Reactive Configuration Research Articles

Design and Control of Thermally-Coupled Reactive Distillation System for Esterification of an Alcohol Mixture Containing n-Amyl Alcohol and n-Hexanol

Semiconductor and pharmaceutical industries often produce waste alcohol mixtures. This study discusses a reactive distillation process of a mixed alcohol feed containing n-amyl alcohol and n-hexanol to react with acetic acid to produce useful esters. In an earlier paper (Lee et al. Ind. Eng. Chem. Res. 2009 48, 7186–7204), optimal design of the same Type-III mixed-alcohol reactive distillation process containing n-butanol and n-amyl alcohol was developed. In that paper, the indirect sequence containing a reactive distillation column with heavier amyl acetate bottom product and a second column to produce butyl acetate gives the lowest total annual cost. In this study, with different mixed alcohol feed (although of the same reaction type), it is found that an alternative direct sequence design is much more economically favorable with 34% reduction in total annual cost as compared to the indirect sequence. The reason for the seemingly contradictory results can be explained by differences in relative volatilities of binary pairs in the stripping sections of the reactive distillation towers. Process intensification technology is also attempted to devise a thermally coupled reactive distillation configuration to further save 13% of the operating energy. The overall control strategy using tray temperatures is also proposed to maintain high-purity products despite various disturbances.

Criticality safety studies for plutonium–uranium metal fuel pin fabrication facility

This study focuses on the criticality safety during the fabrication of fast reactor metal fuel pins comprising of the fuel type U–15Pu, U–19Pu and U–19Pu–6Zr in the Plutonium–Uranium Metal fuel Pin fabrication Facility (PUMP-F). Maximum amount of fissile mass which can be handled safely during master alloy preparation, Injection casting and fuel slug preparation following fuel pin fabrication were identified and fixed based on this study. In the induction melting furnace, the fissile mass can be limited to 10.5kg. During fuel slug preparation and fuel pin fabrication, fuel slugs and pins were arranged in hexagonal and square lattices to identify the most reactive configuration. The number of fuel slugs which can be handled safely after injection casting can be fixed to be 53, whereas after fuel fabrication it is 71.

Ab initio characterization of Ti decorated SWCNT for hydrogen storage

Characterization has been performed on basis of several physicochemical parameters. The results indicate that the preferential adsorption is on Ti atom deposited on the top site of the (5,5) armchair SWCNT with energies (−0.44 and −0.71) eV for H2 oriented parallel to the (x) and (y) axes respectively. The binding of H2 is mostly dominated by the support-metal E (i)S⋯Ti term. The role of the SWCNT is not restricted to support the metal. Significant reduction of the energy gap is observed when H2 are anchored on the external surface of the SWCNT. The SWCNT⋯Ti⋯H2(x) complex is the least reactive configuration with nucleophiles. The calculated parameters characterize H2 that is oriented parallel to the (x)-[100] axis of the SWCNT to be the most suitable configuration for hydrogen storage based on the recommended adsorption energy range of DOE (−0.2 to −0.6) eV.

Reactive Power Compensation and Configuration of Wind Farm

Wind turbine absorbs reactive power while generating active power. Seriously, it causes voltage drop or even voltage collapse. It is needed to compensate reactive power. In this paper, a combination of capacitor bank and SVC is used in wind farm. Equivalent circuit of two kinds of wind turbine is described firstly. Then, equation of reactive power and active power is derived. Then an optimization method is used to calculate capacity of capacitor bank and SVC. Finally, load flow of IEEE14 system with a wind farm connected to it is calculated to verify the effect of reactive power compensation.

Optimization based conceptual design of reactive distillation for selectivity engineering

Reactive distillation can be effectively used to enhance the selectivity of the desired product in a multi-reaction system. Due to complex interaction of reactions and distillation, identification of an appropriate reactive distillation configuration for the known performance targets has been a challenge. The objective of this contribution is to present an MINLP optimization technique that would assist one to identify a suitable configuration for selectivity maximization at conceptual design level. An illustrative example of industrially important reaction of dimerization of isobutene for maximizing the selectivity toward di-isobutene is considered. The results of the optimization are found to be in agreement with those obtained by performing independent simulation using ASPEN PLUS simulator. Thus, the work highlights the potential of an optimization based tool for conceptual design of reactive distillation that involves complex reaction systems.

Safety-Related Optimization and Analyses of an Innovative Fast Reactor Concept

Since a fast reactor core with uranium-plutonium fuel is not in its most reactive configuration under operating conditions, redistribution of the core materials (fuel, steel, sodium) during a core disruptive accident (CDA) may lead to recriticalities and as a consequence to severe nuclear power excursions. The prevention, or at least the mitigation, of core disruption is therefore of the utmost importance. In the current paper, we analyze an innovative fast reactor concept developed within the CP-ESFR European project, focusing on the phenomena affecting the initiation and the transition phases of an unprotected loss of flow (ULOF) accident. Key phenomena for the initiation phase are coolant boiling onset and further voiding of the core that lead to a reactivity increase in the case of a positive void reactivity effect. Therefore, the first level of optimization involves the reduction, by design, of the positive void effect in order to avoid entering a severe accident. If the core disruption cannot be avoided, the accident enters into the transition phase, characterized by the progression of core melting and recriticalities due to fuel compaction. Dedicated features that enhance and guarantee a sufficient and timely fuel discharge are considered for the optimization of this phase.

Reactive Wetting Processes and Triple-Line Configuration of Sn-3.5Ag on Cu Substrates at Elevated Temperatures

Reactive wetting processes of molten Sn-3.5Ag on Cu substrates at elevated temperatures were investigated by the sessile drop method. Equilibrium contact angles of Sn-3.5Ag on Cu substrates are 36.5°, 32.9°, 25.25°, and 32.1° at 523 K, 573 K, 623 K, and 673 K, respectively, indicating that the contact angle does not decrease monotonically with increasing temperature. It is also found that the maximal triple-line mobility does not increase linearly with temperature. The complicated temperature effects on the equilibrium contact angles and triple-line mobility are attributable to the fact that Cu substrates dissolve easily in the liquid solder, hindering solder spreading. A description of the equilibrium state helped explain the triple-line region of the Sn-3.5Ag/Cu joint. The calculated results, based on the experimental values of tension balances along each of the three interfaces, show good agreement with the theoretical analysis. The present results are of practical interest for composite lead-free solder preparations and joining of Sn-3.5Ag to Cu substrates.

Three-dimensional boundary conditions for numerical simulations of reactive compressible flows with complex thermochemistry

The Navier–Stokes characteristic boundary conditions (NSCBC) is a very efficient numerical strategy to treat boundary conditions in fully compressible solvers. The present work is an extension of the 3D-NSCBC method proposed by Yoo et al. and Lodato et al. in order to account for multi-component reactive flows with detailed chemistry and complex transport. A new approach is proposed for the outflow boundary conditions which enables clean exit of non-normal flows, and the specific treatment of all kinds of edges and corners is carefully addressed. The proposed methodology is successfully validated on various challenging multi-component reactive flow configurations.

Interfacial hydration, dynamics and electron transfer: multi-scale ET modeling of the transient [myoglobin, cytochrome b5] complex

Formation of a transient [myoglobin (Mb), cytochrome b(5) (cyt b(5))] complex is required for the reductive repair of inactive ferri-Mb to its functional ferro-Mb state. The [Mb, cyt b(5)] complex exhibits dynamic docking (DD), with its cyt b(5) partner in rapid exchange at multiple sites on the Mb surface. A triple mutant (Mb(3M)) was designed as part of efforts to shift the electron-transfer process to the simple docking (SD) regime, in which reactive binding occurs at a restricted, reactive region on the Mb surface that dominates the docked ensemble. An electrostatically-guided brownian dynamics (BD) docking protocol was used to generate an initial ensemble of reactive configurations of the complex between unrelaxed partners. This ensemble samples a broad and diverse array of heme-heme distances and orientations. These configurations seeded all-atom constrained molecular dynamics simulations (MD) to generate relaxed complexes for the calculation of electron tunneling matrix elements (T(DA)) through tunneling-pathway analysis. This procedure for generating an ensemble of relaxed complexes combines the ability of BD calculations to sample the large variety of available conformations and interprotein distances, with the ability of MD to generate the atomic level information, especially regarding the structure of water molecules at the protein-protein interface, that defines electron-tunneling pathways. We used the calculated T(DA) values to compute ET rates for the [Mb(wt), cyt b(5)] complex and for the complex with a mutant that has a binding free energy strengthened by three D/E → K charge-reversal mutations, [Mb(3M), cyt b(5)]. The calculated rate constants are in agreement with the measured values, and the mutant complex ensemble has many more geometries with higher T(DA) values than does the wild-type Mb complex. Interestingly, water plays a double role in this electron-transfer system, lowering the tunneling barrier as well as inducing protein interface remodeling that screens the repulsion between the negatively-charged propionates of the two hemes.

Probing quantum and dynamic effects in concerted proton-electron transfer reactions of phenol-base compounds.

The oxidation of three phenols, which contain an intramolecular hydrogen bond to a pendent pyridine or amine group, has been shown, in a previous experimental study, to undergo concerted proton-electron transfer (CPET). In this reaction, the electron is transferred to an outer-sphere oxidant, and the proton is transferred from the oxygen to nitrogen atom. In the present study, this reaction is studied computationally using a version of Hammes-Schiffer's multistate continuum theory where CPET is formulated as a transmission frequency between neutral and cation vibrational-electronic states. The neutral and cation proton vibrational wave functions are computed from one-dimensional potential energy surfaces (PESs) for the transferring proton in a fixed heavy atom framework. The overlap integrals for these neutral/cation wave functions, considering several initial (i.e., neutral) and final (i.e., cation) vibrational states, are used to evaluate the relative rates of oxidation. The analysis is extended to heavy atom configurations with various proton donor-acceptor (i.e., O-N) distances to assess the importance of heavy atom "gating". Such changes in d(ON) dramatically affect the nature of the proton PESs and wave functions. Surprisingly, the most reactive configurations have similar donor-acceptor distances despite the large (~0.2 Å) differences in the optimized structures. These theoretical results qualitatively reproduce the experimental faster reactivity of the reaction of the pyridyl derivative 1 versus the CH(2)-pyridyl 2, but the computed factor of 5 is smaller than the experimental 10(2). The amine derivative is calculated to react similarly to 1, which does not agree with the experiments, likely due to some of the simplifying assumptions made in applying the theory. The computed kinetic isotope effects (KIEs) and their temperature dependence are in agreement with experimental results.

Silicon-rich oxynitride hosts for 1.5μm Er3+ emission fabricated by reactive and standard RF magnetron sputtering

Abstract This study compares the erbium emission from different Si-rich silicon oxynitrides matrices fabricated by magnetron sputtering. The Er-doped layers were grown by two different sputtering configurations: (i) standard co-sputtering of three confocal targets (Er 2 O 3 , Si 3 N 4 and SiO 2 ) under Ar plasma, and (ii) reactive co-sputtering under Ar + N 2 plasma of either three (Er 2 O 3 , pure Si and SiO 2 ) or two targets (Er 2 O 3 and pure Si). The last reactive configuration was found to offer the best Er 3+ PL intensity at 1.5 μm. This highest PL intensity was found comparable to the corresponding emission from Er-doped silicon-rich silicon oxide.

Sizeable Increase of Kinetic Isotope Effects and Tunnelling in Coupled Electron–Proton Transfers in Presence of the Quaternary Ions. PCET Processes and Hydrogen Tunnelling as a “Probe” for Structuring and Dynamical Phenomena in Water Solution

Abstract The presence of quaternary ammonium ions unexpectedly leads to a sizable increase of the kinetic isotope effects in the coupled electron–proton transfer (PCET) reaction of an ascorbate monoanion with the hexacyanoferrate(III) ions in water and this, in “neat” water over-the-barrier coupled electron–proton transfer interaction, entered into tunnelling regime in the presence of the quaternary ions. The kinetic isotope effect between ascorbate monoanion and its 2-OD derivative in the investigated reaction with hexacyanoferrate(III) increased from k H/k D=4.40(0.08) in the reaction in water (in the presence of 8 × 103 M NaCl) without the added quaternary ions, to k H/k D=10.08(0.07) in the presence of 1.0 M tetraethylammonium ion, to k H/k D=8.01(0.19) in the presence of 1.0 M of benzyltrimethyl ammonium ion and to k H/k D=7.25(0.02) in the presence of only 0.1 M of tetraethylammonium ion. In contrast, k H/k D=4.06(0.15) has been observed in presence of 0.1 M NaCl. The isotopic ratio of Arrhenius pre-factors A H/A D=0.16(0.01) has been obtained in the presence of only 0.1 M of tetraethylammonium ions and A H/A D=0.10(0.02) in the presence of 0.5 M of the ions. The corresponding observed value is A H/A D=0.23(0.02) in the presence of 0.5 M of benzyltrimethylammonium ions and A H/A D=0.35(0.06) in the presence of 0.5 M tetramethylammonium ions. The differences in the enthalpies of activation Δ Δ H‡ between D2O and H2O all are well beyond the semiclassical value of 5 .1 kJ/mol for the difference between zero-point energies E o D–E o H for dissociation of an O–H bond. The observed tunnelling phenomena point to a role of dynamics of the transition configuration of the PCET process, coupled with dynamics of hydrogen-bonded structures related to the solvent shell of the reactive configuration and its environment including the nearby quaternary ammonium ions.

Synergistic effect of coupling zero-valent iron with iron oxide-coated sand in columns for chromate and arsenate removal from groundwater: Influences of humic acid and the reactive media configuration

A column study was conducted using a combination of zero-valent iron (Fe 0) and iron oxide-coated sand (IOCS) for removing Cr(VI) and As(V) from groundwater. The removal efficiency and mechanism of Cr(VI) and As(V), the effects of humic acid (HA), and the various configurations of Fe 0 and IOCS were investigated. The results showed that the use of an Fe 0 and IOCS mixture in a completely mixed configuration can achieve the highest removal of both Cr(VI) and As(V), whilst the effects of HA were marginal in using these reactive materials. The solid phase analysis revealed the occurrence of the synergistic effect in these reactive materials as Fe 2+ can be adsorbed onto the IOCS and transform the iron oxides to magnetite, providing more reactive surface area for Cr(VI) reduction and reducing the passivation on the Fe 0. As(V) can then be removed by adsorption onto these iron corrosion products. HA can be adsorbed onto the IOCS so that the impacts of the deposition of HA aggregates on the Fe 0 surface can be reduced, thus enhancing the Fe 0 corrosion.

Feasibility analysis, synthesis, and design of reactive distillation processes: A focus on double‐feed processes

AbstractA new approach for the feasibility analysis of reactive distillation processes based on the reactive extractive curve maps (rExCM) concept is introduced. A method dedicated to reactive distillation feasibility analysis, and design has been developed in our team since 1999. From minimal information concerning the physicochemical properties of the system, three steps lead to the design of the unit and the specification of its operating conditions. Currently, the procedure permits the conceptual design of hybrid reactive column configuration with one or two feed plates, for any number of equilibrium reactions (provided that the degree of freedom of the system is equal to 2) occurring in liquid or vapor phase. This contribution focuses on the most recent developments: the generalization of the feasibility analysis step to double‐feed processes thanks to the introduction of the rExCM concept. This methodology is illustrated through two examples: the emblematic methyl acetate example and the production of dimethyl methyl glutarate. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2346–2356, 2012

Inherent Prevention and Mitigation of Severe Accident Consequences in Sodium-Cooled Fast Reactors

Safety challenges for sodium-cooled fast reactors include maintaining core temperatures within design limits and assuring the geometry and integrity of the reactor core. Due to the high power density in the reactor core, heat removal requirements encourage the use of high-heat-transfer coolants such as liquid sodium. The variation of power across the core requires ducted assemblies to control fuel and coolant temperatures, which are also used to constrain core geometry. In a fast reactor, the fuel is not in the most neutronically reactive configuration during normal operation. Accidents leading to fuel melting, fuel pin failure, and fuel relocation can result in positive reactivity, increasing power, and possibly resulting in severe accident consequences including recriticalities that could threaten reactor and containment integrity. Inherent safety concepts, including favorable reactivity feedback, natural circulation cooling, and design choices resulting in favorable dispersive characteristics for failed fuel, can be used to increase the level of safety to the point where it is highly unlikely, or perhaps even not credible, for such severe accident consequences to occur.

Analysis of control properties of intensified distillation sequences: Reactive and extractive cases

In this work, we obtain and compare the control properties of thermally coupled reactive distillation sequences and thermally coupled extractive distillation sequences with those of conventional reactive and extractive distillation configurations. All sequences have been designed using a multiobjective genetic algorithm with restrictions. The theoretical control properties of those schemes were obtained using the singular value decomposition technique in all frequency domain. In order to complete the control study, the distillation options were subjected to closed-loop dynamic simulations. The effects of total stages, reactive stages, and extractant/feed ratio on the energy consumption and control properties are obtained for the intensified distillation options. The results show that there are cases in which integrated reactive and extractive sequences do not only provide significant energy savings with respect to the conventional reactive and extractive arrangements, but also may offer dynamic advantages in high energy consumption conditions.

Inherent Prevention and Mitigation of Severe Accident Consequences in Sodium-Cooled Fast Reactors

Safety challenges for sodium-cooled fast reactors include maintaining core temperatures within design limits and assuring the geometry and integrity of the reactor core. Due to the high power density in the reactor core, heat removal requirements encourage the use of high-heat-transfer coolants such as liquid sodium. The variation of power across the core requires ducted assemblies to control fuel and coolant temperatures, which are also used to constrain core geometry. In a fast reactor, the fuel is not in the most neutronically reactive configuration during normal operation. Accidents leading to fuel melting, fuel pin failure, and fuel relocation can result in positive reactivity, increasing power, and possibly resulting in severe accident consequences including recriticalities that could threaten reactor and containment integrity. Inherent safety concepts, including favorable reactivity feedback, natural circulation cooling, and design choices resulting in favorable dispersive characteristics for faile...

Mechanism of N-methylation by the tRNA m1G37 methyltransferase Trm5

Trm5 is a eukaryal and archaeal tRNA methyltransferase that catalyzes methyl transfer from S-adenosylmethionine (AdoMet) to the N(1) position of G37 directly 3' to the anticodon. While the biological role of m(1)G37 in enhancing translational fidelity is well established, the catalytic mechanism of Trm5 has remained obscure. To address the mechanism of Trm5 and more broadly the mechanism of N-methylation to nucleobases, we examined the pH-activity profile of an archaeal Trm5 enzyme, and performed structure-guided mutational analysis. The data reveal a marked dependence of enzyme-catalyzed methyl transfer on hydrogen ion equilibria: the single-turnover rate constant for methylation increases by one order of magnitude from pH 6.0 to reach a plateau at pH 7.0. This suggests a mechanism involving proton transfer from G37 as the key element in catalysis. Consideration of the kinetic data in light of the Trm5-tRNA-AdoMet ternary cocrystal structure, determined in a precatalytic conformation, suggests that proton transfer is associated with an induced fit rearrangement of the complex that precedes formation of the reactive configuration in the active site. Key roles for the conserved R145 side chain in stabilizing a proposed oxyanion at G37-O(6), and for E185 as a general base to accept the proton from G37-N(1), are suggested based on the mutational analysis.

Esterification of fatty acids in a thermally coupled reactive distillation column by the two-step supercritical methanol method

Biodiesel fuel has been shown as a clean energy alternative to petroleum diesel. Conventional biodiesel production involves the use of catalyst, which implies high energy consumptions for the separation of both the catalyst and the by-products of the reaction, including those of the undesirable reaction of saponification. Recently, a process involving the use of short-chain alcohols at supercritical conditions has been proposed (Saka-Dadan process); one of the main advantages of that process is that it avoids the need for a catalyst as well as the occurrence of the saponification reaction. However, although the process requires less pieces of equipment than the conventional one, its energy requirements are still high, making biodiesel fuel more expensive than petroleum diesel. This work proposes the use of reactive distillation and thermally coupled reactive distillation configurations to produce biodiesel fuel by the supercritical methanol method. First-order kinetics is used to represent the esterification reaction, obtaining high conversions in a single shell. Both of the configurations proposed reduce energy requirements when compared to the conventional (Saka-Dadan) process. Calculations were also performed to estimate CO 2 emissions, thermodynamic efficiency and cost. The thermally coupled reactive distillation configuration shows to be the best alternative in terms of energy consumption, CO 2 emissions and thermodynamic efficiency. Further, cost estimations also show that the use of a thermally coupled scheme considerably reduces both utilities and capital costs.

Power of Confinement: Adsorbate Dynamics on Nanometer-Scale Exposed Facets

The diffusion and arrangements of CO adsorbates within nanometer-scale pores on a copper surface are investigated by low-temperature scanning tunneling microscopy. In contrast to extended terraces, confinement stabilizes dislocation lines that expose more than one-fourth of the adsorbate population to potentially more reactive adsorption configurations. Confinement allows correlation between adsorbate diffusivity and the number of adsorbates in the pore. A marked increase is found that coincides with the absence of dense films on the exposed facets. In combination, we find that in confinement CO molecules are much more likely to be at adsorption sites that allow lateral access, in contrast to the dense and uniform films on extended terraces.