Dehydrogenation of Light Alkanes Over Rhenium Catalysts on Conventional and Mesoporous MFI Supports

Recently, Re/HZSM-5 (Si/Al = 15) was shown to be an efficient catalyst for ethane dehydrogenation and aromatization at 823 K and atmospheric pressure. In this reaction, the major initial products were benzene, toluene and xylene (BTX), but increasing amounts of ethene were produced with time on stream due to deactivation of the catalyst. We show that by use of rhenium impregnated MFI supports with very few or no acidic sites (Si/Al > 500), highly selective ethane dehydrogenation catalysts are obtained with ethene selectivities of 98%. By use of mesoporous MFI supports (Si/Al >500) the lifetime of the catalyst appears to be slightly improved compared to conventional MFI crystals. The beneficial effect of a mesoporous MFI support is convincingly demonstrated in propane dehydrogenation, where both conversion and selectivities on the mesoporous MFI (Si/Al > 500) impregnated with Re are significantly higher than on Re supported on a comparable conventional MFI support.     

Cation Transport at 25°C from Binary Cd2+–Mn+ Mixtures in a H2O-CHCl3–H2O Liquid Membrane System Containing a Series of Macrocyclic Carriers[1]

Macrocycle-mediated fluxes of Cd(NO₃)₂ and of several binary mixtures of Cd(NO₃)₂ with the nitrate salt of either Na⁺, K⁺, Rb⁺ Cs⁺, Ag⁺, Ca²⁺, Sr²⁺, Pb²⁺, Zn²⁺, or Cu²⁺ have been determined in a H₂O-CHCl₃–H₂O liquid membrane system. Of the macrocycles studied, 2.2 and 2.2DD most successfully transported Cd²⁺ In the Cd²⁺–Mⁿ⁺ mixtures, Cd²⁺ was transported selectively with 2.2 when Mⁿ⁺ was either an alkali or an alkaline earth cation. However, when Mⁿ⁺ was either Ag⁺, Pb²⁺, or Cu²⁺ the Cd²⁺ flux was reduced sharply. Generally, cation flux was greater for 2.2DD than for 2.2 with selectivity for Cd²⁺ being altered also in several cases. Relative fluxes from binary cation mixtures depend on metal cation radius, macrocycle cavity diameter, ligand ring substituent and log K for metal ion-macrocycle interaction.     

Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH₃. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH₃ is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH₃/N₂ mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V₂O₅/TiO₂ catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.     

Effect of catalyst type on the kinetics of the photoelectrochemical disinfection of water inoculated with E. coli

The rates of the photoelectrochemical disinfection of Escherichia coli at TiO₂ electrodes were measured as a function of concentration and applied potential. Two different TiO₂ photoelectrodes were used: a thermally treated titanium plate and a porous film prepared by a sol–gel hydrolysis technique. The kinetics of the disinfection process were found to depend upon the nature of the electrode material. For the thermal film they were first order, and half order for the sol–gel film. It was also found that the catalytic activity per unit surface area of catalyst is many orders of magnitude greater than that observed using TiO₂ slurries; this was attributed to the reduced rate of electron-hole recombination afforded by the application of a small potential bias (1 V vs Ag/AgCl), and hence the exploitation of the electric field enhancement (EFE) effect.     

Interpretation of the impedance spectroscopy of cement paste via computer modelling

The d.c. conductivity, , and low-frequency relative dielectric constant, k, of Portland cement paste were monitored, using impedance spectroscopy, during cooling from room temperature down to -50 °C. Dramatic decreases in the values of and k, as great as two orders of magnitude, occurred at the initial freezing point of the aqueous phase in the macropores and larger capillary pores. This result provides strong experimental support for the dielectric amplification mechanism, proposed in Part II of this series, to explain the high measured low-frequency relative dielectric constant of hydrating Portland cement paste. Only gradual changes in the electrical properties were observed below this sudden drop, as the temperature continued to decrease. The values of and k of frozen cement paste, at a constant temperature of -40 °C, were dominated by properties of calcium-silicate-hydrate (C-S-H) and so increased with the degree of hydration of the paste, indicating a C-S-H gel percolation threshold at a volume fraction of approximately 15%–20%, in good agreement with previous predictions. Good agreement was found between experimental results and digital-image-based model computations of at -40 °C. Freeze-thaw cycling caused a drop in the dielectric constant of paste in the unfrozen state, indicating that measurements of k could be useful for monitoring microstructural changes during freeze-thaw cycling and other processes that gradually damage parts of the cement paste microstructure.     

Long‐term effects of angiotensin II blockade with irbesartan on inflammatory markers in hemodialysis patients: A randomized double blind placebo controlled trial (SAFIR study)

Introduction: Low‐grade chronic inflammation is common in hemodialysis (HD) patients. Previous studies suggest an anti‐inflammatory effect of angiotensin II receptor blocker (ARB) treatment. The aim of this study was to compare the effect of ARB vs. placebo on plasma concentrations of inflammatory markers in HD patients. Methods: Adult HD patients were randomized for double‐blind treatment with the ARB irbesartan 150–300 mg/day or placebo. At baseline, 1 week, 3, 6, 9, and 12 months plasma high sensitivity C‐reactive protein (hsCRP), interleukin (IL)?1β, IL‐6, IL‐8, IL‐18, and transforming growth factor‐β (TGF‐β) were measured using Luminex and enzyme‐linked immunosorbent assay (ELISA) technology. Findings: Eighty‐two patients were randomized (placebo/ARB: 41/41). The groups did not differ in initial levels of any of the inflammatory markers (placebo/ARB median(range)): hsCRP 3.3(0.2–23.4)/2.7(0.2–29.6) μg/mL; IL‐1β 1.1(0.0–45.9)/1.1(0.0‐7.2) pg/mL; IL‐6 10(1–90)/12(1–84) pg/mL; IL‐8 31(9–134)/34(5–192) pg/mL; IL‐18 364(188–1343)/377(213–832) pg/mL; TGF‐β 3.2(0.8–13.9)/3.6(1.3–3.8) ng/mL. Overall, there was no significant difference in hsCRP, IL‐6, IL‐8, and TGF‐β between placebo and ARB‐treated patients during the study period, and hsCRP, IL‐6, IL‐8, and TGF‐β were relatively stable during the study period (P ≥ 0.18 in all tests for parallel curves, equal levels, and constant levels). The IL‐1β level was slightly different in the two groups over time, but not significantly (P = 0.09 in test for parallel curves) and it was also relatively stable during the study period (P ≥ 0.49 in tests for equal levels and constant level). IL‐18 was the only inflammatory marker which was not constant during the study period (P = 0.001 in test for constant level), but there was no significant difference between placebo and ARB‐treated (P ≥ 0.51 in tests for parallel curves and equal levels). Discussion: Inflammatory biomarkers were neither acutely, nor in the long‐term significantly affected by the ARB irbesartan. Our findings suggest that ARB treatment in HD patients does not offer protective anti‐inflammatory effects.     

The mitigation hierarchy upside down – a study of nature protection measures in Danish infrastructure projects

This paper presents a Danish study of mitigation directed at nature protection in environmental impact assessment (EIA) of infrastructure projects. The study is based on a document analysis of EIA reports, a workshop held with EIA professionals, and a study of two cases. The paper takes a point of departure in the mitigation hierarchy as a central conceptual framework, identifies which mitigation measures have been suggested in the EIA reports, and compares this to the mitigation hierarchy. Further, the paper explores the dynamics behind which mitigation measures are chosen and later implemented. The findings point to a discrepancy between the prevention principle embedded in the mitigation hierarchy and the actual EIA practice with increased use of nature compensation. Further, the research reveals significant variation in the design of mitigation measures, e.g. in the level of detail used in describing them and the level of clarity as to aims and actions.     

Engineering analysis of biological variables: an example of blood pressure over 1 day

Almost all variables in biology are nonstationarily stochastic. For these variables, the conventional tools leave us a feeling that some valuable information is thrown away and that a complex phenomenon is presented imprecisely. Here, we apply recent advances initially made in the study of ocean waves to study the blood pressure waves in the lung. We note first that, in a long wave train, the handling of the local mean is of predominant importance. It is shown that a signal can be described by a sum of a series of intrinsic mode functions, each of which has zero local mean at all times. The process of deriving this series is called the "empirical mode decomposition method." Conventionally, Fourier analysis represents the data by sine and cosine functions, but no instantaneous frequency can be defined. In the new way, the data are represented by intrinsic mode functions, to which Hilbert transform can be used. Titchmarsh [Titchmarsh, E. C. (1948) Introduction to the Theory of Fourier Integrals (Oxford Univ. Press, Oxford)] has shown that a signal and i times its Hilbert transform together define a complex variable. From that complex variable, the instantaneous frequency, instantaneous amplitude, Hilbert spectrum, and marginal Hilbert spectrum have been defined. In addition, the Gumbel extreme-value statistics are applied. We present all of these features of the blood pressure records here for the reader to see how they look. In the future, we have to learn how these features change with disease or interventions.