Energy and exergy analysis and optimization of a gas turbine cycle coupled by a bottoming organic Rankine cycle

Journal of Thermal Analysis and Calorimetry - In this study, the numerical analysis of energy and exergy has been performed for a gas turbine cycle coupled with an ORC cycle. Validation of current...     

Enhancement of vapor compression cycle performance using nanofluids

Journal of Thermal Analysis and Calorimetry - Recently, Egypt is facing an energy problem due to the increase in consumption and population. There are two ways to face this issue; first, the world...     

Anthropogenic chemical carbon cycle for a sustainable future

Nature's photosynthesis uses the sun's energy with chlorophyll in plants as a catalyst to recycle carbon dioxide and water into new plant life. Only given sufficient geological time, millions of years, can new fossil fuels be formed naturally. The burning of our diminishing fossil fuel reserves is accompanied by large anthropogenic CO(2) release, which is outpacing nature's CO(2) recycling capability, causing significant environmental harm. To supplement the natural carbon cycle, we have proposed and developed a feasible anthropogenic chemical recycling of carbon dioxide. Carbon dioxide is captured by absorption technologies from any natural or industrial source, from human activities, or even from the air itself. It can then be converted by feasible chemical transformations into fuels such as methanol, dimethyl ether, and varied products including synthetic hydrocarbons and even proteins for animal feed, thus supplementing our food chain. This concept of broad scope and framework is the basis of what we call the Methanol Economy. The needed renewable starting materials, water and CO(2), are available anywhere on Earth. The required energy for the synthetic carbon cycle can come from any alternative energy source such as solar, wind, geothermal, and even hopefully safe nuclear energy. The anthropogenic carbon dioxide cycle offers a way of assuring a sustainable future for humankind when fossil fuels become scarce. While biosources can play a limited role in supplementing future energy needs, they increasingly interfere with the essentials of the food chain. We have previously reviewed aspects of the chemical recycling of carbon dioxide to methanol and dimethyl ether. In the present Perspective, we extend the discussion of the innovative and feasible anthropogenic carbon cycle, which can be the basis of progressively liberating humankind from its dependence on diminishing fossil fuel reserves while also controlling harmful CO(2) emissions to the atmosphere. We also discuss in more detail the essential stages and the significant aspects of carbon capture and subsequent recycling. Our ability to develop a feasible anthropogenic chemical carbon cycle supplementing nature's photosynthesis also offers a new solution to one of the major challenges facing humankind.     

Comparative analysis and multi-criteria optimization of a supercritical recompression CO2 Brayton cycle integrated with thermoelectric modules

Journal of Thermal Analysis and Calorimetry - Regarding the high expense of the exploiting energy from energy resources, each innovation or modification on the energy systems with the aim of...     

The artificial water cycle: emergy analysis of waste water treatment

The artificial water cycle can be divided into the phases of water capture from the environment, potabilisation, distribution, waste water collection, waste water treatment and discharge back into the environment. The terminal phase of this cycle, from waste water collection to discharge into the environment, was assessed by emergy analysis. Emergy is the quantity of solar energy needed directly or indirectly to provide a product or energy flow in a given process. The emergy flow attributed to a process is therefore an index of the past and present environmental cost to support it. Six municipalities on the western side of the province of Bologna were analysed. Waste water collection is managed by the municipal councils and treatment is carried out in plants managed by a service company. Waste water collection was analysed by compiling a mass balance of the sewer system serving the six municipalities, including construction materials and sand for laying the pipelines. Emergy analysis of the water treatment plants was also carried out. The results show that the great quantity of emergy required to treat a gram of water is largely due to input of non renewable fossil fuels. As found in our previous analysis of the first part of the cycle, treatment is likewise characterised by high expenditure of non renewable resources, indicating a correlation with energy flows.     

Multi-stage artificial neural network structure-based optimization of geothermal energy powered Kalina cycle

Journal of Thermal Analysis and Calorimetry - In this study, the geothermal energy powered Kalina cycle (GEP-KC) was optimized by using a multi-stage artificial neural network (ANN) analysis. The...     

Thermodynamic cycle for the calculation of ab initio pKa values for hydroxamic acids

A thermodynamic cycle to calculate pK_a values (Minus log of acid dissociation constants) of hydroxamic acids is presented. Hydroxamic acids exist mainly as amide isomers in the aqueous medium. The amide form of hydroxamic acids has two deprotonation sites and may yield either an N-ion or an O-ion upon deprotonation. The thermodynamic cycle proposed includes the gas-phase N–H deprotonation of the hydroxamic acid, the solvent phase transformation of the N-ion to the O-ion and the solvation of the hydroxamic acid molecule and the O-ion in water. The CBS-QB3 method was employed to obtain gas-phase free energy differences between 12 hydroxamic acids and their respective anions. The aqueous solvation Gibbs free energy changes were calculated at the HF/6-31G(d)/CPCM and HF/6-31+G(d)/CPCM levels of theory using HF/6-31+G(d)/CPCM geometries. For the proton, literature values of the gas-phase free energy of formation and the solvation free energy change were used. The free energy change for the transformation of the N-ion to O-ion in the aqueous medium was calculated by employing CBS-QB3/CPCM in the aqueous medium. For this, the hydroxamic acids were divided in two classes according to the substituent at the carbonyl carbon. A common transformation free energy difference for aliphatic substituted hydroxamic acids and a separate common transformation free energy difference for aromatic substituted hydroxamic acids were obtained. The pK_a calculation yielded a root mean square error of 0.32 pK_a units.     

Photo-induced proton-transfer cycle of 2-naphthol in faujasite zeolitic nanocavities

The excited-state deprotonation and ground-state reprotonation of a 2-naphthol molecule encapsulated in the zeolitic nanocavity of NaX have been studied by measuring static and time-resolved spectra of fluorescence and reflectance. The excited molecule undergoes enol dissociation within 300 ps to form an isolated ion pair, which undergoes geminate recombination in 1200 ps or separation to produce the anionic species of 2-naphtholate on the time scale of 2500 ps. Ground-state reprotonation, controlled by the diffusion rate of a proton, is then followed in 0.8 ms with an activation energy of 13 kJ mol(-1).     

Born-Haber-Fajans cycle generalized: linear energy relation between molecules, crystals, and metals

Classical procedures to calculate ion-based lattice potential energies (U(POT)) assume formal integral charges on the structural units; consequently, poor results are anticipated when significant covalency is present. To generalize the procedures beyond strictly ionic solids, a method is needed for calculating (i) physically reasonable partial charges, delta, and (ii) well-defined and consistent asymptotic reference energies corresponding to the separated structural components. The problem is here treated for groups 1 and 11 monohalides and monohydrides, and for the alkali metal elements (with their metallic bonds), by using the valence-state atoms-in-molecules (VSAM) model of von Szentpály et al. (J. Phys. Chem. A 2001, 105, 9467). In this model, the Born-Haber-Fajans reference energy, U(POT), of free ions, M(+) and Y(-), is replaced by the energy of charged dissociation products, M(delta)(+) and Y(delta)(-), of equalized electronegativity. The partial atomic charge is obtained via the iso-electronegativity principle, and the asymptotic energy reference of separated free ions is lowered by the "ion demotion energy", IDE = -(1)/(2)(1 - delta(VS))(I(VS,M) - A(VS,Y)), where delta(VS) is the valence-state partial charge and (I(VS,M) - A(VS,Y)) is the difference between the valence-state ionization potential and electron affinity of the M and Y atoms producing the charged species. A very close linear relation (R = 0.994) is found between the molecular valence-state dissociation energy, D(VS), of the VSAM model, and our valence-state-based lattice potential energy, U(VS) = U(POT) - (1)/(2)(1 - delta(VS))(I(VS,M) - A(VS,Y)) = 1.230D(VS) + 86.4 kJ mol(-)(1). Predictions are given for the lattice energy of AuF, the coinage metal monohydrides, and the molecular dissociation energy, D(e), of AuI. The coinage metals (Cu, Ag, and Au) do not fit into this linear regression because d orbitals are strongly involved in their metallic bonding, while s orbitals dominate their homonuclear molecular bonding.     

Applications of life cycle assessment to NatureWorks™ polylactide (PLA) production

NatureWorks™ polylactide (PLA)¹ is a versatile polymer produced by Cargill Dow LLC. Cargill Dow is building a global platform of sustainable polymers and chemicals entirely made from renewable resources. Cargill Dow's business philosophy is explained including the role of life cycle assessment (LCA), a tool used for measuring environmental sustainability and identifying environmental performance-improvement objectives. The paper gives an overview of applications of LCA to PLA production and provides insight into how they are utilized. The first application reviews the contributions to the gross fossil energy requirement for PLA (54 MJ/kg). In the second one PLA is compared with petrochemical-based polymers using fossil energy use, global warming and water use as the three impact indicators. The last application gives more details about the potential reductions in energy use and greenhouse gasses. Cargill Dow's 5–8 year objective is to decrease the fossil energy use from 54 MJ/kg PLA down to about 7 MJ/kg PLA. The objective for greenhouse gasses is a reduction from +1.8 down to −1.7 kg CO₂ equivalents/kg PLA.     

Pre-constructed SEI on graphite-based interface enables long cycle stability for dual ion sodium batteries

Lithium batteries have been widely used in all over the world for its high energy density, long-term cycle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries (DISBs) possess higher energy density, especially owning high power density for its higher operating voltage (> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier (artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG (covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage. Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are significantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.     

Study of polyethylene coating to improve the cycle stability of Ni-rich cathode for Li-ion batteries

Journal of Solid State Electrochemistry - Ni-rich cathode materials can be used to manufacture high energy density lithium-ion batteries because of their higher specific capacity. However, Ni-rich...     

Chaperonin GroEL: structure and reaction cycle

The structure of Escherichia coli chaperonin GroEL was studied using various experimental tools. Such studies produced information about its structure with increasing details. Moreover, remarkable advances in experimental methods provided a step forward in understanding the reaction cycle involved in GroEL-mediated protein folding. In the current review we summarize recent progress, focus on the structure of GroEL and understand the mechanism involved in GroEL-mediated protein folding. This review is divided into the following sections: (i) Section 1 provides basic understanding on protein folding, (ii) Section 2 not only describes various tools used to elucidate the structural aspects of GroEL but also provides details about its structure with particular emphasis, (iii) Section 3 describes allosteric transitions and the reaction cycle involved in GroEL-mediated protein folding, (iv) Section 4 explains iterative annealing and smoothing of the energy landscape model and finally (v) Section 5 discusses applications and recent progress.     

Effect of light/dark cycle on bacterial hydrogen production by Rhodobacter sphaeroides RV

Hydrogen production by photosynthetic bacteria provides an efficient energy conversion method under low light intensity. However, under strong illumination, such as midday sunlight, the efficiency drops. This prevents the method from being applied industrially. To overcome this problem, we examined a method to thin out the excessive illumination. Light was given intermittently to reduce the total energy flux. The on/off ratio was set at 1/1 throughout the study, so that the time average of the light energy flux became half the continuous illumination. By keeping the time-average light flux constant (0.6 kW·m⁻²), the effects of the cycle period were examined in the range of hours to seconds. The hydrogen production rate was greatly affected by the cycle period, but cell growth and substrate consumption rates remained almost constant. The 30-min light/dark cycle (30 min on and 30 min off) provided the highest rate of hydrogen production (22 L·m⁻²·24 h⁻¹). At the shorter cycles, the rate decreased except that there was a suboptimum at about 40 s. Under excessive light intensity (1.2 kW·m⁻²), the light-to-hydrogen conversion efficiency was greatly enhanced. The hydrogen production rate during the 30-min cycle was twice as high as during a 12-h cycle under the same conditions.     

Compression ratio energy and exergy analysis of a developed Brayton-based power cycle employing CAES and ORC

Journal of Thermal Analysis and Calorimetry - Energy consumption growth in the world is one of the primary concerns of researchers in the energy fields. Providing demanded power, especially in peak...     

Enclosing the nitrogen cycle: Ammonia synthesis by NOx reduction

Nitrogen cycling (N₂-NO_x-NH₃) is essential for maintaining life as it is crucial in fertilizers and nucleic acids. However, the current NH₃ synthesis (N₂-to-NH₃) for fertilizers and energy requires large amounts of fossil fuels and greenhouse gas emissions, compromising its eco-economic significance. Meanwhile, approaches like selective catalytic reaction are applied to neutralize the toxic NO_x into N₂ but call for value-added NH₃ as the reduction agent. In this regard, directly converting harmful NO_x, one of the major environmental pollutants, into NH₃ is a promising way to balance the nitrogen cycle eco-friendly, which is still in its infancy. Recently, the electrocatalytic NO_x reduction reaction (NO_xRR) unveiled a potential route for the NO_x-to-NH₃ conversion. This review presents the latest progress in the electrocatalytic NO_xRR in reaction mechanism and catalysts design. It will provide a comprehensive understanding to guide future research in NO_xRR, aiming to offer sustainable chemistry and energy feedstocks for the carbon-zero economy.     

Simulation of crystallization evolution of polyoxymethylene during microinjection molding cycle

A mathematical model coupled with a numerical investigation of the evolving material properties due to thermal and flow effects and in particular the evolution of the crystallinity during the full microinjection molding cycle of poly (oxymethylene) POM is presented using a multi‐scale approach. A parametric analysis is performed, including all the steps of the process using an asymmetrical stepped contracting part. The velocity and temperature fields are discussed. A parabolic distribution of the velocity across the part thickness, and a temperature rise in the thin zone toward the wall have been obtained. It is attributed to the viscous energy dissipation during the filling phase, but also to the involved characteristic times for the thermal behavior of the material. Depending on the molding conditions and the locations within the micro‐part, different evolution of crystallization rates are obtained leading to at least three to five morphological layers, obtained in the same part configuration of a previously work, allowing a clear understanding of the process‐material interaction.     

Calculation of relative binding free energy differences for fructose 1,6-bisphosphatase inhibitors using the thermodynamic cycle perturbation approach.

An iterative, computer-assisted, drug design strategy that combines molecular design, molecular mechanics, molecular dynamics (MD), and free energy perturbation (FEP) calculations with compound synthesis, biochemical testing of inhibitors, and crystallographic structure determination of protein-inhibitor complexes was successfully used to predict the rank order of a series of nucleoside monophosphate analogues as fructose 1,6-bisphosphatase (FBPase) inhibitors. The X-ray structure of FBPase complexed with 5-aminoimidazole-4-carboxamide-1-beta-D-ribofuranosyl 5'-monophosphate (ZMP) provided structural information used for subsequent analogue design and free energy calculations. The FEP protocol was validated by calculating the free energy differences for the mutation of ZMP (1) to AMP (2). The calculated results showed a net gain of 1.7 kcal/mol, which agreed with the experimental result of 1.3 kcal/mol. FEP calculations were performed for 18 other AMP analogues. Inhibition constants were determined for over half of these analogues, usually after completion of the calculation, and were consistent with the predictions. Solvation free energy differences between AMP and various AMP analogues proved to be an important factor in binding free energies, suggesting that increased desolvation costs associated with the addition of polar groups to an inhibitor must be overcome by stronger ligand-protein interactions if the structural modification is to enhance inhibitor potency. The results indicate that FEP calculations predict relative binding affinities with high accuracy and provide valuable insight into the factors that influence inhibitor binding and therefore should greatly aid efforts to optimize initial lead compounds and reduce the time required for the discovery of new drug candidates.     

Synthesis of Co-Ni oxide microflowers as a superior anode for hybrid supercapacitors with ultralong cycle life

Li-ion hybrid capacitors (LIHCs), composing of a lithium-ion battery (LIB) type anode and a supercapacitor (SC) type cathode, gained worldwide popularity due to harmonious integrating the virtues of high energy density of LIBs with high power density of SCs. Herein, nanoflakes composed microflower-like Co-Ni oxide (CoNiO) was successfully synthesized by a simple co-precipitation method. The atomic ratio of as-synthesized CoNiO is determined to be 1:3 through XRD and XPS analytical method. As a typical battery-type material, CoNiO and capacitor-type activated polyanilinederived carbon (APDC) were used to assemble LIHCs as the anode and cathode materials, respectively. As a result, when an optimized mass ratio of CoNiO and APDC was 1:2, CoNiO//APDC LIHC could deliver a maximum energy density of 143 Wh kg^-1 at a working voltage of 1-4 V. It is worth mentioning that the LIHC also exhibits excellent cycle stability with the capacitance retention of 78.2% after 15,000 cycles at a current density of 0.5 A g^-1.     

Cytochrome P450CAM enzymatic catalysis cycle: a quantum mechanics/molecular mechanics study

The catalytic pathway of cytochrome P450cam is studied by means of a hybrid quantum mechanics/molecular mechanics method. Our results reveal an active role of the enzyme in the different catalytic steps. The protein initially controls the energy gap between the high- and low-spin states in the substrate binding process, allowing thermodynamic reduction by putidaredoxin reductase and molecular oxygen addition. A second electron reduction activates the delivery of protons to the active site through a selective interaction of Thr252 and the distal oxygen causing the O--O cleavage. Finally, the protein environment catalyzes the substrate hydrogen atom abstraction step with a remarkably low free energy barrier ( approximately 8 kcal/mol). Our results are consistent with the effect of mutations on the enzymatic efficacy and provide a satisfactory explanation for the experimental failure to trap the proposed catalytically competent species, a ferryl Fe(IV) heme.