Investigation of Petroleum Coke Gasification with CO2/H2O Mixtures and S/N Removal Mechanism via ReaxFF MD Simulation.

The removal of environmentally harmful S/N is crucial for utilization of high-S petroleum coke (petcoke) as fuels. Gasification of petcoke enables enhanced desulfurization and denitrification efficiency. Herein, petcoke gasification with the mixture of two effective gasifiers (CO2 and H2O) was simulated via reactive force field molecular dynamics (ReaxFF MD). The synergistic effect of the mixed agents on gas production was revealed by altering the CO2/H2O ratio. It was determined that the rise in H2O content could boost gas yield and accelerate desulfurization. Gas productivity reached 65.6% when the CO2/H2O ratio was 3:7. During the gasification, pyrolysis occurred first to facilitate the decomposition of petcoke particles and S/N removal. Desulfurization with the CO2/H2O gas mixture could be expressed as thiophene-S → S → COS → CHOS, thiophene-S → S → HS → H2S. The N-containing components experienced complicated mutual reactions before being transferred into CON, H2N, HCN, and NO. Simulating the gasification process on a molecular level is helpful in capturing the detailed S/N conversion path and reaction mechanism.

Thermogravimetric Analysis of the Combustion Characteristics and Combustion Kinetics of Coals Subjected to Different Chemical Demineralization Processes.

In order to explore the influence of different chemical demineralizations on coal combustion characteristics and combustion kinetics, five coals subjected to different chemical demineralization processes were investigated via thermogravimetric analysis. The ash contents of clean coal was reduced to 0.1-1.55% after different chemical demineralizations. The ignition temperature of coal decreased by 12-69 °C, and the peak temperature decreased by 7-62 °C. The burnout temperature of clean coal increased by 63 °C after demineralization by NaOH. The adsorption of noncombustible NaOH into the porous structure of TaiXi-3 caused an increase in burnout temperature. Alkali-soluble minerals were proven to have a negative effect on the combustion performance of coal, while acid-soluble minerals had the opposite effect. The combustion kinetics of five kinds of coals at a heating rate of 10 °C/min was investigated. The activation energy of coal obviously changes before and after demineralization (58.39-91.39 kJ mol-1). The activation energy of clean coal is obviously lower than that of raw coal.

A Novel Low-Temperature Fluorination Roasting Mechanism Investigation of Regenerated Spent Anode Graphite via TG-IR Analysis and Kinetic Modeling.

Spent anode graphite, a hazardous solid waste discarded from the recovery of spent lithium-ion batteries (LIBs), had created social and environmental issues but has been scarcely investigated. Thus, a feasible, environmentally friendly, and economical process of low-temperature fluorination roasting and water leaching technology was proposed to regenerate spent graphite anodes. The results showed that the physical and chemical properties of regenerated graphite with a purity of 99.98% reached the graphite anode standard of LIBs and exhibited a stable specific capacity (340.9 mAh/g), capacity retention (68.92% after 470th cycles), and high initial Coulombic efficiency (92.13%), much better than that of waste carbon residue and similar to that of commercial graphite. Then the reaction mechanism and kinetic modeling of fluorination roasting of spent anode material was mainly explored by differential thermogravimetry and nonisothermal analysis methods. The results showed that the complexation and phase-transformation process of non-carbon valuable components in spent anode graphite occurred through three consecutive reactions in the 80-211 °C temperature intervals. The reaction mechanism of the whole process can be kinetically characterized by three successive reactions: third-order chemical reaction, Z-L-T eq, and second-order chemical reaction. Moreover, the thermodynamic functions of the fluorination roasting were calculated by the activated complex theory (transition state), which indicated the process was nonspontaneous. The mechanistic information was in good agreement with thermogravimetric-infrared spectroscopy (TG-IR), electron probe microanalysis, scanning electron microscopy, energy-dispersive spectrometry, and simulation experiments results.

Theoretical study of the mechanism of the manganese catalase KatB.

The mechanism of the H2O2 disproportionation catalyzed by the manganese catalase (MnCat) KatB was studied using the hybrid density functional theory B3LYP and the quantum chemical cluster approach. Compared to the previous mechanistic study at the molecular level for the Thermus thermophilus MnCat (TTC), more modern methodology was used and larger models of increasing sizes were employed with the help of the high-resolution X-ray structure. In the reaction pathway suggested for KatB using the Large chemical model, the O-O homolysis of the first substrate H2O2 occurs through a µ-η1:η1 coordination mode and requires a barrier of 10.9 kcal/mol. In the intermediate state of the bond cleavage, two hydroxides form as terminal ligands of the dimanganese cluster at the Mn2(III,III) oxidation state. One of the two Mn(III)-OH- moieties and a second-sphere tyrosine stabilize the second substrate H2O2 in the second-sphere of the active site via hydrogen bonding interactions. The H2O2, unbound to the metals, is first oxidized into HO2· through a proton-coupled electron transfer (PCET) step with a barrier of 9.5 kcal/mol. After the system switches to the triplet surface, the uncoordinated HO2· replaces the product water terminally bound to the Mn(II) and is then oxidized into O2 spontaneously. Transition states with structural similarities to those obtained for TTC, where µ-η2-OH-/O2- groups play important roles, were found to be higher in energy.

Distal Proton Shuttle Mechanism of Ribosome Catalysed Peptide Bond Formation-A Theoretical Study.

In this work, we have investigated a novel distal proton shuttle mechanism of ribosome catalyzed peptide bond formation reaction. The reaction was found to follow a two-step mechanism. A distal water molecule located about 6.1 Šaway from the attacking amine plays as a proton acceptor and results in a charge-separated intermediate that is stabilized by the N terminus of L27 and the A-site A76 5'-phosphate. The ribose A2451 bridges the proton shuttle pathway, thus plays critical role in the reaction. The calculated 27.64 kcal•mol-1 free energy barrier of the distal proton shuttle mechanism is lower than that of eight-membered ring transition state. The distal proton shuttle mechanism studied in this work can provide new insights into the important biological peptide synthesis process.

A theoretical study on oxidative cleavage of olefins to carbonyls catalysed by Fe(iii)-PyBisulidine.

An environmentally friendly new protocol for the selective aerobic cleavage of styrene to carbonyl compounds using the Fe(iii)-PyBisulidine catalyst has been reported recently. The catalyst features several unusual characteristics, such as its high efficiency lies on the ferric center instead of ferrous used by most iron-containing oxygenases and the catalyst specifically oxidizes phenyl-substituted olefins but exhibits no activity on nonconjugated olefins. Herein, we have investigated the mechanism of the oxidative cleavage reaction catalyzed by Fe(iii)-PyBisulidine at the quantum chemistry level. Our computational study shows that the catalyst uses a dioxygen ligation mechanism to activate dioxygen to receive one electron from olefin, which triggers the oxidative cleavage reaction. Our study rationalizes that the Fe(ii)-PyBisulidine catalyst is inactivated because ferrous is unable to raise the oxidizing ability of dioxygen. The exclusive oxidative cleavage of the phenyl-substituted olefin mainly results from the stability of the carbon cation, the orbital symmetry between the conjugated olefin and dioxygen, as well as a lower energy level of HOMO in conjugated olefin.