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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Utilizing waste heat in wastewater treatment plants for water desalination: Modeling and Multi-Objective optimization of a Multi-Effect desalination system using Decision Tree Regression and Pelican optimization algorithm

This paper examines the feasibility of using waste heat from wastewater treatment plants (WWTPs) for water desalination. A model was developed to utilize waste heat from the gensets at As Samra WWTP in Jordan, using real data and TRNSYS® software to calculate available waste heat. The desalination process was then modeled with ASPEN PLUS® software, focusing on multi-effect desalination (MED). Both series and parallel configurations for the MED system were compared. The study investigated the effects of system feeding flow rate, feeding pressure, and heat input on productivity, performance ratio, and recovery ratio. The study also introduces a novel optimization technique combining machine learning and modern optimization algorithms to maximize system productivity and performance. Initially, a decision tree regression (DTR) model is developed to establish relationships between key independent variables (flow rate, feed pressure, and heat input) and dependent variables (productivity, performance ratio, and recovery ratio). The Pelican Optimization Algorithm (POA) is then used to identify the optimal values of the independent variables for maximum productivity and performance. The results show that using a series configuration yields a system productivity of 3984.2 kg/hr, a performance ratio of 3.78, and a recovery ratio of 0.991 at a feed flow rate of 4000 kg/hr, feed pressure of 3 bars, and heat input of 719 kW. Optimal productivity (4421 kg/hr), performance ratio (3.81), and recovery ratio (0.851) are achieved at a feed flow rate of 5166 kg/hr, feed pressure of 3.2 bars, and heat input of 794 kW. In conclusion, the techno-economic assessment indicates a levelized cost of water of 1.63 USD/m 3 for parallel configurations and 1.65 USD/m 3 for series configurations, with a payback period of less than two years.

42 ENGINEERING↗
DOE OSTI2022

Gasification of Coal and Biomass: The Route to Net-Negative-Carbon Power and Hydrogen

One promising process that is a candidate for meeting the goals of the US Department of Energy’s 21st Century Power Plant initiative is to gasify a mixture of coal and biomass to yield a syngas, which can have CO2 removed and then be used to produce hydrogen as well as an off-gas that can be used to flexibly produce power. This concept would overall be carbon net-negative and readily meet the 21st Century Power Plant initiative targets of smaller scale MW generation, high ramp rates and turndown, feedstock flexibility, and high efficiency—at a reasonable cost. Moreover, adding the large-scale production of “ultra-green” hydrogen yields a system tailored for the coming hydrogen economy, providing long-term energy storage and an attractive co-product for sale. The objective of the work being led by the Electric Power Research Institute, Inc. (EPRI), with support by Bechtel Corporation (Bechtel), Gas Technology Institute (GTI), Hamilton Mauer International, Inc. (HMI), Nebraska Public Power District (NPPD), NexantECA, Inc. (Nexant), and Wärtsilä, is to perform a front-end design and engineering (FEED) study on an oxygen-blown gasification system coupled with water-gas shift, pre-combustion CO2 capture, and pressure-swing adsorption working off a coal/biomass mix to yield high-purity hydrogen and a fuel off-gas that can generate power. Several designs are being considered that will be capable of producing 50 MW net from a flexible generator, over 8500 kg/hr of hydrogen, and net-negative CO2 emissions, at an efficiency of 50% net HHV. The plant would be hosted at an NPPD site, where opportunities for enhanced oil recovery and sequestration have been investigated and the need for low-carbon power and hydrogen is imminent. The principal biomass to be used is corn stover—prevalent in Nebraska where the plant will be located—mixed with Powder River Basin (PRB) coal, necessitating a gasifier that can use this feedstock and be flexible to allow other types. Waste plastics will also be reviewed for use. Two oxygen-blown gasifiers have been identified as candidates that have done testing with biomass including corn stover: the GTI gasifier—a high-pressure, fluidized-bed type—and HMI’s, a lower pressure moving-bed type. Both have relative advantages that are being investigated in the Phase I design study, with a resultant down select of one system for which the FEED will be performed in Phase II. The technical tasks for the proposed project are: • Design Development: Completion of design activities necessary to provide inputs for the FEED study. Multiple design cases will be assessed with the selection of the optimal one for the FEED. • Investment Case Preparation: Development of the draft investment case for the proposed process with business cases performed for the proposed host site and two other locations. • Host Site Selection: Evaluation of the two potential host sites within NPPD’s portfolio to select the preferred candidate based on technical, economic, and environmental considerations. • Environmental Information Volume (EIV) Development: Completion of the EIV for the host site. • FEED Study: Completion of a FEED study based on the design selected in Phase I. A Greenhouse Gas Life Cycle Analysis will also be performed for the process. • Update Investment Case: Finalization of the investment case based on findings from the FEED. The advantages of the proposed project are significant. Having an engaged U.S. power utility willing to provide a host site that will produce energy from coal plus a deep and experienced team is critical; the process meets all the goals of DOE’s 21st Century Power Plant initiative at an estimated total plant cost of ~$880M and a production cost of hydrogen of ~$2/kg-H2 while producing net-negative carbon power. If developed, this process has real commercial potential in the United States—supported by EPRI’s initial review of the considerable interest from selected U.S. utilities—and elsewhere around the globe. The process has fewer environmental hurdles compared to other concepts, lowering regulatory and protest risks—providing a pathway to preserving the viability of a critical indigenous energy source by transforming its use to match a changing world. This presentation will outline the motivation for the effort, summarize project plans, work completed to date, results of the Design Development task, and detailed work scope for the remainder of the project.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

Filtration of Hanford Tank 241-AN-107 Supernatant at 16 °C

Approximately 9 liters of supernatant from Hanford waste tank 241-AN-107 was delivered by Washington River Protection Solutions to the Radiochemical Processing Laboratory (RPL) at Pacific Northwest National Laboratory. The thirty-six AN-107 sample bottles consisted of six sets of six samples, with each set pulled from a unique tank sampling level. Prior to testing, samples from each level were composited to provide nominally level-independent feed for dead end filtration and ion exchange testing. The composited 241-AN-107 supernatant was chilled to 16 °C for 1 week prior to testing. Filtration testing was then conducted using a backpulse dead-end filter (BDEF) system equipped with a feed vessel and a Mott inline filter Model 6610 (Media Grade 5) in the hot cells of the RPL. The purpose of this testing is to a) demonstrate dead-end filtration (DEF) of AN-107 feed at reduced temperature to obtain prototypic tank side cesium removal (TSCR) flux rates and identify issues that may impact filtration after dilution to 5.5M Na, and b) provide feed for a follow on ion exchange unit operation. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft 2 . During filtration the differential pressure required to effect filtration at 0.065 gpm/ft 2 was slow to increase for most of the filtration campaign. After all the feed bottles had been pumped into the slurry reservoir, the bottoms of the bottles were added to the reservoir and transmembrane pressure (TMP) reached 2.0 psid (the TSCR action limit). The prototypic filter cleaning process was unable to effectively restore filter performance, and cleaning with oxalic acid was required before flow through the filter could be restored. This indicates that the Media Grade 5 filter may require an alternative cleaning protocol when processing AN-107 supernatant. After completing filtration of the AN-107 feed, the filter was cleaned. Solids concentrated from the backpulse solutions were composed of natrophosphate, Mn-Fe phases, and fluoro-natrophosphate that occurred as particle agglomerates. The individual particles were in some cases 100s of micrometers across which is consistent with prior observations from AN-107 supernate waste characterizations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Filtration of Hanford Tank 241-AW-105 Supernatant at 16 °C

Approximately 9 L of supernatant from Hanford waste tank 241-AW-105 was delivered by Hanford Tank Waste Operations and Closure (H2C) to the Radiochemical Processing Laboratory (RPL) at Pacific Northwest National Laboratory (PNNL). The thirty-six 241-AW-105 sample bottles consisted of four sets of nine samples, with each set pulled from a unique tank sampling level. Prior to testing, samples from each level were composited and diluted to 5.5 M Na to provide nominally level-independent feed for dead-end filtration and ion exchange testing. The composited 241-AW-105 supernatant was chilled to 16 °C for 1 week prior to testing. Filtration testing was then conducted using a backpulse dead-end filter (BDEF) system equipped with a feed vessel and a Mott inline filter (Model 6610, Media Grade 5) in the hot cells of the RPL. The purpose of this testing was to (a) demonstrate dead-end filtration (DEF) of 241-AW-105 feed at reduced temperature to obtain prototypic Tank Side Cesium Removal (TSCR) flux rates and identify issues that may impact filtration after dilution to 5.5 M Na, and (b) provide feed for follow-on ion exchange unit operation. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft2. For most of the filtration campaign, the differential pressure required to effect filtration at 0.065 gpm/ft2 was slow to increase. After all the feed bottles had been pumped into the slurry reservoir, the bottoms of the bottles were added to the reservoir and transmembrane pressure (TMP) reached 2.0 psid (the TSCR action limit). A backpulse was performed after >50 hours of filtration to remove fouled solids and reduce the TMP. The filter was cleaned after completing filtration of the 241-AW-105 feed, and clean water flux tests showed filter performance was effectively restored. Solids concentrated from the backpulse solutions were composed of steel-like particles, uranium-bearing phases, Mn-Fe phases, a Ce-bearing phase, Zr phases, and some smaller Ca-bearing particles. The Ca-bearing and U bearing phases were identified as calcite and clarkeite, respectively.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Pilot-Scale Testing of an Integrated Circuit for the Extraction of Rare Earth Minerals and Elements from Coal and Coal Byproducts Using Advanced Separation Technologies

The primary objective of this project was to develop and demonstrate an integrated pilot-scale circuitry for recovering high-value rare earth elements (REEs) from coal and coal byproducts. The target performance was to produce a mixed REE product with content of at least two percent by weight on a dry mass basis in a cost-effective and environmentally benign manner. During the first nine months of the project period (Phase 2 Budget Period 2), pilot plant construction was completed including all field site startup activities such as permitting, engineering design, procurement/bidding, unit fabrication, site construction, equipment installation, module assembly, safety training, and circuit shakedown. During the remaining 21 months of project period (Phase 2 Budget Period 3), detailed field-testing activities were performed including feedstock sample collection and preparation, exploratory testing, circuit modification, detailed parametric study, and performance optimization. A detailed techno-economic analysis was performed based on the pilot plant testing findings which provided various scenarios for REE production. The project successfully accomplished the proposed target performance by producing mixed rare earth oxide (REO) with greater than 90% purity by weight in a continuous pilot scale operation from two distinctly different coarse refuse materials (i.e., West Kentucky No. 13 and Fire Clay coal seams), and at least three secondary sources (i.e., heap leach process and naturally formed acid mine drainage system). Project partners included the University of Kentucky, Virginia Tech, West Virginia University, Alliance Coal, Blackhawk Mining, Mineral Refining Company, and Mineral Separation Technologies. The pilot scale test facility was constructed at a former mining complex owned by Alliance Natural Resource Partners (Alliance Coal). The site was rehabilitated to accommodate the equipment installation, construction and fabrication, electrical power requirement, water line management and containment. The process units constructed and installed included X-ray sorting unit, crushing and grinding unit, physical separation unit, acid leaching unit, solvent extraction unit, and wastewater management unit. A rare earth mineral concentration unit was constructed as a standalone unit for flexible operation. A detailed environmental assessment and control plan was carried out to identify and quantify any potential impacts of the pilot-scale processing circuitry on the human and eco-system health and well-being. Corresponding mitigation strategies and control measures were provided. A conceptual flowsheet was developed to effectively remove thorium and uranium from high purity rare earth oxide mix or any potential radionuclide enriched stream. The two distinct feedstock materials were secured from the Blackhawk Mining Complex in eastern Kentucky where the Fire Clay (Hazard No. 4) seam is processed. The West Kentucky No. 13 (Baker) coarse refuse material was collected from an active process stream at an Alliance coal preparation plant located in western Kentucky. Characterization analysis indicated that both of feed materials generated from the two sources contained >300 ppm of TREEs on a dry whole mass basis which met the requirements for a qualified feed stock. The two feedstocks were further upgraded using a dual x-ray sorter to prepare the feed material for hydrometallurgical circuit. Thermal treatment on feed material prior to leaching was found to: 1) improve the leaching recovery of REEs, 2) increase the leaching kinetics, and 3) allow the leaching reaction to occur at lower acidity. Roasting at 600°C was selected as the pre-treatment condition for both West Kentucky No. 13 and Fire Clay coarse refuse material. Over 40% of leaching recovery was achieved by roasting West Kentucky No. 13 material having a top particle size of 3 mm in the pilot scale operation using 1.2M sulfuric acid leaching at 75OC. Initial pilot scale testing involved continuous operation of the pilot plant for 94 hours. The leaching unit was operated at solid-to-liquid ratio of 1 to 10 (w/v) using 0.5M sulfuric acid solution at a temperature of 75°C. The continuous solvent extraction circuit utilized rougher and cleaner units with DEHPA and TBP as the extractants. An innovative stripping circuit was developed to accumulate the REE concentration in the stripping solution to a level above 600 ppm. A bleed stream from the recycled strip solution was treated using oxalic acid precipitation which produced a high grade rare earth oxalate. The oxalate product was roasted to remove the oxalate which produced a rare earth oxide product having a purity greater 90%. Due to high concentrations of contaminant ions in the pregnant leach solution (PLS), a modified flowsheet was developed that involved pre-concentration of the REEs using multiple stages of precipitation and redissolution. The advantage of this process was improved removal of contamination before the downstream purification process and a significant cost reduction relative to the circuit that utilized the solvent extraction process. The modified circuitry included processes involving leaching, multistage precipitation, redissolution, and oxalate precipitation followed by roasting of the oxalate product. The circuit produced a mixed REO that was 92.96% pure from the initial test. A detailed parametric test plan was carried out which involved varying key parameters including solids feed rate, acid flowrate, acid concentration, multistage precipitation pH, redissolution pH, oxalate precipitation dosage and pH. The response variables included REE recovery, contaminant recovery, REO product grade and overall chemical consumption. Test results indicated that the acid-to-solid ratio is the key parameter to leaching efficiency as performance deteriorated with an increase in solids concentration. The optimal pH determined for REE precipitation and redissolution was 6.5 and 2.5, respectively. Additional tests were conducted to further improve the flowsheet. Recirculating a portion of the PLS to the feed of the leach tanks improved the leaching performance by lowering the pH of the leaching system and reducing the contamination recovery by shortening the residence time. Moreover, the removal of Al prior to REE precipitation significantly reduced the oxalic acid consumption in the oxalate precipitation circuit. The modified circuit produced over 90% grade REO by weight from both West Kentucky No. 13 and Fire Clay coarse refuse material in pilot scale continuous test programs. A case analysis model was developed to project the REE and major contaminants concentration in each PLS stream based on the leaching condition, pH cut point, and oxalic acid dosage. A correlation was established using empirical and semi-empirical models. Using the models, chemical consumption required for each stage was predicted based on the projected performance of the hydrometallurgy circuit. After identifying the optimum conditions, validation tests were carried out for the treatment of both West Kentucky No. 13 and Fire Clay coarse refuse materials in the pilot plant. The actual circuit performance and chemical consumptions were very close to the model predictions. Other than the two coarse refuse sources, several secondary feedstocks were also tested in the pilot plant facility. A “heap leach” system was constructed using the coarse refuse material generated from cleaning the West Kentucky No. 13 seam coal. Using the two stage SX rougher and cleaner circuit, a concentrate with a grade >90% REO was produced while recovering >97% of the REEs from the heap leach PLS. Naturally generated acid mine drainage (AMD) from West Kentucky No.13 mine was processed using the multistage precipitation circuit in the pilot plant in a test conducted for a period of 32 hours. The final grade of the mix RE oxide produced from the AMD was 90.84% with an overall circuit recovery of 64%. The primary source of REE was the selective precipitation steps involving iron and aluminum rejection. The hydrophobic-hydrophilic separation (HHS) process was proven to effectively recover coal from fine waste materials. For REM recovery, the HHS process was able to produce concentrates at grades of approximately 1.8% REE on an ash basis; however, recovery values were typically low, <10%, under the optimal conditions determined in the laboratory-scale testing. Staged testing of the pilot-scale HHS process for coal recovery and semi-continuous laboratory testing for REM testing showed that a total concentration ratio of more than 15x was observed for the REM recovery process. A circuit simulation package was developed for REE extraction and purification using a spreadsheet-based platform (Microsoft Excel). The REESim circuit simulation package is configured to track the mass and volume flows of components passing through a series of unit operations specified and configured by the user. The mass rates can then be utilized by the user to determine important performance indicators such as product mass yields, concentrate purity levels, element-by-element recoveries, and so forth. The techno-economic analysis showed that the roasting and leaching operations were the most expensive capital items, each contributing approximately 30% to the total capital cost. One notable contributor to the high production costs was the low REE recovery observed in the pilot scale trials. The product basket price was shown to have a strong influence on the economic viability of the scenarios, with the scandium price being the most significant influencer. Operating cost was shown to be extremely sensitive to REE recovery, REE feed grade, and leaching acid consumption. An analysis of ten different scenarios for a 500 t/h commercial operation revealed that three were economically favorable, producing internal rates of return varying from 27.7% to 33.1% and payback periods of 4 to 5 years. The project successfully developed and demonstrated a process to recover REEs from coal and coal byproducts in a pilot-plant operation which consistently produced over 90% grade REO mix from varies types of feedstocks. Commercialization analysis showed that the technology readiness level successfully achieved TRL 6 at the end of the project and demonstrated the need and the potential for scaling the process to further advance the technologies toward the goal of providing a domestic supply of REEs at a commercial scale.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Cost details from front-end engineering design of piperazine with the advanced stripper

This Front-End Engineering Design (FEED) was funded by the U.S. Department of Energy (DOE) to estimate the cost to capture and compress 90% of the CO 2 from an existing natural gas combined cycle (NGCC) in Denver City, Texas, USA. The FEED used the PZAS (Piperazine with the Advanced Stripper) 2G amine scrubbing technology developed and modeled by The University of Texas at Austin. This FEED is unique in providing more public cost details than other FEEDs funded by DOE. The primary objective of the FEED was to provide a comprehensive estimate for the total installed cost of the capture plant. The estimated capital cost of NGCC at the Mustang Station is $\$727$ million for a capacity of 460 MW and 1.6 million tonnes CO 2 /yr. This includes a contingency of $\$104.6$ million and a contractor’s profit of $\$60.1$ million. The total direct field cost is $\$384.1$ million. With an optimistic fuel value of $\$3$/MMBtu, the estimated cost of capture varies from $\$85$/t at 4% IRR/85% load to $\$170$/t at 10% IRR/52% load. Air cooling is technically feasible but expensive. The air cooling systems for the water wash and pump-around intercooling account for 23.4% of the direct cost. The gas-fired boilers represent only 4% of the direct costs, but steam extraction would reduce energy cost, free up cooling water, and reduce the direct costs of processing additional flue gas and CO 2 from the boilers. The absorbers represent 9.6% of the direct cost in this FEED with no direct contact cooler and only 7.6 m of packing. Furthermore, the solvent cross exchangers are less expensive than expected (2.5% of direct costs). Doubling the number of these exchangers could reduce the heat duty from 3.0 to 2.5 GJ/t CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Front-End Engineering Design for Piperazine with the Advanced Stripper

This Department of Energy (DOE) funded project was executed with the goal of preparing a Front-End Engineering Design (FEED) for the capture and compression of 90% of the CO2 that would normally be emitted from an existing natural gas combined cycle (NGCC) plant. The FEED focused on the application of the piperazine advanced stripper (PZAS) process at Mustang Station of the Golden Spread Electric Cooperative (GSEC), which consists of two gas turbines with common heat recovery steam generator (HRSG). The University of Texas at Austin (UT) served as the prime contractor, and subcontracted AECOM Technical Services and Trimeric Corporation to support FEED development. This project team has worked together to advance PZAS for more than a decade. ExxonMobil, Chevron, and Total provided project co-funding. The objectives of this work included: 1. To advance engineering design such that a comprehensive estimate for the total installed cost of a full-scale PZAS CO2 Capture Plant with CO2 compression can be developed on an existing NGCC power plant. a. These detailed costs can also be used to qualify PZAS and other related second generation (2G) amine scrubbing processes for use on cogeneration facilities in refineries and chemical plants that use gas turbines with HRSGs to produce steam. b. These detailed costs will help qualify 2G amine scrubbing for use on NGCC power plants and establish a more accurate baseline cost to be used as a target by other capture technologies. 2. To provide cost details to be used in the economic optimization of the process features of PZAS and other 2G amine scrubbing processes. 3. To provide DOE with a more detailed understanding of carbon capture costs in a commercial application, enabling DOE to better design its R&D program to improve the economics for carbon capture. 4. To provide the host site and cost share partners with the information necessary to determine whether a commercial project to capture and use CO2 for enhanced oil recovery (EOR) or for sequestration can be justified (when accounting for the 45Q tax credit). A key component of the FEED is the estimated total installed cost, which provides a basis for the likely capital investment necessary to implement the PZAS carbon capture process at this location and scale. In combination with the included economic analysis, which accounts for potential revenue from the produced CO2, potential avenues to profitability are explored. The major findings of the FEED are as follows: The Mustang Station PZAS CO2 Capture Plant estimated total project cost of $698 MM of which $384 MM was direct costs. The annual operating costs were $32.6 MM. The total investment for a PZAS facility at Mustang Station is $725 MM. This estimate includes owner’s cost of $25 million and a contingency of $110 MM. • The study estimated the CO2 capture plant at Mustang Station would generate CO2 at $110/tonne for EOR, assuming a 12% IRR (internal rate of return) and an 85% capacity factor. For CO2 storage, the same case would achieve a 12% IRR at about $114/tonne. At a capacity factor of 52%, the storage and EOR cases would break even when carbon is priced ~$150/tonne. The economic analysis determined that the capacity factor and utility pricing, among other variable factors, had a significant effect on the economics and will need additional studied. • The energy penalty of the PZAS plant would be about 46 MW in connected power and 35 MW in operating load. The natural gas requirement (for the Gas Boiler package) would be about 354 MMBTU/hr. • The FEED revealed no major risks in process maturity. However, some areas were outlined for further engineering during detailed design, which included the Gas Boiler system, general arrangement and site layout, air coolers, schedule development, and optimization of the process for higher CO2 removal. • If PZAS were to be implemented at another host site, additional opportunities for cost reduction for would include cost reduction through use of cooling water and steam extraction.

03 NATURAL GAS↗
DOE OSTI2021

Deactivation trends of Pd/SSZ-13 under the simultaneous presence of NO, CO, hydrocarbons and water for passive NO x adsorption

Pd-functionalized chabazite (Pd/SSZ-13) was evaluated for passive NO x adsorption (PNA) using low temperature combustion with diesel (LTC-D) reaction feed of the “United States Driving Research and Innovation for Vehicle efficiency and Energy sustainability” (U.S.DRIVE) protocol. Notably as per the protocol conditions, 12% O 2 + 6% CO 2 + 6% H 2 O was flown in all cases. NO-uptake studies in the presence of the LTC-D feed showed a systematic decline with (NO:Pd)molar changing from 0.5 to 0.4 after 10 trials. Control experiments showed more pronounced decline for NO + CO case, with appreciable intial (NO:Pd)molar value of 0.4 yet comparable-to-the-LTC-D-feed decline after 8 trials. CO-induced particle formation and larger extent of particle sintering was also evident from TEM analysis. Other controls did not exhibit trial-dependent deactivation as(NO:Pd)molar values were constant, at 0.3, 0.2, 0.5 and 0.2 for the NO, NO+H 2 , NO + unsaturated hydrocarbon (C 2 H 4 , C 3 H 6 ) and NO + saturated HC (C 3 H 8 , C 10 H 22 ) feeds respectively. In addition to these quantitative differences, desorption behaviors are qualitatively different. While only one major desorption event is observed for the full LTC-D, NO+ CO and NO+ unsaturated HC-controls, desorption occurs in two distinct stages for NO, NO + saturated HCs and initial-NO+H 2 trials. This arises due to inherent differences in Pd sites while exposed to these chemically distinct feeds. Furthermore, presence of reducing agents such as CO and unsaturated HCs in the feed result in almost complete elimination of lower, sub-200 °C desorption peak. The higher temperature desorption peaks, at > 300 °C is associated with NO strongly bound to ionic Pd sites and are prevalent under reducing conditions. Using DRIFTS also, three complexes leading to PNA are assigned, [O = N–Pd 2 +(OH)–Z], [O = N–Pd 2 +(Z2)] and [O = N–Pd 2 +(H 2 O)y–Z] with the latter being clearly observed upon water exposure. Pd/SSZ-13 showed higher hydrocarbon trapping than the SSZ-13 counterpart.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Machine learning modeling and model predictive control of a closed-circuit reverse osmosis system

Closed-circuit reverse osmosis (CCRO) offers a flexible and energy-efficient alternative to conventional reverse osmosis by operating in a semi-batch mode that recycles brine, enabling higher recovery rates and reduced specific energy consumption (SEC). However, developing accurate, system-level dynamic models for CCRO remains challenging due to its nonlinear, multi-phase operation and sensitivity to variable feed water conditions. Traditional modeling approaches, such as NARMAX (nonlinear autoregressive moving average with exogenous inputs), often struggle to generalize across varying inlet feed concentrations, necessitating frequent parameter re-estimation and limiting their utility for real-time control applications. To address these limitations, we developed a long short-term memory (LSTM) neural network model trained on an extensive experimental data set from a CCRO pilot plant. The model accepts three inputs, feed flow rate, recirculation flow rate, and initial feed conductivity, and predicts three key outputs: reject conductivity, feed pump power draw, and recirculation pump power draw. We validated the LSTM model against experimental data, demonstrating its ability to distinguish between different feed conductivities and adapt to variable flow rates. Subsequently, we incorporated the LSTM model within a nonlinear model predictive control (MPC) scheme and conducted closed-loop simulations to optimize the integrated SEC (iSEC). In conclusion, the results project up to a 6% reduction in iSEC by using MPC to optimize performance over the entire experiment duration, without requiring any random excitation for data collection or parameter re-estimation.

Desalination↗
DOE OSTI2022

Production and Catalytic Upgrading of 2,3-Butanediol Fermentation Broth into Sustainable Aviation Fuel Blendstock and Fuel Properties Measurement

With the increasing demand for sustainable supplies of aviation fuel and need to address climate change, new conversion technologies are needed to efficiently process biomass, produce high quality jet fuel blendstock, and meet carbon emission targets. This study demonstrates the synthesis, conditioning, and catalytic upgrading of 2,3-butanediol (BDO) fermentation broth into a jet fuel blendstock candidate. A high-titer 2,3-BDO fermentation broth (i.e., ~90 g/L) was produced at a 100-L scale and pretreated via nanofiltration to decrease the impurities level in the broth from 4.6 to 0.6 wt%. A novel process for catalytic upgrading of aqueous 2,3-BDO into a jet fuel blendstock candidate was developed, and each step was efficiently demonstrated. The catalytic steps include 1) 2,3-BDO dehydration into methyl ethyl ketone (MEK) over AlPO4, 2) MEK conversion into olefins over Zn1Zr10Ox, 3) oligomerization of olefins over a zeolite beta, and 4) hydrogenation over platinum/carbon. Both the model feed and real 2,3-BDO fermentation broth were tested for upgrading 2,3-BDO to MEK. With the real feed, a continuous loss of conversion (i.e., >50% loss over ~140 h time-on-stream [TOS]) was partly attributed to reversible deactivation from coking species. However, the conversion remained stable with the model feed, which demonstrates the efficiency of the first step for converting aqueous 2,3-BDO (10 wt% in water). For upgrading MEK to olefins, high selectivity to olefins (i.e., 82.5%) was obtained at high conversion levels (i.e., 93-98%) with stable conditions being achieved for > 70-hours TOS. Oligomerization of light olefins, which was demonstrated for > 270 h TOS, mainly led to the formation of dimers (C8-10) and trimers (C13-14). The oligomerized product was hydrogenated and distilled to recover the jet fraction (35 mass% or 40.9% carbon based yield), which consists mostly of desired isoalkanes (31.7 wt%), n-alkanes (24.5 wt%), and cycloalkanes (29.6 wt%). While some improvement is still needed to meet ASTM D7566 specifications for viscosity and final boiling point temperature, freezing point, density, aromatics content, and sulfur content of the jet blendstock candidate were within acceptable ranges, thus highlighting the potential of this process for production of jet fuel blendstock.

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗
DOE OSTI2020

Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts

Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research

Dagle, Vanessa↗
DOE OSTI2020

A Hybrid Pathway to Biojet Fuel via 2,3-Butanediol

Production of biomass-derived sustainable alternative jet fuels (SAJF) has been considered as an important approach to decarbonize the aviation industry but still possesses various challenges in technology advancement, particularly in achieving high carbon efficiency. Here we report a hybrid pathway to SAJF from 2,3-butanediol (2,3-BDO), integrating biologically converting biomass to 2,3-BDO with catalytically upgrading of 2,3-BDO to jet-range hydrocarbons. This pathway is demonstrated to have a high carbon recovery to liquid hydrocarbons from corn stover (25–28%) (74–82% of the theoretical maximum efficiency). The catalytic conversion steps involve 2,3-BDO to C3+ olefins, oligomerization, and hydrogenation where the first two steps are the focus of this study. Under optimum reaction conditions (523 K, 115 kPa, 1.0 h-1 weight hourly space velocity), 2,3-BDO conversion and C3+ olefin selectivity are >97% and 94–98% during 40 h time on stream, respectively. To demonstrate the adaptability of this technology with bio-derived 2,3-BDO, we also investigated the impact of water and other organic coproducts (acetoin and acetic acid) inherited from the fermentation broth on the catalyst performance and product selectivities. We have shown that the catalyst can handle a significant amount of water in the liquid feed (40 wt% water/60 wt% 2,3-BDO) and maintain catalyst stability for ~40 h. Acetoin can be converted to similar C3+ olefins as 2,3-BDO with complete conversion of acetoin. Co-feeding 10 wt% acetoin with 2,3-BDO is found to have no impact on 2,3-BDO conversion, C3+ olefin selectivity, and catalyst stability. The utilization of organic coproduct like acetoin can help to improve overall carbon conversion efficiency when using real biomass-derived 2,3-BDO. On the other hand, the presence of 10 wt% acetic acid is shown to drastically inhibit methyl ethyl ketone (MEK) hydrogenation and butene oligomerization as revealed by the increased MEK and butene selectivities, implying the importance of separating organic acids when feeding bio-derived 2,3-BDO. The formed C3–C6 olefins from 2,3-BDO are further oligomerized over Amberlyst-36 catalyst to longer-chain hydrocarbons with >70 wt% jet-range hydrocarbons including predominantly iso-olefins/iso-paraffins. The overall carbon efficiency for the jet-range hydrocarbons is 19–22%, exceeding most of the reported biojet pathways, which makes it a promising approach for SAJF production.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2025

Separation of dilute plutonium(IV) from nitric acid solutions via Reillex HPQ anion exchange resin

Anion exchange is a common method for the separation of plutonium (Pu) in aqueous systems, providing high recovery and decontamination from impurities. Reillex HPQ anion exchange resin has been used around the Department of Energy complex in this application for decades but has typically been used for Pu feed concentrations greater than 1 g/L. It is desirable to recover Pu at more dilute concentrations from a dissolved used fuel or target element, for example. In this work, the performance of Reillex HPQ anion exchange resin was characterized with feed solutions of ca. 0.24 g/L Pu. A significant reduction in the performance of the resin was realized with this dilute concentration relative to a feed solution of 2.35 g/L Pu with similar feed flow rates and the same resin column, likely due to the increased driving force for mass transfer with a higher feed concentration. The maximum capacity of Reillex HPQ resin for Pu can be improved by reducing the flow rate and increasing the feed Pu concentration. Furthermore, the breakthrough point of Pu can be improved in the same manner and by increasing the resin bed height. Diffusion of Pu into the resin was illustrated to be the rate limiting step.

Plutonium separations↗
DOE OSTI2022

The Electromagnetic Characteristics of the Tianlai Cylindrical Pathfinder Array

A great challenge for 21 cm intensity mapping experiments is the strong foreground radiation which is orders of magnitude brighter than the 21 cm signal. Removal of the foreground takes advantage of the fact that its frequency spectrum is smooth while the redshifted 21 cm signal spectrum is stochastic. However, a complication is the non-smoothness of the instrument response. This paper describes the electromagnetic simulation of the Tianlai cylinder array, a pathfinder for 21 cm intensity mapping experiments. Due to the vast scales involved, a direct simulation requires a large amount of computing resources. We have made the simulation practical by using a combination of methods: first simulate a single feed, then an array of feed units, finally with the feed array and a cylindrical reflector together, obtain the response for a single cylinder. We studied its radiation pattern, bandpass response and the effects of mutual coupling between feed units, and compared the results with observation. Many features seen in the measurement result are reproduced well in the simulation, especially the oscillatory features which are associated with the standing waves on the reflector. The mutual coupling between feed units is quantified with S-parameters, which decrease as the distance between the two feeds increases. Based on the simulated S-parameters, we estimate the correlated noise which has been seen in the visibility data, and the results show very good agreement with the data in both magnitude and frequency structures. These results provide useful insights on the problem of 21 cm signal extraction for real instruments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

KOH vs Deionized Water Operation in Anion Exchange Membrane Electrolyzers

Anion exchange membrane water electrolyzers (AEMELs) have recently received significant attention due to their potential advantages over proton exchange membrane electrolyzers (PEMELs). However, some AEMELs feed an aqueous salt solution to the cell where PEMELs typically feed deionized (DI) water. DI water is preferred to keep the system and maintenance costs low. Because of this, many AEMEL researchers report performance both in the salt solution (typically KOH) and DI water. However, the methodology for switching between KOH and DI water is often poorly defined, and it is unclear what impact the residual salt has on cell performance after switching from salt to DI water. Having a fully deionized environment is important because the presence of salts in the water feed increase the effective electrochemical surface area of the catalyst in the three-dimensional electrode and residual salt remaining after switching to DI water feed can have a misleading transient effect on cell performance. This paper focuses on understanding the transition from KOH to DI water testing in AEMELs. It is shown that when switching from salt to DI water feed, a large volume of DI water must be fed over several hours to achieve true DI-water performance. It is also shown that starting AEMELs from the beginning with DI water feed (without any KOH ever being fed to the cell) results in better cell durability. Lastly, a cell is demonstrated having operated exclusively on DI water at 1.0 A cm −2 for 500 h at an operating voltage of ca. 2 V and a low degradation rate.

08 HYDROGEN↗
DOE OSTI2021

Fiscal Year 2021 Filtration of Hanford Tank 241-AP-107 Supernatant Samples Obtained at Prototypic Tank Level and Filtered at 16 °C

Bench-scale filtration testing of 8.5 liters of supernatant from Hanford waste tank 241-AP-107, chilled to 16 °C, was conducted using a backpulse dead-end filter (BDEF) filtration system equipped with a feed vessel and a Mott inline filter Model 6610 (Media Grade 5) in the hot cells of the Radiochemical Processing Laboratory at Pacific Northwest National Laboratory. This was done to assess the impact of a lower sampling location within the tank as well the lowered filtration temperature on supernatant stability and fouling. The as-received samples were transferred to 1.5-liter poly bottles and held at 16 °C for approximately 1 week prior to filtration. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft 2 to match the prototypic operation of the TSCR system. During the initial period of filtration, the differential pressure required to effect filtration at 0.065 gpm/ft 2 increased until it reached 2 psid [the Tank Side Cesium Removal (TSCR) action limit] at 26 hours. After this, the filter was backpulsed to dislodge accumulated solids and reduce this pressure differential. An additional eight backpulses were conducted during the initial filtration period; each time, the target pressure was reached sooner than during the previous interval. Volume filtered decreased from 0.9 to 0.03 m 3 /m 2 over the course of 14 processing hours. After the ninth backpulse, the backpulse frequency had become unsustainable, and it was decided to perform an extensive filter cleaning. The filter was cleaned by draining the chilled AP-107 feed into chilled holding containers, introducing 0.1 M NaOH into the feed vessel, and recirculating the NaOH through the system for 20 minutes before allowing the system to soak for 2 hours without temperature control. A measurable decrease in filter resistance during this recirculation indicated that the 0.1 M NaOH was likely dissolving some of the solids that had deposited on the filter. Post cleaning, the filter resistance was effectively restored to initial conditions as the initial transmembrane pressure was restored to original levels. However, resumed processing of the AP-107 feed at 16 °C continued to result in an increased rate of filter resistance. An additional five backpulses were conducted (four during feed processing, one during subsequent cleaning) before the conclusion of the test. Solids concentrated from the backpulse solutions displayed sodium oxalate-type phases, Al-oxides and sodium Al-oxides/carbonates, iron oxides, and Ca-bearing phases (calcite). The scanning electron microscopy analyses also revealed a large distribution of particles, with some particles, notably sodium phosphate dodecahydrate, having diameters close to 0.5 mm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Reduced Temperature Cesium Removal from AP-101 Using Crystalline Silicotitanate

The Tank Side Cesium Removal (TSCR) system, currently operational under Washington River Protection Solutions LLC (WRPS), sends initial low-activity Hanford waste tank supernate feed to the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility. In addition to entrained solids removal from the supernate, the primary goal of TSCR is to remove cesium-137 ( 137 Cs) by ion exchange, allowing contact handling of the liquid effluent product at the WTP. Crystalline silicotitanate (CST) ion exchange media, manufactured by Honeywell UOP, LLC (product IONSIV™ R9140-B), was selected as the ion exchange media at TSCR. Laboratory-scale ion exchange processing using TSCR prototypic unit operations continues to contribute toward WRPS establishing accurate process flowsheets for the individual feed campaigns planned for TSCR. This report describes the small-scale ion exchange testing with 14.0 L of diluted and filtered supernate from tank 241-AP-101 (AP-101DF) at 16 °C (62 °F) to demonstrate processing at temperature conditions that are more prototypic of what the TSCR system could experience during colder seasons of the year. Since CST Cs capacity increases with decreasing contact temperature, testing at the lower operating temperature will help to predict the maximum 137 Cs loading onto the CST in the TSCR system. One of the waste acceptance criteria (WAC) for the WTP Low-Activity Waste Facility is that the waste must contain less than 3.18×10 -5 Ci 137 Cs per mole of Na. For the AP-101DF tank waste to meet this criterion, only 0.144% of the influent 137 Cs concentration may be delivered to the WTP; this requires a Cs decontamination factor of 694. Testing with AP-101DF matched TSCR prototypic operations where a lead-lag configuration was used until the lag column reached the WAC limit, then a polish column was brought online for continued processing in a lead-lag-polish column configuration. Feed was processed at 1.9 bed volumes (BVs) per hour; the flowrate, in terms of contact time with the CST bed, matched the expected flowrate at TSCR. The Cs-decontaminated product was retained for vitrification testing (to be reported separately). The lead column reached 62% Cs breakthrough after processing ~1400 BVs of feed; the 50% Cs breakthrough occurred at 1250 BVs. Testing compared to previous AP-107 testing at 16 °C showed ~80 BV increases in volume processed to reach the WAC limit for both lead and lag columns. A similar slope in breakthrough curves for both tests indicates similar kinetic behavior, with variations in feed matrices (Na and Cs concentrations) likely responsible for the deviations in reaching the WAC limit. The Cs effluent from the lag column reached the WAC limit after processing 875 BVs. Anticipating this breakthrough point, the polish column was preemptively installed at 770 BVs. Cs breakthrough from the lag column began at 300 BVs, reaching 5.32×10 0 µCi/mL, or 5.6 % Cs breakthrough, after processing all 1400 BVs of feed. Table S.1 and Figure S.1 summarize the observed column performance and relevant Cs loading characteristics.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Ion Exchange Processing of AP-105 Hanford Tank Waste through Crystalline Silicotitanate in a Staged 2- then 3-Column System (Rev.1)

The Tank Side Cesium Removal (TSCR) system, under development by Washington River Protection Solutions LLC (WRPS), will send initial low-activity Hanford waste tank supernate feeds to the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Facility. In addition to entrained solids removal from the supernate, the primary goal of TSCR is to remove cesium-137 ( 137 Cs) by ion exchange, allowing contact handling of the liquid effluent product at the WTP. Crystalline silicotitanate (CST) ion exchange media, manufactured by Honeywell UOP, LLC (product IONSIVTM R9140-B), was selected as the ion exchange media at TSCR. CST is a non-elutable inorganic material that has demonstrated robust chemical, physical, and radiation tolerance while maintaining functionality. However, exchange kinetics of Cs onto CST is slow, resulting in low utilization of the CST Cs load capacity before unacceptable Cs breakthrough. Two process flow designs have been tested, as follows. 1. Lead-lag column processing: The lead column was removed after the lag column effluent reached the waste acceptance criteria (WAC) limit, the lag column was moved into the lead position, and a new lag column was installed. This format used ~52% Cs load capacity on the lead column. 2. Lead-lag-polish column processing: The processing was stopped when the polish column effluent reached the WAC limit. This format resulted in 81% Cs load capacity on the lead column. Testing with diluted feed from Hanford tank AP-105 (AP-105DF) incorporated a nuanced change to the lead-lag-polish column system where the polish column was inserted when the lag column effluent reached WAC limit. A 10.9-L volume of AP-105DF (diluted to 5.6 M Na) was processed through the Direct Feed Test Platform system, established at Pacific Northwest National Laboratory to support small-scale waste qualification efforts. The columns consisted of 10-mL CST beds (CST Lot 2002009604, sieved to screen out >30-mesh particles) placed in 1.5-cm-inner-diameter columns. Feed was processed at 1.83 bed volumes (BV) per hour; the flowrate, in terms of contact time with the CST bed, matched the expected flowrate at TSCR. The <30-mesh CST sieve cut was expected to provide appropriate performance scaling to a full-height column. The installation of the polish column later in processing (after processing 523 BVs) did not appear to fundamentally change the utilization of the lead column for Cs exchange nor did it extend the total feed processing volume when compared to the previous test with AP-107 feed. Table ES.1 and Figure ES.1 summarize the measured AP-105DF Cs load performance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗