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At least 631 records · Page 35

Reaction Temperature Manipulation as a Process Intensification Approach for CO 2 Absorption

Reactor temperature manipulation to increase product yields of chemical reactions is a known technique used in many industrial processes. In the case of exothermic chemical reactions, the well-known Le Chatelier’s principle predicts that a decrease in temperature will displace the chemical reaction toward the formation of products by increasing the value of the equilibrium constant. The reverse is true for endothermic reactions. Reactor temperature manipulation in an industrial system, however, affects the values of many variables, including physical properties, transport parameters, reaction kinetic parameters, etc. In the case of reactive absorption, some variables change with increasing temperatures due to solute absorption, while others change in such a way that the solute absorption rate decreases. For example, temperature drop increases product formation for exothermic reactions but reduces the value of transport parameters, leading to decreasing interfacial concentrations and absorption rates. Therefore, temperature manipulation strategies must be designed carefully to achieve the process goals. In this work, we theoretically study the use of temperature as a tool to increase CO 2 absorption by solvents in a semi-batch reactor. A computer code has been developed and validated using reported experimental data. Calculated results demonstrate an increase in absorbed CO 2 of more than 28% with respect to the highest temperature used. Despite high agitation and high gas flow rate, the system is mass transfer controlled at short times, becoming kinetically controlled as time increases. An operating strategy to decrease cooling energy costs is also proposed. This study reveals that reactor temperature manipulation can be an effective process to improve CO 2 absorption by solvents in two-phase semi-batch reactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fabrication of Six Degrees-of-Freedom Hexflex Positioner With Integrated Strain Sensing Using Nonlithographically Based Microfabrication

In this study, a process flow is described for the low cost, flexible fabrication of metal micro-electromechanical systems (MEMS) with high performance integrated sensing. The process is capable of producing new designs in ≈1 week at an average unit cost of <$1 k/device even at batch sizes of ≈1–10, with expected sensing performance limits of about 135 dB over a 10 kHz sensor bandwidth. This is a ≈20× reduction in cost, ≈25× reduction in time, and potentially >30× increase in sensing dynamic range over comparable state-of-the-art compliant nanopositioners. The nonlithographically based microfabrication (NLBM) process is uniquely suited to create high performance nanopositioning architectures which are customizable to the positioning requirements of a range of nanoscale applications. These can significantly reduce the cost of nanomanufacturing research and development, as well as accelerate the development of new processes and the testing of fabrication process chains without excess capital investment. A six degrees-of-freedom (6DOF) flexural nanopositioner with integrated sensing for all 6DOF was fabricated using the newly developed process chain. The fabrication process was measured to have ≈30 μ m alignment. Sensor arm, flexure, and trace widths of 150 μ m, 150 μ m, and 800 μ m, respectively, were demonstrated. Process capabilities suggest lower bounds of 25 μ m, 50 μ m, and 100 μ m, respectively. Dynamic range sensing of 52 dB was demonstrated for the nanopositioner over a 10 kHz sensor bandwidth. Improvements are proposed to approach sensor performance of about 135 dB over a 10 kHz sensor bandwidth.

42 ENGINEERING↗

Cesium Ion Exchange Testing Using a Three-Column System with Crystalline Silicotitanate and Hanford Tank Waste 241-AP-107

Washington River Protection Solutions (WRPS) is working to support early production of immobilized low-activity waste by feeding Hanford tank supernate from tank farms to the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) facility. This goal incorporates the design of a Tank-Side Cesium Removal (TSCR) system, which in effect filters tank waste supernate and processes it through a cesium ion exchange medium to remove 137Cs. The 137Cs-depleted product is sent to the WTP for vitrification. Rovira et al. (2018) reported the successful Cs removal from Hanford tank 241-AP-107 waste (hereafter called AP-107) using crystalline silicotitanate (CST) ion exchange media manufactured by Honeywell UOP, LLC (product IONSIVTM R9140-B, Batch 2081000057) in a lead-lag column system. Since that testing, WRPS has changed the column design to a three-column system. WRPS requested a repeated study with AP-107 tank waste using a different batch of IONSIVTM R9140-B, Lot 2002009604, in a three-column format. A small-scale test platform was constructed to demonstrate solids filtration, Cs removal, and LAW vitrification and installed at Pacific Northwest National Laboratory. This report describes the small-scale ion exchange testing system component of the test platform and the processing of approximately 8.55 L of filtered AP-107 supernate using CST, Lot 8056262-999, that passed through a 25-mesh filter. This report also describes the Cs ion exchange batch contact testing to determine the Cs distribution coefficient and the maximum Cs loading capacity in the AP-107 tank waste matrix. Batch contact testing helps to evaluate CST performance on tank waste supernate and is often used prior to processing tank waste through ion exchange columns to assess some performance metrics (e.g., 50% Cs breakthrough). Batch contact tests were performed with the filtered AP-107 tank waste at four Cs concentrations at a phase ratio of 200 (liquid volume to exchanger mass). The distribution coefficient (K d ) at the equilibrium condition of 9.2 µg Cs/mL (AP-107 feed condition) was determined to be 806 mL AP 107/g CST. With a CST bed density of 1.01 g/mL (<25 mesh CST), this K d corresponded to a predicted 50% Cs breakthrough of 814 bed volumes (BVs). The Cs load capacity at the equilibrium feed condition was determined to be 8.3 mg Cs/g dry CST. The three-column format testing was prototypic to the intended TSCR operations, albeit on a small scale with 10-mL CST beds. Flowrate was adjusted to match the CST contact time expected for the full-scale operation, i.e., matched bed volumes per hour (BV/h) flow rate. The feed was processed downflow through the lead column, then through the middle column, and then through the polish column. Loading continued at an average of 1.88 BV/h (1.83 to 2.04 BV/h range) until the entire available AP-107 feed was processed. The Cs-decontaminated product will be provided for vitrification testing. The lead column only reached 45% Cs breakthrough after processing 855 BVs of feed. The 50% Cs breakthrough was extrapolated to occur at ~900 BVs. This extrapolated 50% Cs breakthrough value differed from the batch contact estimate (814 BVs) by 13%. The waste acceptance criteria (WAC) or contract limit for the WTP LAW vitrification facility is 3.18E-5 Ci 137 Cs per mole Na. For the AP-107 tank waste, only 0.127% of the influent 137 Cs concentration may be delivered to the WTP; this required a Cs decontamination factor of 787. The Cs effluent from the middle column reached the WAC after processing 590 BVs. Cs breakthrough from the polish column began at 590 BVs, reaching 6.3E-3 µCi/mL or 4.3E-3% Cs breakthrough after processing 844 BVs of feed.

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Exploring small-scale chemostats to scale up microbial processes: 3-hydroxypropionic acid production in S. cerevisiae

The physiological characterization of microorganisms provides valuable information for bioprocess development. Chemostat cultivations are a powerful tool for this purpose, as they allow defined changes to one single parameter at a time, which is most commonly the growth rate. The subsequent establishment of a steady state then permits constant variables enabling the acquisition of reproducible data sets for comparing microbial performance under different conditions. We performed physiological characterizations of a 3-hydroxypropionic acid (3-HP) producing Saccharomyces cerevisiae strain in a miniaturized and parallelized chemostat cultivation system. The physiological conditions under investigation were various growth rates controlled by different nutrient limitations (C, N, P). Based on the cultivation parameters obtained subsequent fed-batch cultivations were designed.We report technical advancements of a small-scale chemostat cultivation system and its applicability for reliable strain screening under different physiological conditions, i.e. varying dilution rates and different substrate limitations (C, N, P). Exploring the performance of an engineered 3-HP producing S. cerevisiae strain under carbon-limiting conditions revealed the highest 3-HP yields per substrate and biomass of 16.6 %C-mol and 0.43 g gCDW -1 , respectively, at the lowest set dilution rate of 0.04 h -1 . 3-HP production was further optimized by applying N- and P-limiting conditions, which resulted in a further increase in 3-HP yields revealing values of 21.1 %C-mol and 0.50 g gCDW -1 under phosphate-limiting conditions. The corresponding parameters favoring an increased 3-HP production, i.e. dilution rate as well as C- and P-limiting conditions, were transferred from the small-scale chemostat cultivation system to 1-L bench-top fermenters operating in fed-batch conditions, revealing 3-HP yields of 15.9 %C-mol and 0.45 g gCDW -1 under C-limiting, as well as 25.6 %C-mol and 0.50 g gCDW -1 under phosphate-limiting conditions. Small-scale chemostat cultures are well suited for the physiological characterization of microorganisms, particularly for investigating the effect of changing cultivation parameters on microbial performance. In our study, optimal conditions for 3-HP production comprised (i) a low dilution rate of 0.04 h -1 under carbon-limiting conditions and (ii) the use of phosphate-limiting conditions. Similar 3-HP yields were achieved in chemostat and fed-batch cultures under both C- and P-limiting conditions proving the growth rate as robust parameter for process transfer and thus the small-scale chemostat system as powerful tool for process optimization.

59 BASIC BIOLOGICAL SCIENCES↗

Preliminary Analysis of Species Partitioning in the DWPF Melter - Sludge Batch 7b

The goal of the work described in this report is to provide additional off-gas carryover data from the Defense Waste Processing Facility (DWPF) melter to support the estimation of off-gas carryover rates from the Low Activity Waste (LAW) melter at the Hanford Site. Of particular interest is to determine the volatility of technetium-99 (Tc-99), which is a key isotope of concern for disposal and is a significant challenge to retain in glass in the Hanford waste treatment flowsheet. Since the DWPF melter is not equipped with routine offgas monitoring and/or sampling capabilities, the off-gas carryover data had to be extracted using component mass balance of the measured feed and pour stream (PS) glass compositions under time-averaged melter operating conditions over the duration of one canister-filling cycle, typically 20-25 hours. The method was first tested using the Sludge Batch 6 (SB6) PS sample data taken while Canister #3472 was being filled on 12/20/2010, approximately three months after the (argon) glass bubblers were installed. The method was tested again using the SB7a PS sample data taken while Canister #3619 was being filled on 8/5/2011 with the glass bubblers in operation.

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On silica's roles in controlling americium migration in contaminated sediments

Two studies in the early 1980s described the leaching behavior of americium (Am) disposed as part of acidic high-salt processing wastes from the Hanford Site’s Plutonium Finishing Plant to nearby ground sediments. Here these batch leach experiments showed that the Am concentrations followed a linear log [Am] versus pH relationship with a slope of –1. Column leach experiments in the second study, however, did not follow this relationship and only ~30% of the americium desorbed even after extensive column leaching. Here, the 1980s research is re-examined along with previously unpublished information and, in light of recent published work, a plausible mechanism is proposed to explain these phenomena. Amorphous silica in the contaminated sediments is postulated to be the substrate responsible for both the exchangeable Am available for leaching and the retained low-leachable Am made evident in the column leach experiments. The exchangeable Am 3+ in the contaminated sediment leach experiments behaves with pH dependence similar to that observed for uptake onto amorphous silica of sodium (Na + ), calcium (Ca 2+ ), barium (Ba 2+ ), cadmium (Cd 2+ ), uranyl (UO 2 2+ ), ferric (Fe 3+ ), chromic (Cr 3+ ), cupric (Cu 2+ ), plumbous (Pb 2+ ), uranium(IV) (U 4+ ), plutonium(IV) (Pu 4+ ), zirconium (Zr 4+ ), analogue lanthanide (gadolinium, Gd 3+ , europium, Eu 3+ , and lutetium, Lu 3+ ) and curium (Cm 3+ ) ions as well as other studies with Am 3+ . Correspondingly, the residual low-leachable Am 3+ revealed in the column leach experiments is attributed to incorporation of Am 3+ within amorphous silica by dynamic Am 3+ sorption and silica precipitation processes.

58 GEOSCIENCES↗

Scalable economic extracellular synthesis of CdS nanostructured particles by a non-pathogenic thermophile

We report microbially facilitated synthesis of cadmium sulfide (CdS) nanostructured particles (NP) using anaerobic, metal-reducing Thermoanaerobacter sp. The extracellular CdS crystallites were <10 nm in size with yields of ~3 g/L of growth medium/month with demonstrated reproducibility and scalability up to 24 L. During synthesis, Thermoanaerobacter cultures reduced thiosulfate and sulfite salts to H2S, which reacted with Cd2+ cations to produce thermodynamically favored NP in a single step at 65oC with catalytic nucleation on the cell surfaces. Photoluminescence (PL) analysis of dry CdS NP revealed an exciton-dominated PL peak at 440 nm, having a narrow full width at half maximum of 10 nm. A PL spectrum of CdS NP produced by dissimilatory sulfur reducing bacteria was dominated by features associated with radiative exciton relaxation at the surface. High reproducibility of CdS NP PL features important for scale-up conditions was confirmed from test tubes to 24L batches at a small fraction of the manufacturing cost associated with conventional inorganic NP production processes.

Moon, Ji Won↗

Removal of Nitrate from Water by Alginate-Derived Carbon Aerogel Modified by Protonated Cross-Linked Chitosan

In this study, a carbonaceous aerogel with superior structural properties was synthesized from sodium alginate with a specific surface area and density of about 470 m{sup 2} g{sup −1} and 0.05 g cm{sup −3}, respectively. In order to adsorb nitrate from water, the surface of the aerogel was modified by protonated cross-linked chitosan. To investigate the morphology, elemental composition, crystalline phases and surface functional groups of the adsorbent, various techniques such as field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction analysis, Fourier transform infrared spectroscopy were employed. To study the performance of this green adsorbent in nitrate removal process, the effect of nitrate initial concentration, adsorbent dosage, pH of solutions were investigated in batch mode. It was revealed that the Langmuir isotherm model could properly describe the experimental equilibrium data and the maximum adsorption capacity was evaluated to be about 18 mg g{sup −1} at neutral pH and room temperature. Besides, the kinetic data perfectly followed the pseudo-second order model. Thermodynamic analysis showed that the adsorption reaction was spontaneous, exothermic with decreased randomness at the solid–liquid interface. The macroscopic size of the adsorbent allowed its facile separation from the solution.

36 MATERIALS SCIENCE↗

Anaerobic Co-Digestion of Vegetable and Fruit Market Waste in LBR + CSTR Two-Stage Process for Waste Reduction and Biogas Production

Vegetable and fruit waste (VFW) is becoming a heavy burden of municipal waste disposal because of its huge amount, but it is a potentially valuable resource that can be developed into high value products such as methane. Conventional anaerobic digestion processes are not suitable for solving the problem of easy acidification of VFW. Thus, a two-stage laboratory-scale anaerobic digestion system was assembled for waste reduction and biogas production of VFW in the mesophilic temperatures. The biphasic system consists of a 70-L leach bed reactor (LBR) and a 35-L continuous stirred tank reactor (CSTR). Water is sprinkled over the material to enhance the extraction process of acidification phase. The leachate was then transferred to the CSTR for biogas production. Batch digestion was lasted 120 h until no biogas was produced. Leachate with a volatile fatty acid (VFA) concentration of 7.6 g/L was obtained within 10 h. The results showed that overall 70.9% of the volatile solids (VS) was removed in the solid-phase system. Over 90% of VFAs were reduced in the methanogenic reactor, and it has been observed that the maximum biogas production rate was 51.26 mL/(d gVS). The maximum methane concentration in the produced biogas was 71%.

60 APPLIED LIFE SCIENCES↗

Vision and Development of a Design, Implementation, and Verification Automation (DIVA) Software Platform for DNA Construction

Abstract DNA construction, while a prerequisite to many biological endeavors, is often a time-consuming distraction from an individual’s primary research objectives. We envisioned that with the right software infrastructure and cultural mindset, a single person could execute in parallel the batched DNA construction tasks of an entire research institute, at scales realizing efficiency gains through process and laboratory automation. In pursuit of this vision, we developed the Design, Implementation, and Verification Automation (DIVA) software platform. DIVA’s web interface enables researchers to design DNA constructs (using visual biological computer-aided design tools and biological parts repositories), submit designs for construction to dedicated staff, and track DNA construction as it progresses. DIVA supports the dedicated staff through the DNA construction process and records both successful and unsuccessful attempts toward improving the overall process. The platform is publicly available at public-diva.jbei.org and its open-source code through github.com/JBEI/DIVA.

Plahar, Hector [DOE Agile BioFoundry , , ,; DOE Jo↗

Recommended Guanidine Suppressor for the Next-Generation Caustic-Side Solvent Extraction Process

The guanidine recommended for the Next-Generation Caustic-Side is N,N',N'-tris(3,7-dimethyloctyl)guanidine (TiDG). Systematic testing has shown that it is significantly more lipophilic than the previously recommended guanidine DCiTG, the active extractant in the commercial guanidine product LIX -79, while not otherwise changing the solvent performance. Previous testing indicated that the extent of partitioning of the DCiTG suppressor to the aqueous strip solution is significantly greater than expected, potentially leading to rapid depletion of the suppressor from the solvent and unwanted organic concentrations in process effluents. Five candidate guanidines were tested as potential replacements for DCiTG. The tests included batch extraction with simulated waste and flowsheet solutions, third-phase formation, emulsion formation, and partition ratios of the guanidine between the solvent and aqueous strip solution. Preliminary results of a thermal stability test of the TiDG solvent at one month duration indicated performance approximately equivalent to DCiTG. Two of the guanidines proved adequate in all respects, and the choice of TiDG was deemed slightly preferable vs the next best guanidine BiTABG.

cesium↗

Analysis of Harrell Monosodium Titanate Lot #46000908120

Monosodium titanate (MST) for use in the Actinide Removal Process (ARP) must be qualified and verified in advance. A single qualification sample for each batch of material is sent to SRNL for analysis, as well as a statistical sampling of verification samples. The Harrell Industries Lot #46000908120 qualification and the 16 verification samples failed to meet the specification for weight percent solids. All of the pails sampled and tested contained less than 15 wt % MST solids.

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Analysis of Harrell Monosodium Titanate Lot #46000824120

Monosodium titanate (MST) for use in the Actinide Removal Process (ARP) must be qualified and verified in advance. A single qualification sample for each batch of material is sent to SRNL for analysis, as well as a statistical sampling of verification samples. The Harrell Industries Lot #46000824120 qualification and the 16 verification samples failed to meet the specification for weight percent solids. All of the pails sampled and tested contained less than 15 wt % MST solids.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Integrated Oxygen Production and CO 2 Separation through Chemical Looping Combustion with Oxygen Uncoupling (Final Report)

The project "Integrated Oxygen Production and CO 2 Separation through Chemical Looping Combustion with Oxygen Uncoupling" focused on advancing fluidized bed chemical looping combustion technology to semi-pilot scale. An important aspect of technology scale-up is production of well-performing oxygen carrier materials economically and at a scale sufficient for industrial-scale systems. Under this program, a new technique for oxygen carrier production was developed and a prototype system capable of producing up to 150 lb per batch of oxygen carrier was constructed. Chemical looping combustion testing was performed in a large process development unit designed for operation at more than 200 kW using coal as fuel. Complementary evaluation of carbon conversion pathways was conducted and quantitative analysis of the fate of carbon in a CLOU-based chemical looping system was performed. As an aid for design, optimization, troubleshooting and scale-up, robust CFD models for fluidized bed chemical looping combustion systems were developed.

01 COAL, LIGNITE, AND PEAT↗

Report on Updated Properties Handbook of Printed Stainless Steel 316

This report focuses on summarizing mechanical behavior of 316H stainless steel (SS) printed using laser powder bed fusion (LPBF). 316H SS is one of the six alloys that has been qualified for use in nuclear reactors. The Advanced Materials and Manufacturing Technologies (AMMT) program has identified the use of the additive manufacturing (AM) process of LPBF as one of the manufacturing modalities to fabricate components for nuclear applications. Unlike wrought material, AM material displays significant heterogeneity in properties, resulting from changes in process parameters, machine-to-machine variability, and minor changes in feedstock chemistry from one batch to another. Although significant work has been done on 316L SS in the literature and has been summarized in several review papers, very limited data exist on 316H SS. Therefore, this report aims to provide a concise summary of the properties of 316H SS printed using different machines and at different locations as a part of the AMMT program.

36 MATERIALS SCIENCE↗

Laboratory and Field Investigations of In-Situ Remediation of Cr(VI) in the LANL Regional Aquifer - 18683

Two biogeochemical in-situ remediation strategies are currently being evaluated to help manage a Cr(VI) plume present in deep groundwater beneath Los Alamos National Laboratory. The first is the addition of a chemical reductant, sodium dithionite, and the second is the use of a bio-stimulant, molasses. This paper summarizes the results to date of laboratory and field investigations of the effectiveness of these two amendments in the Los Alamos aquifer. A semi-empirical model based on the results of laboratory batch and column experiments has been developed to describe dithionite reactions and subsequent cation exchange processes in the aquifer. The model is being used to predict the effective 'reach' of dithionite in field deployments, and so far the predictions of the model are consistent with observations in a field push-pull test involving dithionite. Contrary to what has been frequently assumed, the laboratory data suggest that the resulting Cr(VI) reduction capacity depends more strongly on the amount of dithionite consumed than on the amount of iron reduced during the treatment, and an empirical approach is being used to predict reduction capacity generated in the field test. Laboratory experiments have demonstrated a robust ability of molasses to promote biomass growth that imparts significant Cr(VI) reduction capacity to sediments. Molasses has been deployed in a field push-drift test (no active pumping) in a well in which the aquifer Darcy velocity is known to be high. To date, the molasses has not drifted out of the injection well, so it has not been possible to make comparisons with laboratory experiments. (authors)

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Results Of Hg Speciation Testing On DWPF SMECT-1, SMECT-3, And SMECT-5 Samples

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team. The thirteenth shipment of samples was designated to include Defense Waste Processing Facility (DWPF) Slurry Mix Evaporator Condensate Tank (SMECT) from Sludge Receipt and Adjustment Tank (SRAT) Batch 736 and 738 samples. Triplicate samples of each material were prepared for this shipment. Each replicate was analyzed for seven Hg species: total Hg, total soluble (dissolved) Hg, elemental Hg [Hg(0)], ionic (inorganic) Hg [Hg(I) and Hg(II)], methyl Hg [CH 3 Hg-X, where X is a counter anion], ethyl Hg [CH 3 CH 2 -Hg-X, where X is a counter anion], and dimethyl Hg [(CH 3 ) 2 Hg]. The difference between the total Hg and total soluble Hg measurements gives the particulate Hg concentration, i.e. Hg adsorbed to the surface of particulate matter in the sample but without resolution of the specific adsorbed species. The average concentrations of Hg species in the aqueous samples derived from Eurofins reported data corrected for dilutions performed by SRNL are tabulated.

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