Energy and techno-economic analysis of bio-based carboxylic acid recovery by adsorption
Recent works have established bio-based carboxylic acids as adaptable precursors to renewable biofuels and chemicals.
Saboe, Patrick O.↗
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Deep Eutectic Solvents as Candidates for Lithium Isotope Enrichment
Nuclear fusion is a phenomenon that is well known within the nuclear physics community as a viable option for alternative energy as many natural gases and fossil fuels are phased out of commercial use. Deuterium and tritium fusion reactions are currently the leading candidates for nuclear fusion, with a major limiting factor being a means to produce tritium on an industrial scale. Lithium-6 is a well-known isotope that can produce tritium and helium following a fission reaction with a neutron. Unfortunately, the lithium-6 enrichment methods are limited to the COLEX process, which leaves behind an alarming amount of mercury waste as a potential environmental contaminant. Deep eutectic solvents are believed to be a potential alternative to lithium isotope separations due to the ease of generation, in addition to the minimum environmental waste generated when these solvents are employed. Previous studies have suggested that deep eutectic solvents are capable of separating lithium isotopes by utilizing a 2-thenoyltrifluoroacetone and trioctylphosphine oxide system that can biphasically react with a buffered solution containing lithium chloride. This system displays a separation factor of 1.068, which when compared to the 1.054 separation within the COLEX process, makes it a potential candidate for lithium-6/7 separation. Within this study, we investigate this system in comparison to two newly synthesized deep eutectic solvents and find that within these acetylacetone-based systems, little isotopic separation is observed. We investigate these systems both experimentally and computationally, showing the different lithium cation affinities, in addition to proposing how the electron-donating or -withdrawing nature can influence these systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Recovery of Carbon and Valuable Components from Spent Pot Lining by Leaching with Acidic Aluminum Anodizing Wastewaters
A three-step process was employed to separate cryolite from used carbon cathodes, known as spent pot lining (SPL), and obtain valuable carbon. The process comprised leaching of NaF from the imbedded electrolyte with water, followed by leaching of Na{sub 3}AlF{sub 6}, CaF{sub 2}, and NaAl{sub 11}O{sub 17} with acidic anodizing wastewater, and then precipitating the electrolyte components from the mixed filtrate from the previous two steps. The influences of stirring rate, liquid–solid ratio, temperature, and time on the extent of leaching of cryolite and recovery of carbon were studied. Additionally, the effects of pH value, F/Al ratio, temperature, and time on the recovery of valuable components in the mixed filtrate were evaluated. The results showed that most NaF in the SPL was dissolved by water leaching. The residual electrolyte in SPL was mainly cryolite and contained approximately 0.95 pct NaF. The purity of the carbon obtained reached 95.5 pct under optimal experimental conditions (leaching temperature: 80 °C; stirring rate: 300 rpm; liquid–solid ratio: 8 mL/g; leaching time: 180 minutes). The recovery of cryolite and the purity of the sodium sulfate crystal from the mixed filtrate were 98.4 and 92.0 pct, respectively, under suitable conditions (pH 9; 75 °C; 4 hour; F/Al ratio of 6:1).
36 MATERIALS SCIENCE↗
Fiber optic sensors with internal referencing
The main problem with amplitude modulating type sensors is that any variation in the intensity of the optical signal which occurs throughout the sensing system is interpreted by the photodetector as resulting from the sensor itself and is reflected as an error in the sensed parameter. To account for these errors, a referencing technique with the signal and reference channels separated in the time domain over the same fiber link can be used. Selected sensing and signal processing techniques involving temporally separated signal and referencing channels are described. A transition from the time into the frequency domain is also discussed. Experimental data are presented.
Adamovsky, Grigory↗
Hydrocyclone pre-processing of wastewater algae: A strategy for inorganic ash separation
Microalgae cultivation on wastewater can provide remediation and generate valuable feedstocks for biofuel production. Wastewater algae typically have a high percentage of inorganic ash, which can reduce yield and quality of biocrude produced during hydrothermal liquefaction (HTL). Here, in this work, we evaluated the ability of hydrocyclone pre-processing to remove inorganic ash from wastewater algae. The pH of the algae slurry was adjusted to 9.5 to encourage the formation of precipitates and create a density differential between ash particles and algal cells. Hydrocyclone processing successfully concentrated ash particles in the underflow fraction and reduced the total ash percentage in the overflow fraction. Overall, hydrocyclone processing reduced the total ash by 21%, while only 8% of organics were lost. Elemental and mineral analysis showed that Mg and P were concentrated in the underflow in the form of baricite (an isomorph of vivianite). Future research should focus on improving vivianite and/or baricite formation, and therefore ash removal, by providing a reducing environment. The addition of multiple hydrocyclones in series could also improve the removal of ash. We concluded that hydrocyclone treatment of wastewater algae is a feasible method to remove inorganic ash, but further process optimization is required.
09 - BIOMASS FUELS↗
A decentralized software bus based on IP multicas ting
We describe decentralized reconfigurable implementation of a conference management system based on the low-level Internet Protocol (IP) multicasting protocol. IP multicasting allows low-cost, world-wide, two-way transmission of data between large numbers of conferencing participants through the Multicasting Backbone (MBone). Each conference is structured as a software bus -- a messaging system that provides a run-time interconnection model that acts as a separate agent (i.e., the bus) for routing, queuing, and delivering messages between distributed programs. Unlike the client-server interconnection model, the software bus model provides a level of indirection that enhances the flexibility and reconfigurability of a distributed system. Current software bus implementations like POLYLITH, however, rely on a centralized bus process and point-to-point protocols (i.e., TCP/IP) to route, queue, and deliver messages. We implement a software bus called the MULTIBUS that relies on a separate process only for routing and uses a reliable IP multicasting protocol for delivery of messages. The use of multicasting means that interconnections are independent of IP machine addresses. This approach allows reconfiguration of bus participants during system execution without notifying other participants of new IP addresses. The use of IP multicasting also permits an economy of scale in the number of participants. We describe the MULITIBUS protocol elements and show how our implementation performs better than centralized bus implementations.
Callahan, John R.↗
Ash reduction strategies in corn stover facilitated by anatomical and size fractionation
There is growing interest internationally to produce fuels from renewable biomass resources. Inorganic components of biomass feedstocks, referred to collectively as ash, damage equipment and decrease yields in thermal conversion processes, and decrease feedstock value for biochemical conversion processes. Decreasing the ash content of feedstocks improves conversion efficiency and lowers process costs. Because physiological ash is unevenly distributed in the plant, mechanical processes can be used to separate fractions of the plant based on ash content. This study focuses on the ash separation that can be achieved by separating corn stover by particle size and anatomical fraction. Baled corn stover was hand-separated into anatomical fractions, ground to <19.1 mm, and size separated using six sieves ranging from 9.5 to 0.150 mm. Size fractions were analyzed for total ash content and ash composition. Particle size distributions observed for the anatomical fractions varied considerably. Cob particles were primarily 2.0 mm or greater, while most of the sheath and husk particles were 2.0 mm and smaller. Particles of leaves greater than 0.6 mm contained the greatest amount of total ash, ranging from approximately 8 to 13% dry weight of the total original material, while the fractions with particles smaller than 0.6 mm contained less than 2% of the total ash of the original material. As a result, based on the overall ash content and the elemental ash, specific anatomical and size fractions can be separated to optimize the feedstocks being delivered to biofuels conversion processes and minimize the need for more expensive ash reduction treatments.
09 BIOMASS FUELS↗
Anhydrous volatile fatty acid extraction through omniphobic membranes by hydrophobic deep eutectic solvents: Mechanistic understanding and future perspective
Volatile fatty acids (VFAs) derived from arrested anaerobic digestion (AD) can be recovered as a valuable commodity for value-added synthesis. However, separating VFAs from digestate with complex constituents and a high-water content is an energy-prohibitive process. This study developed an innovative technology to overcome this barrier by integrating deep eutectic solvents (DESs) with an omniphobic membrane into a membrane contactor for efficient extraction of anhydrous VFAs with low energy consumption. Here, a kinetic model was developed to elucidate the mechanistic differences between this novel omniphobic membrane-enabled DES extraction and the previous hydrophobic membrane-enabled NaOH extraction. Experimental results and mechanistic modeling suggested that VFA extraction by the DES is a reversible adsorption process facilitating subsequent VFA separation via anhydrous distillation. High vapor pressure of shorter-chain VFAs and low Nernst distribution coefficients of longer-chain VFAs contributed to DES-driven extraction, which could enable continuous and in-situ recovery and conversion of VFAs from AD streams.
59 BASIC BIOLOGICAL SCIENCES↗
Circulating fluidized bed connected to a desublimating heat exchanger
Condensable vapors such as carbon dioxide are separated from light gases in a process stream. The systems and methods employ a circulating fluidized particle bed cooled by an out-bed heat exchanger to desublimate the solid form of condensable vapors from the process stream. Gas and solids may be sorted in a separator, and the solids may then be subcooled in a heat exchanger. The condensable vapors may be condensed on the bed particles or in the heat exchanger while the light gases from the process stream, which are not condensed, form a separated light-gas stream.
Baxter, Larry↗
A New Group Crystallization Approach in Used Nuclear Fuel Recycling: A Look at Fission Product Behaviors
Nuclear energy has the potential to play a large role in meeting future needs of the U.S. sustainable energy strategy, as a clean, carbon-free power source. However, to take advantage of the inherent benefits, many hurdles must be overcome in order for nuclear power to achieve these expectations. One of the largest challenges faced, is the management of used nuclear fuel (UNF). Currently, no strategy has been identified to deal with the growing UNF problem, and so the UNF remains stored on site at nuclear power plants either in cooling pools or in dry cast storage. The amount of stored UNF continues to grow, and with it, so does the concern surrounding its long-term radiotoxicity. This material could be reprocessed to recover the actinides, maximizing the energy potential of the UNF and minimizing the waste generation. Not only do U and Pu, the major energy producing actinides, need to be recovered, but recovering Np and Am would make waste generated from reprocessing significantly safer for long-term storage in a geological repository. There are a number of methods currently in use to reprocess UNF; throughout Europe, the Purex process is widely implemented, while the Japanese have developed the Next process. The Next process removes a bulk of the U by crystallization prior to a Purex-like separation scheme. In the Next process, it is undesirable to have any other species removed from solution in the crystallization step, but rather the goal is to obtain a pure uranyl nitrate hexahydrate (UNH) product. Alternatively, a group separation of U-Am by a crystallization process would provide an elegant solution. Such a process has become attainable with the renewed interest in accessing Am(VI) in nitric acid solutions. In order to synthesize and stabilize Am(VI), a highly oxidizing system is required, which has only been demonstrated on a limited basis. By oxidizing Np, Pu, and Am to their hexavalent state, they can be co-crystallized with UNH, and thereby removed from solution. Recent results have demonstrated that all the hexavalent actinide (An) species are removed from solution in near proportion, by a simple reduction of temperature in 6-8 M HNO{sub 3}. (authors)
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
A New Group Crystallization Approach in Used Nuclear Fuel Recycling: A Look at Fission Product Behaviors
Nuclear energy has the potential to play a large role in meeting future needs of the U.S. sustainable energy strategy, as a clean, carbon-free power source. However, to take advantage of the inherent benefits, many hurdles must be overcome in order for nuclear power to achieve these expectations. One of the largest challenges faced, is the management of used nuclear fuel (UNF). Currently, no strategy has been identified to deal with the growing UNF problem, and so the UNF remains stored on site at nuclear power plants either in cooling pools or in dry cask storage. The amount of stored UNF continues to grow, and with it, so does the concern surrounding its long-term radiotoxicity. This material could be reprocessed to recover the actinides, maximizing the energy potential of the UNF and minimizing the waste generation. Not only do U and Pu, the major energy producing actinides, need to be recovered, but recovering Np and Am would make waste generated from reprocessing significantly safer for long-term storage in a geological repository. There are a number of methods currently in use to reprocess UNF; throughout Europe, the Purex process is widely implemented, while the Japanese have developed the Next process. The Next process removes a bulk of the U by crystallization prior to a Purex-like separation scheme. In the Next process, it is undesirable to have any other species removed from solution in the crystallization step, but rather, the goal is to obtain a pure uranyl nitrate hexahydrate (UNH) product. Alternatively, a group separation of U-Am by a crystallization process would provide an elegant solution. Such a process has become attainable with the renewed interest in accessing Am(VI) in nitric acid solutions. In order to synthesize and stabilize Am(VI) which has only been demonstrated on a limited basis, a highly oxidizing system is required. By oxidizing Np, Pu, and Am to their hexavalent state, they can be co-crystallized with UNH, and thereby removed from solution. Recent results have demonstrated that all the hexavalent actinide (An) species are removed from solution in near proportion, by a simple reduction of temperature in 6-8 M HNO{sub 3}.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Ionic liquid-enhanced recycling of lithium-ion battery black mass via heavy liquid centrifugal separation
Direct recycling of lithium-ion batteries (LIBs) is of great significance to supply chain security and environmental protection by restoring spent battery materials to their original purpose without destroying their chemical structure. One of the key processes for direct recycling is to separate valuable anode and cathode active materials from black mass. This study evaluates ionic liquid-enhanced Heavy Liquid Centrifugal Separation (HLCS) as an efficient method for separating LIB black mass into its constituent anode and cathode materials. The optimized HLCS process achieved a separation efficiency of over 95%, yielding a graphite-rich upper layer and an NMC-rich lower layer. Characterization by thermogravimetric analysis (TGA), X-ray diffraction (XRD), and inductively coupled plasma-optical emission spectroscopy (ICP-OES) confirmed the purity and structural integrity of the recovered fractions. The addition of N-methyl-2-pyrrolidone and ionic liquid 1-ethyl-3-methylimidazolium bromide decoupled entangled particles, while subsequent treatment of the anode layer with 1-(2,3-dihydroxypropyl)-3-methylimidazolium chloride further enhanced separation purity. The recycled graphite exhibited comparable battery performance to pristine graphite. These results demonstrate HLCS as a promising LIB recycling strategy, advancing sustainable battery manufacturing.
Adigun, Babafemi [Univ. of Tennessee, Knoxville, T↗
Above‐T g Annealing Benefits in Nanoparticle‐Stabilized Carbon Molecular Sieve Membrane Pyrolysis for Improved Gas Separation
Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol-gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource-H 2 separation processes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chemical Recycling of Mixed Plastics in Electronic Waste Using Solvent-Based Processing
Currently, less than 20% of electronic waste (E-waste) produced in the U.S. is recycled. To improve the recycling rate of E-waste, the study aimed to: (1) identify the major plastics found within electronic shredder residue (ESR), (2) design solvents and processing conditions capable of separating out 90% of the plastic in ESR, and (3) estimate the energy efficiency of the solvent-based process developed. Preliminary screening showed 25 wt.% of the ESR was composed of plastics, with two polymers dominating the sorted plastic fraction—polystyrene (PS, 40 wt.%) and acrylonitrile butadiene styrene (ABS, 25 wt.%). Subsequently, solvents and anti-solvents were screened using Hansen Solubility Parameter Theory for PS, ABS, and ESR dissolution. The pre-screening results showed dichloromethane (DCM) and tetrahydrofuran (THF) as the most effective solvents for PS and ABS, with methanol (MeOH) and ethylene glycol (EG) as the most effective anti-solvents. By optimizing the dissolution time and the solvents used, the highest polymer dissolution yield (99 wt.%) was achieved using DCM for 48 h. Both MeOH and EG precipitated 71 wt.% of the polymer fraction of ESR. EG removed more phosphorus containing flame retardants (94 wt.%) than MeOH (69 wt.%). Energy analysis indicated that the solvent-based processes could save 25–60% of the embodied energy for PS and ABS. Characterization showed that the solvent-based processing could preserve the high molecular weight fraction of the polymers while removing flame retardants at the same time. The results from this study prove the potential of solvent-based processing to produce secondary plastic materials from E-waste for cross-industry reuse.
Anderson, Lester↗
Vibroacoustic Process Monitoring of 5-Stage Centrifugal Contactors
Vibroacoustic monitoring was investigated to aid in informing process operators with parameters regarding aqueous separation techniques. These techniques have a wide range of applications including nuclear fuel reprocessing. A small-scale solvent extraction system was set up with five magnetic drive contactors and two piston pumps to collect realistic operation. Vibration sensors were placed on three of the contactors and both pumps, and a microphone was placed near the system. Contactor rotational speed and pump flow rate were varied with known values to compare against measured vibroacoustic signatures. Spectral analysis allowed for the determination of contactor rotational speed and the ratio of organic to aqueous flow rate, an important parameter for ensuring optimal extraction. Vibration metrics such as kurtosis and crest factor provided additional details regarding individual rotational speeds and have potential in examination of faults for predictive maintenance. Overall, results indicate the capability of vibroacoustic monitoring to improve operator awareness and process outcomes.
11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Unconventional desalination: The use of cyclone separators in HDH desalination to achieve zero liquid discharge
Research in water desalination technologies is constantly growing to meet global demands for freshwater. Though acting to meet these demands, the rapid growth and spread of desalination technologies poses environmental issues due to the increasing brine concentrates that are ultimately discharged back to nature. This article presents a cyclone separator to transform a humidification-dehumidification (HDH) cycle to a dual-product cycle to produce freshwater and solid salt crystals for highly saline streams. A desalination cycle equipped with a cyclone separator is used to treat water with 3.5%–81% salinity. The separation efficiency is well above 99% and can produce potable water from hyper saline feed in a once-through process. Further, the cyclone separator performance was tested under different conditions including humidity ratios, relative humidities, and feed stream's salinities. The cyclone separator is self-cleaning and overcomes salt scaling. This behavior is a direct function of the walls' temperature and the carrier air dew point. Self-cleaning capability allows the cyclone separator to treat feed water of extreme salinities (up to 810,000ppm) down to freshwater salinity with zero liquid discharge. The cyclone separator was utilized in a novel HDH desalination technology to treat different salinities. The product was freshwater of salinity <500ppm.
42 ENGINEERING↗
Thermal Stir Welding: A New Solid State Welding Process
Thermal stir welding is a new welding process developed at NASA's Marshall Space Flight Center in Huntsville, AL. Thermal stir welding is similar to friction stir welding in that it joins similar or dissimilar materials without melting the parent material. However, unlike friction stir welding, the heating, stirring and forging elements of the process are all independent of each other and are separately controlled. Furthermore, the heating element of the process can be either a solid-state process (such as a thermal blanket, induction type process, etc), or, a fusion process (YG laser, plasma torch, etc.) The separation of the heating, stirring, forging elements of the process allows more degrees of freedom for greater process control. This paper introduces the mechanics of the thermal stir welding process. In addition, weld mechanical property data is presented for selected alloys as well as metallurgical analysis.
Ding, R. Jeffrey↗
Thermal Stir Welding: A New Solid State Welding Process
Thermal stir welding is a new welding process developed at NASA's Marshall Space Flight Center in Huntsville, AL. Thermal stir welding is similar to friction stir welding in that it joins similar or dissimilar materials without melting the parent material. However, unlike friction stir welding, the heating, stirring and forging elements of the process are all independent of each other and are separately controlled. Furthermore, the heating element of the process can be either a solid-state process (such as a thermal blanket, induction type process, etc), or, a fusion process (YG laser, plasma torch, etc.) The separation of the heating, stirring, forging elements of the process allows more degrees of freedom for greater process control. This paper introduces the mechanics of the thermal stir welding process. In addition, weld mechanical property data is presented for selected alloys as well as metallurgical analysis.
Ding, R. Jeffrey↗