Sewage sludge ash as an alternative low-cost oxygen carrier for chemical looping combustion

In this paper, novel low-cost oxygen carriers containing Fe₂O₃ are evaluated for use in chemical looping combustion. Sewage sludge ashes and reference samples were prepared and used in cyclic reduction and oxidation experiments in a thermogravimetric analyzer (TG). A gaseous (3 % H₂) fuel and a solid fuel (hard coal) were tested. Three-cycle CLC tests were carried out in the 600–800 °C temperature range and long-term testing was performed at 950 °C. A reactivity study showed that the natural sewage sludge ash sample was stable during the cycling TG tests when hydrogen was used as a fuel at all of the temperatures investigated. Strong temperature effects on the oxygen transport capacity were observed. An one-cycle test at 900 °C showed also that the sewage sludge ash successfully reacted with coal. The oxygen released was fully used for coal combustion, with appreciable reaction rate at temperature of ~750–800 °C, that is significantly lower than that obtained for pure Fe₂O₃-based oxygen carrier. The oxidation reaction was much faster than the reduction reaction. Moreover, the sewage sludge ash showed a low tendency toward agglomeration in the cyclic test, which was superior to the behavior of synthetic materials. The sewage sludge ash exhibited also high mechanical strength, an attrition index of 1 % and a high-temperature resistance of 1,170 °C in a reducing atmosphere. We conclude that sewage sludge ash can be effectively used as a low-cost, valuable oxygen carrier in practical application in chemical looping combustion technology for power generation.     

Effective direct chemical looping coal combustion with bi-metallic Fe–Cu oxygen carriers studied using TG-MS techniques

This paper contains the results of research on a promising combustion technology known as chemical looping combustion (CLC). The noteworthy advantage of CLC is that a concentrated CO₂ stream can be obtained after water condensation without any energy penalty for CO₂ separation. The objective of this work was to prepare novel bi-metallic Fe–Cu oxygen carriers and to evaluate the performance of these carriers for the CLC process with hard coal/air. One-cycle CLC tests were conducted with supported Fe–Cu oxygen carriers in thermogravimetric analyzer (TG) utilizing hard coal as a fuel. The effects of the oxygen carrier chemical composition, particle size, and steam addition on the reaction rates were determined. The fractional reduction, fractional oxidation, and the reaction rates were calculated from the TG data. Notably, the support had a considerable effect on the reaction performance. Moreover, bi-metallic Fe–Cu oxygen carriers exhibited significantly improved reactivity compared with monometallic Fe oxygen carriers. Furthermore, the addition of a second reactive metal oxide stabilized the oxygen carrier structure. The oxidation reaction was significantly faster than the reduction reaction for all supported Fe–Cu oxygen carriers. The TG data indicated that these oxygen carriers had stable performances up to 900 °C and may be effectively used for direct coal CLC reactions.     

Effects of compositional and structural features on corrosion behavior of nickel–tungsten alloys

Ni–W alloys were electrodeposited onto copper foil from citrate solution. Coatings containing from 11 to 21 at.% W and having 7–52 μm in thickness were obtained. The structure of these alloys was analyzed by X-ray diffraction and by using electron and light microscopy techniques. Alloys with 11 and 15% W are composed of two phases: solid solution of W in fcc Ni and solid solution of Ni in bcc W. An increase in W content in the Ni–W alloys to ca. 18–19% of W resulted in the grain refinement and the transition to amorphous structure. The corrosion behavior of obtained Ni–W and unalloyed Ni coatings was studied in 0.5 M NaCl solution by means of electrochemical impedance spectroscopy, potentiodynamic polarization and light microscopy. Comparing to pure Ni, the obtained Ni–W coatings exhibited a clearly decreased corrosion resistance (in terms of corrosion current density and polarization or charge transfer resistance at the open circuit potential). Despite of the quite wide range of composition of the alloys under test, the related grain refinement, and the transition to the amorphous structure, no clear relation between the corrosion rate and W content was detected. This behavior can be a result of the interplay of the activating effect of grain refinement or preferential dissolution of W from one side and diffusion barrier action or inhibition provided by the surface film of W oxidation products from the other side. The differences observed in the corrosion resistance of Ni–W coatings are more related to their morphological imperfections arising from various deposition conditions than to the W content. Some samples showed a rather non-uniform nature of corrosion (pronounced attack along cracks). An inversion in the dissolution behavior of Ni–W and unalloyed Ni was observed with increasing anodic potential. Contrary to pure Ni, Ni–W coatings were resistant to pitting corrosion in NaCl solution. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials, Warsaw, 17th–21st September, 2007.     

Static and dynamic superheated water extraction of essential oil components from Thymus vulgaris L.

Superheated water extraction (SWE) performed in both static and dynamic condition (S‐SWE and D‐SWE, respectively) was applied for the extraction of essential oil from Thymus vulgaris L. The influence of extraction pressure, temperature, time, and flow rate on the total yield of essential oil and the influence of extraction temperature on the extraction of some chosen components are discussed in the paper. The SWE extracts are related to PLE extracts with n‐hexane and essential oil obtained by steam distillation. The superheated water extraction in dynamic condition seems to be a feasible option for the extraction of essential oil components from T. vulgaris L.     

Exact profiles of (13)CO(2) recovery in breath air after per oral administration of [(13)C]methacetin in two groups of different ages

The aim of this study is to determine if age is a factor influencing the results of a [(13)C]methacetin breath test ((13)C-MBT). Two groups of healthy volunteers, each comprising six men and six women, but differing in average age (Y=young, 25.1+/-0.6 years, MA=middle-aged;, 46.0+/-2.1 years) orally took 75 mg [(13)C]methacetin. Samples of expiratory air for (13)CO(2) measurement were collected up to 48 h after intake of the substrate. A maximum momentary (13)CO(2) breath exhalation of 37.0+/-2.6%dose/h was observed at 18 min (median, range: 9-30 min) in the young subjects and of 38.4+/-2.5%dose/h at 18 min (median, range: 12-30 min) in the middle-age volunteers. The cumulative (13)C elimination in expiratory air was statistically significantly higher in the MA compared with the Y group as from 75 min up to 180 min, indicating a greater microsomal metabolic efficiency of the liver in the middle-aged healthy subjects. Gender, use of hormonal contraception, cigarette smoking, or body mass index did not modify the age-related effect on the cumulative (13)C elimination in breath air. The study results imply a necessity of composing control groups well matched with regard to the age structure for a proper interpretation of clinical (13)C-MBT results.     

Preparation of bicyclic β-lactam and bicyclic 1,3-oxazinone scaffolds using combined cycloaddition and metathesis processes

A simple, efficient two-step method for the preparation of heterobicyclic compounds was developed. Starting from 5-acyl or 5-carbamoyl-2,2-dimethyl-1,3-dioxa-4,5-dione bicyclic scaffolds of 1-azabicyclo[5.2.0]non-3-en-9-one, 6,9,10,10a-tetrahydro-4H-[1,3]oxazino[3,2-a]azepin-4-one, and 6,9,10,10a-tetrahydro-2H-[1,3]oxazino[3,2-a]azepine-2,4(3H)-dione were prepared using cycloaddition of thermally generated ketenes to aldimines with unsaturated side chains, followed by metathesis. The method was applied to ring closing metathesis (RCM) of different heterocyclic substrates to demonstrate its versatility.     

The Comparison of Physicochemical Parameters,Antioxidant Activity and Proteins for the Raw Local Polish Honeys and Imported Honey Blends

Many imported honeys distributed on the Polish market compete with local products mainly by lower price, which can correspond to lower quality and widespread adulteration. The aim of the study was to compare honey samples (11 imported honey blends and 5 local honeys) based on their antioxidant activity (measured by DPPH, FRAP, and total phenolic content), protein profile obtained by native PAGE, soluble protein content, diastase, and acid phosphatase activities identified by zymography. These indicators were correlated with standard quality parameters (water, HMF, pH, free acidity, and electrical conductivity). It was found that raw local Polish honeys show higher antioxidant and enzymatic activity, as well as being more abundant in soluble protein. With the use of principal component analysis (PCA) and stepwise linear discriminant analysis (LDA) protein content and diastase number were found to be significant (p < 0.05) among all tested parameters to differentiate imported honey from raw local honeys.     

Micropatch‐arrayed pads for non‐invasive spatial and temporal profiling of topical drugs on skin surface

Micropatch‐arrayed pads (MAPAs) are presented as a facile and sensitive sampling method for spatial profiling of topical agents adsorbed on the surface of skin. MAPAs are 28 × 28 mm sized pieces of polytetrafluoroethylene containing plurality of cavities filled with agarose hydrogel. They are affixed onto skin for 10 min with the purpose to collect drugs applied topically. Polar compounds are absorbed by the hydrogel micropatches. The probes are subsequently scanned by an automated nanospray desorption electrospray ionization mass spectrometry system operated in the tapping dual‐polarity mode. When the liquid junction gets into contact with every micropatch, polar compounds absorbed in the hydrogel matrix are desorbed and transferred to the ion source. A 3D‐printed interface prevents evaporation of hydrogel micropatches assuring good reproducibility and sensitivity. MAPAs have been applied to follow dispersion of topical drugs applied to human skin in vivo and to porcine skin ex vivo, in the form of self‐adhesive patches. Spatiotemporal characteristics of the drug dispersion process have been revealed using this non‐invasive test. Differences between drug dispersion in vivo and ex vivo could be observed. We envision that MAPAs can be used to investigate spatiotemporal kinetics of various topical agents utilized in medical treatment. Copyright © 2015 John Wiley & Sons, Ltd.     

High‐performance countercurrent chromatography separation of Peucedanum cervaria fruit extract for the isolation of rare coumarin derivatives

For the first time, rare major and minor compounds from fruits of Peucedanum cervaria were isolated. High‐performance countercurrent chromatography with two different solvent systems, heptane/ethyl acetate/methanol/water (3:2:3:2 and 2:1:2:1, v/v), was successfully used in the reversed‐phase mode. A scale‐up process from analytical to semipreparative in a very short time was developed. The structures of isolated compounds were evaluated by high‐performance liquid chromatography with diode array detection and electrospray ionization mass spectrometry, gas chromatography with mass spectrometry, and one‐ and two‐dimensional NMR spectroscopy. (8S,9R)‐9‐(3‐Methylbutenoyloxy)‐O‐acetyl‐8,9‐dihydrooroselol (compound B), (8S,9R)‐9‐(2‐methyl‐Z‐butenoyloxy)‐O‐acetyl‐8,9‐dihydrooroselol (edultin, compound C), and (8S,9R)‐9‐acetoxy‐O‐(2α‐methylbutyryl)‐8,9‐dihydrooroselol (compound D) were obtained using heptane/ethyl acetate/methanol/water (2:1:2:1, v/v) in <40 min. The method yielded 4.6 mg of a mixture of compounds B and C (11:89) and 3.7 mg of compound D. These amounts were obtained from the crude extract (0.5 g) in a single run. Although the compounds are known, their isolation by countercurrent chromatography and the analysis of their relative stereochemistry by two‐dimensional NMR spectroscopy have been performed for the first time. Additionally, heptane/ethyl acetate/methanol/water (3:2:3:2, v/v) led to the isolation of oxypeucedanin (1.2 mg; compound A). This is the first time that angular dihydrofuranocoumarin was isolated from plant extract by countercurrent chromatography.