Development of refinery scheduling system using mixed integer programming and expert system

This paper presents a hybrid refinery scheduling system combining mathematical programming model and expert system. Mixed-integer linear programming models for crude oil movement between units are merged into the expert system that is for qualitative issues concerning crude vessel unloading operations. The target problem ranging from the crude unloading to the crude charging to distillation towers is decomposed into several module problems for efficiency. Compared with existing scheduling approaches for oil movement, the proposed hybrid refinery scheduling system is very effective in dealing with timing decisions involving vessel unloading operations due to the advantages of an expert system. Since the proposed scheduling system can generate solutions so fast, it is expected to play a key role in the real processes. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Wet oxidation of wastewater containing hydrocarbons by novel supported Pd catalysts

Pd catalysts supported on TiO₂, ZrO₂, ZSM-5, MCM-41 and activated carbon were used in catalytic wet oxidation of hydrocarbons such as phenol, m-cresol and m-xylene. It was found that the Pd/TiO₂ catalyst was highly effective in the wet oxidation of hydrocarbon. The activities of catalysts with various hydrocarbon species, catalyst support, oxidation state of catalyst performed in a 3-phase slurry reactor show that reaction on Pd surface is more favorable than that in aqueous phase and that the active site is oxidized Pd in catalytic wet air oxidation of hydrocarbons. Based on the experimental results, a plausible reaction mechanism of wet oxidation of hydrocarbons catalyzed over Pd/TiO₂ catalyst was proposed. This catalyst is superior to other oxide catalysts because it suppressed the formation of hardly-degradable organic intermediates and polymer.     

Decane reforming reaction over Pt,Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite

Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on NaY- and HY-zeolite were examined as a catalyst for producing gasoline from n-decane via simultaneous reforming and cracking. The catalysts were prepared by calcining and reducing metal-ion-exchanged Y-zeolite with O₂ and H₂ at 300°C., respectively. Thus prepared catalysts were characterized by hydrogen chemisorption and temperature programmed desorption of ammonia. Pt-Ni/NaY and Pt-Ir/NaY bimetallic catalysts offered the improved activity maintenance compared to Pt/NaY monometallic catalyst. The catalysts supported on HY-zeolite showed higher selectivity toward C₅–C₇ and skeletal isomers of C₅–C₇- and C₈–C₁₀ than those of the catalysts supported on NaY-zeolite, which is a desired characteristic for increasing octane value of gasoline these days. However, deactivation with reaction time was much more pronounced on HY-zeolite-supported catalyst. When the catalyst was prcsulfided with H,S, the stability with time on stream was enhanced and the selectivity was quite different from that of the catalyst before presulfiding. The acidity of Y-zeolite and presulfiding of catalyst greatly influenced the activny, selectivity and stability of Pt, Ir, Pt-Ir and Pt-Ni bimetallic catalysts supported on Y-zeolite in n-decane reforming reaction.     

Effect of temperature on polymer migration II: Concentration equation

Polymer migration is a generally well-known phenomenon in a flow field, and it has been verified that the sources of such phenomena are nonhomogeneity of the flow, concentration effects and hydrodynamic interactions between the polymer molecules. In addition, temperature effects were found to be another source of polymer migration. The Langevin equation for a polymer molecule was first derived from single chain dynamics using a kinetic theory for the bead-spring elastic harmonic dumbbell model, as described in part I (reference [1]). In this paper the diffusion equation and concentration profile of the polymer molecules induced by a temperature gradient are obtained from the Fokker-Planck equation. A new differential operator is also introduced to calculate the concentration profile. From the concentration equation obtained in the general flow geometry, we find that in dilute polymer solution there are significant effects on the polymer migration not only due to the nonhomogeneity of the flow field but also due to temperature gradients.     

A novel layered Li [Li0.12NizMg0.32−zMn0.56]O2 cathode material for lithium-ion batteries

Layered Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ oxide cathodes containing lithium atoms in the transition metal layers were synthesized and characterized using X-ray diffraction (XRD), galvanostatic cycling, and differential scanning calorimetry (DSC). The Li[Li_0.12Ni_zMg_0.32−zMn_0.56]O₂ cathodes deliver a specific discharge capacity of about 190 mAh/g at room temperature and 236 mAh/g at 55 °C when cycled between 2.7 and 4.6 V versus Li/Li⁺. Excellent capacity retention and smooth potential profiles at room and elevated temperatures over extended cycles suggest that this material does not convert into a spinel structure.     

Characteristics of selective adsorption using D-phenylalanine imprinted terpolymer beads

A D-Phenylalanine (Phe) imprinted terpolymer, Polyacrylonitrile-Poly(acrylic acid)-Poly(acryl amide) (Poly(AN-AA-AAm)) bead was prepared by the wet-phase inversion method. Acrylamide (AAm) and acrylic acid (AA) were used as the functional monomer and acrylonitrile (AN) was used as a physical cross linker. The characteristics of selective adsorption by the D-Phe imprinted terpolymer beads were investigated at high concentrations of Phe racemate solution, 1 g Phe/L, and 10 g Phe/L. The adsorption selectivity of the D-Phe imprinted terpolymer beads prepared by anin-situ implanting method reached 0.82 and 0.8 at 1.0 g and 10 g Phe/L racemate solution, respectively, and almost all of the adsorbed D-Phe and about 43% of the adsorbed L-Phe were desorbed by 4% acetic acid. The uptake capacities of the terpolymer beads were maintained for several repeated batches.     

Microwave Dielectric Properties of (1−x)(Na1/2Nd1/2)TiO3−xLa(Mg1/2Ti1/2)O3 via Ordering and Far IR Reflectivity Spectra

Microwave dielectric properties of (1− x )(Na_1/2Nd_1/2)TiO₃(NNT)− x La(Mg_1/2Ti_1/2)O₃(LMT) system have been investigated with focus on structural ordering and far IR reflectivity spectra. A single perovskite phase was found to exist with various superlattice reflections over the entire compositional range. 1:1 ordering observed in the (111) reflection of X-ray diffraction patterns was found to progress significantly in the specimens above x =0.8. The ordering characteristics that presumably related to B-site Mg/Ti ordering were assumed to affect favorably the quality factor at microwave frequencies. The increase of the quality factor also could be explained in terms of the decrease of lattice anharmonicity with LMT by analysis of far IR reflectivity spectra. As expected from the values of pure NNT and LMT, the dielectric constant and the temperature coefficient of frequency tended to gradually decrease with increasing LMT content.     

Enhanced surface morphologies of screen-printed carbon nanotube films by heat treatment and their field-emission properties

A heating process for obtaining free-standing carbon nanotube emitters is presented with the aim of improving field-emission properties from the screen-printed multiwalled carbon nanotube (MWCNT) films. Using an atmosphere with an optimum combination of nitrogen and air for heat treatment of CNT films, the CNT emitters can be made to protrude from the surface. This allows for a high emission current and the formation of very uniform emission sites without special surface treatment. The morphological change of the CNT film by this technique has eliminated additional processing steps, such as surface treatment which may result in secondary contamination and damage to the film. Despite its simplicity the process provides a high reproducibility in emission current density which makes the films suitable for practical applications.     

Thermodynamic Analysis of Chemical Vapor Deposition of BN + AIN Composite Coatings

Thermodynamic calculations were performed using a modified solgasmix-pv computer program in order to study the feasibility of codepositing boron nitride (BN) plus aluminum nitride (AIN) by chemical vapor deposition. Reactants considered were AICl₃, BCl₃ or B₂H₆, NH₃, and H₂. Deposition diagrams were generated for the BCl₃-AICl₃-NH₃ system over a range of processing conditions such as temperature, total system pressure, and reagent concentrations. Codeposition of BN + AIN was predicted by the calculations for temperatures in the range of 900 to 1700 K and pressures of 10.13 to 101.3 kPa. The predicted deposition efficiency at equilibrium was much higher for BN than for AlN at most reagent compositions. The AlN deposition efficiency increased with decreasing temperature and decreasing BCl₃ content, with increasing NH₃ content, or with the addition of H₂. Aluminum chlorides were found to be the dominant gaseous species.     

Desulfurization in a plate-type gas-lift photobioreactor using light emitting diodes

Hydrogen sulfide gas was removed in a 2-dimensional gas-lift reactor by the photosynthetic microorganismChlorobium thiosulfatophilum using light emitting diodes (LEDs) as a light source. LEDs saved light energy by 99% compared with the incandescent light source. The plate-type gas-lift reactor removed hydrogen sulfide five times better per unit mg of protein, and performed two times better in the maximum performance per unit luminous flux, compared with cylindrical fermentors.