Reducing Solvent Consumption in Reductive Catalytic Fractionation through Lignin Oil Recycling
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We introduce a comprehensive conceptual framework for selecting solvents for reactive extraction in biphasic organic-water systems and demonstrate it for the separation of HMF (5-hydroxylmethylfurfural), a platform chemical produced in the acid-catalyzed dehydration of hexoses. We first perform in silico screening of ~2500 solvents, from the ADFCRS-2018 database using the ADF COSMO-RS implementation, and classification, based on the solvent partition coefficient. We then determine experimentally the partition coefficients for HMF, fructose, and products of HMF rehydration (levulinic acid (LA), and formic acid (FA)), the mutual water-organic solvent solubilities, and the separation factors in >50 select solvents spanning multiple homologous series at room temperature and a typical reaction temperature with in situ sampling. We find that COSMO-RS is excellent for screening purposes (typical error in most cases within a factor of ~2). Increased temperatures lead to significant reduction in partitioning, and room temperature measurements are clearly inadequate for solvent selection. Upon down selecting classes of solvents based on separation performance, we perform experimental thermal stability and reaction compatibility studies of a small set of solvents at relevant reactive-extraction temperatures. We discover that many substituted phenols exhibit an order-of-magnitude increase in partitioning compared to conventional solvents due chiefly to hydrogen bond interactions and show the necessary stability but retain a significant fraction of water and LA, factors that need to be considered in technoeconomic analysis. In contrast, anilines, aldehydes, and acids are good to excellent regarding separation but incompatible with this specific reaction medium. Furthermore, this multifaceted framework can be extended to other biomass-derived products and processes.
Intensified lauric acid self-ketonization and its impact on biolubricant base oil production.
The goal of this project is to aggressively support the near-term commercialization of a new technology platform – based on the integration of solar concentrators and micro- and meso-channel process technology (MMPT) – that was evaluated and identified as a strong candidate for near-term commercialization at EERE’s inaugural Lab-Corps program during early FY2016. Known as STARS, for Solar Thermochemical Advanced Reactor System, or Dish-STARS TM when paired with parabolic dish concentrators, STARS is a promising energy-related technology developed at the Pacific Northwest National Laboratory (PNNL) that efficiently converts solar energy into chemical energy. Combined with economies through hardware mass production, the efficiency of Dish-STARS TM provides a near-term opportunity for the production of renewable electricity, fuels and chemicals. The project supported the cooperative development of Dish-STARSTM by PNNL and industry partners including California Gas Company (SoCalGas) and the startup company, STARS Technology Corporation (STC), which was founded by the PNNL Lab-Corps team that evaluated STARS on behalf of EERE. Under this project, the team advanced the Technology Readiness Level 6 (TRL 6) STARS reaction system, developed under the previous DOE SunShot project, to TRL 7 through on-sun testing in California by PNNL. The advances made in this project enabled STC to accelerate commercial development and initiate work towards a major technology demonstration in California for a hydrogen filling station application.
Compilation of reports on individual projects completed as part of the RAPID Manufacturing Institute cooperative agreement, award number DE-EE0007888.
The process of intensification of 500-mb cyclones and anticyclones as represented in NMC's 500-mb analyses is investigated, using a sample of records for 500-mb cyclones and anticyclones drawn from the cool season of September 1983 through May 1984 to determine the statistically large intensification rates and thus to establish criteria for rapid intensification. From the catalog of all rapidly intensifying 500-mb cyclones and anticyclones defined by these criteria, seasonal and geographical frequency distributions of cyclogenesis and anticyclogenesis is constructed. It is shown that, for the data sample used in this analysis, the operational forecast models tend to underpredict rapid developments of 500-mb cyclones and anticyclones.
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Thermal diffusion separation process intensified in Clusius-Dickel column using perforated barrier
A model for the fluidized-bed pyrolysis of biomass is extended to enable the simulation of intensified autothermal operation. In this system, partial oxidation of char and pyrolysate species replaces an external heat source to supply the enthalpy of pyrolysis, greatly increasing the throughput of a given fast pyrolysis reactor. Oxidation reactions are compiled from CRECK and other literature sources and extended to cover the species found in pyrolysis products, including a derivation of the catalytic effect of ash on char combustion from experimental studies at Iowa State University (ISU). Results indicate a roughly 3-fold increase in biomass throughput for a given reactor volume at the pilot scale with minimal loss of valuable products, in agreement with published data from the 3 × 10 -2 m 3 reactor operated by ISU. Additionally, a proposal for a 250 ton/day commercial-scale biomass pyrolysis reactor is analyzed, showing that the same size reactor operated by heating the fluidizing gas externally would have only one-tenth the capacity; if operated by heating the sand externally, the sand would need to circulate at an impractical 0.7 bed volume per minute rate to maintain a 250 ton/day biomass throughput.
We review the impact of control systems and strategies on the energy efficiency of chemical processes. We show that, in many ways, good control performance is a necessary but not sufficient condition for energy efficiency. The direct effect of process control on energy efficiency is manyfold: Reducing output variability allows for operating chemical plants closer to their limits, where the energy/economic optima typically lie. Further, good control enables novel, transient operating strategies, such as conversion smoothing and demand response. Indirectly, control systems are key to the implementation and operation of more energy-efficient plant designs, as dictated by the process integration and intensification paradigms. Our conclusions are supported with references to numerous examples from the literature.
It is now known that Batchelor's trailing-line vortex is extremely unstable to small amplitude disturbances for swirl numbers in the neighborhood of 0.83. The results of numerical calculations are presented that show the response of the vortex in this range of swirl numbers to finite amplitude, temporal, helical disturbances. Phenomena observed include: (1) ejection of axial vorticity and momentum from the core resulting in the creation of secondary, separate vortices; (2) a great intensification of core axial vorticity and a weakening of core momentum; and (3) the production of azimuthal vorticity in the form of a tightly wrapped spiral wave. The second phenomenon eventually stablizes the vortex, which then smooths and gradually returns to an axisymmetric state. The calculations are mixed spectral-finite-difference, fourth-order accurate, and have been carried out at Reynolds numbers of 1000 to 2000. Some linearized results are also discussed in an attempt to explain the process of vortex intensification.
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.
Abstract Hydrogel-encapsulated catalysts are an attractive tool for low-cost intensification of (bio)-processes. Polyvinyl alcohol-sodium alginate hydrogels crosslinked with boric acid and post-cured with sulfate (PVA-SA-BS) have been applied in bioproduction and water treatment processes, but the low pH required for crosslinking may negatively affect biocatalyst functionality. Here, we investigate how crosslinking pH (3, 4, and 5) and time (1, 2, and 8 h) affect the physicochemical, elastic, and process properties of PVA-SA-BS beads. Overall, bead properties were most affected by crosslinking pH. Beads produced at pH 3 and 4 were smaller and contained larger internal cavities, while optical coherence tomography suggested polymer cross-linking density was higher. Optical coherence elastography revealed PVA-SA-BS beads produced at pH 3 and 4 were stiffer than pH 5 beads. Dextran Blue release showed that pH 3-produced beads enabled higher diffusion rates and were more porous. Last, over a 28-day incubation, pH 3 and 4 beads lost more microspheres (as cell proxies) than beads produced at pH 5, while the latter released more polymer material. Overall, this study provides a path forward to tailor PVA-SA-BS hydrogel bead properties towards a broad range of applications, such as chemical, enzymatic, and microbially catalyzed (bio)-processes.
The National Alliance for Water Innovation (NAWI) is the U.S. DOE's 5-year, $110M research Hub focused on desalination and water reuse. NAWI is organized into three Topic Areas in which projects are managed and coordinated: Materials and Manufacturing R&D (M&M), Process Innovation and Intensification R&D (PI&I), and Data, Modeling, and Analysis (DMA). In its first 3.5 years, NAWI has established the largest integrated DOE Innovation Hub (108 Research Consortium member organizations, 440 Alliance member organizations) anchored around its APRIME vision for lowering the cost and energy of desalination and water reuse. NAWI has selected 74 research projects to date, and several have reported major advances in desalination research and technology in leading scientific publications.
A series of cobalt-promoted indium–titanium composite oxides was synthesized using a microemulsion method. Their functional properties were investigated for the photothermal reduction of carbon dioxide. In this series, the indium content varied between 2.5 and 20%, while the cobalt percentage was kept constant at 4% throughout the series. In all cases, carbon monoxide formation occurred selectively through the reverse water gas shift reaction. The sample with 2.5% In maximized the synergistic use of the two energy sources, while the sample with 10% In showed the highest catalytic activity under both thermal and dual photo-thermo conditions. A physicochemical characterization was performed for all samples. The use of microscopy and X-ray absorption spectroscopy demonstrated that sub-nanometric indium entities, in combination with atomically dispersed cobalt oxide entities, achieved a balance between high thermal activity and significant synergy between light and heat in a catalytic process. The system with 10% indium is thus able to improve the thermal catalytic process through the use of light, providing an intensification procedure for the classic process.
In this study, it is proposed that twin tropical cyclones (TCs), Kesiny and 01A, in May 2002 formed in association with the scale interactions of three gyres that appeared as a convectively coupled mixed Rossby gravity (ccMRG) wave during an active phase of the Madden-Julian Oscillation (MJO). This is shown by analyzing observational data, including NCEP reanalysis data and METEOSAT 7 IR satellite imagery, and performing numerical simulations using a global mesoscale model. A 10-day control run is initialized at 0000 UTC 1 May 2002 with grid-scale condensation but no sub-grid cumulus parameterizations. The ccMRG wave was identified as encompassing two developing and one non-developing gyres, the first two of which intensified and evolved into the twin TCs. The control run is able to reproduce the evolution of the ccMRG wave and thus the formation of the twin TCs about two and five days in advance as well as their subsequent intensity evolution and movement within an 8-10 day period. Five additional 10-day sensitivity experiments with different model configurations are conducted to help understand the interaction of the three gyres, leading to the formation of the TCs. These experiments suggest the improved lead time in the control run may be attributed to the realistic simulation of the ccMRG wave with the following processes: (1) wave deepening (intensification) associated with a reduction in wavelength and/or the intensification of individual gyres, (2) poleward movement of gyres that may be associated with boundary layer processes, (3) realistic simulation of moist processes at regional scales in association with each of the gyres, and (4) the vertical phasing of low- and mid-level cyclonic circulations associated with a specific gyre.
The evolution of three cyclones which originated in the South Pacific Convergence Zone, two of which propagated into middle latitudes, are traced. The analysis is based on IR imagery from GOES-W, island meteorological station data, and estimates of heat and moisture budget residuals. A European Center for Medium-range Weather Forecasting Level III-b analysis was used to model the cyclones. The northward-propagating storms exhibited strong vertical shear of the horizontal wind, implicating baroclinic effects in the development of the storms. The processes which enhanced storm intensification are discussed. Attention is given to the spatial and temporal behavior of dynamic atmospheric components which were significant to baroclinicity and latent heat release, which the analysis demonstrates were coupled processes.
For a number of years our project has been studying the cross-equatorial (winter to summer hemisphere) processs that can lead to the day-to-day alterations in the strength of the monsoon trough. These processes are also related to the genesis and intensification of tropical storms. The cross-hemispheric processes that occurred during the FGGE year are currently being studied with the use of the ECMWF analysis. How the winter hemisphere can affect low level cold surge penetration across the equator following cold front passage, and how upper tropospheric anticyclones of the winter hemisphere can produce an intensification of a tropical cyclone of the opposite hemisphere is described. ECMWF analysis of the 00Z versus 12Z diurnal difference in the clear region (10 deg diameter) subsidence occurring in the subtropical Pacific Ocean during FGGE is presented. The general reliability of the FGGE ECMWF analysis with regard to the specification of the large scale structure of tropical cyclones is shown.