Oxidative Dehydrogenation of Propane with CO2 Over Cr/H[B]MFI Catalysts

Abstract  

Cr/silicalite-1 and Cr/H[B]MFI catalysts were prepared by the impregnation method, and Cr/H[B]MFI were further treated by steaming. The catalysts were employed for the oxidative dehydrogenation of propane to propylene with CO₂ as the oxidant. Cr/H[B]MFI showed significantly higher catalytic activity than Cr/silicalite-1, and steamed Cr/H[B]MFI was superior in the reaction stability to Cr/H[B]MFI. The nature of the supported chromium species have been characterized by a number of physicochemical techniques, such as Raman, UV–vis and NMR. It is concluded that the steaming led to the auto-reduction of some Cr⁶⁺ to Cr³⁺, and resultant Cr³⁺ species might be located near the boron center in the borosilicate framework to counterbalance the negative charge of the framework. The transformation of Cr⁶⁺ species to Cr³⁺ species, facilitated by the steaming process and the presence of boron in the catalyst, is responsible for the enhanced stability of oxidative dehydrogenation of propane to propylene with carbon dioxide as the oxidant.     

Mammalian Cytochrome P450-Dependent Metabolism of Polychlorinated Dibenzo-p-dioxins and Coplanar Polychlorinated Biphenyls

Polychlorinated dibenzo-p-dioxins (PCDDs) and coplanar polychlorinated biphenyls (PCBs) contribute to dioxin toxicity in humans and wildlife after bioaccumulation through the food chain from the environment. The authors examined human and rat cytochrome P450 (CYP)-dependent metabolism of PCDDs and PCBs. A number of human CYP isoforms belonging to the CYP1 and CYP2 families showed remarkable activities toward low-chlorinated PCDDs. In particular, human CYP1A1, CYP1A2, and CYP1B1 showed high activities toward monoCDDs, diCDDs, and triCDDs but no detectable activity toward 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-tetraCDD). Large amino acids located at putative substrate-recognition sites and the F-G loop in rat CYP1A1 contributed to the successful metabolism of 2,3,7,8-tetraCDD. Rat, but not human, CYP1A1 metabolized 3,3'',4,4'',5-pentachlorobiphenyl (CB126) to two hydroxylated metabolites. These metabolites are probably less toxic than is CB126, due to their higher solubility. Homology models of human and rat CYP1A1s and CB126 docking studies indicated that two amino acid differences in the CB126-binding cavity were important for CB126 metabolism. In this review, the importance of CYPs in the metabolism of dioxins and PCBs in mammals and the species-based differences between humans and rats are described. In addition, the authors reveal the molecular mechanism behind the binding modes of dioxins and PCBs in the heme pocket of CYPs.     

Polymerization of styrene with a simple rare earth metal initiator

The catalytic activity in the polymerization of styrene has been examined using commercially available simple rare earth metal compounds such as Sm(OiPr)₃, Sm(acac)₃, Sm(OCOMe)₃, SmI₂(THF)₂ or SmCl₃ coupled with Et₃Al or methylaluminoxane (MAO). Among these compounds, the Sm(OiPr)₃/AlEt₃ system shows the highest catalytic activity, especially in the presence of a minor amount of toluene at 60 °C. The random copolymerization of styrene with methyl methacrylate suggests that the present polymerization proceeds with a radical polymerization mechanism. (C₅Me₅)SmCl₃Na(THF) and (C₅Me₅)SmCl₃Li(THF) systems exhibit relatively low catalytic activity, even in the presence of AlEt₃. © 2001 Society of Chemical Industry     

Decay of material properties of degraded MEA caused by repeated cold starts under subzero conditions in polymer electrolyte fuel cells

This study investigated the characteristics of cell performance degradation, decline of component performance, and changes in the properties of membrane electrode assembly materials caused by repeated cold starts under a subzero condition of ?30 °C. It was made clear that functional decay appeared mainly at the cathode due to increased proton conductive impedance and reduction of reactivity of the electrode catalyst. Among the cathode components, an increase in proton conductive impedance in the cathode electrolyte was dominant. Furthermore, the application of ion chromatography and a newly developed proton‐induced gamma‐ray emission method to measure fluorine in the off‐gas drain revealed that decomposition of the electrolyte was dominant in the cathode catalyst layer. A decrease in fluorine in the cathode electrolyte measured by fluorine‐19 nuclear magnetic resonance confirmed this decomposition. A hypothesis is also presented concerning the cause of the performance degradation. © 2012 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.20394     

A method for testing the interface toughness of ceramic environmental barrier coatings (EBCs) on ceramic matrix composites (CMCs)

A simple interface fracture test for ceramic environmental barrier coatings (EBCs) on ceramic matrix composites (CMCs) was developed. A variation on the asymmetric double cantilever beam (ADCB) test was proposed so that the interface toughness could be measured in a small specimen of simple shape without applying interlaminar loading to the CMC substrate. The proposed test was applied to an EBC consisting of a mullite layer and Si bond coat on a monolithic SiC substrate. A pre-crack was introduced by pop-in cracking, and then a notch overlapping the pre-crack was machined. The pre-crack was opened by inserting a wedge into the notch. From the critical notch opening displacement the crack starts to propagate, interface toughness is calculated. The measured interface toughness was 4.1?J/m2. Finally, the application range of the test was discussed and suggestions were made for introduction of the notch and pre-crack.     

Color registration error reduction method compensating the influence of belt thickness variation in electrophotographic process

This paper proposes a new belt drive control method for reducing a belt velocity-fluctuation that is caused by a belt thickness-variation in the circumferential direction. A belt driving system performs feedback control with a rotary encoder-output mounted on a driven roller. This proposed method correct the reference value of the feedback control for the purpose of the belt velocity regulation. The correction includes two steps. The first step acquires the encoder-output of the driven roller and calculates the rotational angular velocity-fluctuation with one cycle of the belt rotation. The second step converts from the velocity-fluctuation to the correction value of the feedback reference. The correction value cancels a detection error of the driven roller caused by the belt thickness-variation. After these steps, the belt driving system controls the belt velocity as compensating the belt velocity-fluctuation. Experimental result showed the significant fluctuation reduction on a typical tandem-engine printer.     

An energy trading system with consideration of CO2 emissions

Abatement of CO₂ emission is one of the most important issues in the 21st century regarding preservation of the earth environment. This paper addresses a utility operations planning problem for distributed energy management systems (DEMSs), where we are to obtain optimal plans that minimize both costs and CO₂ emissions. A DEMS consists of multiple entities that seek their own economic profits. In this paper, we give a mathematical formulation of the utility operations planning problem for each entity, and propose an energy trading market, which utlizes a multi‐attribute auction protocol in order to deal with both a price and a CO₂ emission rate. Experimental results show that collaboration among entities through the market provides a more profitable plan for each entity and abatement of CO₂ emission is also achieved. © 2007 Wiley Periodicals, Inc. Electr Eng Jpn, 162(4): 54–63, 2008; Published online in Wiley InterScience ( www.interscience.wiley. com ). DOI 10.1002/eej.20418     

Osteoinduction by Functionally Graded Apatites of Bovine Origin Loaded with Bone Morphogenetic Protein-2

Bioresorbable and functionally graded apatites (fg-HAp) ceramics, which are characterized by gradations in crystallinity and the grain size of hydroxyapatite (HAp:Ca₁₀(PO₄)₆(OH)₂), were designed using bovine bone by the calcination and partial dissolution–precipitation method. The fg-HAp ceramics had macropores of 100–600 μm originated from spongy bone, and micropores of 10–160 nm. Fg-HAp ceramics loaded with recombinant human bone morphogenetic protein-2 (rhBMP-2/fg-HAp) were implanted into the subcutaneous tissue of rats. Eight weeks after the implantation, the surface and bulk degradations of the fg-HAp-containing body fluid occured, and small pieces of fg-HAp were incorporated into the induced bone and fatty marrow, suggesting that osteoinduction occurred in conjunction with bone remodeling. The rhBMP-2/fg-HAp ceramics developed could become a resorbable biomimetic material with fast bioresorption and osteoinduction characteristics.     

Comparison between Y-doped ceria and Ho-doped ceria: Electrical conduction and microstructures

The electrical conduction and microstructure in Y-doped ceria and Ho-doped ceria were investigated. Visible differences between the two doped ceria were observed. The plots of conductivity of Y-doped ceria are well fit to the Arrhenius behavior, while curvature and kinks were observed on the plots of Ho-doped ceria. Such deviation from the Arrhenius behavior could be related to the existence of precipitates in Ho-doped ceria. It indicates that the electrolytic conductivity of doped ceria could be significantly influenced by microstructure features.