Understanding selective oxidations

Functionalizing organic molecules is an important value-creating step throughout the entire chemical value-chain. Oxyfunctionalization of e.g. C-H or C=C bonds is one of the most important functionalization technologies used industrially. The major challenge in this field is the prevention of side reactions and/or the consecutive over-oxidation of the desired products. Despite its importance, a fundamental understanding of the intrinsic chemistry, and the subsequent design of a tailored engineering environment, is often missing. Industrial oxidation processes are indeed to a large extent based on empirical know-how. In this mini-review, we summarize some of our previous work to help to bridge this knowledge gap and elaborate on our ongoing research.     

Soil water erosion on road embankments in eastern Spain

Road embankments erosion is a serious problem in Spain. By means of simulated rainfall experiments (45 mm h(-1) during one hour on 0.41 m(2) plots) soil and water losses were measured on five road embankments located on the SW of the Valencia province, Spain. The bare road embankments, still under construction, contributed with 30 times more soil erosion than the vegetated ones. The measurements here presented demonstrate that road embankments are an important source of sediments, especially during the construction works, and it is recommended that restoration works should be undertaken after the road construction to reduce sediment removal, protect the road and avoid traffic accidents.     

Characterization of precipitates formed in X7R 0603 BME-MLCC during sintering

In the current study two different batches of X7R-0603 BME-MLCCs displayed dissimilar electrical performance, despite having the same chemical composition, tape casting, and sintering conditions; with the only difference between them being the ore deposits where the raw materials were extracted from to synthesize the BaTiO₃. Specifically, they presented different electrical response to highly accelerated life tests (HALT). Although the chemical analysis of each slip showed the same composition, the trace elements of the BaTiO₃ sources could have acted as dopants or produced different secondary phases. A search for precipitates in the two samples was conducted by means of Scanning (SEM) and Transmission Electron Microscopy (TEM) techniques. SEM observations confirmed the presence of precipitates formed within the structure of the MLCCs exhibiting the greatest decrement in their electrical resistance results during the HALT. In order to further characterize the observed precipitates, samples were prepared by Focused Ion Beam (FIB) lift-out method, to make TEM characterization of specific precipitates feasible. TEM studies were performed on the precipitates to obtain electron diffraction patterns and complementary Energy Dispersive X-Ray Spectroscopy (EDXS) chemical analysis. Based on the crystal and chemical data obtained, it can be concluded that the precipitates are a hexagonal anhydrous silicate oxyapatite phase with a stoichiometry of Ca₃Y₁₆Si₁₀O₁₃, and lattice parameters of a = 0.9353 nm and c = 0.6970 nm; this phase was not found in the JCPDS data base. Differences in raw materials coming from different ore deposits can produce undesired precipitates that affect the electrical performance of MLCCs.     

Long-Chain-Amine Metal Complexes as Hydrogenation Catalysts. Heterogenisation on Activated Carbon

The catalytic activity of [PdCl₂(NH₂(CH₂)₁₂CH₃)₂] (named [Pd(TDA)]) and [RhCl(NH₂(CH₂)₁₂CH₃)₃] (named [Rh(TDA)]) complexes for the hydrogenation of cyclohexene has been analysed both in homogeneous phase and heterogenised on activated carbon. The [Rh(TDA)] complex has been found to be more active than the [Pd(TDA)], both homogeneous and heterogenised. Experimental and modelled results indicate that these complexes follow a similar reaction mechanism, but with different rates. A clear positive effect of the carbon support has been found in the case of the complex [Rh(TDA)], which has been related to the anchorage of the aliphatic chains of the amine ligands on the activated carbon pores. Experiments in consecutive catalytic runs show that the heterogenised complexes can be used several times giving an acceptable conversion level.     

Modeling the effect of a superabsorbent polymer material as desiccant in maize drying using CFD

Maize is an important foodstuff in many countries, and one of most susceptible crops to mold and aflatoxin contamination, which results in considerable postharvest losses and is a burden to consumers’ health, especially in developing countries. The timely drying of harvested maize is essential to halt mold development, ensuring safe storage. The effect of the incorporation of a superabsorbent polymer (SAP) as desiccant in a maize dryer was studied using computational fluid dynamics simulations which accounted for heat and mass transfer between maize, SAP and air. The adsorption capacity and adsorption rate of a commercial SAP material were experimentally determined at different temperature and relative humidity levels, which served as basis for the adsorption model required in the simulations. A maize bulk with SAP packages distributed in it was modeled. Results showed that the SAP material increases the drying rate substantially, particularly in the upper bulk zone where the air reaching it is dehumidified the most. The maize closer to the upper bulk surface starts drying from the beginning of the process instead of lagging for hours or days before the drying front reaches it. An inconvenience of the SAP material is the tendency of granules to swell and stick together as moisture reaches a threshold, which may reduce its performance. Thus, provided this issue is resolved or minimized, SAP materials could successfully assist the rapid drying of maize and other crops. They may also be used during storage to avoid rewetting of the crops during periods of high relative humidity.     

Responses of Hexaplex (Murex) trunculus to selected pollutants

We report the results of a recent survey of the concentration of natural estrogens (17beta-estradiol, 17alpha-estradiol, estrone, estriol) and the synthetic estrogen, 17alpha-ethynylestradiol in representative animal wastes and sewage treatment plant (STP) effluents in the Waikato region of New Zealand. Dairy farm effluent samples showed high levels of estradiol (19-1360 ng/L) and its breakdown product estrone (41-3123 ng/L) compared with piggery or goat farm effluents. The combined load for these estrogens (excluding beta epimer) varied from 60 to >4000 ng/L. The piggery effluent provided the lowest total estrogen load (46 ng/L), with estrone accounting for nearly 60% of the measured estrogens in this sample. The synthetic analogue, 17alpha-ethynylestradiol was detected only in one wastewater treatment plant sample, albeit at trace level. An estrogen receptor competitive binding assay was used to test the biological activity of the samples and confirmed that most agricultural waste samples contain high levels of estrogenic compounds. The potential of these wastes to cause endocrine disruption in the receiving ecosystem is unknown at present.     

Heavy metal bioaccumulation and macroinvertebrate community changes in a Mediterranean stream affected by acid mine drainage and an accidental spill (Guadiamar River, SW Spain)

In the 1998 Aznalcóllar mining accident, 5 million cubic meters of toxic waste were spilled into the Guadiamar River (SW Spain). This paper describes the likely effects of metal pollution on the macroinvertebrate community in the first 15 km of the river adjacent to the mine, 2 years after the spill. The contents of Zn, Cu, Pb, As, Cd, Tl, and Sb in water, sediment, and in the caddisfly Hydropsyche were analysed, together with some physico-chemical parameters. From the results of physico-chemical and community parameters, the studied area was divided into three sections: the first section contained upstream control stations, not affected by current mining activities, and with a diverse macroinvertebrate community structure (mean number of families = 19); the second section, close to the mine, was severely polluted, with more than 50 mg l(-1) of Zn or 1.6 mg l(-1) of Cu in water, a pH of nearly 4, and a very diminished macroinvertebrate community (three families); in the last section, 6-15 km downstream from the mine, the water quality improved, metal concentrations decreased, pH reached neutrality and the macroinvertebrate community comprised eight families. We also determined metal concentrations in the larvae of Hydropsyche and found increases of 3- to 35-fold (for Cu and Cd, respectively) compared to control sites. As far as we are aware, these values are the highest concentrations so far detected in this caddisfly anywhere in the world. Different patterns of metal and pH tolerance were identified in macroinvertebrates. Most of the species were intolerant to present pollution levels and were only present in control sites. Others were tolerant to metal pollution but not to low pH and were present in the main river downstream of the mine, while a very few species managed to live in the most polluted section, with very low pH and high metal concentrations.     

Air and HST Multimodal Products. A Segmentation Analysis for Policy Makers

Different solutions for the integration of high-speed rail (HSR) and air transport could be implemented, ranging from very basic integration to more sophisticated systems that include ticket and handling integration. This paper uses two statistical techniques, name cluster analysis and discrete choice models in order to investigate how different market segments have a determining influence in being more proactive to change to HSR for the second leg in multimodal trips. A discrete choice experiment is conducted to better understand passengers’ preferences. We obtain a number of clusters and estimate flexible choice models, taking into account the panel nature of stated preference data. We obtain a range of willingness-to-pay values for service quality attributes, finding results that can be used to infer policy conclusions about the real attractiveness of the Air-HSR integrated alternative. In this respect, clusters and schedule coordination, which reduces connecting time, are crucial to explain HSR attractiveness.     

Optimal channel coordination in use-based product-service system contracts

Nowadays, service economy efficiencies are key to keep competitiveness and increase market advantages. The development of Product-Service Systems (PSS) can be an interesting strategy as they seek to improve the business performance of all the participants in the value chain. This paper proposes a novel reliability-based reward scheme for use-oriented PSS contracts. In a PSS instead of paying for the product, the client pays a fee for its performance. The contribution of this work to the existing literature is to provide a quantitative tool for the development of a use-oriented PSS contract based on non-repairable component reliability and risk sharing. It can be extended to other performance metrics such as availability and reliability. A well designed PSS achieves a mutual growth agreement for the client and the supplier if it aligns their interests through channel coordination. This is achieved by balancing the improvement in the expected cost and profit for the client and the supplier, respectively. The improvement is measured with respect to a baseline scenario where no PSS contract exists. The methodology is tested using a case study that analyses mining haul truck tires. The results show a significant overall improvement in the main key performance indicators and environmental impact of the value chain.     

Probabilistic linear models for multiresolution estimation in gray-level images

A multiresolution analysis of digital gray-level images is presented. A gray-level multi-scale framework is determined from two main assumptions: the gray scale is binary at the finest spatial resolution, and the gray levels of composed regions are obtained additively. In order to interrelate the gray-level histograms of the same image at different resolutions, probabilistic linear models are developed, which are then applied for estimation. Linear-optimization theory is used as a way of constructing such models. A general procedure for image processing is sketched, based on gray-level estimation. A versatile algorithm for nonlinear filtering is derived. Some examples of prospective applications are given.This work was partially supported by grant TIC91-646 from the DGYCIT of the Spanish Government.