Effect of hydrogen spillover on the hydrogenation of 1-hexene over diluted carbon molecular sieve supported Pt catalyst

Pt supported on a carbon molecular sieve (Pt/CMS) was prepared by pyrolysis of polyfurfuryl alcohol containing pre-reduced Pt particles. The catalysts were characterized by hydrogen chemisorption, XRD, N₂ adsorption/desorption and TEM. Hydrogen chemisorption showed that not all the Pt particles were exposed to H₂ molecules. Oxidation treatment made Pt particles more accessible to H₂. Catalyst activity was evaluated by hydrogenation of 1-hexene. Hydrogen spillover was demonstrated by diluting Pt/CMS with activated carbon or hydrogen type zeolite Y. The initial conversion of 1-hexene was increased from 86.5% to 98.5% and to 100% when Pt/CMS was diluted with activated carbon and hydrogen type zeolite, respectively. The high initial conversion was sustained for 6 h in the presence of diluents while the conversion decreased quickly for Pt/CMS alone.     

Effect of nitrogen removal from light cycle oil on the hydrodesulphurization of dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene

Five light cycle oil feeds (LCO) with nitrogen contents ranging from 744.9 to 16.5 mg/L were prepared by removing organic nitrogen compounds gradually through adsorption on a silica column. These feeds were hydrotreated over a commercial Ni-Mo/Al₂O₃ catalyst to study the effect of nitrogen compounds on the hydrodesulphurization (HDS) of dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. It was found that nitrogen compounds had the most negative impact on the HDS of 4- and/or 6-substituted dibenzothiophenes. The temperatures to achieve 50% HDS conversion were 5, 20 and 25 °C lower for dibenzothiophene, 4-methyldibenzothiphene and 4,6-dimethyldibenzothiophene, respectively, when the nitrogen content in the feed was reduced from 744.9 to 16.5 mg/L. Our results also revealed that, at lower temperatures, about 20% of the nitrogen compounds from the original light cycle oil were adsorbed on the catalyst's surface. The HDS of 4,6-dimethyldibenzothiophene was retarded until the HDN rate became greater than the adsorption rate, which might have freed some hydrogenation sites for adsorption. This phenomenon was not observed for the HDS of DBT. Our results suggest that nitrogen compounds and 4,6-dimethyldibenothiophene competed for the same type of active sites, and dibenzothiophene also could have been converted over a different site. In addition, the hydrodenitrogenation activity was also enhanced by the removal of nitrogen compounds. The experimental data was fitted to a Langmuir–Hinshelwood type of kinetic equation by assuming that the inhibition only affected the hydrogenation pathway.     

Negative Differential Conductivity of Lanthanum-Oxide-Based Structures

Semiconductors - Transparent surface-hydrogenated lanthanum-oxide films (OH–La2O3) 40, 140, and 545 nm in thickness are fabricated using electron-beam evaporation. The electrical and optical...     

Miniaturized method for separation and quantification of nitrogen species in petroleum distillates

The properties of nitrogen compounds are a subject of interest to petroleum refiners due to the detrimental role, these compounds play in catalyst deactivation and product stability. It is thought that basic nitrogen is a major contributor to these phenomena, and therefore identification and quantification of nitrogen species by type would be of great importance.A practical miniaturized method for quantitative separation of nitrogen compounds by type in petroleum distillates is described. Solid phase extraction methodology was used to concentrate the nitrogen compounds and to separate them further into neutral and basic types. The basic nitrogen compounds could not be fully recovered, while full recovery was achieved for the neutral nitrogen types. The amount of basic nitrogen was calculated by difference, and boiling point distribution profiles were produced. For identification of nitrogen compounds in separated fractions, a combined GC-MS/AED method with retention time locking was used. Carbazole and its substituted derivatives methyl, dimethyl, and trimethylcarbazoles were identified in the product from fluid catalytic cracking.     

Operations scheduling under electricity time-varying prices

Global climate change requires stakeholders to consider energy elements in their decision-making. Electricity costs, in particular, constitute a significant portion of operational costs in most manufacturing systems. The electricity bills can be lowered if electricity-consuming operations are correctly scheduled. We consider a manufacturing operations control problem with known time-varying electricity prices in a finite planning horizon. Each operation is unique and has its own concave electricity consumption function. Pre-emptions of operations are allowed, yet postponing an operation incurs a cumulative penalty for each time period. In addition, each pre-emption is considered a new operation. The electricity cost in each time period is exogenous and there exists a capacity constraint on the total electricity amount consumed in each period due to infrastructure and provider’s limitations. There is a fixed start-up cost incurred for switching on the machine and a fixed reservation cost incurred for keeping the machine ‘On’. The system also includes a rechargeable battery. The customer has to determine when to process each operation within the time horizon so as to minimise total electricity consumption and operations postponement penalty costs. A dynamic programming solution is proposed and the complexity of the models is analysed. After examining several special cases of the model, the optimum times to charge and discharge the rechargeable battery are determined. A polynomial time algorithm for a special case of a single operation with uniform capacity is proposed.