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Production of synthesis gas from natural gas with copper—iron—manganese oxide oxygen carriers/catalysts via partial oxidation and dry reforming processes

Materials, methods of making, and methods of providing a trimetallic oxygen carrier for converting methane containing fuel to synthesis gas. The trimetallic oxygen carrier comprises CuxFeyMnzOt, where CuxFeyMnzOt is a chemical composition with 0 < x ≤ 3 and 0 < y ≤ 3 and 0 < z ≤ 3 and, 0 < t ≤ 5. For example, CuxFeyMnzOt may be one of CuMnFeO 4 , CuFe 0.5 Mn 1.5 O 4 , CuFeMn 2 O 4 , CuFe 2 MnO 4 , or Cu impregnated on FerMnsOu, Fe impregnated on CurMnsOu, Mn impregnated on CurFesOu where r > 0, s > 0 and u > 0 and combinations thereof. Reaction of trimetallic CuxFeyMnzOt with methane generates a product stream comprising at least 50 vol. % CO and H 2 .

Siriwardane, Ranjani V.↗

High-sensitivity gas-mapping 3D imager and method of operation

Measurement apparatuses and methods are disclosed for generating high-precision and -accuracy gas concentration maps that can be overlaid with 3D topographic images by rapidly scanning one or several modulated laser beams with a spatially-encoded transmitter over a scene to build-up imagery. Independent measurements of the topographic target distance and path-integrated gas concentration are combined to yield a map of the path-averaged concentration between the sensor and each point in the image. This type of image is particularly useful for finding localized regions of elevated (or anomalous) gas concentration making it ideal for large-area leak detection and quantification applications including: oil and gas pipeline monitoring, chemical processing facility monitoring, and environmental monitoring.

Kreitinger, Aaron Thomas↗

The Effect of Heat Distribution on the Production of Benzene Using Microwaves

The conversion of methane into aromatics with microwaves has the potential to be developed into a modular process for associated natural gas flaring reduction. Microwaves provide advantages of rapid, selective heating of heterogenous catalyst systems, but the heating is non-homogeneous. This body of work is a study performed by NETL researchers to evaluate the effect of silicon carbide as a microwave susceptor with a benchmark Mo/ZSM-5 catalyst to provide uniform bed heating and improved benzene yields. We demonstrate microwave can provide more efficient benzene production than a conventionally heated system.

Haynes, Daniel↗

Novel Geochemistry Determined from High P-T Simulation Experiments of HFTS 2

A standard method in unconventional oil and gas production is the process of hydraulic fracturing followed by a shut-in period, during which the fracture fluid remains pressurized in the reservoir for up to three weeks before production begins. Despite this widely used process, very little is known about what occurs in the reservoir during this shut-in process. In order to properly delineate potential reservoir reactions that may occur during shut-in that would lead to corrosion and scaling events, experiments were conducted in high pressure, high temperature reactors to simulate conditions of the Wolfcamp Formation in the Delaware Basin. Experimental design allowed the assessment of the effect of proppant, microbiology, and time on the mineralogy and fluid chemistry in the reservoir. Results suggest the biggest impact on fluid chemistry and shale mineralogy during shut-in is time. Analyses demonstrate dissolution of the shale material, with maximum dissolved ions occurring after 7 days of the shut-in period. After 21 days, results suggest precipitation occurs. The Delaware Basin is demonstrated to be high in sulfate content, which further increases in the fluid due to dissolution reactions during shut-in. The pressure vessel experiments suggest there was no significant contribution to reactions from microbiology during the shut-in period. However, early production samples demonstrate a significant selection of the microorganism Caminicella, a genus of which has previously been correlated to corrosion and sulfide production. Results suggest shut-in conditions may provide high sulfate concentrations that could later be utilized by a shifted microbial community to drive potential well infrastructure failure. This is the first study to incorporate microbiology, mineralogy, and fluid chemistry to investigate the fundamental geochemical reactions that occur during shut-in and early phase production of the Delaware Basin. Results from this study can complement observations from the Hydraulic Fracture Test Site 2 observations.

Gulliver, Djuna↗

High-sensitivity gas-mapping 3D imager and method of operation

Measurement apparatuses and methods are disclosed for generating high-precision and -accuracy gas concentration maps that can be overlaid with 3D topographic images by rapidly scanning one or several modulated laser beams with a spatially-encoded transmitter over a scene to build-up imagery. Independent measurements of the topographic target distance and path-integrated gas concentration are combined to yield a map of the path-averaged concentration between the sensor and each point in the image. This type of image is particularly useful for finding localized regions of elevated (or anomalous) gas concentration making it ideal for large-area leak detection and quantification applications including: oil and gas pipeline monitoring, chemical processing facility monitoring, and environmental monitoring.

Kreitinger, Aaron Thomas↗

Chapter 11: Biochar Production

In production of biochar, thermochemical processes that can be used to treat biomass include pyrolysis, gasification, hydrothermal processing, and combustion. Each of these processes is defined by specific operating conditions (e.g., temperature, presence of oxygen) and feedstock requirements for optimal conversion to the product of primary interest. Each process results in varying fractions of gaseous, liquid, and solid products. Though other publications have emphasized the gaseous bio-energy products of such processes (e.g., bio-oil, synthesis gas or "syngas") with biochar as a co-product, in this discussion, we focus primarily on biochar as the In production of biochar, thermochemical processes that can be used to treat biomass include pyrolysis, gasification, hydrothermal processing, and combustion. Each of these processes is defined by specific operating conditions (e.g., temperature, presence of oxygen) and feedstock requirements for optimal conversion to the product of primary interest. Each process results in varying fractions of gaseous, liquid, and solid products. Though other publications have emphasized the gaseous bio-energy products of such processes (e.g., bio-oil, synthesis gas or "syngas") with biochar as a co-product, in this discussion, we focus primarily on biochar as the main product, with heat and electrical energy as co-products of secondary interest. The reasons for this are as follows: when producing biochar, heat is the simplest form of energy to capture and utilize, electrical energy can be generated from heat energy with a wide range of available technologies small and large; rather than immediately combusting the gases released from biomass, there is potential to refine the gases into bio-oil and syngas. However, much larger investments of capital are needed to build facilities for which gaseous fuel production is the primary goal, as compared to those focused on biochar production with heat and electrical energy co-products. While the economic viability of biochar production will be improved by production of high-value co-products (e.g., wood acids for use in pesticides), the simplest production scheme is one in which biochar and heat are the primary products. Here we aim to provide a broader overview of thermochemical processes and technologies most relevant to biochar production in its current state of commercialization. All biochar is a result of pyrolysis (the reaction) but not all biochar is made with a dedicated pyrolysis reactor (the technology type). Further, all biochar is the result of a lack of complete combustion (the reaction), even biochar produced in a combustion or gasification reactor (the technology type). This is an important distinction to acknowledge in the following sections in which we discuss both thermochemical conversion reactions and technology types.

biochar↗

A New Process for Carbon Dioxide Conversion to Fuel

In this project, TDA developed a new mixed metal oxide-based sorbent that converts CO 2 (captured from coal fired power plant) to CO, which can then be combined with renewable H 2 generated by water electrolysis to produce different liquid fuels. TDA’s absorbent-based CO 2 conversion process uses a redox process, which splits the reverse water gas shift reaction steps into two stages: CO 2 reduction to CO and H 2 oxidation to H 2 O and eliminates the equilibrium limitations. The CO produced in the two-stage reactor system can then be further reacted with renewable H 2 to produce methanol, naphtha, diesel, or gasoline. We worked with the Gas Technology Institute (GTI) and Advanced Power & Energy Program (APEP) of University of California, Irvine (UCI) to design and develop the liquid fuel synthesis process that is built around this new material. We demonstrated the techno-economic viability of the new sorbent based redox process to convert CO 2 into synthesis gas by: 1) demonstrating continuous carbon dioxide reduction in a prototype test system for over 500 hours while converting up to 0.4 kg CO 2 /day. With the successful completion of the R&D effort, the technology is now ready for a larger pilot-scale demonstration and the technology readiness has been raised from TRL 3 to TRL 5. In collaboration UCI, we also completed a high-fidelity process design and economic analysis. The required selling price (RSP) for methanol (Case 1 H2-MeOH) is $\$$3.06/gal, naphtha and diesel (Case 2 H2-FT) are $\$$6.21/gal and $\$$8.91/gal, and for gasoline (Case 3 H2-MTG) is $\$$6.96/gal on a 2011 dollar basis. To put these costs in perspective, the recent (June 2020) U.S. price for methanol made from natural gas is about $\$$1.19/gal according to Methanex, a major methanol producer in North America. The recent (June 2, 2020) California prices for gasoline and diesel with California’s strict specifications are $\$$3.35/gal and $\$$3.73/gal according to the U.S. Energy Information Agency. On the other hand, it should be noted that the gasoline and diesel produced by the designs of Case 2 and Case 3 would be both nitrogen and sulfur free. These RSPs are based on a cost of imported electricity of $\$$64/MWh based on the low-end current wind generated electricity cost (Genevieve and Ramsden, Wind Electrolysis: Hydrogen Cost Optimization, Technical Report, June 2011, NREL/TP-5600-50408). This cost is by far the largest component of the variable costs used in computing the RSPs. The cost of the imported electricity has to approach zero for the RSP to be competitive for methanol produced in Case 1 and naphtha and diesel produced in Case 2 while the cost of electricity has to be less than $\$$10/MWh for gasoline produced in Case 3.

01 COAL, LIGNITE, AND PEAT↗

Enabling Staged Pressurized Oxy-Combustion: Improving Flexibility and Performance at Reduced Cost

Introduction: The staged pressurized oxy-combustion (SPOC) process, developed by Washington University in St. Louis (WUSTL), is an oxy-combustion carbon capture technology that employs a steam power cycle to generate electricity. As with atmospheric-pressure oxy-combustion processes, carbon dioxide (CO 2 ) capture rates of 90% or higher can be achieved. The staged-combustion approach of the SPOC process, when operated at elevated gas pressure, allows for near elimination of flue gas recycle (FGR) and leads to significant improvements in efficiency and reduced costs. The primary goal of this project was to investigate the potential for SPOC for flexible operation beyond the capabilities of conventional coal-fired power plants, particularly those employing carbon capture and storage (CCS). Oxy-combustion differs from conventional coal combustion in that the combustion of coal is carried out using oxygen as opposed to air. The resultant flue gas is a mixture of primarily CO 2 and water, greatly simplifying CO 2 capture. As SPOC does the oxy-combustion process under pressure, it is higher efficiency and lower cost than atmospheric oxy-combustion. The project was led by the Electric Power Research Institute, Inc., with the assistance of WUSTL, Doosan Babcock (DBL – boiler plant original equipment manufacturer), and Air Liquide (AL – air separation experts). The specific objectives of the project were to: (1) Evaluate the SPOC concept and develop a risk-based approach to the heating surface layout ensuring that performance (gas and steam side), manufacturing, transportation, and plant erection considerations were fully accounted for in the system design. (2) Improve the technology to ensure its performance and cost potential are substantially better than today’s baseline pulverized coal power plant with post-combustion capture (PCC) or atmospheric oxy-combustion, and show progress toward performance commensurate with projected commercial operation, including 90% or more CO 2 capture. (3) Address critical technology gaps and improving overall system performance for the technology. (4) Perform combustion tests at scale under commensurate pressure to the commercial operating system validate combustor and advance the SPOC combustion modeling tools that will facilitate full-scale design. Combustion Testing: Testing was initially carried out at atmospheric pressure with methane to ensure that all systems were correctly operating. Following this, the testing then proceeded to moderate pressure operation at 4 bara, where different stoichiometric conditions were used across an extended heat input range, showing that a stable flame could be maintained. Testing then proceeded at 10 and 15 bara where it was shown that the ignition system needed to be replaced at these operating conditions. When testing recommenced, a similar stable flame shape was achieved, without any methane support, and the full 100 kWth coal oxy-combustion was demonstrated. Heat flux measurements showed 400 kW/m 2 (0.126 MMBtu/hr-ft 2 ) from the flame, within the 450 kW/m 2 (0.142 MMBtu/hr-ft 2 ) preferred limit defined by DBL for the full-scale design case. Carbon monoxide and carbon-in-ash measurements showed that complete combustion was possible with ultra-low excess oxygen at 1 vol % in the product flue gas. This allowed the full-scale models to be calculated based on this level of excess oxygen, improving the performance of the system as lower feed oxygen is produced in the air separation unit (ASU), saving auxiliary power. Full-Scale Design: The full-scale design is sized to deliver 550 MWe net electrical power output to allow direct comparison with the National Energy Technology Laboratory (NETL) baseline cases using the same Montana Powder River Basin (PRB) fuel. The cases used for direct comparison are: Case S12A (supercritical [SC] coal without CO 2 capture), Case S12B (SC coal with PCC at 90% CO 2 capture, and Case S12F (atmospheric oxy-combustion SC coal with 90% CO 2 capture). The SPOC stages were configured to be identical arrangements, allowing for a more straightforward design, construction, and control strategy. Each stage consists of two PVs, the first being the combustor PV module and the second being the convective PV module. The combustor module is the tallest vessel, with local coal feeding equipment and the burner FGR and oxygen plenums at the top and ash management at the bottom. The combustor module is effectively an open cross section with membrane tubes around the circumference – this unobstructed slender profile ensures that the relatively slower burnout mechanism needed for the low-speed turbulent mixing burner can proceed unimpeded and that molten ash will not attach to any surfaces at an angle to the predominant flue gas flow. The steam turbine used in the SPOC design is essentially the same unit utilized in the atmospheric oxy-combustion case except the degree of heat recovery possible allows the low-pressure (LP) feedwater heater train to be eliminated. This is a result of being able to capture the latent heat of evaporation of the moisture produced in the combustion (normally lost to the stack). The SPOC system outperforms the NETL atmospheric oxy-combustion baseline case by 3.3% points and the PCC case by 7.5% points. This performance increase is mainly a result of the improved heat recovery possible from the product flue gas and from the reduced auxiliary power consumption from the ASU and the CO 2 compression and purification unit over the atmospheric equivalent. The combined improvement in boiler efficiency and reduction in the steam turbine heat rate resulted in a net improvement in the overall plant efficiency by 0.61%, to 35.6% on a HHV basis. This relatively small improvement in plant efficiency between sub-bituminous and bituminous coals shows the value of useful moisture latent heat recovery offered by the SPOC system when using low rank fuels. Flexibility and Turndown: The SPOC system has inherent high turndown capabilities because of a demonstrated high range of combustion stability and the ability to bypass stages, thereby reducing steam generation rates proportionally without altering firing rates in operating stages. ASU units do not generally offer significant turndown opportunities as they are limited by the performance of the compression plant. The baseline SPOC design has a 2-train ASU configuration, needed to be able to meet the 10,500 tonnes per day duty, that can deliver efficient turndown points between 85–100% load with both trains operating, and at 45–50% load with a single train operating. Outside these operating points, the flexibility and efficiency are limited and may be uncompetitive at loads below 45% as the ASU systems are unable to turndown beyond 85% for the base case and 70% for the flexible case. The ASU cold box for the flexible case was designed to operate at loads between 40-100%, below this operating range the purity of the produced oxygen cannot be guaranteed, resulting in additional load for the CPU equipment. The additional power consumption of these cases yields an uneconomic operating condition with poor efficiency when operating at low loads such as 25% and 12%. To address this flexibility constraint, AL evaluated how the ASU configuration could be altered to deliver efficient oxygen supply over the load range. This involved integrating the compressor duties across both ASU trains into a shared duty arrangement with multiple compressors, strategically sized to deliver the duty required across all load ranges between 40–100% by enabling different combinations of the main air compressors and the booster air compressors. The oxygen purity cannot be guaranteed below 40% load for each train – the power consumption at 25% and 12% loads were estimated based on the multi-compressor configuration at maximum turndown as these load cases were not considered in the flexible ASU design. With a different cold box configuration, i.e. number of trains, the entire load range could be delivered within oxygen purity specifications. Although there is a small efficiency reduction at full load, there are significant improvements in overall plant performance during low-load operation. The exact ASU configuration needed will therefore be dependent on the expected operating profile of the unit. Economic Analysis: Cost estimates for the baseline and the flexible cases were developed using NETL baseline case data for common BOP items and an Association for the Advancement of Cost Engineering International Class 5 (conceptual/screening study) assessment of key components unique to the SPOC system. The capital, operating, and maintenance costs were assessed along with the first-year power cost, levelized cost of electricity, and CO 2 captured and avoided cost for the SPOC cases were compared against the relevant NETL baseline cases in January 2019 dollars. Both SPOC cases achieve a lower cost that the alternative NETL baseline cases (with the flexible SPOC case being slightly higher than the baseline SPOC case due to the compounded impact of higher capital costs and lower efficiency at full load). The SPOC cases deliver a lower cost of CO 2 avoided than the NETL baseline cases due to greater efficiency in generating low-carbon power. However, the cost of CO 2 captured is higher because the higher efficiency of the SPOC process generates less CO 2 , hence less needs to be captured, resulting in a high capital cost being shared over a reduced CO 2 quantity. The flexible ASU adds 1.6% overall to the plant cost in comparison to the baseline case, but the efficiency improvements at loads below 50% are significant. Subsequently, depending on the plant load-profile expectation, the flexible ASU would be beneficial if the plant spends a significant portion of its operating life below 50% load. This kind of operating profile is likely to be required for all fossil plants when more renewable electricity generators are installed on the local grid, particularly solar power that can be predicted ahead of time, allowing for appropriate pricing signals to be incorporated into the diurnal cycle. R&D Recommendations: SPOC, while a promising technology, is a relatively recent concept and, as such, operability issues of combustor design and steam-side integration for such systems at a scale relevant to commercial deployment have not been evaluated. WUSTL has conducted extensive small pilot-scale (100 kWth) research to understand and advance pressurized oxy-combustion processes, including investigation of combustion and flame characteristics, radiative heat flux, burner operability, turn down, char burnout, ash characteristics, water-wash column operation, etc. for pressurized oxy-combustion systems. Nonetheless, at this stage in the development of the SPOC process, what is needed is a large-scale pilot plant that can serve to study pressurized oxy-combustion systems and components at a scale commensurate with the maturity of the technology. A scale of 10 MWth, which includes steam-side integration and two stages would yield essential information with respect to heat transfer characteristics both in the radiative and convective sections of the pressure vessels, and the ability to operate the fuel staging process. In addition, while modeling results indicate that combustion and flame characteristics improve with scale, direct studies of the combustor at this scale will ensure that the models can be relied upon for scale up to commercial scale. Furthermore, a detailed analysis must be performed to understand the scaling aspects of key components and systems.

20 FOSSIL-FUELED POWER PLANTS↗

Evolution of the Thermodynamic Properties of Clusters of Galaxies out to Redshift of 1.8

The thermodynamic properties of the hot plasma in galaxy clusters retains information on the processes leading to the formation and evolution of the gas in their deep, dark matter potential wells. These processes are dictated not only by gravity but also by gas physics, e.g. AGN feedback and turbulence. Here, we study the thermodynamic properties, e.g. density, temperature, pressure, and entropy, of the most massive and the most distant (z > 1.2) SPT-selected clusters, and compare them with those of the nearby clusters (z < 0.1) to constrain their evolution as a function of time and radius. We find that thermodynamic properties in the outskirts of high redshift clusters are remarkably similar to the low redshift clusters, and their evolution follows the prediction of the self-similar model. Their intrinsic scatter is larger, indicating that the physical properties that lead to the formation and virialization of cluster outskirts show evolving variance. On the other hand, thermodynamic properties in the cluster cores deviates significantly from self-similarity indicating that the processes that regulate the core are already in place in these very high redshift clusters. This result is supported by the unevolving physical scatter of all thermodynamic quantities in cluster cores.

79 ASTRONOMY AND ASTROPHYSICS↗

Evolution of the Thermodynamic Properties of Clusters of Galaxies out to Redshift of 1.8

The thermodynamic properties of the hot plasma in galaxy clusters retains information on the processes leading to the formation and evolution of the gas in their deep, dark matter potential wells. These processes are dictated not only by gravity but also by gas physics, e.g. AGN feedback and turbulence. In this work, we study the thermodynamic properties, e.g. density, temperature, pressure, and entropy, of the most massive and the most distant ($z > 1.2$) SPT-selected clusters, and compare them with those of the nearby clusters ($z<0.1$) to constrain their evolution as a function of time and radius. We find that thermodynamic properties in the outskirts of high redshift clusters are remarkably similar to the low redshift clusters, and their evolution follows the prediction of the self-similar model. Their intrinsic scatter is larger, indicating that the physical properties that lead to the formation and virialization of cluster outskirts show evolving variance. On the other hand, thermodynamic properties in the cluster cores deviates significantly from self-similarity indicating that the processes that regulate the core are already in place in these very high redshift clusters. This result is supported by the unevolving physical scatter of all thermodynamic quantities in cluster cores.

79 ASTRONOMY AND ASTROPHYSICS↗

Optimal Methanol Production via Sorption-Enhanced Reaction Process

To counter the equilibrium limitations in traditional methanol production from synthesis gas, a periodic and sorption-enhanced methanol synthesis process (SE-MeOH) with in situ removal of water byproduct is designed and optimized. A generalized reaction–adsorption modeling and simulation framework is coupled with a simulation-based constrained gray-box optimizer to obtain the optimal cycle configuration, design parameters, process specifications, and operating conditions. The best-case results indicate that SE-MeOH processes can break the barrier of the current limit of industrial methanol yield and improve it by 55–87% with a slight compromise (9–46%) on CH 3 OH production capacity. This trade-off is a result of periodic operation which is required for sorption enhancement. The techno-economic optimization of a base industrial reactor also leads to more than 7% improvement in methanol yield with only 2% decrease in production capacity while keeping the cost of syngas-to-methanol production competitive. The SE-MeOH system is further optimized through varying the feed specifications and number of reactor tubes. Furthermore, the results suggest that the synthesis gas composition, flow rate, and number of tubes are the major factors in determining methanol process performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Initial Engineering and Design for CO 2 Capture from Ethanol Facilities

The Energy & Environmental Research Center, in partnership with the U.S. Department of Energy (DOE) and North Dakota ethanol producer Red Trail Energy, LLC (RTE) and with technical support from Trimeric Corporation and the KLJ engineering firm, completed an initial engineering design (IED) for a hybrid capture system to estimate associated costs for retrofitting the operational RTE ethanol plant. The project goal supports the DOE objective to achieve negative emissions using commercially available technologies to attain Technology Readiness Level 6+ from a facility emitting >100,000 tonnes of carbon dioxide (CO 2 ) annually. The RTE CCS (carbon capture and storage) Project is currently operating a CO 2 capture facility, adjacent to the RTE ethanol facility in western North Dakota, and injecting the CO 2 more than a mile below RTE property for permanent storage. This novel hybrid capture system would process about 310,000 tonnes of CO 2 annually for the RTE host site and includes CO 2 capture and compression from bioprocessing as well as capturing CO 2 produced from natural gas boilers. The bioprocessing capture process, based on past RTE studies investigating ammonia liquefaction technology with CO 2 produced from natural gas boilers captured utilizing chemical absorption with amine, was shown to be technically feasible for the RTE site. Activities conducted to support the project goal included 1) designing a hybrid capture system using CO 2 emissions from both bioprocessing and heat production at the host site facility; 2) conducting a pre-front-end engineering and design analysis of the hybrid capture system to include environmental health and safety, a constructability report, identification of permits, and corporate approvals; and 3) performing a techno-economic assessment in accordance with DOE’s methodology, as demonstrated by the bituminous baseline study. In addition, a life cycle assessment (LCA) was completed for the RTE site to estimate the carbon life cycle for ethanol-CCS implementation using the designed hybrid capture system to determine potential for net-negative carbon emissions. Results of the IED showed the hybrid system to be technically viable, with a moderate estimated cost of $55/tonne CO 2 captured for the hybrid system. The cradle-to-gate LCA showed preliminary net-negative carbon emissions potential anticipated from implementing a hybrid CCS system at a commercial scale. Recommended next steps toward potential implementation include hybrid capture system demonstration testing for detailed engineering and LCA model comparisons with low-carbon fuel incentive programs for financial support.

01 COAL, LIGNITE, AND PEAT↗

Effect of hollow fiber membrane packing on the performance of modules formed with fiber tows

Membrane processes are the preferred option for many gas separations. Hollow fiber membranes are commonly used in these processes. Commercial hollow fiber membrane modules are often fabricated from small groups of fibers (i.e., a tow) that are arranged into a larger cylindrical bundle. The existence of fiber tows can lead to packing non-uniformity. This nonuniformity can result in nonideal fluid distribution in the shell and be detrimental to module performance. In this work, full three-dimensional models of flow and mass transfer within fiber bundles formed from tows have been developed. These models account for the detailed fiber arrangement within modules and are solved to evaluate module separation performance in terms of stage cut and required membrane area as a function product gas purity for carbon capture applications. Results are presented illustrating the effects of varying fiber packing arrangements within a tow and varying tow packing arrangements. Further, the results suggest smaller tows are preferred over larger tows, at fixed overall fiber packing and lower intra- and inter-tow packings are preferred. To reduce the computational cost of simulating large fiber bundles, the use of an equivalent planar bundle is proposed (EPB). A simple procedure for determining the geometry of the EPB is described and validated through comparisons of calculated performance metrics with results obtained from full three-dimensional simulations.

42 ENGINEERING↗

Initial Series of Ruthenium Adsorption Optimization Studies

The processing of used nuclear fuel releases volatile and semivolatile radionuclides into the off-gas streams associated with the various processing steps. Ongoing efforts to develop methods to control the release of gaseous radionuclides to the environm ent have identified ruthenium (specifically 106 Ru) as one of the semivolatile nuclides requiring a high degree of abatement. The tritium pretreatment process will release a fraction of the ruthenium as volatile ruthenium tetroxide (RuO 4 ). Tests were conducted to examine the deposition phenomena and provide prelim inary information pertinent to an engineering design of a sorption bed to remove RuO 4 from a gas stream (e.g., approximate length of the mass transfer zone and the loading per unit mass of sorbent).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Membrane Contactors for Ammonia Recovery from Anaerobic Digester Centrate: Pretreatment and Process Optimization

Haber-Bosch process allows for the production of modern fertilizers and is crucial for meeting increasing demands for agricultural production. The process requires large amounts of natural gas and contributes to global warming. An alternative to the Haber-Bosch process utilizes membrane contactors to recover nitrogen from the anaerobic digester centrate. In previous studies, high recoveries have been achieved, but membrane fouling decreased the performance and required maintenance to clean the membranes. Furthermore, this study investigated the effect of a settling and ultrafiltration system to pretreat centrate from an anaerobic digester to prevent fouling of the membrane contactor system. The system achieved high recoveries of over 90% for 10 cycles without any performance decline. Tests with increasing distillate concentrations of ammonium sulfate up to 165,000 mg/L-N could not identify a significant decline in membrane performance either. This allows for concentration up to crystallization in a single stage.

09 BIOMASS FUELS↗

Soft interface instability and gas flow channeling in low-permeability deformable media

Understanding gas percolation through a clay layer or a shale formation is of great importance for the development of a geologic repository for nuclear waste disposal, a subsurface system for gas storage, and an engineering approach for hydrocarbon extraction from unconventional reservoirs. Gas injection experiments have revealed complex dynamic behaviours of gas percolation through water saturated compacted bentonite, characterized by a high breakthrough pressure, rapid breakthrough, a pressure/stress decay after the breakthrough, a relatively high migration rate, high-frequency periodic/nonperiodic variations in flow rate, stepwise rate reductions during relaxation, and low gas saturation over the whole process, all indicating channelling nature of the processes. Using linear stability analyses, we show that this channelling can autonomously emerge from the instability of the deformable interface between the injected gas and the compacted bentonite matrix driven by local stress concentration, pore dilation, and hydrologic gradient. Channel patterns formed would possess a fractal geometry. We further show that, once a percolating channel is established, the gas injected would percolate through the channel in a chain of gas bubbles, also due to the interface instability, resulting in periodic/chaotic variations in gas flow rate. Our work provides a unified explanation for key features observed for gas percolation in low-permeability deformable media. The work also suggests a possibility of designing an engineered barrier system for a nuclear waste repository that can have controllable gas release while limit water transport.

Bentonite↗

Modeling Flow and Mass Transfer within Hollow Fiber Packaging for Gas Separation

Hollow fiber membrane modules are used for gas purification by their selective permeation properties. Intensification of the process to minimize the retentate loss and gas pressure involves optimization at various scales. In this work, we outline a numerical investigation of the gas separation performance at the scale of fiber bundles and its impact on module performance. Flow channeling and anisotropy govern the mass-transfer coefficient in axial and cross-flow configurations. These effects are quantified in terms of a permeability tensor or an anisotropy ratio and the effective mass-transfer coefficient or the Sherwood number. The results show a trade-off between purification and recovery. While smaller fibers offer a large specific surface area to enable high purification, it comes at a huge penalty on the separation performance due to reduced penetration within bundles. Optimum performance indicators are emphasized.

Fibers↗

Identification of Yarrowia lipolytica as a platform for designed consortia that incorporate in situ nitrogen fixation to enable ammonia-free bioconversion

Bioconversion processes require nitrogen for growth and production of intracellular enzymes to produce biofuels and bioproducts. Typically, this is supplied as reduced nitrogen in the form of ammonia, which is produced offsite from N 2 and H 2 via the Haber-Bosch process. While this has revolutionized industries dependent on fixed nitrogen (e.g., modern agriculture), it is highly energy-intensive and its reliance on natural gas combustion results in substantial global CO 2 emissions. Here we investigated the feasibility of in situ biological nitrogen fixation from N 2 gas as a strategy to reduce greenhouse gas impacts of aerobic bioconversion processes. We developed an efficient and cost-effective method to screen fungal bioconversion hosts for compatibility with the free-living diazotrophic bacterium Azotobacter vinelandii under nitrogen fixing conditions. Our screening revealed that the genus Yarrowia is particularly enriched during co-culture experiments. Follow-up experiments identified four Y. lipolytica strains (NRRL Y-11853, NRRL Y-7208, NRRL Y-7317, and NRRL YB-618) capable of growth in co-culture with A. vinelandii. These strains utilize ammonium secreted during diazotrophic fixation of N 2 , which is provided as a component of the air input stream during aerobic fermentation. This demonstrates the feasibly of in situ biological nitrogen fixation to support heterotrophic fermentation processes for production of fuels and chemicals.

09 BIOMASS FUELS↗