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.     

Densification mechanism during reactive hot pressing of B4C-ZrO2 mixtures

The densification behaviors of pure B₄C and B₄C-ZrO₂ mixtures were compared during hot pressing. The results showed that in-situ formed ZrB₂ effectively enhanced the densification process of B₄C-ZrO₂ mixtures, more significantly during the intermediate stage. Within the relative density ranging from 0.75 to 0.90, the B₄C-15?wt%ZrO₂ mixture (B15Z) achieved the maximum densification rate as twice much as that of pure B₄C. The stress exponent n>3 indicated plastic deformation was the dominant densification mechanism of B15Z. The viscosities of plastic flow were evaluated using Murray-Rodger-William equation and the viscosity of B15Z was only a quarter of that in pure B₄C. The sintering activation energy was calculated to be 305.9?kJ/mol for pure B₄C and 197?kJ/mol for B15Z, respectively. It was proposed that the lower viscosity of plastic flow and activation energy accelerated the sliding and propagating motions of plastic flow, by which underlain the enhanced densification behaviors of B₄C-ZrO₂ mixtures.     

Perfluorocarbons in Chemical Biology

Perfluorocarbons, saturated carbon chains in which all the hydrogen atoms are replaced with fluorine, form a separate phase from both organic and aqueous solutions. Though perfluorinated compounds are not found in living systems, they can be used to modify biomolecules to confer orthogonal behavior within natural systems, such as improved stability, engineered assembly, and cell-permeability. Perfluorinated groups also provide handles for purification, mass spectrometry, and ¹⁹F NMR studies in complex environments. Herein, we describe how the unique properties of perfluorocarbons have been employed to understand and manipulate biological systems.     

岩矿稀有金属化学分析技术浅析

分析当前较为常用的岩矿稀有元素分析技术方法,并对几种常见的稀有元素分析方法进行了阐述,希望为我国矿产勘探领域提供一些有价值的参考借鉴。     

Site-Specific PEGylation of Therapeutic Proteins

The use of proteins as therapeutics has a long history and is becoming ever more common in modern medicine. While the number of protein-based drugs is growing every year, significant problems still remain with their use. Among these problems are rapid degradation and excretion from patients, thus requiring frequent dosing, which in turn increases the chances for an immunological response as well as increasing the cost of therapy. One of the main strategies to alleviate these problems is to link a polyethylene glycol (PEG) group to the protein of interest. This process, called PEGylation, has grown dramatically in recent years resulting in several approved drugs. Installing a single PEG chain at a defined site in a protein is challenging. Recently, there is has been considerable research into various methods for the site-specific PEGylation of proteins. This review seeks to summarize that work and provide background and context for how site-specific PEGylation is performed. After introducing the topic of site-specific PEGylation, recent developments using chemical methods are described. That is followed by a more extensive discussion of bioorthogonal reactions and enzymatic labeling.     

Effects of structural characteristics on microwave dielectric properties of low-loss (Zn1-xNix)ZrNbTaO8 ceramics

Low-loss (Zn_1-xNi_x)ZrNbTaO₈ (0.02?≤?x?≤?0.10) ceramics possessing single wolframite structure are initiatively synthesized by solid-state route. Based on the results of Rietveld refinement, complex chemical bond theory is used to establish the correlation between structural characteristics and microwave performance in this ceramic system. A small amount of Ni²⁺ (x?=?0.06) in A-site with the fixed substitution of Ta⁵⁺ in B-site can effectually raise the Q?×?f value of ZnZrNb₂O₈ ceramic, embodying a dense microstructure and high lattice energy. The dielectric constant and τ_f are mainly affected by bond ionicity and the average octahedral distortion. The (Zn_0.94Ni_0.06)ZrNbTaO₈ ceramic sample sintered at 1150?°C for 3?h exhibits an outstanding combination of microwave dielectric properties: ε_r =?27.88, Q?×?f?=?128,951?GHz, τ_f =?–39.9?ppm/°C. Thus, it is considered to be a candidate material for the communication device applications at high frequency.     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

PREDICTING THE TIMING AND CHARACTERISTICS OF PETROLEUM FORMATION USING TAR MATS AND PETROLEUM ASPHALTENES: A CASE STUDY FROM THE NORTHERN NORTH SEA

The Northern Viking Graben area in the Norwegian North Sea was studied in order to investigate the petroleum formation characteristics of the Upper Jurassic Draupne Formation. In this area, the organofacies of the Draupne Formation, and consequently its petroleum generation characteristics, show significant variations. These variations represent a major risk, particularly in the context of basin modelling studies. Therefore, tar‐mat asphaltenes, oil asphaltenes and source‐rock samples from this area were studied in order to evaluate the use of migrated asphaltenes from petroleum reservoirs and tar mats in basin modelling. The samples were studied using bulk kinetic analysis, open‐system pyrolysis‐gas chromatography and elemental analyses, and the results were integrated into a basin modelling study. The results from these different sample materials were compared both to each other and to natural petroleum, in order to assess their significance for future petroleum exploration activities. We show that in cumulative petroleum systems, the transformation characteristics of the asphaltenes incorporate those of the individual source rock intervals which have contributed to the relevant reservoir system. Thus, the petroleum formation window predicted by the use of asphaltene kinetics is broad, and covers the majority of the formation windows predicted from the individual source rock samples. In addition, the molecular characteristics of asphaltene‐derived hydrocarbons show that compositional characteristics, such as aromaticity, correspond more closely to natural oils than to the respective source‐rock products. Our results confirm that the heterogeneous nature of the Draupne Formation results in a significantly broader petroleum formation window than is conventionally assumed. We propose that oil and tar‐mat asphaltenes from related reservoirs represent macromolecules which account for this heterogeneity in the source rock, since they represent mixtures of charges from the different organofacies. One conclusion is that the use of oil and tar‐mat asphaltenes in kinetic studies and compositional predictions may significantly improve definitions of petroleum formation characteristics in basin modelling.