Design of fluidized bed photoreactors: Optical properties of photocatalytic composites of titania CVD-coated onto quartz sand

Volumetric optical properties (spectral absorption, scattering and extinction coefficients) of differently expanded narrow-path fluidized beds (FB) of a photocatalyst obtained by plasma-CVD deposition of titania onto quartz sand, relevant for photoreactor design purposes, are determined by using an unidirectional and unidimensional (1DD) model for the solution of the radiative transfer equation (RTE). Two simplified approaches are used: a Kubelka-Munk (KM) type of solution, by which the RTE is transformed into a pair of ordinary differential equations, and a discrete ordinate method (DOM) by which the complete RTE is transformed into an algebraic system that can be solved computationally. The second approach was validated by introducing the obtained optical parameters into a more elaborated bi-directional and two-dimensional (2DD) DOM model. Despite its simplicity, the KM method was able to yield fair order-of-magnitude estimates of the spectral optical properties of these FB.     

Steady state multiplicity depending on coalescence in liquid—liquid continuous stirred reactors with reaction in the dispersed phase

The influence of drop coalescence and breakup on the existence of multiple steady states is studied for a two-phase stirred isothermal reactor where the chemical reaction in the d?ispersed phase obeys the rate expression ? r = kC/(1 + KC)². The random coalescence model developed by Curl was simulated using a modified Spielman and Levenspiel Monte Carlo technique.For certain range of the coalescence rate, Damköhler number, and dimensionless feed concentration, multiple steady states have been investigated.A special case has also been considered wherein the existence of multiple steady states for finite values of the coalescence rate is contrasted to the unique steady state solution for an infinite coalescence rate.     

Styrene-butadiene branched star-shaped asphalt modifiers: Synthesis and mechanical characterization

Abstract

The synthesis and the corresponding characterization of styrene-butadiene (SB), branched, star-shaped copolymers was investigated as part of a research project on asphalt modification using polymers with precise molecular structures. The method of anionic polymerization was followed to prepare samples of block copolymers of SB, a synthesis method that controls chain-architecture, molecular weight distribution, monomer distribution, and the average molecular weight. The research studies are the synthesis of block copolymers including linear, three- and four-arms constructs, depending on the coupling agent used. The techniques of nuclear magnetic resonance (1NMR), differential scanning calorimetry (DSC), gel permeation chromatography (GPC), and rheology were carried out to characterize the copolymers. From the results of the 1NMR, DSC, and GPC analyses, all star-shaped copolymers investigated showed a similar block copolymer composition. Furthermore, the rheological behavior of one of the synthesized star-shaped copolymers was nearly the same as a four-branched commercial copolymer. Rheologically, the four-arm block copolymer sample had the largest storage modulus (G′) among the branched copolymers synthetized, indicating that such architecture produces a highly structured material. In regard to polymer-modified asphalt formulations, the three-branched copolymer architecture yielded better elastic behavior than the four-branch version. In summary, the findings of this investigation provide new insight about a polymer system that may offer advantages in industrial asphalt paving applications.     

Resolution proof transformation for compression and interpolation

Verification methods based on SAT, SMT, and theorem proving often rely on proofs of unsatisfiability as a powerful tool to extract information in order to reduce the overall effort. For example a proof may be traversed to identify a minimal reason that led to unsatisfiability, for computing abstractions, or for deriving Craig interpolants. In this paper we focus on two important aspects that concern efficient handling of proofs of unsatisfiability: compression and manipulation. First of all, since the proof size can be very large in general (exponential in the size of the input problem), it is indeed beneficial to adopt techniques to compress it for further processing. Secondly, proofs can be manipulated as a flexible preprocessing step in preparation for interpolant computation. Both these techniques are implemented in a framework that makes use of local rewriting rules to transform the proofs. We show that a careful use of the rules, combined with existing algorithms, can result in an effective simplification of the original proofs. We have evaluated several heuristics on a wide range of unsatisfiable problems deriving from SAT and SMT test cases.     

Catalytic hydrogenation of nitrile rubber using palladium and ruthenium complexes

The catalytic hydrogenation of acrylonitrile‐butadiene copolymer (nitrile rubber, NBR) using Pd(OAc)₂ or RuCl₂(PPh₃)₃ catalysts has been investigated in order to produce a totally saturated nitrile rubber. The hydrogenation of NBR is effective with both catalysts and achieved total conversion under the appropriate reaction conditions. In the case of palladium the effects of reaction parameters such as reaction temperature, pressure, time, catalyst concentration, and NBR concentration have been investigated. Even though both ruthenium‐ and palladium‐based catalysts are effective in the production of HNBR, the former requires harsh reaction conditions and has the drawback of gel formation under high conversion, motivating the migration to RuCl₂ (PPh₃)₃ as an alternative catalyst. The degree of hydrogenation was determined by IR and NMR spectroscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effects of preparation conditions on the surface modification and performance of polyethersulfone ultrafiltration membranes

The impact that some membrane preparation steps had on ultrafiltration (UF) membrane characteristics and performance was studied. Polyethersulfone (PES) was employed as base polymer, while N‐methyl pyrrolidone (NMP) was used as a solvent, and polyvinylpyrrolidone (PVP) was used as a nonsolvent pore‐forming additive. The manufacturing variables studied were solvent evaporation time and membrane surface modification, using a fluorine‐based copolymer referred to as surface‐modifying macromolecule (SMM). The flat sheet membranes, prepared via phase inversion, were characterized using solute transport data, X‐ray photoelectron spectroscopy (XPS), and contact angle measurements. Membrane performance was evaluated via filtration test protocol that included a 6‐day filtration of concentrated river water. The flux reduction with time was modeled using single and dual mechanisms of fouling. The pore blockage/cake filtration model described better the behavior of the permeation rate along the experiments. Increasing the solvent evaporation time decreased the size of the pores and the permeation rate. However, it did not significantly affect the removal of the organic compounds naturally present in the river water used as feed. XPS and contact angle measurements proved that the short evaporation periods did not allow enough SMM migration to the surface to provoke a significant effect on the membrane performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Optimal Operating Conditions For Lab-Scale Ozonation Reactors

A method for the assessment of the optimal operating conditions for a mechanically stirred gas–liquid reactor is presented. The method exploits both fluid dynamic and chemical information. First, the behavior of the specific stirring power as a function of the stirrer speed allows singling out the dispersion region, in which the most efficient gas–liquid mass transfer is achieved. Inside this region, the analysis of experimental data obtained when considering a chemical system reacting at moderate Hatta numbers (i.e., Ha < about 2) allows determination of the rate constants and the fluid dynamic parameters (i.e., the mass transfer coefficient in the absence of chemical reaction and the characteristic diffusion time).     

ALKYD PAINT WASTE CHARACTERIZATION AND DISTILLATION

In the present study the characterization and distillation of alkyd paint waste have been carried out in order to establish the technical viability of organic solvents recovery and to decide upon the best environmental management for the waste stream from a paint spray-booth application in an automotive component factory. The paint is a black primer based on an alkyd resin with toluene and xylene as solvents, black carbon as pigment, fillers, and other minor components.

The paint, paint wastes, and distillation wastes have been characterized by determination of the physicochemical properties of the solid (solvents content and flash point) and determination of ecotoxicity (EC₅₀), total organic carbon (TOC), and metals concentration of the leachates. The highly volatile matter (HVM) content, determined by the weight loss at 200°C, has been used as a parameter to relate with the hazardous wastes regulations based on the characterization parameters EC₅₀, TOC, and flash point.

Distillation experiments have been performed in a simple batch mode with mixtures of paint waste, water, and additives in order to obtain high efficiencies in the recovery of volatile organic compounds and to obtain a final solid with nonhazardous behavior and good manageability qualities. A fractional factorial design (2^3-1) of experiments was carried out in order to study the influence of the distillation variables: water/paint waste ratio (2/1-3/1 (g/g)), temperature (110°-145°C), alkaline additives (Na(OH),CaO, Ca(OH)₂), and amount of other additives (wt.% of bentonite, cement, and Ca(OH)₂) on the solvent recovery, [% VOCs]_Recovery, on the residual volatile organic compounds, [% VOCs]_{Distillation Waste}, and on the total organic content (TOC) of the waste leachates. The present work shows the quantitative results of the alkyd paint waste distillation process under optimum conditions.     

Kinetic modeling of pentachlorophenol adsorption from aqueous solution on activated carbon fibers

The adsorption equilibrium data of pentachlorophenol (PCP) onto activated carbon fiber (ACF) in felt form were obtained in a batch adsorber at T = 25 °C and pH 12 and the Langmuir isotherm fitted reasonably well with the experimental data. The rate of adsorption of PCP on ACF was investigated in this work and the experimental concentration decay data were obtained in a differential column batch adsorber. The overall rate of adsorption of PCP was interpreted by a diffusional model that takes into account the external mass transport and intrafiber diffusion. The experimental concentration decay can be described quite well with the diffusional model if the overall rate of adsorption is mainly controlled by intrafiber diffusion and the external mass transport is not important to the overall rate of adsorption. Moreover, intrafiber diffusion was significantly affected by restricted diffusion since the molecular diameter of the PCP was closed to 55% of the average pore diameter. The effect of restricted diffusion was estimated using correlations reported in the literature. The molecules of PCP adsorbed on the surface of the pore also hindered the diffusion of PCP molecules inside the pores.