Parametric sensitivity and runaway in chemical reactors

In certain regions of operating conditions, chemical reactors may exhibit parametric sensitivity; i.e., small changes in one or more of the reactor input parameters lead to much larger changes in the output variables. Since such behaviour leads to deleterious performance, it is of practical interest to identify regions of parametric sensitivity in the reactor parameter space. Until recently, this could be done only to describe thermal runaway, and only for those systems where a temperature profile could be defined. Both of these limitations can be removed by consideringthe generalized criterion for parametric sensitivity, whereby sensitivity ofany output of the model toany input can be treated. Applications of the generalized criterion are discussed, with specific examples including pseudohomogeneous and heterogeneous model tubular reactors, a nonisothermal CSTR, and a polymerization reactor. Dedicated to Dr L K Doraiswamy — Gentleman, Scholar, Friend — on his sixtieth birthday.     

Microwave-assisted photochemical reactor for the online oxidative decomposition and determination of p-hydroxymercurybenzoate and its thiolic complexes by cold vapor generation atomic fluorescence detection

We developed a photochemical method for the online oxidation of p-hydroxymercurybenzoate (PHMB), an organic mercury species widely used for mercaptan and thiolic compound labeling. The method is based on a fully integrated online UV/microwave (MW) photochemical reactor for the digestion of PHMB, followed by cold vapor generation atomic fluorescence spectrometry (CVG-AFS) detection. The MW/UV process led to the quantitative conversion of PHMB and thiol-PHMB complexes to Hg(II), with a yield between 91% and 98%, without using chemical oxidizing reagents and avoiding the use of toxic carcinogenic compounds. This reaction was followed by the reduction of Hg(II) to Hg(0), performed in a knitted reaction coil with NaBH(4) solution, and AFS detection in an Ar/H(2) miniaturized flame. The low MW power applied (18 W) allowed us to keep constant the temperature of the photochemical reactor (21 ± 1 °C), using a flowing water bath. This avoided peak widening due to diffusion processes generally occurring at high temperatures and in the additional cooling coil. This method has been applied to the determination of thiols in human plasma, blood, and wine.     

New Approach to Water Distribution Network Calibration

A new approach is proposed for calibrating hydraulic network models. This procedure uses a nonlinear optimization algorithm along with a standard, off-the-shelf, network solver. Pipe roughness is adjusted until simulation results agree with the values observed in the field. To achieve realistic calibrated roughness values, the objective is to minimize the sum of the squares of the differences between the calibrated and initial pipe roughness estimates, under a set of constraints determined from a sensitivity matrix. The algorithm is applied to a sample network, and the resulting calibrated network is tested under different loading conditions.     

Connections for composite concrete slab and LVL flooring systems

Composite concrete slab and timber flooring systems are commonly used in many parts of the world to exploit the high strength-to-weight ratio of timber and the good acoustic separation provided by concrete floor slabs. This paper describes the results of an experimental programme that investigated the suitability of a range of connectors to transfer shear between a concrete slab and a laminated veneer lumber (LVL) beam. Shear tests on reduced scale specimens were performed with the aim of comparing the strength, stiffness, and post-peak performance of different connectors such as round and rectangular concrete plugs with and without screw and steel pipe reinforcement, proprietary (SFS) screws, coach screws with different diameters, sheet brace anchors, and framing brackets. The rectangular concrete plug reinforced with a coach screw was found to provide the greatest stiffness and strength, as well as favourable post-peak behaviour. Such a system can be used for cost-effective composite floor systems due to its efficient cost-to-capacity ratio, which reduces the number of connectors needed along the beam axis to achieve the composite action.     

Low-enthalpy geothermal energy: An opportunity to meet increasing energy needs and reduce CO2 and atmospheric pollutant emissions in Piemonte,Italy

The scope for diffusion of very low-enthalpy geothermal plants in the Piemonte region of Italy, using groundwater heat pumps (GWHP), was analyzed to check environmental sustainability and the benefits in terms of reducing greenhouse gas emissions from fossil fuels. GWHP implementation seemed particularly suitable to the specific characteristics of the Piemonte plain. An important thick and productive shallow aquifer is present across the entire plain beneath the major energy users and is therefore appropriate for geothermal energy development purposes. The building stock could be adapted to heat pumps in different ways, but objective-oriented policies will be required to reach the best results in terms of environmental benefits.     

Morphology and electrochemical activity of SOFC composite cathodes: II. Mathematical modelling

This paper presents a mathematical model of mass and charge transport and electrochemical reaction in porous composite cathodes for application in solid oxide fuel cells. The model describes a porous composite cathode as a continuum, and characterises charge and mass transfer and electrochemical kinetics using effective parameters (i.e. conductivity, diffusivity, exchange current) related to morphology and material properties by percolation theory. The model accounts for the distribution of morphological properties (i.e. porosity, tortuosity, density of contacts among particles) along cathode thickness, as experimentally observed on scanning electron microscope images of LSM/YSZ cathodes of varying thickness. This feature allows the model to reproduce the dependence of polarisation resistance on thickness, as determined by impedance spectroscopy on LSM/YSZ cathodes of varying thickness. Polarisation resistance in these cathodes is almost constant for thin cathodes (up to 10 μm thickness), it sharply decreases for intermediate thickness, to reach a minimum value for about 50 μm thickness, then it slightly increases in thicker cathodes.