is to (1) selectively convert biogenic polymers such as lignin and synthetic polymers such as polyethylene into hydrocarbons via electrocatalytic and thermocatalytic processes, and (2) optimize (electro)catalyst composition and reaction conditions to mitigate deactivation and control product selectivity.

09 BIOMASS FUELS↗

Hydrotreatment of Nylon 66 and Amide Model Compounds Over Sulfided NiMo Catalysts

Molybdenum sulfide-based catalysts, such as nickel–molybdenum on alumina (NiMoS x /Al 2 O 3 ), are widely used in hydrotreating and have potential for catalyzing waste plastic conversion via hydrogenolysis, yet their performance, such as reaction kinetics and network, for amide-rich polymer feeds is poorly defined. Here we combine Nylon 66 with the amide model compound, N,N-dibutylhexanediamide (DBDAD), to quantify hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) chemistry in a stirred batch reactor (53 bar H 2 , 280–320°C). DBDAD conversion is near-linear with time, indicating strong adsorption of the substrates on the active sites. Time-resolved product identification indicates parallel C─O first-cleavagedeoxygenation (DO) and C─N first-cleavagedenitrogenation (DN) sequences proceeding through amine and diol intermediates, respectively, to C 4 ─C 6 alkanes. Increasing temperature shifts selectivity toward DN, decreasing the initial r(DO)/r(DN) from 1.38 (280°C) to 0.69 (320°C), with an apparent activation energy of 173 kJ mol −1 for DBDAD conversion. At 300°C, nylon 66 converts faster than DBDAD, producing a complex mixture of oxygen- and nitrogen-containing species and an initial rate ratio r(DO)/r(DN) of 1.6. No heteroaromatic nitrogen products are detected by the method used. These results provide reaction pathways and product signatures relevant to hydro-processing catalysts exposed to polyamide-derived streams.

Nylon 66↗

The pH and Potential Dependence of Pb–Catalyzed Electrochemical CO 2 Reduction to Methyl Formate in a Dual Methanol/Water Electrolyte

The conversion of waste CO 2 to value-added chemicals through electrochemical reduction is a promising technology for mitigating climate change while simultaneously providing economic opportunities. The use of non-aqueous solvents like methanol allows for higher CO 2 availability and novel products. In this work, the electrochemistry of CO 2 reduction in acidic methanol catholyte at a Pb working electrode was investigated while using a separate aqueous anolyte to promote a sustainable water oxidation half-reaction. The selectivity among methyl formate (a product unique to reduction of CO 2 in methanol), formic acid, and formate was critically dependent on the catholyte pH, with higher pH conditions leading to formate and low pH favoring methyl formate. Furthermore, the potential dependence of the product distribution in acidic catholyte was also investigated, with a faradaic efficiency for methyl formate as high as 75% measured at -2.0 V vs Ag/AgCl.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

PERFORMANCE ANALYSIS OF AN ENGINEERING SCALE HYDROTHERMAL LIQUEFACTION SYSTEM

This work evaluates the Modular Hydrothermal Liquefaction System (MHTLS), an engineering-scale, integrated continuous HTL plant operated at the Pacific Northwest National Laboratory (PNNL), for converting realistic wet wastes into energy-dense biocrudes. The production campaigns discussed here processed algae, sewage sludges, lignocellulosic blends, Industrial food waste, and engineered food-waste slurries at 350?°C and around 200?bar, with nominal feed rates of ~12?L?h?¹. We report biocrude yields and composition, establish mass and elemental (C, N) balances, and quantify energy performance via heater duties, heat-exchanger behavior, and system-level efficiencies. Biocrudes contained 76–80?wt?% C (dry, ash-free) with HHVs of 38-41?MJ?kg?¹, substantially higher than feed materials HHVs of 16.6–26.1?MJ?kg?¹ and approaching petroleum fuels. Dry, ash-free biocrude yields of 32–53?wt?% corresponded to 43–71?wt?% carbon yields, with 18–40?wt?% of feed carbon routed to the aqueous phase. Thermal efficiencies were 50-65%, and total energy efficiencies, including reactor heat input, were 35-55%. A counter-current tube-in-tube heat exchanger delivered U values of 200–450?W?m?²?K?¹, with fouling-induced declines impacting heat recovery and heater duty. The analysis highlights three priorities for the process intensification of HTL: robust, fouling-resistant heat recovery, hydrodynamically suitable reactor and heat-exchanger designs, simplified and predictable solids management, and biocrude-water separation.

Biocrude production↗

Bifunctional tandem catalytic upcycling of polyethylene to surfactant-range alkylaromatics

Catalytic conversion of waste polyolefins to value-added alkylaromatics could contribute to carbon recycling. Compared with tandem hydrogenolysis/aromatization of polyethylene (PE) catalyzed by Pt/γ-Al 2 O 3 at 280°C, both a 5-fold enhancement in the rate of C–C bond scission and a doubling of the molar yield of alkylaromatics were achieved using a more acidic Pt/F-Al 2 O 3 catalyst instead. Bifunctional (metal/acid) catalysts also generate alkylaromatic products with lower average carbon numbers (ca. C 20 ), similar to conventional anionic surfactants. Because physical mixtures of weakly acidic Pt/γ-Al 2 O 3 or non-acidic Pt/SiO 2 with strongly Brønsted acidic Cl-Al 2 O 3 or F-Al 2 O 3 are also effective, the tandem reaction does not require nanoscale intimacy between metal and acid active sites. Kinetic studies using triacontane (norm-C 30 H 62 ) as a model for PE show that the Pt-catalyzed dehydrogenation/hydrogenation reactions are quasi-equilibrated, while the acid-catalyzed C–C bond scission and skeletal transformations (isomerization and cyclization) determine the overall rates of depolymerization and aromatic formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conversion of Compositionally Diverse Plastic Waste over Earth-Abundant Sulfides

Chemical deconstruction of polyolefin plastic wastes via hydroconversion is promising for mitigating plastic accumulation in landfills and the environment. However, hydroconversion catalysts cannot handle complex feedstocks containing multiple polymers, additives, and heteroatom impurities. Here, we report a single-step strategy using earth-abundant metal sulfide catalysts to deconstruct these wastes. We show that NiMoS x /HY catalysts deconstruct polyolefin feedstocks, achieving ~81–94% selectivity to liquid products. Postsynthetic zeolite modification enhances the catalyst’s activity by >2.5 times, achieving over 95% selectivity to liquid fuels with controllable product distribution in the naphtha, jet fuel, and diesel range. The catalyst is resilient to increasingly complex feedstocks, such as additive-containing polymers and mixed plastics composed of polyolefins and heteroatom-containing polymers, including poly(vinyl chloride). As a result, we extend the strategy to single-use polyolefin wastes that can generate toxic byproducts, such as HCl and NH 3 , and eliminate their emissions by integrating reaction and sorption in a one-step process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High thermoelectric figure of merit of porous Si nanowires from 300 to 700 K.

Thermoelectrics operating at high temperature can cost-effectively convert waste heat and compete with other zero-carbon technologies. Among different high-temperature thermoelectrics materials, silicon nanowires possess the combined attributes of cost effectiveness and mature manufacturing infrastructures. Despite significant breakthroughs in silicon nanowires based thermoelectrics for waste heat conversion, the figure of merit (ZT) or operating temperature has remained low. Here, we report the synthesis of large-area, wafer-scale arrays of porous silicon nanowires with ultra-thin Si crystallite size of ~4 nm. Concurrent measurements of thermal conductivity (κ), electrical conductivity (σ), and Seebeck coefficient (S) on the same nanowire show a ZT of 0.71 at 700 K, which is more than ~18 times higher than bulk Si. This ZT value is more than two times higher than any nanostructured Si-based thermoelectrics reported in the literature at 700 K. Experimental data and theoretical modeling demonstrate that this work has the potential to achieve a ZT of ~1 at 1000 K.

36 MATERIALS SCIENCE↗

Stepping on the Gas to a Circular Economy: Accelerating Development of Carbon-Negative Chemical Production from Gas Fermentation

Owing to rising levels of greenhouse gases in our atmosphere and oceans, climate change poses significant environmental, economic, and social challenges globally. Technologies that enable carbon capture and conversion of greenhouse gases into useful products will help mitigate climate change by enabling a new circular carbon economy. Gas fermentation using carbon-fixing microorganisms offers an economically viable and scalable solution with unique feedstock and product flexibility that has been commercialized recently. Here, we review the state of the art of gas fermentation and discuss opportunities to accelerate future development and rollout. We discuss the current commercial process for conversion of waste gases to ethanol, including the underlying biology, challenges in process scale-up, and progress on genetic tool development and metabolic engineering to expand the product spectrum. We emphasize key enabling technologies to accelerate strain development for acetogens and other nonmodel organisms.

59 BASIC BIOLOGICAL SCIENCES↗

Comments on dual-mode nuclear space power and propulsion system concepts

Some form of Dual-Mode Nuclear Space Power & Propulsion System (D-MNSP&PS) will be essential to spacefaring throughout teh solar system and that such systems must evolve as mankind moves into outer space. The initial D-MNPSP&PS Reference System should be based on (1) present (1990), and (2) advanced (1995) technology for use on comparable mission in the 2000 and 2005 time period respectively. D-MNSP&PS can be broken down into a number of subsystems: Nuclear subsystems including the energy source and controls for the release of thermal power at elevated temperatures; power conversion subsystems; waste heat rejection subsystems; and control and safety subsystems. These systems are briefly detailed.

Layton, J. Preston↗

Enhancing the Value of Wasted and Stranded Natural Gas Resources Through Conversion Into Aromatics Using Microwaves

Natural gas flaring results in the waste of significant amounts of valuable domestic energy resources while also producing undesirable environmental impacts. Transforming natural gas into value-added chemicals via direct nonoxidative reactions presents a compelling alternative to flaring. However, traditional thermal reactor systems face challenges due to thermodynamic limitations and poor catalyst stability. Microwave-assisted reactions offer a sustainable, on-demand approach for chemical production from natural gas, suitable for compact, flexible reactor systems at the well-site that can be powered by renewable energy. This method offers a novel, non-traditional approach in catalyst activation and product selectivity compared to a conventional thermal method, potentially leading to faster rates, higher selectivities, and higher conversion efficiencies. Despite these advantages, challenges exist, such as the low microwave-sensitivity of the state-of-the-art zeolite catalyst that is highly active for the methane dehydroaromatization reaction. This presentation will discuss recent research from the National Energy Technology Laboratory concerning microwave-assisted natural gas conversion directly into aromatics. It will address the difficulties with microwave heating of traditional thermochemical catalysts, and the application of Multiphysics modeling to understand temperature and field strength in the reactor, to enhance chemical conversion. The presentation will also cover how heating aids can mitigate heating challenges and transform microwave catalysis into a quasi-thermal kinetic problem. Additionally, catalyst activation and deactivation under microwave conditions will be examined, along with the future outlook and needs for microwave enhanced catalysis applications.

catalysis↗

Conversion kinetics during melting of simulated nuclear waste glass feeds measured by dissolution of silica

In this work, we experimentally investigated the batch-to-glass conversion kinetics of two low-activity and two high-level nuclear waste melter feeds that represent widely different behavior during melting; tests comprised thermogravimetric analysis, the feed expansion test, evolved gas analysis, and x-ray diffraction. Our study indicates that the conversion processes, which include gas-evolving reactions, dissolution of crystalline phases, and primary foam expansion and collapse, are interconnected and influenced by the feed’s thermal history. The fraction of dissolved silica was adopted as a measure of the extent of conversion inside the cold cap—the floating layer of feed material on the top surface of the melt in an electric melter. The interface between the cold cap and the free-flowing melt below was associated with a constant fraction of dissolved silica. The estimated viscosity of glass-forming melt at this interface lies within a narrow range for the feeds studied.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Energy and cost savings results for advanced technology systems from the Cogeneration Technology Alternatives Study /CTAS/

The Cogeneration Technology Alternatives Study (CTAS), a program undertaken to identify the most attractive advanced energy conversion systems for industrial cogeneration applications in the 1985-2000 time period, is described, and preliminary results are presented. Two cogeneration options are included in the analysis: a topping application, in which fuel is input to the energy conversion system which generates electricity and waste heat from the conversion system is used to provide heat to the process, and a bottoming application, in which fuel is burned to provide high temperature process heat and waste heat from the process is used as thermal input to the energy conversion system which generates energy. Steam turbines, open and closed cycle gas turbines, combined cycles, diesel engines, Stirling engines, phosphoric acid and molten carbonate fuel cells and thermionics are examined. Expected plant level energy savings, annual energy cost savings, and other results of the economic analysis are given, and the sensitivity of these results to the assumptions concerning fuel prices, price of purchased electricity and the potential effects of regional energy use characteristics is discussed.

Sagerman, G. D.↗

Operation of magnetically assisted fluidized beds in microgravity and variable gravity: experiment and theory

The conversion of solid waste into useful resources in support of long duration manned missions in space presents serious technological challenges. Several technologies, including supercritical water oxidation, microwave powered combustion and fluidized bed incineration, have been tested for the conversion of solid waste. However, none of these technologies are compatible with microgravity or hypogravity operating conditions. In this paper, we present the gradient magnetically assisted fluidized bed (G-MAFB) as a promising operating platform for fluidized bed operations in the space environment. Our experimental and theoretical work has resulted in both the development of a theoretical model based on fundamental principles for the design of the G-MAFB, and also the practical implementation of the G-MAFB in the filtration and destruction of solid biomass waste particles from liquid streams. c2004 COSPAR. Published by Elsevier Ltd. All rights reserved.

manned↗

Sustainable Li-ion anode material from Fe-catalyzed graphitization of paper waste

We report a novel method for the conversion of paper towel waste to biographite anode material is developed and optimized for use in Li-ion batteries. The surge in demand for Li-ion battery anode materials coupled with the unsustainable and inefficient methods of producing battery-grade graphite necessitate alternative carbon feedstocks and graphitization technologies. Paper waste (PW) is identified as a suitable carbon feedstock for iron-catalyzed graphitization due to its sustainability, low cost, low ash content, and ample supply for the intended end use. A Box Behnken experimental design for statistical optimization is pursued for untreated and pre-carbonized PW with factors of temperature (1100-1300 °C), hold time (1-5 h), and iron catalyst loading (0.5-1.5x fixed carbon content) with biographite crystal size as the primary response variable. Temperature and iron catalyst loading are found to be significant factors, whereas hold time is found to be insignificant. Reversible capacities of the biographite anodes are found to be 340-355 mAh g-1 with 99% capacity retention over 100 cycles, indicating good electrochemical performance relative to commercial graphite anodes. The initial Coulombic efficiency of untreated and pre-carbonized biographites, however, are 77% and 75%, respectively, suggesting parasitic reactions including electrolyte decomposition.

25 ENERGY STORAGE↗