Hydrogen production from thermal decomposition of ammonia-contaminated acid gas using a detailed reaction mechanism

The increase in the production of acid gas consisting of H₂S, CO₂, and associated impurities such as ammonia and hydrocarbons from oil and gas plants and gasification facilities has stimulated the interest in the development of alternative means of acid gas utilization to produce hydrogen and sulfur, simultaneously. The present literature lacks a detailed reaction mechanism that can reliably predict the thermal destruction of NH₃ and its blend with H₂S and CO₂ to facilitate process optimization and commercialization. In this paper, a detailed mechanism of NH₃ pyrolysis is developed and is merged with the reactions of NH₃ oxidation and H₂S/CO₂ thermal decomposition from our previous works. The mechanism is validated successfully using different sets of experimental data on the pyrolysis and oxidation of NH₃, H₂S, and CO₂. The proposed mechanism predicts the experimental data on NH₃ pyrolysis remarkably better than the existing mechanisms in the literature. The mechanism is used to investigate the effects of NH₃ concentration (0–20%) and reactor temperature (1000–1800 K) on the thermal decomposition of H₂S and CO₂. A synergistic effect is observed in the simultaneous decomposition of NH₃ and CO₂, i.e., NH₃ conversion is improved in the presence of CO₂ and the decomposition CO₂ to CO is enhanced in the presence of NH₃. The presence of H₂S suppressed NH₃ conversion, while the conversion of H₂S remained unchanged with increasing NH₃ concentration at temperature below 1400 K due to the low conversion of NH₃ (up to 18%). At temperature above 1400 K, NH₃ conversion increased rapidly and it triggered a decrease in H₂S conversion as well as the yields of H₂ and S₂. The major reactions involved in the decomposition of H₂S, CO₂, and NH₃ and the production of major products such as H₂, S₂, and CO are identified. The detailed reaction mechanism can facilitate the design and optimization of acid gas thermal decomposition to produce hydrogen and sulfur, simultaneously.     

Design and performance study of phase‐locked loop using fractional‐order loop filter

The present work reports the realization of an analog fractional‐order phase‐locked loop (FPLL) using a fractional capacitor. The expressions for bandwidth, capture range, and lock range of the FPLL have been derived analytically and then compared with the experimental observations using LM565 IC. It has been observed that bandwidth and capture range can be extended by using FPLL. It has also been found that FPLL can provide faster response and lower phase error at the time of switching compared to its integer‐order counterpart. Copyright © 2014 John Wiley & Sons, Ltd.     

致密油藏注天然气提高采收率研究现状

随着我国石油需求量不断增加,致密油藏的开发也愈发重要。如何高效开发致密油藏是一项重点难点,其中致密油藏注天然气提高采收率是一个极具潜力的研究方向。因此,本文着重介绍以天然气作为能量补充介质在国内外的研究现状和应用现状,并且从两相特征等方面总结了理论研究中的一些机理,对致密油藏注天然气提高采收率的发展前景进行了一定的展望。     

Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

Recycling of multilayer packaging using a reversible cross-linking adhesive

Plastic-based multilayer packaging has an important function on the packaging market, but is currently not recyclable as the polymer layers used are usually thermodynamically immiscible. This work therefore follows the approach to prepare separable multilayer packaging using a packaging adhesive modified with thermally unstable adducts, and proposes a corresponding recycling process. For this purpose, typical multilayer structures (polyethylene (PE)// polyethylene terephtalate (PET), PET//aluminum, and PE//aluminum) were prepared by curing furan-/maleimide-functionalized polyurethane (PU)-prepolymers with a three-functional cross-linking agent. Adhesions of up to over 3N per 15 mm test specimen were measured or substrate failures of PET films were observed. However, heating in dimethylsulfoxide, the retro-Diels–Alder reaction takes place and the cross-linked adhesive turns thermoplastic and dissolves in the solvent. Thus, the laminate separates and the pure PE, PET, and aluminum foils can be recovered without any PU residue.     

Occurrence and distribution of dibenzofurans and benzo[b]naphthofurans in the crude oils from the Northern and offshore Niger Delta basin,Nigeria

The occurrence and distributions of dibenzofurans (DBFs) and benzo[b]naphthofurans were investigated in crude oils from Niger Delta, Nigeria, by gas chromatography-mass spectrometry-mass spectrometry. The distribution of DBFs was characterized by the predominance of C₂-dibenzofurans. 4-Methyldibenzofuran was the most abundant among the methyldibenzofurans isomers while dimethyldibenzofuran-2 (DMDBF-2), ethyldibenzofuran-1, DMDBF-3, and DMDBF-6 occurred in higher amounts when compared with other DMDBFs. Among the benzonaphthofurans, the abundance of benzo[b]naphtho[2,1-d]furan was higher than other isomers. The DBFs distributions in the oils were not affected by source facies and depositional environments. However, the DBFs concentrations increased with increasing maturity in oils from ADL and MJO oilfields.     

Temperature- and frequency-dependent hysteresis scaling behaviour and phase transitions in a [001]c 0.73Pb(Mg1/3Nb2/3)O3-0.27PbTiO3 single crystal

The dielectric properties and bipolar polarization-electric field (P-E) and strain-electric field (S-E) dynamic hysteresis of a relaxor [001]_c 0.73Pb(Mg_1/3Nb_2/3)O₃-0.27PbTiO₃ (PMN-0.27PT) single crystal were investigated to reveal more details of the temperature-induced phase transitions. Different linear scaling relations for ferroelectric hysteresis area <A>, coercive field E_c, saturation polarization P_s and remnant polarization P_r versus temperature τ were measured in different temperature regions. For each measurement frequency f, all hysteresis parameters were found to decrease linearly with temperature in the temperature range of the single rhombohedral (R) phase or tetragonal (T) phase, and the rate of decrease in the T phase was observed to be much larger than the corresponding rate in the R phase. In the temperature range near the R-T phase transition, the exponent α in the power law <A>∝f ^α for the R phase was found to be smaller than that for the T phase, and the magnitude of α depended strongly on temperature when the crystal was in the R-T coexisting phase state. Our experimental and theoretical results indicate that the difference in the activation energy and dipole moment in the R and T phases may lead to the observed discrepancy for the P-E and S-E hysteresis behaviour in different temperature regions.     

Predicting the thermodynamics of aluminum dross denitrification of flue gas

Existing alumina extraction and material production methods result in the formation of harmful ammonia gas or ammonia water originating from aluminum nitride (AlN) in dross. Therefore, in this study, aluminum dross was used as a denitration reagent to eliminate nitrogen oxides in flue gas and AlN in dross. Based on the proposed scheme, thermodynamic calculations were performed to investigate the denitrification effect and reduction of aluminum dross in flue gas. The results show that equilibrium concentrations of NO, NO₂, and HF in the flue gas were influenced mainly by temperature; their concentrations increased with an increase in the temperature, reaching 4.4 × 10⁻²⁰, 1.7 × 10⁻³⁸, and 7.0 × 10⁻⁸ g/m³, respectively, at 923 K. The Gibbs free energy corresponding to the reaction of CO₂ with Al/AlN in aluminum dross was −377/–120 kJ/mol. HF, originating from the reaction of NaF and water vapor, maintained an extremely low concentration of 6.99 × 10⁻⁸ g/m³ at 923 K. These results indicate that aluminum dross processing may clean the flue gas and increase the calorific value while eliminating the hazards of AlN. The results obtained herein will provide theoretical guidance toward new avenues of aluminum dross utilization.     

Corrosion behaviors of Cr2AlC/α-Al2O3 composites in 3.5 wt. % NaCl aqueous solution

Cr₂AlC and its composites containing α-Al₂O₃ (6.1 and 15.2 wt %) were prepared by hot pressing and their corrosion behaviors in air-saturated 3.5 wt % NaCl aqueous solution were investigated by electrochemical testing methods. It was revealed that the secondary phase of Al₂O₃ particles mainly distributed along grain boundaries of Cr₂AlC matrix. The potentiodynamic polarization measurements showed that the corrosion current densities of these Cr₂AlC composites were lower than that of the pure Cr₂AlC. The Aluminum in Cr₂AlC was prone to be attacked more easily. When immersed at open circuit potential (OCP), Al readily slipped out from Cr₂AlC matrix into NaCl solution in the form of dissoluble species. But in the case of polarization, regardless of potentiostatic polarization or potentiodynamic polarization, more de-intercalated Al, reacted with the electrolyte to form corrosion products of Al₂O₃ and/or AlOOH and deposited on the sample surface. For Cr₂AlC/α-Al₂O₃ composites, the presence of Al₂O₃ weakened the corrosion along grain boundaries by partly blocking the permeation of electrolyte and inhibiting the anodic dissolution process.