Industrial experience in the scale-up of reactive distillation with examples from C4-chemistry

The objective of this paper is to illustrate process design from the industrial point of view for a heterogeneous reactive distillation exemplified by the decomposition of MTBE. Based on thermodynamics a plausible column concept is suggested. Open questions concerning scale-up of structured catalytic packings are discussed on the basis of experiments in the lab and pilot plant scale. Lab scale experiments were modelled satisfactorily with an equilibrium stage approach. In order to perform the scale-up from lab to pilot scale with the equilibrium stage approach the reaction rate constant had to be reduced significantly. Incomplete catalyst wetting due to maldistribution effects or mass transfer phenomena might be possible reasons.     

Synthesis and Crystal Structure Characterization of Oxysilicate Apatites for Stabilization of Sr and Rare‐Earth Elements

Strontium (Sr) containing rare‐earth oxysilicate apatite A^I₄A^II₆(SiO₄)₆O₂ is considered a good matrix to accommodate radionuclide as its cation sites can incorporate lanthanide elements other than Sr. Here, we report a study on the synthesis of Nd₈Sr₂(SiO₄)₆O₂ and Yb₈Sr₂(SiO₄)₆O₂, which adopt P6₃/m apatite symmetry, as well as the characterization of crystallographic structures using X‐ray diffraction and electron microscopy. It is found that A^I position is shared by Nd, Yb and Sr, and A^IO₆ polyhedra are face‐connected, forming column structures, which are linked to SiO₄ tetrahedra, creating continuous channels. The Rietveld refinement shows that Nd and Yb prefer the A^II position in the channel. The twisted angle of adjacent triangle faces in an A^I‐O polyhedron along [001] is a critical parameter to identify the channel volume and its value varies when different cations are incorporated. The twisted angles for Nd‐apatite and Yb are 24.2° and 22.7° The findings provide a new insight into nuclear waste stabilization by apatite‐type structure.     

Process analysis and optimisation of hybrid processes for the dehydration of ethanol

Promising hybrid processes for ethanol dewatering consist of different combinations of distillation with adsorption and/or vapour permeation. This paper presents an analysis and optimisation of these hybrid processes using non-equilibrium models and an evolutionary algorithm. Four different membrane assisted configurations are compared with a benchmark process consisting of distillation and pressure swing adsorption. In total 12 cases were investigated while assuming different feed and product compositions at different production capacities: three ethanol mass fractions in feed 45, 80, 92 wt.%, two product purities 99.6, 99.95 wt.% and two production capacities 25,000, 250,000 m³/year. The influence of decisive operating and structural variables on important target variables such as total membrane area is demonstrated. Finally, the processes are evaluated regarding operating costs and energy consumption depending on product purity and production capacity. The operating costs of the membrane assisted configurations differ only in a small range of −3% to 6% from those of the benchmark. The energy consumption of the membrane assisted configurations without distillation is up to 30% lower compared to the benchmark. Especially the combination of vapour permeation and adsorption is a promising alternative allowing for producing ethanol with high purities at lower operating pressures compared to the vapour permeation as stand alone process.     

Oxygen Vacancy Relaxation and Domain Wall Hysteresis Motion in Cobalt-Doped Barium Titanate Ceramics

Mechanical and dielectric loss measurements were carried out in the BaTiO₃ ceramics doped with Co at frequencies between 0.01 Hz and 1 MHz as a function of temperature from −150° to 150°C. The relaxation peak observed in the ferroelectric phase with an activation energy of 0.27 eV is assumed to be related to the motion of oxygen vacancies. This peak could be because of the reorientation of an electrical dipole made of oxygen vacancies and Co³⁺ ions in the lattice. Furthermore, another loss peak located just below the Curie temperature T _c could be interpreted as hysteretic motion of the domain walls in a regime where the domain wall density is changing.     

Templated Pt-Sn electrocatalysts for ethanol, methanol and CO oxidation in alkaline media

In this work, we have investigated an aerosol-derived templated electrocatalyst for electro-oxidation of small organic molecules in alkaline media. Templated Pt-Sn electrocatalysts are compared to templated Pt catalysts both synthesized in an aerosol synthesis technique. In this synthesis approach, mono-disperse silica nanoparticles are used to template the metallic precursors. Structural and compositional analysis of the nanostructured materials are performed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and BET surface area measurements. The aerosol-derived templated electrocatalysts are examined in conjunction with an anion exchange ionomer for ethanol, methanol and CO oxidation in alkaline media. The electrochemical studies include cyclic voltammetry, chronoamperometry and voltammetric adsorption of adsorbed CO.     

Homology Model Adjustment and Ligand Screening with a Pseudoreceptor of the Human Histamine H4 Receptor

A new pseudoreceptor modeling method (PRPS) was applied to the refinement of a homology model of the human histamine H₄ receptor (H₄R), the prediction of a ligand binding site, and virtual screening. Retrieval of two new H₄R ligands demonstrates the biological relevance of the pseudoreceptor model and provides a means for finding new hits and leads in the early phases of drug discovery.

     

Growth and characterization of tetragonal bismuth ferrite–lead titanate thin films

Thin films of tetragonal bismuth ferrite–lead titanate (1 − x)BiFeO₃–xPbTiO₃ with x = 0.9–0.7 were prepared by pulsed laser deposition (PLD). The films exhibit a dense columnar grain growth. XRD analysis reveals that the films have a perovskite structure and exhibit a preferred (1 1 1) texture. The film microstructure was studied using SEM. The ferroelectric properties of the films are discussed in the light of polarization-field hysteresis behaviour and impedance spectroscopy. The remanent polarization values ranged between 2P_r  45 and 60 μC cm⁻² at a field amplitude of 500 kV cm⁻¹ and −10 °C, while the dielectric permittivity of the films ranged between 375 and 1096 at a frequency of 2 kHz.     

Drivers and barriers for implementation of environmental strategies in manufacturing companies

In order for environmental strategies to come into effect in industry practice, they need to be implemented and applied in daily business routines. Based on a dedicated comprehensive international survey in product developing and manufacturing companies, this paper identifies major current drivers for implementing product life cycle oriented environmental strategies but also barriers and obstacles that need to be addressed. On this basis it provides a number of recommendations for manufacturing companies as well as policy makers to consider for a successful implementation of strategic environmental goals in manufacturing industry.     

Recent studies of particle packing in organic coatings

Organic coatings often contain sufficient pigmentation that the pigment volume concentration (PVC) and the critical PVC (CPVC) must be carefully considered. Past work has shown that the CPVC can be identified with the random densest packing of pigment particles after considerations of the adsorbed polymer layer on the particles is taken into account, and that this packing can be predicted by empirical particle packing algorithms developed for mixtures of particle sizes. Recent studies have shown that local fluctuations of pigment and polymer concentrations in a film can lead to local film volumes that can exceed the CPVC even though the average PVC for the whole film (the global PVC) is below the CPVC. These effects are consistent with observations of void formation in films below the CPVC, and can be analyzed by local film statistics. We have also recently performed simulations of particle packing by the compression of multiple hard spheres that allows further insight into local concentration fluctuations in PVC within a film.