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The removal of nitrogen from coal tar pitch (CTP) through the hydrodenitrogenation (HDN) of CTP and its molecular behavior were evaluated in the presence of NiMo/γ-alumina and CoMo/γ-alumina catalysts. Fourier transform ion cyclotron resonance mass spectrometry with atmospheric pressure photoionization was used to analyze the complicated chemical classes and species of CTP and the treated products at the molecular level. Nitrogen species were qualitatively analyzed before and after hydrotreatment. A single-stage hydrotreatment with an HDN catalyst resulted in a high sulfur removal performance (85.6-94.7%) but a low nitrogen removal performance (26.8-29.2%). Based on relative abundance analyses of nitrogen and binary nitrogen species, CcHh-NnSs was the most challenging species to remove during HDN treatment. Furthermore, prior hydrodesulfurization was combined with HDN treatment, and the dual hydrotreatments yielded a significantly improved nitrogen removal performance (46.4-48.7%).
Assuntos
Alcatrão , Nitrogênio/química , Óxido de Alumínio , Desnitrificação , Espectrometria de Massas/métodosRESUMO
Nanogels-internally crosslinked macromolecules-have a growing palette of potential applications, including as drug, gene or radioisotope nanocarriers and as in vivo signaling molecules in modern diagnostics and therapy. This has triggered considerable interest in developing new methods for their synthesis. The procedure based on intramolecular crosslinking of polymer radicals generated by pulses of ionizing radiation has many advantages. The substrates needed are usually simple biocompatible polymers and water. This eliminates the use of monomers, chemical crosslinking agents, initiators, surfactants, etc., thus limiting potential problems with the biocompatibility of products. This review summarizes the basics of this method, providing background information on relevant aspects of polymer solution thermodynamics, radiolysis of aqueous solutions, generation and reactions of polymer radicals, and the non-trivial kinetics and mechanism of crosslinking, focusing on the main factors influencing the outcomes of the radiation synthesis of nanogels: molecular weight of the starting polymer, its concentration, irradiation mode, absorbed dose of ionizing radiation and temperature. The most important techniques used to perform the synthesis, to study the kinetics and mechanism of the involved reactions, and to assess the physicochemical properties of the formed nanogels are presented. Two select important cases, the synthesis of nanogels based on polyvinylpyrrolidone (PVP) and/or poly(acrylic acid) (PAA), are discussed in more detail. Examples of recent application studies on radiation-synthesized PVP and PAA nanogels in transporting drugs across the blood-brain barrier and as targeted radioisotope carriers in nanoradiotherapy are briefly described.
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A detailed understanding of the catalytic upgrading of light cycle oil (LCO) is important to achieve effective deep hydrodesulfurization (HDS) when LCO is mixed with straight run gas oil in the diesel pool. Herein, HDS of polyaromatic-rich LCO was studied at the molecular level over three NiMo catalysts on silica-alumina supports, which were synthesized on the pilot scale using different silica/alumina mixing procedures. Gas chromatography with atomic emission detection and two-dimensional gas chromatography with time-of-flight mass spectrometry were used to evaluate the HDS performance through determining the feed and product compositions, respectively, at the molecular level. Furthermore, the textural properties of the catalysts were evaluated using Raman spectroscopy, transmission electron microscopy, and the temperature-programmed desorption of NH3. The performance of the best catalyst was attributed to its higher content of octahedrally coordinated Mo oxide species, a lower number of layered stacks, and the more acidic sites on the surface. In addition, the hydrotreating reactivity of various family groups in LCO over the catalyst was investigated.
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PtPd nanoparticles on carbon black were prepared to investigate the role of Pd in the anode and cathode of a direct methanol fuel cell (DMFC). The PtPd catalysts in the anode showed a significantly lower performance than the PtRu catalyst. However, the cell performances of these catalysts in the cathode were comparable to that of the Pt catalyst. From cyclic voltammetry, it was observed that the Pd with the Pt catalyst lowered the peak potential and increased the coulombic charge for oxide reduction on the surface of the catalyst. Also, the Pd catalyst without Pt showed relatively high activity for oxygen reduction reaction.
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Pulse radiolysis with spectrophotometric and conductometric detection was utilized to study the formation and reactions of radicals from benzene and dienes in aqueous solutions. The benzene OH adduct, *C6H6OH, reacts with O2 (k = 3 x 10(8) L mol(-1) s(-1)) in a reversible reaction. The peroxyl radical, HOC6H6O2*, undergoes O2*- elimination, bimolecular decay, and reaction with benzene to initiate a chain reaction, depending on the dose rate, benzene concentration, and pH. The occurrence of the chain reaction is demonstrated in low-dose-rate gamma radiolysis experiments where the consumption of O2 was monitored. 1,4-Cyclohexadiene, 1,4-hexadiene, and 1,4-pentadiene form OH-adducts and undergo H-abstraction by O*- radicals. The OH-adducts react with O2 to form peroxyl radicals. These peroxyl radicals, however, do not undergo unimolecular O2*- elimination but rather decay by second-order processes, which lead to subsequent steps of O2*- elimination.