Effect of the plant waste onto the properties of use and the microstructure of phyllosilicates based ceramics

The present study aimed at using plant waste (Musa Paradisiaca) for manufacturing clay-based ceramics in order to promote lower sintering temperature while preserving the properties of use. Two kaolinic-illitic clays (NZ1 and KO) from Central African Republic were used mixed with 1 to 10 mass% of the plant waste (MP). The clays and the waste exhibited accessory phases: quartz and iron oxides, and K₂O respectively. MP was collected, dried and sieved (<100 μm) previously to its mixture with clays. According to the sintering behavior of KO and NZ1 derived from thermodilatometry, the densification was obtained after firing at 1200°C. Results showed that open porosity decreased from 35% to 17% with increasing temperature in the range 900 to 1200°C for KO and NZ1. This porosity remained in the range 30%-40% while increasing the MP content (firing at 1000°C for 1h.). The optimized MP content was 3 and 5 mass% for KO and NZ1 clay materials respectively. The compressive strength and thermal conductivities were improved compared to clay samples without MP fired at 1200°C. Moreover a significant decrease in the sintering temperature was achieved, leading to energy saving in line with sustainability issues.     

Guaiacol HDO on La-modified Pt/Al2O3: Influence of rare-earth loading

The stability of the catalyst used in hydrodeoxygenation (HDO) of biomass-derived oils needs improvement. La has been applied in delaying Al₂O₃ phase-change under reaction conditions. Lanthanum (0.5–8 wt.%)-γ-alumina was studied as Pt (1 wt.%) carrier aimed at guaiacol (GUA) HDO. Materials characterization included N₂ physisorption, X-ray diffraction (XRD), thermal analysis, FTIR, UV–vis, and TPR. Solids pore size (~8–10 nm) was suitable for GUA (kinetic diameter~0.668 nm) hydrotreating. Mixed carriers were amorphous (XRD), suggesting well-dispersed La domains; meanwhile, carbonates/bicarbonates were formed (from CO₂) due to the basic surface properties of modified supports (FTIR). That could impart catalyst stability by inhibiting coking through the passivation of Lewis acidity on Al₂O₃. Pt reducibility increased with La loading in various formulations. However, that was not reflected in enhanced GUA HDO (T = 488 K and P = 3.2 MPa, batch reactor), presumably due to the strong metal–support interaction (SMSI), where LaO_x covered the metallic Pt particle surface. GUA HDO on various catalysts was approximated by pseudo-first-order kinetics (integral regime, k), where deviations were observed as La loading increased, presumably by an SMSI state that could affect the rate-determining step of the reaction mechanism. Basic sites provided by rare-earth could contribute to altering HDO reaction pathways as well. At 1 wt.% rare-earth, GUA HDO was maximized (k~25% higher than that on Pt/Al₂O₃), with that material also exhibiting similar deoxygenation (85%–90% at total GUA conversion) to the latter Pt over pristine alumina. Conversely, both parameters significantly diminished over the catalyst of the highest La content. Materials at low rare-earth concentrations deserve further studies focused on catalyst stability under HDO conditions.     

Parameter estimation and prediction uncertainties for multi-response kinetic models with uncertain inputs

Error-in-variables model (EVM) methods are used for parameter estimation when independent variables are uncertain. During EVM parameter estimation, output measurement variances are required as weighting factors in the objective function. These variances can be estimated based on data from replicate experiments. However, conducting replicates is complicated when independent variables are uncertain. Instead, pseudo-replicate runs may be performed where the target values of inputs for repeated runs are the same, but the true input values may be different. Here, we propose a method to estimate output-measurement variances for use in multivariate EVM estimation problems, based on pseudo-replicate data. We also propose a bootstrap technique for quantifying uncertainties in resulting parameter estimates and model predictions. The methods are illustrated using a case study involving n-hexane hydroisomerization in a well-mixed reactor. Case-study results reveal that assumptions about input uncertainties can have important influences on parameter estimates, model predictions and their confidence intervals.     

Simulation of polymer flow through a coat-hanger die: A comparison of two numerical approaches

Coat-hanger dies are commonly used for the extrusion of plastic sheets and films. To describe the flow of a molten polymer through a coat-hanger die, a two-dimensional approach is necessary. Moreover, the thermal effects, which play an important role in the flow distribution, have to be taken into account. In this paper, two numerical models for the simulation of coat-hanger dies are described and compared. These models differ mainly in the simplifying assumptions used and in the treatment of the thermal problem. The simulations obtained with the two models were compared with each other and with experimental data. The discrepancies between the two models can be explained by the different theoretical treatments.     

Environmental assessment of flue gas cleaning processes of municipal solid waste incinerators by means of the life cycle assessment approach

Life cycle assessment (LCA) is an environmental assessment tool generally applied to products but also to processes. Features of the LCA of processes are presented in this paper. This approach was used to compare two flue gas cleaning processes: the typical wet-type process and the new transported droplets column process. The LCA result shows that the global environmental burden is similar between the two processes, which confirms the viability of the transported droplets column. The distribution of the environmental burden, however, is different between the two processes. The weak points of the transported droplets column are the pollution transfer from air to water and a larger volume to stabilize. Its strong point: it is more efficient in capturing dust particles and toxic pollutants. This process could be improved from an environmental standpoint by adding an electrostatic filter upstream of the transported droplets column to capture the particles. The laboratory results of the transported droplets column need, however, to be confirmed at a larger scale.     

Thioether Analogues of Disulfide‐Bridged Cyclic Peptides Targeting Death Receptor 5: Conformational Analysis,Dimerisation and Consequences for Receptor Activation

Cyclic peptides containing redox‐stable thioether bridges might provide a useful alternative to disulfide‐bridged bioactive peptides. We report the effect of replacing the disulfide bridge with a lanthionine linkage in a 16‐mer cyclic peptide that binds to death receptor 5 (DR5, TRAIL‐R2). Upon covalent oligomerisation, the disulfide‐bridged peptide has previously shown similar behaviour to that of TNF‐related apoptosis inducing ligand (TRAIL), by selectively triggering the DR5 cell death pathway. The structural and biological properties of the DR5‐binding peptide and its desulfurised analogue were compared. Surface plasmon resonance (SPR) data suggest that these peptides bind DR5 with comparable affinities. The same holds true for dimeric versions of these peptides: the thioether is able to induce DR5‐mediated apoptosis of BJAB lymphoma and tumorigenic BJELR cells, albeit to a slightly lower extent compared to its disulfide homologue. NMR analysis revealed subtle variation in the conformations of the two peptides and suggests that the thioether peptide is slightly less folded than its disulfide homologue. These observations could account for the different capability of the two dimers to cluster DR5 receptors on the cell surface and to trigger apoptosis. Nevertheless, our results suggest that the thioether peptide is a potential candidate for evaluation in animal models.     

Two‐dimensional modeling of an absorbing falling film in its development zone

This work presents the modeling of a vertical falling film expanding or shrinking from the inlet manifold. Considering a stationary approach, the film shape, the flow field and the absorption rate of an ambient gas are computed. For the flow field, one dimensional (1‐D) second‐order weighted integral boundary layer (WIBL) model is shown to accurately reproduce the film deformations. The gas transfer is then solved in a 2‐D predeformed domain to investigate the impact of the film deformations on the gas absorption rate. It is found that a significant mass transfer enhancement, as compared to a flat film, is obtained when the film is expanding due to the concomitant increase of the concentration gradient perpendicular to the interface. On the contrary, a slight hindrance of the mass transfer is observed when the film is shrinking, although it remains in this case very close to the flat film analytical solution. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4370–4378, 2017     

Photochromic nanocomposite films of mononitrosyl complexes embedded in polymer matrices

New photochromic nanocomposite films based on mononitrosyl ruthenium complex [RuCl(NO)py₄]²⁺ have been synthesized by dispersion in polymer matrices. Infrared study under irradiation reveals that the composites present very high population of metastable state (≈45%). Nanoparticles of molecular complex stabilized in different matrices have been observed by transmission electron microscopy.