No abstract

Acidity in crude oils has long been a problem for refining. Knowledge of the detailed chemical composition of the acids responsible for corrosion can facilitate identification of problem crude oils and potentially lead to improved processing options for corrosive oils. A highly aerobically biodegraded crude from the San Joaquin Valley, which has a long history of causing corrosion problems during refining, was the subject of this study. The oil was first extracted with base, then acidified and extracted with petroleum ether. A portion of the resulting acid fraction was methylated. The unmethylated extract was analyzed by FTIR, NMR, and the methylated sample was analyzed by high-resolution mass spectrometry (HRMS). Over 96% of the ions observed in HRMS have been assigned reliable formulas. Considerably greater functionality is seen in this sample than would be presumed from the "naphthenic acid" title typically assigned to these species. Although over 60% of the compounds contained two or more oxygens, compounds containing only oxygen heteroatoms accounted for less than 10% of the acidic compounds identified. Approximately one-half of the species contained nitrogen and about one-fourth contained sulfur. It is believed that microbial degradation is a major source of these acidic components. It was also observed that acid species with higher degrees of heteroatom substitution generally also had a higher degree of saturation than those species having less heteroatoms, possibly due to impeded migration of highly substituted, less-saturated species.

Chronic airway disorders, including chronic obstructive pulmonary disease (COPD), cystic fibrosis, and asthma, are associated with persistent pulmonary inflammation and goblet cell metaplasia and contribute to significant morbidity and mortality worldwide. While the molecular pathogenesis of these disorders is actively studied, little is known regarding the transcriptional control of goblet cell differentiation and mucus hyperproduction. Herein, we demonstrated that pulmonary allergen sensitization induces expression of FOXM1 transcription factor in airway epithelial and inflammatory cells. Conditional deletion of the Foxm1 gene from either airway epithelium or myeloid inflammatory cells decreased goblet cell metaplasia, reduced lung inflammation, and decreased airway resistance in response to house dust mite allergen (HDM). FOXM1 induced goblet cell metaplasia and Muc5AC expression through the transcriptional activation of Spdef. FOXM1 deletion reduced expression of CCL11, CCL24, and the chemokine receptors CCR2 and CX3CR1, resulting in decreased recruitment of eosinophils and macrophages to the lung. Deletion of FOXM1 from dendritic cells impaired the uptake of HDM antigens and decreased cell surface expression of major histocompatibility complex II (MHC II) and costimulatory molecule CD86, decreasing production of Th2 cytokines by activated T cells. Finally, pharmacological inhibition of FOXM1 by ARF peptide prevented HDM-mediated pulmonary responses. FOXM1 regulates genes critical for allergen-induced lung inflammation and goblet cell metaplasia.

SUMMARYIn order to meet U.S. biofuel objectives over the coming decade the conversion of a broad range of biomass feedstocks, using diverse processing options, will be required. Further, the production of both gasoline and diesel biofuels will employ biomass conversion methods that produce wide boiling range intermediate oils requiring treatment similar to conventional refining processes (i.e. fluid catalytic cracking, hydrocracking, and hydrotreating). As such, it is widely recognized that leveraging existing U.S. petroleum refining infrastructure is key to reducing overall capital demands. This study examines how existing U.S. refining location, capacities and conversion capabilities match in geography and processing capabilities with the needs projected from anticipated biofuels production.At a national level, there appears to be adequate conversion and hydrotreating facilities in existing refineries to process anticipated bio-derived oils into transportation fuels. However, numerous concerns are apparent, including: a potential shortfall in both overall hydrotreating capacity and hydrogen production capacity in refineries to manage the conversion of certain biomass derived intermediates having high oxygen content; a regional concentration of anticipated biofuel resources, placing added stress in particular refining regions (e.g. the Gulf Coast); uncertainties surrounding the impact of biomass derived intermediates on the refiner's ability to meet product performance and product quantity demands, and the need for better and more comprehensive chemical composition information; the need for considerably more data and experience on the behavior of projected biofuels intermediates in refining processes (e.g. impacts on process performance and reliability); and  the need to examine the optimum capital investment locations for additional processing equipment. For example, whether it is better to produce finished biofuels at the new production sites, or whether existing refining facilities should be expanded to better handle a more 'raw' bio-oil intermediate.Responding to these concerns may be best accomplished by creating a strong collaboration between the refining industry and the national programs that are working in the field of biomass research. The intent is to identify priorities and opportunities for filling critical knowledge and experience gaps and directing investments in a manner that best supports biofuels objectives.

Nitrogen molecular species in several gas oils were analyzed by gas chromatograph with an atomic emission detector (GC-AED) and mass spectrometer (GC-MS). Nitrogen species in gas oils were divided through acidic extraction into basic species (such as aniline, quinoline, benzoquinoline, and their derivatives) and nonbasic species (such as indole, carbazole, and their derivatives). To be mostly identified, their distribution depended on the cutting point and origins of gas oils. Denitrogenation reactivities of nitrogen species in gas oils were followed in the hydrotreating reactions at 340 °C under 5MPa of H2 to quantify by GC-AED their respective reactivities in GOs. The reactivities orders and reactivity dependence on their chemical structures and matrix compositions are discussed on molecular bases. The reactivity order was found as indole > methylated aniline > methylated indole > quinoline > benzoquinoline > methylated benzoquinoline > carbazole > methylated carbazoles. The number and position of methyl groups were very influential on the reactivities of carbazole derivatives. Methyl groups neighboring the N atom inhibited remarkably the HDN reactions. Comparison of the reactivities of the same species in the GOs must be discussed by taking account of all components and products in the respective oil.