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At least 109 records · Page 6

A Process with Decoupled Absorber Kinetics and Solvent Regeneration through Membrane Dewatering and In-Column Heat Transfer (Final Report)

This report summarizes the work conducted on project DE-FE0031604 where University of Kentucky Center for Applied Energy (UK CAER) has validated its intensified CO 2 capture process through substantial enhancements to the kinetics of the absorption process and energy reductions by absorber temperature profile modification, dewatering and heat integration technologies for achieving significant capital and operating cost reductions. To address DOE’s objective of improving post-combustion CO 2 capture technology and reducing associated cost, UK CAER employed an intensified process which combined three key aspects targeted at overcoming inherent limitations or barriers in the conventional CO 2 capture and desorption process. The process designed to be independent of the type of solvent used, included (1) the use of 3-D printed two-channel structured packing material to control the temperature profile and increase the CO 2 absorption rate in the absorber, (2) a zeolite membrane dewatering unit for dewatering of the carbon-rich solvent to decouple solvent concentration needs for CO 2 absorption and desorption, and (3) a rich-split feed with two-phase flow heat transfer prior to the stripper that provided a secondary point of vapor generation to provide energy savings in steam extraction and solvent regeneration. The project was executed over two budget periods. This involved testing of individual process components which included the advanced heat transfer packing and the dewatering membrane on UK CAER’s 30 liter per minute (L/min) CO 2 (3” Column) capture bench unit with simulated flue gas in the first budget period. Subsequent scaled-up testing of these components together with the split-feed configuration were also tested in UK CAER’s 0.1 MWth CO 2 capture unit with coal-derived flue gas in the second-budget period. Long term studies were done during this period to assess process and solvent performance over extended duration. Project partners Lawrence Livermore National Laboratory (LLNL) and Media & Process Technology (MPT) led the development efforts for the advanced packing material and dewatering membrane respectively. Data from the long term testing was used as input for an environmental, health and safety (EH&S) assessment for the process and scaled technology performed by ALL4 LLC. Trimeric Corporation also completed a techno-economic analysis (TEA) for the UK CAER technology which was compared to the DOE reference Case B12B. Tests on the 3” column capture unit showed that the advanced heat transfer packing could be used to lower the bulge temperature in the absorber, and this was also proven in the scaled testing in the 0.1 MWth CO 2 capture unit. The bulge temperature could be lowered by >10 °C, changing the temperature profile in the absorber, and showed potential to enhance absorption with the ability to tailor the profile to provide conditions suitable for a solvent’s properties and kinetics. Conditions for short term evaluation of a 19” zeolite dewatering membrane on the 3” column capture unit yielded desirable fluxes and sustained rejection rates of >80%. However, for the scaled testing of six membrane modules consisting of 21 parts of 31-inch-long membrane tubes in each bundle (surface area 0.3 m 2 ), over a more extended duration, similar rejection rates could not be achieved. With the split-feed of the rich stream to the stripper, improved heat recovery minimized waste heat exiting the top of the stripper. The stripper exhaust temperatures could be reduced by >10 °C; reducing the amount of water vaporization contributed to lowering the regeneration energy by ~ 15%. The energy benefit could be sustained from the long term monitoring of the solvent performance. The solvent properties were not significantly impacted over the long-term operations. The benefits of the UK CAER process demonstrated experimentally were mostly validated from the TEA comparing a commercial scale application of the technology to DOE reference Case B12B. The cost of CO 2 capture for the UK CAER technology was estimated to be ~$34.97/tonne of CO 2 captured; a reduction of 23% compared to Case B12B. The increase in cost of electricity was also shown to be 16% lower than that of Case B12B. The total parasitic demand was also shown to be 11% lower. The key drivers for the benefits are a result of the process intensification approaches employed in the UK CAER technology for enhanced solvent performance, effective heat recovery and improved energy performance. The EH&S assessment did not find any major environmental concerns or barriers to the full scale implementation of the technology.

20 FOSSIL-FUELED POWER PLANTS↗

A Panoramic View of Temperature and Field Distributions of the Structured Catalyst Under Microwave Irradiation Using Experimental and Modeling Approaches

This is a presentation covers NETL's recent research outcome in numerical modeling of microwave-assisted catalytic reaction. In this presentation, the intrinsic microwave-material interaction was demonstrated in this study through numerical modeling and experimental measurement. Different material combinations and reactor setups were investigated and compared. By combining numerical modeling with advanced measurement techniques, the microwave-material interaction and the relationship between electromagnetic field and heating can be better understood, which further benefits the development of microwave-assisted reactors and their application in process intensification.

Bai, Xinwei↗

Isolated Single Metal Atoms Supported on Silica for One Step Non-Oxidative Methane Upgrading to Hydrogen and Value-Added Hydrocarbons

Natural gas in the United States offers substantial economic opportunities due to its abundance but its transportation is challenging because its primary component, methane (CH 4 ), does not liquefy at ambient temperature and typical pressures. As a result, a significant portion of natural gas is either used for heat, flared in remote locations, or remains unutilized, presenting a lost economic opportunity and an environmental harm. Converting natural gas to larger hydrocarbons in an economically competitive manner would enable transportation of products and further boost the economy and reduce environmental footprint. Our research goal is to enable efficient non-oxidative methane conversion (NMC) via catalyst innovation to convert CH 4 in one-step to olefins and aromatics and hydrogen (H 2 ) co-product. The catalysts are made of supported single metal atoms and operated at medium-high temperatures. The single metal atoms achieve methane activation by heterogeneous surface dehydrogenation to generate a hydrocarbon pool and importantly limit coke formation. The integration of novel single atom catalysts in a short contact time microreactor enable unprecedented NMC performance that could lead to economically-feasible, distributed natural gas upgrading by advanced manufacturing and process intensification. Our innovated catalyst and reactor technology promise to tap into previously uneconomic natural gas resources, such as stranded, vented, and flared methane.

03 NATURAL GAS↗

Multifunctional Catalysts for the Tandem Reactions of Oxygenates

Industrially-relevant catalytic reactions rarely consist of a simple sequence of elementary steps. Moreover, kinetic coupling of multiple reactions on a catalyst surface is highly desired for process intensification and improved energy efficiency for large scale chemical transformations. The shifting landscape of hydrocarbon chemical feedstocks in the US also motivates research on the selective conversion of more complex molecules. One desirable type of catalytic reaction is the reduction of carboxylic acids that are produced from biomass feedstocks to their corresponding alcohols. The proposed research explores the fundamental importance of hydrogen spillover on a multifunctional catalyst for carboxylic acid reduction with H 2 composed of metal particles coupled to metal oxide particles. Recent work has demonstrated the excellent performance of supported tungsten oxide clusters for carboxylic acid reduction, but only after they are promoted with a late transition metal such as palladium. Elucidating the active state of the catalyst and the associated reaction mechanism for acid reduction on that active state are the overall goals of the proposed project and successful completion will enable future design of efficient multifunctional catalysts. The critically important role of the metal promoter is hypothesized to be its ability to dissociate H2 and spillover atomic H to the support. Although hydrogen spillover is a well-recognized phenomenon in catalysis, its role in both catalyst activation and catalytic turnover are still unresolved. The study combined materials synthesis, characterization, reactivity testing, and molecular simulations, to explore the effect of hydrogen chemical potential on the formation of the active catalytic sites and on the steady state catalytic reduction of carboxylic acid. Varying the hydrogen chemical potential through modification of the gas conditions, support composition, and metal loading to modulated the structure and catalytic performance of the reducible metal oxide. Dual function catalysts containing supported Pd and WO x species co-located on a non-reducible carrier (silica) and a reducible carrier (titania) were synthesized and characterized by electron microscopy, temperature-programmed reduction, and chemisorption. Spectroscopic methods such as X-ray absorption and UV-vis were also used to evaluate the catalysts, which were used in the reduction of propionic acid to aldehyde and alcohol. Quantum chemical calculations, including ab initio phase diagrams provided molecular insights into the H spillover phenomenon.

09 BIOMASS FUELS↗

Urbanization may enhance tornado potential: A single case report

Tornadoes pose a risk of catastrophic economic loss and casualty in the United States. Modification of land use by urbanization alters the meteorological conditions that may impact tornado formation and intensification processes. Here we explored the simulated impact of Kansas City urbanization on the tornado potential of a supercell storm. In this studied case, we found that urbanization might enhance tornado potential by a) strengthening the low-level streamwise vorticity in the storm inflow region, thus forming stronger rotating updrafts; and b) intensifying near-surface horizontal vorticity near the boundary of the forward-flank cold pool which increases the ingestion, tilting, and stretching of streamwise horizontal vorticity into vertical vorticity. The former results from the stronger east-to-west pressure perturbation gradient due to the faster, stronger outflow boundary, and the latter is mainly a result of stronger cold fronts and a better alignment of storm-relative inflow with the horizontal vorticity vector. We emphasize that our conclusions only represent one possibility of how urbanization would affect tornado potential, and a more systematic examination is needed to achieve a more general conclusion.

54 ENVIRONMENTAL SCIENCES↗

Bio-Based Polyisoprene Can Mitigate Climate Change and Deforestation in Expanding Rubber Production

Biomass is a promising renewable feedstock to produce polyisoprene for the rubber industry. Through metabolic engineering, sugars derived from pretreated and hydrolyzed cellulose and hemicellulose can be directly fermented to isoprene to produce rubber. Here we investigate the life cycle environmental impact of isoprene fermentation to produce bio-polyisoprene from agricultural residues (of Zea mays L.). Results show that the greenhouse gas (GHG) intensity of bio-polyisoprene (−4.59 kg CO2e kg−1) is significantly lower than that of natural rubber (Hevea brasiliensis) and synthetic rubber (−0.79 and 2.41 kg CO2e kg−1, respectively), while supporting a circular biogenic carbon economy. We found the land use intensity of bio-polyisoprene to be 0.25 ha metric ton−1, which is 84% lower than that from rubber tree plantations. We compare the direct fermentation to isoprene results with indirect fermentation to isoprene through the intermediate, methyl butyl ether, where dehydration to isoprene is required. The direct fermentation of isoprene reduces reaction steps and unit operations, an expected outcome when employing process intensification, but our results show additional energy conservation and reduced contribution to climate change. Among the ReCiPe life cycle environmental impact metrics evaluated, air emission related impacts are high for bio-polyisoprene compared to those for natural and synthetic rubber. Those impacts can be reduced with air emission controls during production. All other metrics showed an improvement for bio-polyisoprene compared to natural and synthetic rubber.

Batten, Rahamim↗

Alternating conduction and convection drying of paper – an experimental analysis with a continuous data acquisition approach

In conventional multi-cylinder drying of paper and board, both conductive drying from steam-heated dryer cylinders and convective drying by flowing air over the paper surface in the pockets are used. Conductive drying from steam-heated drying cylinders is a critical component in providing the necessary thermal energy to paper and board as they dry. Steam temperature and internal and external resistances at the contacting surface are critical process parameters influencing the conductive drying process. An experimental setup was developed to study the alternating conductive and convective drying of paper and board. Paper sheet moisture, temperature, and temperature distribution within the heated platen and the instantaneous heat flux as the sheet was being dried were measured. The instantaneous heat flux, contact heat transfer coefficient, and drying rates were determined as drying proceeds. Experimental results, as well as comparisons to literature and commercial data, are presented. The conductive heat transfer coefficients determined were compared to traditional correlations normally used in the modeling of paper drying. Similarly, the convective heat and mass transfer coefficients are also determined and compared to literature data. In addition to the evaluation of alternating conductive and convective drying characteristics of paper and board, the potential inclusion of auxiliary energy components will also be included. Experimental results from the conduction and convection drying system are presented. Furthermore, this data will be useful in process development, intensification of manufacturing processes, and modeling and simulation of paper drying processes.

42 ENGINEERING↗

Heat Exchanger Intensification Through Powder Processing and Enhanced Design (HIPPED)

High intensity, supercritical CO 2 heat exchangers capable of operating at temperatures between 800 and 1100 ˚C and pressures greater than 80 bar are considered a critical component for high efficiency power generation and a range of next-generation industrial processes. A novel heat exchanger concept was proposed in this project. The proposed concept involved a plate-type architecture with three-dimensional fins, called twisted s-shaped fins, that capitalize on additive manufacturing. Four manufacturing processes were studied to realize the complex envisioned design: press and sinter of metallic powders, directed energy deposition, laser powder bed fusion, and a novel powder bed process involving a photoreactive polymer called SEAM (scalable expeditious additive manufacturing), that later was developed at MSU. The team was able to manufacture subscale heat exchangers using laser powder bed fusion (LPBF) and SEAM. The team settled on using SEAM as a final manufacturing approach due to its very low cost. The SEAM-manufactured heat exchanger, however, when tested under pressure, exhibited leaks and the process still requires further development beyond the timeline of the project. To support the heat exchanger design and testing, the team developed a new high temperature flow loop allowing testing under high temperature and pressure. Computational modeling of the heat exchanger was also performed for the twisted s-shaped fins and the computations were validated with experimental data. The new twisted fins resulted in enhanced heat transfer and reduced pressure drop. To further minimize pressure drop in the plate heat exchanger, the team also developed a simplified model for flow maldistribution in the manifolds, providing a new tool for designers that eliminates the need for complex CFD calculations. A technoeconomic analysis was also developed to contrast SEAM with LPBF, this tool indicated that SEAM is several times less costly and offer significant promises as a rapid low cost additive manufacturing process for metallic systems.

30 DIRECT ENERGY CONVERSION↗

Optimisation of root traits to provide enhanced ecosystem services in agricultural systems: A focus on cover crops

Roots are the interface between the plant and the soil and play a central role in multiple ecosystem processes. With intensification of agricultural practices, rhizosphere processes are being disrupted and are causing degradation of the physical, chemical and biotic properties of soil. However, cover crops, a group of plants that provide ecosystem services, can be utilised during fallow periods or used as an intercrop to restore soil health. The effectiveness of ecosystem services provided by cover crops varies widely as very little breeding has occurred in these species. Improvement of ecosystem service performance is rarely considered as a breeding trait due to the complexities and challenges of belowground evaluation. Advancements in root phenotyping and genetic tools are critical in accelerating ecosystem service improvement in cover crops. In this study, we provide an overview of the range of belowground ecosystem services provided by cover crop roots: (1) soil structural remediation, (2) capture of soil resources and (3) maintenance of the rhizosphere and building of organic matter content. Based on the ecosystem services described, we outline current and promising phenotyping technologies and breeding strategies in cover crops that can enhance agricultural sustainability through improvement of root traits.

54 ENVIRONMENTAL SCIENCES↗

A simple and practical process modeling methodology for pressure swing adsorption

Although many dynamic models exist for the design and simulation of pressure swing adsorption (PSA) processes, these models involve the solution of a complex system of coupled partial differential equations. Process engineers need a simple, practical, and yet robust short-cut model that helps decide whether to implement a PSA system in a process flowsheet. This work presents a “virtual” moving bed modeling methodology that considers only mass and energy balances and adsorption isotherms to describe the cyclic steady state behavior of PSA systems. Similar to tray efficiencies in distillation calculations, adsorption efficiencies are further introduced to account for system “non-ideality.” Finally, a lab-scale air separation system is used to illustrate the application of this modeling methodology.

42 ENGINEERING↗

Manufacturing Process Design of a Micro-Scale Liquid-Liquid Extractor and Multi-phase Separator

Advances in process innovation within the chemical process industry are impeded by the cost of producing new innovative components. In this paper, various manufacturing process routes were evaluated for scaling up a micro-scale liquid-liquid extractor and multi-phase separator capable of separating immiscible phases that are used for the extraction of a chemical product into a lower boiling point solvent to make downstream distillation easier. A manufacturing process design methodology was used to evaluate both photochemical machining and binder jetting as a means for producing the micropost arrays within the separator. Cost curves show that for a 0.3 mm deep micropost array, photochemical machining was found to be much cheaper than binder jetting. However, because binder jetting processes enable microposts with over 13 times higher depth-to-width aspect ratios, binder jetting was found to decrease the overall costs of the extractor/separator by more than half for a 500 barrel per day plant, with breakeven as low as 15 barrels per day. These economics were confirmed by building extractor/separator plates and characterizing them dimensionally and functionally. The binder jet plates were found to perform better than photochemical plates leading to the complete separation of the organic phase from water. The utilization of slower sintering cycles combined with surface grinding provided acceptable dimensional tolerances for the binder jet plates. Using pressurized air during depowdering improved the economics for the binder jetting process.

42 ENGINEERING↗

Intensification differentially affects the delivery of multiple ecosystem services in subtropical and temperate grasslands

Intensification, the process of intensifying land management to enhance agricultural goods, results in “intensive” pastures that are planted with productive grasses and fertilized. These intensive pastures provide essential ecosystem services, including forage production for livestock. Understanding the synergies and tradeoffs of pasture intensification on the delivery of services across climatic regions is crucial to shape policies and incentives for better management of natural resources. Here, we investigated how grassland intensification affects key components of provisioning (forage productivity and quality), supporting (plant diversity) and regulating services (CO 2 and CH 4 fluxes) by comparing these services between intensive versus extensive pastures in subtropical and temperate pastures in the USDA Long-term Agroecosystem Research (LTAR) Network sites in Florida and Oklahoma, USA over multiple years. Our results suggest that grassland intensification led to a decrease in measured supporting and regulating services, but increased forage productivity in temperate pastures and forage digestibility in subtropical pastures. Intensification decreased the net CO 2 sink of subtropical pastures while it did not affect the sink capacity of temperate pastures; and it also increased environmental CH 4 emissions from subtropical pastures and reduced CH 4 uptake in temperate pastures. Intensification enhanced the global warming potential associated with C fluxes of pastures in both ecoregions. Our study demonstrates that comparisons of agroecosystems in contrasting ecoregions can reveal important drivers of ecosystem services and general or region-specific opportunities and solutions to maintaining agricultural production and reducing environmental footprints. Further LTAR network-scale comparisons of multiple ecosystem services across croplands and grazinglands intensively vs extensively managed are warranted to inform the sustainable intensification of agriculture within US and beyond. Our results highlight that achieving both food security and environmental stewardship will involve the conservation of less intensively managed pastures while adopting sustainable strategies in intensively managed pastures.

60 APPLIED LIFE SCIENCES↗

Selective hydrodeoxygenation of 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) over carbon supported copper catalysts using isopropyl alcohol as a hydrogen donor

Selective hydrodeoxygenation (HDO) of 5-hydroxymethylfurfural to 2,5-dimethylfuran is of great importance. Here, we reveal a simple pathway for green and efficient HDO using readily available copper with in-situ hydrogen generation. A highly dispersed Cu/PBSAC catalyst consisting of small metallic Cu 0 nanoparticles carries out isopropyl alcohol (IPA) dehydrogenation and subsequent HDO of HMF. Density functional theory calculations reveal that the dehydrogenation of IPA is more favorable on Cu(211) with a lower energy barrier of ~0.6 eV. This facet exists in a higher ratio on nanosized catalysts. Batch reactions using Cu/PBSAC at 190 °C exhibited 91.9% HMF conversion and 71.7% DMF selectivity in 6 hr, and > 96% DMF yield in 10 hr. The mechanical strength of the carbon support is ideal for continuous processing for increased productivity; we demonstrate a > 90% DMF yield at 1/WHSV of 2.4 hr. The process demonstrated here can be integrated with upstream HMF separation utilizing carbon adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Temporal performance indicators for an integrated pilot-scale membrane distillation-concentrated solar power/photovoltaic system

Management of concentrate streams in inland applications has uncertain long-term environmental impacts. This study investigates an intensified solar-energy capture desalination system that integrates membrane distillation (MD) with a hybrid concentrated solar power (CSP)/photovoltaic (PV) collector to realize self-sustained zero-waste discharge for effective management of concentrate streams in inland and off-grid applications. The demonstration-scale CSP/PV system can produce up to 178 kWh of thermal energy and 4 kWh of electrical energy per day. The thermal and electrical energy from the CSP/PV system is directly supplied to the air gap MD (AGMD) pilot-scale system producing up to 288 L of distilled water per day. Experiments were performed on the hybrid AGMD-CSP/PV system to evaluate system performance under various operating conditions including AGMD and CSP flow rates, CSP system pre-heating, and AGMD vacuum pressure. Experimental results indicate that doubling the AGMD flow rate results in a 119% increase in thermal energy utilization and a 71% increase in distillate production. Compared to the winter months, operating the system in summer months when direct normal irradiance (DNI) is highest results in nearly double the distillate production (88 L in winter and 168 L in summer) and nearly three times the amount of thermal energy consumption (15 kWh in winter and 43 kWh in summer). Operating with vacuum resulted in a 34% increase in distillate production and allowing the thermal storage reservoir to preheat in the winter resulted in a 61% increase in distillate production. Altogether, experimental results highlight the tradeoff between distillate production and thermal and electrical energy production and consumption under various environmental conditions and the potential for AGMD-CSP/PV to be a stand-alone desalination system.

14 SOLAR ENERGY↗

Silica-encapsulated Fe 2 O 3 oxygen carriers for selective chemical looping combustion of hydrogen

Methane dehydroaromatization (MDA) combined with chemical looping (CL) combustion of hydrogen can overcome the MDA thermodynamic constraints conventionally limiting conversion. Development of selective hydrogen-oxidation oxygen carriers in the presence of aromatics in the CL is key to improve MDA performance in the coupled reaction system. Here, in this paper, we show that a novel oxygen carrier (silica-encapsulated Fe 2 O 3 with Fe/Si mole ratio of 1.2) yields high overall methane conversion (49%) and aromatics yield (up to 36%) during 4 h of recirculating a stream in the developed system. A silica layer encapsulating Fe 2 O 3 favors hydrogen transport and oxidation, preventing aromatics diffusing to the Fe 2 O 3 surface. A close physical contact between iron oxide particles and silica, and near complete encapsulation of the particles by the silica layer can facilitate hydrogen conversion without full depletion of iron oxides by forming iron silicates. The silica-encapsulated iron oxide particles can be reoxidized in air after depletion of its oxidative capacity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Continuous recovery of phosphoric acid and Rare-Earths containing particles from phosphoric acid sludge using a decanter centrifuge

Recovery of rare earth elements (REEs) from various industrial and natural streams currently draws significant attention in efforts to meet the demands of the manufacturing industry. Among many industrial byproducts and waste streams, phosphoric acid sludge could be one of the most economically feasible resources for the recovery of REEs because solid particles in the sludge contain relatively concentrated REEs, up to 3,000 ppm, while the liquid component of the sludge is valuable phosphoric acid (P 2 O 5 ) that can be recovered and returned to the main product. Due to high viscosity and large solids content (e.g., 30–40 %), however, this byproduct stream requires multistep separation and purification processes. In this study, a single-step process involving a continuous-flow decanter centrifuge (CFDC) was employed to investigate its feasibility for continuous solid/liquid separation from real phosphoric acid sludge. High centrifugal forces generated from up to 1500 G gravity acceleration separate solid particles from the sludge, generating a liquid-rich stream and a solids-rich stream at the exit of the CFDC. A single pass of phosphoric-acid sludge through the CFDC yielded 95 % liquid recovery and 90 % recovery of REEs-containing solids from 20 to 34 wt% solids-containing sludge. Finally, a reduced order model developed for the CFDC operation showed good agreement with experimental data, and preliminary technoeconomic analysis revealed potential process feasibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗