Optimization of a multiperiod refinery planning problem under uncertainty

Uncertainty in refinery planning presents a significant challenge in determining the day-to-day operations of an oil refinery. Deterministic modeling techniques often fail to account for this uncertainty, potentially resulting in reduced profit. The stochastic programming framework explicitly incorporates parameter uncertainty in the problem formulation, thus giving preference to robust solutions. In this work, a nonlinear, multiperiod, industrial refinery problem is extended to a two-stage stochastic problem, formulated as a mixed-integer nonlinear program. A crude-oil sequencing case study is developed with binary scheduling decisions in both stages of the stochastic programming problem. Solution via a decomposition strategy based on the generalized Benders decomposition (GBD) algorithm is proposed. The binary decisions are designated as complicating variables that, when fixed, reduce the full-space problem to a series of independent scenario subproblems. Through the application of the GBD algorithm, a feasible mixed-integer solution is obtained that is more robust to uncertainty than its deterministic counterpart.     

Enhancing laccase stability and activity for dyes decolorization using ZIF-8@MWCNT nanocomposite

The continuous use of chemical dyes in various industries, and their discharge into industrial effluents, results in severe problems to human life and water pollution. Laccases have the ability to decolorize dyes and toxic chemicals in industrial effluents as green biocatalysts. Their possible industrial applications have been limited by poor reusability, low stability, and loss of free laccase action. In this research, laccase was immobilized on zeolitic imidazolate framework coated multi-walled carbon nanotubes (Laccase@ZIF-8@MWCNTs) via metal affinity adsorption to develop an easy separable and stable enzyme. The optimum reaction conditions for immobilized laccase are at a pH of 3.0 and a temperature of 60?℃. The immobilized laccase was enhanced in storage and thermal stability. The results indicated that Laccase@ZIF-8@MWCNTs still maintained 68% of its original activity after 10 times of repeated use. Most importantly, the biocatalytic system was applied for decolorization of different dyes (20?mg·L^?1) without a mediator, and up to 97.4% for Eriochrome black T and 95.6% Acid red 88 was achieved in 25 min. Biocatalysts with these properties may be used in a variety of environmental and industrial applications.     

A new Lagrangian decomposition approach applied to the integration of refinery planning and crude-oil scheduling

The aim of this paper is to introduce a methodology to solve a large-scale mixed-integer nonlinear program (MINLP) integrating the two main optimization problems appearing in the oil refining industry: refinery planning and crude-oil operations scheduling. The proposed approach consists of using Lagrangian decomposition to efficiently integrate both problems. The main advantage of this technique is to solve each problem separately. A new hybrid dual problem is introduced to update the Lagrange multipliers. It uses the classical concepts of cutting planes, subgradient, and boxstep. The proposed approach is compared to a basic sequential approach and to standard MINLP solvers. The results obtained on a case study and a larger refinery problem show that the new Lagrangian decomposition algorithm is more robust than the other approaches and produces better solutions in reasonable times.     

New huprine derivatives functionalized at position 9 as highly potent acetylcholinesterase inhibitors

A series of 24 huprine derivatives diversely functionalized at position 9 have been synthesized and evaluated for their inhibitory activity against human recombinant acetylcholinesterase (AChE). These derivatives were prepared in one to five steps from huprine 1 bearing an ester function at position 9. Ten analogues ( 1 , 2 , 6 – 9 , 13 – 15 , and 23 ) are active in the low nanomolar range (IC₅₀ <5 nM ), very close to the parent compound huprine X. Compounds 2 , 6 , and 7 show a very good selectivity for AChE, with AChE inhibitory activities 700–1160‐fold higher than those for butyrylcholinesterase (BChE). The inhibitory potency of these compounds decreases with the steric bulk of the substituents at position 9. According to docking simulations, small substituents fit into the acyl‐binding pocket, whereas the larger ones stick out of the active site gorge of AChE. Determination of the kinetic parameters of three of the most potent huprines ( 2 , 6 , and 7 ) showed that most of the difference in K_D is accounted by a decrease in k_on, which is correlated to the increase of the substituent size. A first in vivo evaluation has been performed in mice for the most active compound 2 (IC₅₀=1.1 nM ) and showed a rather weak toxicity (LD₅₀=40 mg kg^?1) and an ability to cross the blood–brain barrier with doses above 15 mg kg^?1.     

Synthesis of ‘ready-to-adsorb’ polymeric nanoshells for magnetic iron oxide nanoparticles via atom transfer radical polymerization

Polymer-magnetite nanoparticle complexes that respond to both magnetic fields and to temperature have been demonstrated. Novel alkyl halide-functional bis(diethylphosphonate) esters were prepared and utilized as initiators for polymerizing N-isopropylacrylamide by controlled atom transfer radical polymerization. The phosphonate esters were removed after polymerization to afford poly(N-isopropylacrylamide) with a bis(phosphonic acid) moiety precisely placed at one terminus. The bis(phosphonic acid) endgroups were adsorbed onto magnetite nanoparticles to yield nanoscale complexes that were stable against any polymer desorption and that were colloidally-stable in physiological media. Thus, the bis(phosphonate) endgroup provides a robust anchoring moiety onto the magnetite. Hydrodynamic sizes of the complexes were predicted with a density distribution model and using the measured sizes of the magnetite cores. Good agreement between the measured and predicted hydrodynamic sizes suggested that the complexes were primarily discrete, non-agglomerated nanoparticles. The complexes exhibited thermosensitive aggregation behavior near the lower critical solution temperature of the poly(N-isopropylacrylamide) component.     

Improvement of the growth of Arthrospira (Spirulina) platensis from Toliara (Madagascar): Effect of agitation, salinity and CO2 addition

Arthrospira (Spirulina) platensis Toliara isolated from alkaline and salt lakes in the south-western area of Madagascar is a potential source of proteins that could efficiently fight against food deficiency in developing countries like Madagascar. Up to now, productivity in this country has been low, so a better understanding of the growth conditions of this species is needed to improve its production. Growth experiments were undertaken in bubble columns at laboratory scale. The influence of agitation of the culture, medium salinity (ranging from 13 to 35 g L⁻¹) and CO₂ addition (ranging from 0 to 2%, v/v) on growth and protein content was examined. Because Arthrospira cells are fragile, a bubble column without additional mixing gave the best growth. Arthrospira (Spirulina) platensis showed higher specific growth rate (μ_max) and protein content for lower salinity. Addition of 1% of CO₂ improved the productivity by near 60%. The feasability of semi-continuous culture was demonstrated and optimal culture conditions led to a mean productivity of 0.22 ± 0.03 g L⁻¹ d⁻¹, a mean specific growth rate of 0.015 ± 0.002 h⁻¹ and a protein content of 53 ± 2% of total dry weight.     

Effect of addition of nanosized UV absorbers on the physico-mechanical and thermal properties of an exterior waterborne stain for wood

This study describes the effects of the addition of inorganic nanosized UV absorbers on physico-mechanical and thermal properties of an exterior commercial acrylic-based waterborne stain for wood. Electronic microscopy and water vapor (WV) permeability measurements were performed to characterize the free films of the acrylic stain and resulting nanocomposite coatings. An accelerated weathering method was used to evaluate aging behavior of the coatings on wood through appearance, T_g, abrasion resistance, adhesion strength, hardness and Young's modulus changes. In addition to improving the protection against UV, the doped TiO₂ and silica-coated ZnO nanoparticles in powder form have improved the abrasion resistance and barrier effect against water vapor diffusion of the acrylic stain. For most of nanocomposite coatings, the addition of ZnO hydrophilic nanoparticles in predispersed form has resulted in a decrease in WV permeability, while the adhesion strength and abrasion resistance of those coatings were negatively affected. The addition of ZnO nanoparticles has decreased the T_g of the acrylic stain. Finally, the accelerated weathering has induced an increase in T_g, hardness, Young's modulus (stiffness) and an increase in apparent adhesion strength and abrasion resistance of the coatings. The T_g values of the aged nanocomposite coatings were lower than that of unmodified acrylic stain.     

Potential of ionic liquids for VOC absorption and biodegradation in multiphase systems

This work aims to evaluate the feasibility of using imidazolium ionic liquids (ILs) in the design of multiphase bioreactors for the removal of volatile organic compounds (VOCs). The IL affinity for three model VOCs (dimethyl sulfide, dimethyl disulfide and toluene) was evaluated by means of the dimensionless partition coefficient (K). It was observed that ILs showed K values comparable to typical liquid solvents used in multiphase bioreactors for VOC biodegradation (K values ranged from 0.009 to 0.011, 0.0012 to 0.0013 and 0.00061 to 0.00096 for dimethyl sulfide, dimethyl disulfide and toluene, respectively). Toxicity tests showed that both ILs at concentrations of 5% and 10% (v/v) inhibited the glucose uptake of an activated sludge during approximately 24 h. After such lag period, the microorganisms were able to recover its metabolic activity. However, VOC biodegradation experiments showed that ILs at 5% (v/v) were toxic for the activated sludge and a toxic synergistic effect of the IL–VOC combination likely occurred. After acclimation to the target VOCs, only the toluene biodegradation capacity was significantly increased in the presence of ILs. These toxic effects represent a key drawback for the potential of IL-based multiphase systems devoted to VOC biodegradation. Therefore, this study suggests that microbial acclimation only to the VOCs is not enough to get an efficient biodegradation in multiphase systems including ILs as non-aqueous phases.     

Modelling the solubility in Bayer liquors: A critical review and new models

An accurate and tractable model of solubility is a pre-requisite for any careful study of precipitation. Reviewing the abundant literature on the sodium aluminate solutions and Bayer Liquor, the authors point out the need for a new model for the apparent solubility of aluminium in actual Bayer Liquors and propose such a model, based on the well established Wesolowski's expression for the infinite dilution solubility and extended Debye–Hückel expression including a large empirical b I term for the “activity coefficient effect”. They suggest a chemical interpretation for this feature.     

A comparative and mechanistic study on regioselective photooxidative demethylation of N‐heterocyclics using TiO2 and molecular oxygen

Regioselective photooxidative demethylation of methyl‐substituted N‐containing heterocyclic compounds is investigated in non‐aqueous (ethane nitrile) solutions containing semiconductor oxide (TiO₂) as photocatalyst in the presence of molecular oxygen upon irradiation at room temperature conditions. A plausible electron transfer mechanism, in which an electron‐hole pair is generated on the surface of TiO₂ by illumination, is proposed for the semiconductor‐mediated photocatalysis. Molecular orbital calculation by the AM 1 method has been performed for the electron densities of N‐atoms of heterocyclics in the present study. © 2002 Society of Chemical Industry