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Sample records for acyl-coa dehydrogenation deficiency

  1. Specific glutaryl-CoA dehydrogenating activity is deficient in cultured fibroblasts from glutaric aciduria patients

    Patients with glutaric aciduria (GA) have greatly increased urinary excretion of glutarate. Their leukocyte and fibroblast sonicates have deficient ability to produce 14CO2 from [1,5-14C]glutaryl-CoA, an enzymatic process with two sequential reaction steps, dehydrogenation and decarboxylation. In normal individuals, it is not known whether these two reaction steps require one or two enzymes, and currently it is assumed that a single enzyme, glutaryl-CoA dehydrogenase (GDH), carries out these two reactions. Since GA patients also excrete increased amounts of 3-hydroxyglutarate and glutaconate in urine, it was thought that glutaryl-CoA in these patients may be dehydrogenated but not decarboxylated. We developed a new assay specific for glutaryl-CoA dehydrogenation which measures enzyme-catalyzed tritium release from [2,3,4-3H]glutaryl-CoA, and we studied the glutaryl-CoA dehydrogenating activity in cultured normal human fibroblasts and those from patients with GA. The Michaelis constant (Km) of normal human fibroblast GDH for [2,3,4-3H]glutaryl-CoA was 5.9 microM, and activity was severely inhibited by (methylenecyclopropyl)acetyl-CoA at low concentrations. Sonicates from all five GA fibroblast lines examined showed 2-9% of control glutaryl-CoA dehydrogenating activity, corresponding to the deficient 14CO2 releasing activity. These results indicate either that the conversion of glutaryl-CoA to crotonyl-CoA is accomplished by two enzymes, and patients with GA are deficient in the activity of the first component, or alternatively, that this process is carried out by a single enzyme which is deficient in these patients. It is unlikely that urinary glutaconate and 3-hydroxyglutarate in GA patients are produced via GDH

  2. Clear relationship between ETF/ETFDH genotype and phenotype in patients with multiple acyl-CoA dehydrogenation deficiency

    Olsen, Rikke K J; Andresen, Brage S; Christensen, Ernst;

    2003-01-01

    Mutations in electron transfer flavoprotein (ETF) and its dehydrogenase (ETFDH) are the molecular basis of multiple acyl-CoA dehydrogenation deficiency (MADD), an autosomal recessively inherited and clinically heterogeneous disease that has been divided into three clinical forms: a neonatal...

  3. DNA-based prenatal diagnosis for severe and variant forms of multiple acyl-CoA dehydrogenation deficiency

    Olsen, Rikke K J; Andresen, Brage S; Christensen, Ernst;

    2005-01-01

    OBJECTIVES: Multiple acyl-CoA dehydrogenation deficiency (MADD) is a clinically heterogeneous disorder of mitochondrial fatty acid, amino acid, and choline oxidation due to mutations in the genes encoding electron transfer flavoprotein (ETF) or ETF ubiquinone oxidoreductase (ETFQO). So far...

  4. ETFDH mutations as a major cause of riboflavin-responsive multiple acyl-CoA dehydrogenation deficiency

    Olsen, Rikke K J; Olpin, Simon E; Andresen, Brage S;

    2007-01-01

    Multiple acyl-CoA dehydrogenation deficiency (MADD) is a disorder of fatty acid, amino acid and choline metabolism that can result from defects in two flavoproteins, electron transfer flavoprotein (ETF) or ETF: ubiquinone oxidoreductase (ETF:QO). Some patients respond to pharmacological doses of...

  5. The ETFDH c.158A>G Variation Disrupts the Balanced Binding of ESE and ESS Proteins Causing Missplicing and Multiple acyl-CoA Dehydrogenation Deficiency

    Olsen, Rikke K J; Brøner, Sabrina; Sabaratnam, Rugivan;

    2013-01-01

    Multiple acyl-CoA dehydrogenation deficiency is a disorder of fatty acid and amino acid oxidation caused by defects of electron transfer flavoprotein (ETF) or its dehydrogenase (ETFDH). A clear relationship between genotype and phenotype makes genotyping of patients important not only diagnostica......Multiple acyl-CoA dehydrogenation deficiency is a disorder of fatty acid and amino acid oxidation caused by defects of electron transfer flavoprotein (ETF) or its dehydrogenase (ETFDH). A clear relationship between genotype and phenotype makes genotyping of patients important not only...

  6. Lipid-storage myopathy and respiratory insufficiency due to ETFQO mutations in a patient with late-onset multiple acyl-CoA dehydrogenation deficiency

    Olsen, Rikke Katrine Jentoft; Pourfarzam, M; Morris, A A M;

    2004-01-01

    We report a patient with lipid-storage myopathy due to multiple acyl-CoA dehydrogenation deficiency (MADD). Molecular genetic analysis showed that she was compound heterozygous for mutations in the gene for electron transfer flavoprotein:ubiquinone oxidoreductase (ETFQO). Despite a good initial...

  7. Transient multiple acyl-CoA dehydrogenation deficiency in a newborn female caused by maternal riboflavin deficiency

    Chiong, M A; Sim, K G; Carpenter, K;

    2007-01-01

    A newborn female presented on the first day of life with clinical and biochemical findings consistent with multiple acyl-CoA dehydrogenase deficiency (MADD). Riboflavin supplementation corrected the biochemical abnormalities 24 h after commencing the vitamin. In vitro acylcarnitine profiling in i...

  8. Deficiencies

    U.S. Department of Health & Human Services — A list of all deficiencies currently listed on Nursing Home Compare, including the nursing home that received the deficiency, the associated inspection date,...

  9. Catalytic dehydrogenations of ethylbenzene to styrene

    Nederlof, C.

    2012-01-01

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  10. Liver fatty acid binding protein (LFABP) transfers fatty acids and fatty acyl coas to membranes

    De Gerónimo, Eduardo; Hagan, Robert M; Wilton, David C.; Córsico, Betina

    2010-01-01

    The objective of this work was to analyze LFABP´s capacity to transfer acyl CoAs to artificial membranes and compare it to LCFA transfer employing natural ligands, in order to better understand the specific physiological role of LFABP in the cell.

  11. Catalysts for Dehydrogenation of ammonia boranes

    Heinekey, Dennis M.

    2014-12-19

    Several effective homogeneous catalysts for the dehydrogenation of amine boranes have been developed. The best catalyst uses an iridium complex, and is capable of dehydrogenating H3NBH3 (AB) and CH3NH2BH3 (MeAB) at comparable rates. Thermodynamic measurements using this catalyst demonstrate that the dehydrogenation of AB and MeAB is substantially exothermic, which has important implications for regeneration.

  12. Alkane dehydrogenation over supported chromium oxide catalysts

    Weckhuysen, B.M.; Schoonheydt, R.A.

    1999-01-01

    The dehydrogenation of alkanes over supported chromium oxide catalysts in the absence of oxygen is of high interest for the industrial production of propene and isobutene. In this review, a critical overview is given of the current knowledge nowadays available about chromium-based dehydrogenation ca

  13. Shale gas opportunities. Dehydrogenation of light alkanes

    Patcas, F.C.; Dieterle, M.; Rezai, A.; Asprion, N. [BASF SE, Ludwigshafen (Germany)

    2013-11-01

    The discovery and use of shale gas in North America has become a game changer for the chemical industry by access to a cheaper feedstock compared to conventional oil. Increased number of ethane crackers spurred increasing interest in light alkanes dehydrogenation. Several companies have announced their interest in new propane dehydrogenation units in North America. BASF is developing light alkanes dehydrogenation technologies for two decades now. BASF developed jointly with Linde the isothermal C3 dehydrogenation process. The latest dehydrogenation catalyst development at BASF focused on a supported and steam resistant Pt-Sn catalyst which yielded excellent selectivity and activity. Intense research work both internally as well as in cooperation with universities contributed to the understanding of the relationship between the surface structure and catalyst performances like activity, selectivity and coking resistance. Using such type of catalysts BASF developed an autothermal propane dehydrogenation as well as a butane dehydrogenation process. The most recent catalyst development was a dehydrogenation catalyst coated on a honeycomb monolith to improve catalyst usage and pressure drop. This will probably be the first industrial usage of catalytic monoliths in a chemical synthesis process. (orig.) (Published in summary form only)

  14. Dehydrogenation of benzene on Pt(111) surface

    Gao, W.; Zheng, W. T.; Jiang, Q.

    2008-10-01

    The dehydrogenation of benzene on Pt(111) surface is studied by ab initio density functional theory. The minimum energy pathways for benzene dehydrogenation are found with the nudge elastic band method including several factors of the associated barriers, reactive energies, intermediates, and transient states. The results show that there are two possible parallel minimum energy pathways on the Pt(111) surface. Moreover, the tilting angle of the H atom in benzene can be taken as an index for the actual barrier of dehydrogenation. In addition, the properties of dehydrogenation radicals on the Pt(111) surface are explored through their adsorption energy, adsorption geometry, and electronic structure on the surface. The vibrational frequencies of the dehydrogenation radicals derived from the calculations are in agreement with literature data.

  15. Supported organoiridium catalysts for alkane dehydrogenation

    Baker, R. Thomas; Sattelberger, Alfred P.; Li, Hongbo

    2013-09-03

    Solid supported organoiridium catalysts, a process for preparing such solid supported organoiridium catalysts, and the use of such solid supported organoiridium catalysts in dehydrogenation reactions of alkanes is provided. The catalysts can be easily recovered and recycled.

  16. Catalytic Conversion of Methanol by Oxidative Dehydrogenation

    2007-01-01

    This study investigates the effects of addition of oxygen on the oxidative dehydrogenation (ODH) of methanol when a fluorotetrasilicic mica ion-exchanged with palladium (Pd2+-TSM) was used as the catalyst. The reaction proceeded at a very low temperature in the presence of oxygen, and HCOOCH3 was obtained at high selectivity. By calculating the equilibrium conversion, it has been shown that substantial ODH took place for HCOOCH3 production. Consequently, this reaction would make dehydrogenation the dominant reaction at equilibrium. Not all the H dissociated from CH3OH was converted to H2O by oxidation. It has been shown that the H2O was not produced from oxidative dehydrogenation by the direct reaction of CH3OH and O2 when an attempt was made to carry out oxidative dehydrogenation using an isotope oxygen trace method in the gas phase. Therefore, when CH3OH was converted to CO2 and dehydrogenated to HCOOCH3, the C-O bonds were not dissociated.

  17. Oxidative dehydrogenation of light alkanes

    Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany); Hartmann, D.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany)

    2012-07-01

    The demand of light olefins increases steadily and the current steam cracking production is highly energy demanding. This motivates the development of alternative production processes like the oxidative dehydrogenation (ODH) of light alkanes operating at comparably low temperatures. Multi-component oxides are reported to show excellent catalytic performance in the ODH. Especially, MoVTeNbO oxides present high activity and selectivity in ODH of ethane. Synthesis of MoVTeNb oxides was done by a hydrothermal method. Qualitative and quantitative phase analysis were performed by X-ray diffraction and Rietveld refinement. Surface compositions were determined by Low energy ion scattering (LEIS). Catalytic tests were carried out in a fixed bed plug flow reactor using ethane and oxygen diluted in helium, as gaseous feed. Based on laboratory investigations a first upscale to a bench-top-pilot unit was performed in order to evaluate the large scale and long term feasibility of the process under technically relevant conditions. MoVTeNb oxides show high activity combined with excellent selectivity in the ODH of ethane to ethylene (S > 95% at X < 40%). Phase analysis reveals the presence of M1, M2 and amorphous phases. Literature reports the crystalline M1 phase as essential for the performance. Indeed, the crystalline M1 phase impacts on the activity via exposing V on the surface being apparently vital to achieve an active material. A correlation of the apparent activation energy with the surface vanadium composition of the catalysts is noticed, however, surprisingly with no major impact on the ethene selectivity. As this material was identified as most promising for a technical application a scale up from less than 1g to 50g of catalyst was performed in a bench-top-pilot unit. The reaction has a significant adiabatic temperature rise and the handling of the reaction heat is a major challenge for process engineering. Furthermore different diluent media such as Helium, Nitrogen

  18. Dehydrogenation of light alkanes over zeolites

    Narbeshuber, Thomas F.; Brait, Axel; Seshan, Kulathuiyer; Lercher, Johannes A.

    1997-01-01

    The conversion of light paraffins to olefins and the secondary reactions of the unsaturated compounds were investigated on H-ZSM5 and H-Y zeolites between 733 and 823 K. Steady state- and transient response-isotope tracing studies revealed that two mechanisms of dehydrogenation are operative. The ma

  19. Dehydrogenated polycyclic aromatic hydrocarbons and UV bump

    Malloci, G; Cecchi-Pestellini, C; Joblin, C

    2008-01-01

    Recent calculations have shown that the UV bump at about 217.5 nm in the extinction curve can be explained by a complex mixture of PAHs in several charge states. Other studies proposed that the carriers are a restricted population made of neutral and singly-ionised dehydrogenated coronene molecules (C24Hn, n less than 3), in line with models of the hydrogenation state of interstellar PAHs predicting that medium-sized species are highly dehydrogenated. To assess the observational consequences of the latter hypothesis we have undertaken a systematic study of the electronic spectra of dehydrogenated PAHs. We use our first results to see whether such spectra show strong general trends upon dehydrogenation. We used state-of-the-art techniques in the framework of the density functional theory (DFT) to obtain the electronic ground-state geometries, and of the time- dependent DFT to evaluate the electronic excited-state properties. We computed the absorption cross-section of the species C24Hn (n=12,10,8,6,4,2,0) in t...

  20. Positronium formation in dehydrogenated FeTi

    Very efficient positronium formation is observed in hydrogenated/dehydrogenated FeTi after annealing. The effects observed can be interpreted on the basis of defect annealing and mechanisms involved in the self-cleaning of the surface layer of hydrogen sponges. (Auth.)

  1. Thermodynamic aspects of dehydrogenation reactions on noble metal surfaces

    Svane, K. L., E-mail: ksvane@inano.au.dk; Hammer, B., E-mail: hammer@phys.au.dk [Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University (Denmark)

    2014-11-07

    The reaction free energy for dehydrogenation of phenol, aniline, thiophenol, benzoic acid, and 1,4-benzenediol on the close packed copper, silver, and gold surfaces has been studied by density functional theory calculations. Dehydrogenation of thiophenol is found to be favourable on all three surfaces while aniline does not dehydrogenate on any of them. For phenol, benzenediol and benzoic acid dehydrogenation is favourable on copper and silver only, following the general trend of an increasing reaction free energy when going form gold to silver to copper. This trend can be correlated with the changes in bond lengths within the molecule upon dehydrogenation. While copper is able to replace hydrogen, leaving small changes in the bond lengths of the aromatic ring, the metal-molecule bond is weaker for silver and gold, resulting in a partial loss of aromaticity. This difference in bond strength leads to pronounced differences in adsorption geometries upon multiple dehydrogenations.

  2. Disruption of the acyl-coa binding protein gene delays hepatic adaptation to metabolic changes at weaning

    Neess, Ditte; Bloksgaard, Maria; Sørensen, Signe Bek; Marcher, Ann-Britt; Elle, Ida C; Helledie, Torben; Due, Marianne; Pagmantidis, Vasileios; Finsen, Bente; Wilbertz, Johannes; Kruhoeffer, Mogens; Faergeman, Nils; Mandrup, Susanne

    2011-01-01

    , little is known about the in vivo function in mammalian cells. We have generated mice with targeted disruption of ACBP (ACBP-/-). These mice are viable and fertile and develop normally. However, around weaning the ACBP-/- mice go through a crisis with overall weakness, and a slightly decreased growth...... rate. Using microarray analysis we show that the liver of ACBP-/- mice display a significantly delayed adaptation to weaning with late induction of target genes of the sterol regulatory element binding protein (SREBP) family. As a result, hepatic de novo cholesterogenesis is decreased at weaning. The...... delayed induction of SREBP target genes around weaning is caused by a compromised processing and decreased expression of SREBP precursors leading to reduced binding of SREBP to target sites in chromatin. In conclusion, lack of ACBP interferes with the normal metabolic adaptation to weaning and leads to...

  3. Active coke: Carbonaceous materials as catalysts for alkane dehydrogenation

    McGregor, J.; Huang, Z; Parrott, E.; Zeitler, J.; Nguyen, K.; Rawson, J.; Carley, A; Hansen, T.; Tessonnier, J.; Su, D.; Teschner, D; Vass, E.; Knop-Gericke, A.; Schlögl, R.; Gladden, L.

    2010-01-01

    The catalytic dehydrogenation (DH) and oxidative dehydrogenation (ODH) of light alkanes are of significant industrial importance. In this work both carbonaceous materials deposited on VOx/Al2O3 catalysts during reaction and unsupported carbon nanofibres (CNFs) are shown to be active for the dehydrogenation of butane in the absence of gas-phase oxygen. Their activity in these reactions is shown to be dependent upon their structure, with different reaction temperatures yielding structurally dif...

  4. Current-induced runaway vibrations in dehydrogenated graphene nanoribbons

    Christensen, Rasmus Bjerregaard; Lu, Jing Tao; Hedegard, Per;

    2016-01-01

    We employ a semi-classical Langevin approach to study current-induced atomic dynamics in a partially dehydrogenated armchair graphene nanoribbon. All parameters are obtained from density functional theory. The dehydrogenated carbon dimers behave as effective impurities, whose motion decouples from...

  5. Dehydrogenation of ammonia borane through the third equivalent of hydrogen.

    Zhang, Xingyue; Kam, Lisa; Williams, Travis J

    2016-05-01

    Ammonia borane (AB) has high hydrogen density (19.6 wt%), and can, in principle, release up to 3 equivalents of H2 under mild catalytic conditions. A limited number of catalysts are capable of non-hydrolytic dehydrogenation of AB beyond 2 equivalents of H2 under mild conditions, but none of these is shown directly to derivatise borazine, the product formed after 2 equivalents of H2 are released. We present here a high productivity ruthenium-based catalyst for non-hydrolytic AB dehydrogenation that is capable of borazine dehydrogenation, and thus exhibits among the highest H2 productivity reported to date for anhydrous AB dehydrogenation. At 1 mol% loading, (phen)Ru(OAc)2(CO)2 () effects AB dehydrogenation through 2.7 equivalents of H2 at 70 °C, is robust through multiple charges of AB, and is water and air stable. We further demonstrate that catalyst has the ability both to dehydrogenate borazine in isolation and dehydrogenate AB itself. This is important, both because borazine derivatisation is productivity-limiting in AB dehydrogenation and because borazine is a fuel cell poison that is commonly released in H2 production from this medium. PMID:27052687

  6. Acceptorless Photocatalytic Dehydrogenation for Alcohol Decarbonylation and Imine Synthesis

    Ho, Hung-An; Manna, Kuntal; Sadow, Aaron D.

    2012-07-29

    It has come to light: Renewed interest in conversions of highly oxygenated materials has motivated studies of the organometallic-catalyzed photocatalytic dehydrogenative decarbonylation of primary alcohols into alkanes, CO, and H2 (see scheme). Methanol, ethanol, benzyl alcohol, and cyclohexanemethanol are readily decarbonylated. The photocatalysts are also active for amine dehydrogenation to give N-alkyl aldimines and H2.

  7. Microchannel apparatus and methods of conducting catalyzed oxidative dehydrogenation

    Tonkovich, Anna Lee (Dublin, OH); Yang, Bin (Columbus, OH); Perry, Steven T. (Galloway, OH); Mazanec, Terry (Solon, OH); Arora, Ravi (New Albany, OH); Daly, Francis P. (Delaware, OH); Long, Richard (New Albany, OH); Yuschak, Thomas D. (Lewis Center, OH); Neagle, Paul W. (Westerville, OH); Glass, Amanda (Galloway, OH)

    2011-08-16

    Methods of oxidative dehydrogenation are described. Surprisingly, Pd and Au alloys of Pt have been discovered to be superior for oxidative dehydrogenation in microchannels. Methods of forming these catalysts via an electroless plating methodology are also described. An apparatus design that minimizes heat transfer to the apparatus' exterior is also described.

  8. Production of pure hydrogen by ethanol dehydrogenation

    Santacesaria, Elio; Carotenuto, Giuseppina; Tesser, Riccardo; Di Serio, Martino [Naples Univ. (Italy). Dipt. di Chimica

    2011-06-15

    Hydrogen production from bio-ethanol is one of the most promising renewable processes to generate electricity using fuel cells. In this work, we have studied the production of pure hydrogen as a by-product of the ethanol dehydrogenation reaction. This reaction is promoted by copper based catalysts and according to the catalyst used and the operating conditions gives place to acetaldehyde or ethyl acetate as main products. We studied in particular the performance of a commercial copper/copper chromite catalyst, supported on alumina and containing barium chromate as a promoter, which gave the best results. By operating at low pressure and temperature with short residence times, acetaldehyde is more selectively produced, while, by increasing the pressure (10-30 bars), the temperature (200-260 C) and the residence time (about 100 grams hour/mol of ethanol contact time) the selectivity is shifted to the production of ethyl acetate. However, in both cases pure hydrogen is obtained, as a by-product, which can easily be separated. Hydrogen obtained in this way is free of CO and can be directly fed to fuel cells without any inconvenience. In this work, runs performed under different operating conditions have been reported with the scope to select the best conditions. A carrier of H2 6% in N{sub 2} has been used. The studied catalyst has also shown a good thermal stability with respect to sintering phenomena, which generally occur during the dehydrogenation over other copper catalysts. Hydrogen productivities of 8-39 g{sub H2} (Kgcat){sup -1} (h){sup -1} were obtained for the explored temperature range of 200-260 C. Finally the most accredited reaction mechanism is reported and discussed on the basis of the obtained results. (orig.)

  9. Tailored ceria nanoparticles for CO2 mediated ethylbenzene dehydrogenation

    Kovacevic, Marijana

    2016-01-01

    Styrene production via ethylbenzene dehydrogenation (EBDH) is one of the ten most important petrochemical processes. Possessing highly reactive double bond which facilitates self-polymerization and polymerization with other monomers, styrene is the fourth utmost essential bulk monomer at present. Current commercial ethylbenzene dehydrogenation is highly endothermic reaction, thus highly energy demanding. Several alternatives to steam, conventionally used to supply heat have been widely invest...

  10. Adsorption and dehydrogenation of tetrahydroxybenzene on Cu(111)

    Bebensee, Fabian; Svane, K.; Bombis, Christian;

    2013-01-01

    Adsorption of tetrahydroxybenzene (THB) on Cu(111) and Au(111) surfaces is studied using a combination of STM, XPS, and DFT. THB is deposited intact, but on Cu(111) it undergoes gradual dehydrogenation of the hydroxyl groups as a function of substrate temperature, yielding a pure dihydroxy......-benzoquinone phase at 370 K. Subtle changes to the adsorption structure upon dehydrogenation are explained from differences in molecule–surface bonding....

  11. Enhanced dehydrogenation of hydrazine bisborane for hydrogen storage

    Li, Leigang [Department of Materials Science, Fudan University, Shanghai 200433 (China); Shanghai Key Laboratory of Modern Metallurgy and Materials Processing, Shanghai University, Shanghai 200072 (China); Tan, Yingbin; Tang, Ziwei; Xia, Guanglin; Yuan, Feng [Department of Materials Science, Fudan University, Shanghai 200433 (China); Li, Qian, E-mail: shuliqian@shu.edu.cn [Shanghai Key Laboratory of Modern Metallurgy and Materials Processing, Shanghai University, Shanghai 200072 (China); Yu, Xuebin, E-mail: yuxuebin@fudan.edu.cn [Department of Materials Science, Fudan University, Shanghai 200433 (China)

    2014-02-14

    NiCl{sub 2} and CoCl{sub 2} were adopted to enhance the dehydrogenation of hydrazine bisborane (HBB), respectively, of which NiCl{sub 2} showed better performance. By adding 2.0 mol. % NiCl{sub 2}, the dehydrogenation property of HBB was significantly improved, for example, the impurity of NH{sub 3} during the dehydrogenation of HBB was totally suppressed with more than 13.0 wt. % of pure hydrogen evolved. By Kissinger method, the apparent activation energies of the first step for HBB and Ni-doped HBB were calculated to be 143.2 and 60.7 kJ mol{sup −1}, respectively. DSC result showed that the addition of NiCl{sub 2} did not change the enthalpy change of HBB dehydrogenation. Based on theoretical analysis and literature review, the improved dehydrogenation property of HBB was potentially ascribed to the solid state interaction of Ni{sup 2+} with the electronegative N in the NH{sub 2} group of HBB. - Highlights: • NiCl{sub 2} enhanced dehydrogenation of hydrazine bisborane (HBB) was reported. • By adding NiCl{sub 2}, the desorption rate and the hydrogen purity were improved. • A possible explanation was proposed to understand NiCl{sub 2} enhanced desorption of HBB.

  12. The role of adsorbed hydrogen species in the dehydrogenation and hydrocracking of saturated hydrocarbons on supported metal catalysts

    Babenkova, L. V.; Naidina, I. N.

    1994-07-01

    The role of certain hydrogen absorption complexes in the dehydrogenation and hydrocracking of hydrocarbons on low-percentage one-component, (Pt, Pd/Al2O3) and bimetallic (Pd-Co, Pd-Ce, Pt-Co, Pt-Sn/Al2O3) catalysts is discussed. It is shown that the combination of metals in reduced forms and forms oxidised to different extents on the catalyst surfaces is responsible for their high capacity for the chemisorption of hydrogen, the wide range of its energetic inhomogeneity, and the high activity of the catalysts in the conversion of saturated hydrocarbons. Catalysts containing on the surface mainly sites for the type Hδ- chemisorption are the most active in the dehydrogenation of hydrocarbons, whereas specimens chemisorbing hydrogen mainly in the Hδ+ form are the most active in the hydrockracking of hydrocarbons. It is concluded that the strongly bound atomic hydrogen Hδ+ plays a dual role, since it not only participates directly in the dehydrogenation reaction but also promotes the reduction of the electron-deficient surface centres, which optimises the number of centres for the activation of C-H bonds. The bibliography includes 75 references.

  13. Effect of alloying on carbon formation during ethane dehydrogenation

    Rovik, Anne; Kegnæs, Søren; Dahl, Søren;

    2009-01-01

    The structure sensitivity of different transition metals in the hydrogenolysis, dehydrogenation, and coking reactions during ethane conversion has been investigated. The investigated metals, Ni, Ru, Rh, and Pd, are co-impregnated with Ag onto an inactive MgAl2O4 spinel support and tested in the...... coke during the initial period where after dehydrogenation of ethane is observed. It has previously been predicted in surface science studies that Ag covers the steps of certain transition metals. Here it is documented that the hydrogenolysis and coking reactions are significantly suppressed by co......-Pd/spinel due to an alloy formation of Ag and Pd at these conditions. From our results it can therefore be concluded that hydrogenolysis mainly takes place on the steps and kinks of the transition metal particles, dehydrogenation reactions mainly takes place on the terraces, and coking is significantly reduced...

  14. Oxidative dehydrogenation of isobutane over a titanium pyrophosphate catalyst

    IOAN-CEZAR MARCU

    2005-06-01

    Full Text Available The catalytic properties of titanium pyrophosphate in the oxidative dehydrogenation of isobutane to isobutylene were investigated in the 400 – 550 ºC temperature range. Asignificant change of the product distribution and of the apparent activation energy of the reactionwas observed at about 490 ºC. This phenomenon, already observed in the oxidative dehydrogenation of n-butane, has been interpreted by the existence of two reaction mechanisms depending upon the reaction temperature. Comparison with the n-butane reaction allowed different activation pathways for the activation of alkanes to be proposed. The catalytic properties of TiP2O7 in the oxidative dehydrogenation of isobutane was also compared to those obtained previously with several other pyrophosphates and TiP2O7 was found to be less active and selective for this reaction.

  15. Fe-Catalyzed Cross-Dehydrogenative Coupling Reactions.

    Lv, Leiyang; Li, Zhiping

    2016-08-01

    Cross-dehydrogenative coupling (CDC), which enables the formation of carbon-carbon (C-C) and C-heteroatom bonds from the direct coupling of two C-H bonds or C-H/X-H bonds, represents a new state of the art in the field of organic chemistry. Iron, a prominent metal, has already shown its versatile application in chemical synthesis. This review attempts to provide a comprehensive understanding of the evolution of cross-dehydrogenative coupling via iron catalysis, as well as its application in synthetic chemistry. PMID:27573390

  16. Shaking table test study on seismic performance of dehydrogenation fan for nuclear power plants

    Seismic performance of the dehydrogenation fan for nuclear power plants was evaluated based on the shaking table test of earthquake simulation. Dynamic characteristics including the orthogonal tri-axial fundamental frequencies and equivalent damping ratios were measured by the white noise scanning method. Artificial seismic waves were generated corresponding to the floor acceleration response spectra for nuclear power plants. Furthermore, five OBE and one SSE shaking table tests for dehydrogenation fan were performed by using the artificial seismic waves as the seismic inputs along the orthogonal axis simultaneity. Operating function of dehydrogenation fan was monitored and observed during all seismic tests, and performance indexes of dehydrogenation fan were compared before and after seismic tests. The results show that the structural integrity and operating function of the dehydrogenation fan are perfect during all seismic tests; and the performance indexes of the dehydrogenation fan can remain consistent before and after seismic tests; the seismic performance of the dehydrogenation fan can satisfy relevant technical requirements. (authors)

  17. Characterizing the infrared spectra of small, neutral, fully dehydrogenated PAHs

    Mackie, C J; Bauschlicher, C W; Cami, J

    2014-01-01

    We present the results of a computational study to investigate the infrared spectroscopic properties of a large number of polycyclic aromatic hydrocarbon (PAH) molecules and their fully dehydrogenated counterparts. We constructed a database of fully optimized geometries for PAHs that is complete for eight or fewer fused benzene rings, thus containing 1550 PAHs and 805 fully dehydrogenated aromatics. A large fraction of the species in our database have clearly non-planar or curved geometries. For each species, we determined the frequencies and intensities of their normal modes using density functional theory calculations. Whereas most PAH spectra are fairly similar, the spectra of fully dehydrogenated aromatics are much more diverse. Nevertheless, these fully dehydrogenated species show characteristic emission features at 5.2$\\mu$m, 5.5$\\mu$m and 10.6$\\mu$m; at longer wavelengths, there is a forest of emission features in the 16--30$\\mu$m range that appears as a structured continuum, but with a clear peak cent...

  18. Transfer Methane to Fragrant Hydrocarbon by Direct Catalyzed Dehydrogenation

    2006-01-01

    @@ Sponsored by NSFC,a research project -"Transfer methane to fragrant hydrocarbon by direct catalyzed dehydrogenation",directed by Prof.Xin Bao from Dalian Institute of Chemical Physics of CAS,honored the 2nd class National Science & Technology Award in 2005.

  19. Combustion kinetics of the coke on deactivated dehydrogenation catalysts

    Luo, Sha; He, Songbo; Li, XianRu; Li, Jingqiu; Bi, Wenjun; Sun, Chenglin

    2015-01-01

    The coke combustion kinetics on the deactivated catalysts for long chain paraffin dehydrogenation was studied by the thermogravimetry and differential thermogravimetry (TG–DTG) technique. The amount and H/C mole ratio of the coke were determined by the TG and elemental analysis. And the comprehensiv

  20. Propane Dehydrogenation on Metal and Metal Oxide Catalysts

    Sattler, Jesper

    2014-01-01

    In this PhD thesis, the catalytic performance and deactivation of various propane dehydrogenation catalysts is studied. First of all, a literature study is performed, where the three most commonly used formulations, namely Pt-, CrOx- and GaOx-based catalysts are compared in terms of yield relative t

  1. Kinetic modeling of ethylbenzene dehydrogenation over hydrotalcite catalysts

    Atanda, Luqman

    2011-07-01

    Kinetics of ethylbenzene dehydrogenation to styrene was investigated over a series of quaternary mixed oxides of Mg3Fe0.25Me0.25Al0.5 (Me=Co, Mn and Ni) catalysts prepared by calcination of hydrotalcite-like compounds and compared with commercial catalyst. The study was carried out in the absence of steam using a riser simulator at 400, 450, 500 and 550°C for reaction times of 5, 10, 15 and 20s. Mg3Fe0.25Mn0.25Al0.5 afforded the highest ethylbenzene conversion of 19.7% at 550°C. Kinetic parameters for the dehydrogenation process were determined using the catalyst deactivation function based on reactant conversion model. The apparent activation energies for styrene production were found to decrease as follows: E1-Ni>E1-Co>E1-Mn. © 2011 Elsevier B.V.

  2. Carbon mediated catalysis:A review on oxidative dehydrogenation

    De Chen; Anders Holmen; Zhijun Sui; Xinggui Zhou

    2014-01-01

    Carbon mediated catalysis has gained an increasing attention in both areas of nanocatalysis and nanomaterials. The progress in carbon nanomaterials provides many new opportunities to manip-ulate the types and properties of active sites of catalysts through manipulating structures, function-alities and properties of carbon surfaces. The present review focuses on progresses in carbon medi-ated oxidative dehydrogenation reactions of ethylbenzene, propane, and butane. The state-of-the-art of the developments of carbon mediated catalysis is discussed in terms of fundamental studies on adsorption of oxygen and hydrocarbons, reaction mechanism as well as effects of carbon nano-material structures and surface functional groups on the catalytic performance. We highlight the importance and challenges in tuning of the electron density of carbon and oxygen on carbon surfac-es for improving selectivity in oxidative dehydrogenation reactions.

  3. Chromium oxide catalysts in the dehydrogenation of alkanes

    Airaksinen, Sanna

    2005-01-01

    Light alkenes, such as propene and butenes, are important intermediates in the manufacture of fuel components and chemicals. The direct catalytic dehydrogenation of the corresponding alkanes is a selective way to produce these alkenes and is frequently carried out using chromia/alumina catalysts. The aim of this work was to obtain structure–activity information, which could be utilised in the optimisation of this catalytic system. The properties of chromia/alumina catalysts were investigated ...

  4. Membrane catalysis in the dehydrogenation and hydrogen production processes

    Data on the applications of membrane catalysis in the dehydrogenation of organic compounds and hydrogen production are analyzed and generalized. It is shown that the integration of membrane reactors into existing plants is necessary for production of hydrogen of high purity. The steam reforming and oxidative reforming of methane and steam reforming of light alcohols seem to be the most promising processes for hydrogen production in membrane reactors. The bibliography includes 165 references.

  5. Study of the niobium dehydrogenation process by transmission electron microscopy

    The evolution of the micro-structure of Nb-H, during the dehydrogenation process through thermal treatment, has been studied by Transmission Electron Microscopy. The results are used in order to interpret the variation of the line resolution of Electron Channeling Pattern (ECP) of Nb-H as a function of isochronous annealing temperature. It is concluded that the improvement of the ECP line resolution is enhanced of β hydrate in Nb. (Author)

  6. Increased long chain acyl-Coa synthetase activity and fatty acid import is linked to membrane synthesis for development of picornavirus replication organelles.

    Jules A Nchoutmboube

    Full Text Available All positive strand (+RNA viruses of eukaryotes replicate their genomes in association with membranes. The mechanisms of membrane remodeling in infected cells represent attractive targets for designing future therapeutics, but our understanding of this process is very limited. Elements of autophagy and/or the secretory pathway were proposed to be hijacked for building of picornavirus replication organelles. However, even closely related viruses differ significantly in their requirements for components of these pathways. We demonstrate here that infection with diverse picornaviruses rapidly activates import of long chain fatty acids. While in non-infected cells the imported fatty acids are channeled to lipid droplets, in infected cells the synthesis of neutral lipids is shut down and the fatty acids are utilized in highly up-regulated phosphatidylcholine synthesis. Thus the replication organelles are likely built from de novo synthesized membrane material, rather than from the remodeled pre-existing membranes. We show that activation of fatty acid import is linked to the up-regulation of cellular long chain acyl-CoA synthetase activity and identify the long chain acyl-CoA syntheatse3 (Acsl3 as a novel host factor required for polio replication. Poliovirus protein 2A is required to trigger the activation of import of fatty acids independent of its protease activity. Shift in fatty acid import preferences by infected cells results in synthesis of phosphatidylcholines different from those in uninfected cells, arguing that the viral replication organelles possess unique properties compared to the pre-existing membranes. Our data show how poliovirus can change the overall cellular membrane homeostasis by targeting one critical process. They explain earlier observations of increased phospholipid synthesis in infected cells and suggest a simple model of the structural development of the membranous scaffold of replication complexes of picorna-like viruses, that may be relevant for other (+RNA viruses as well.

  7. DISTINCT TRANSCRIPTIONAL REGULATION OF LONG-CHAIN ACYL-COA SYNTHETASE ISOFORMS AND CYTOSOLIC THIOESTERASE 1 IN THE RODENT HEART BY FATTY ACIDS AND INSULIN

    The molecular mechanism(s) responsible for channeling long-chain fatty acids (LCFAs) into oxidative versus nonoxidative pathways is (are) poorly understood in the heart. Intracellular LCFAs are converted to long-chain fatty acyl-CoAs (LCFA-CoAs) by a family of long-chain acyl-CoA synthetases (ACSLs)...

  8. Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

    Masoud Hasany; Mohammad Malakootikhah; Vahid Rahmanian; Soheila Yaghmaei

    2015-01-01

    A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction, removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production. For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used. Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogena-tion method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and significant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

  9. Rhodium-technetium catalysts in dehydrogenation of cyclohexane

    Catalytic properties of Rh-Tc/support (γ-Al2O3, SiO2 or MgO) system in dehydrogenation of cyclohexane were studied. A nonadditive increase in catalytic activity of bimetallic catalysts in comparison with monometallic catalysts has been established. Diffuse reflectance spectra have shown the presence of ionic forms of the metals in bimetallic catalysts. From the comparison of catalytic and optical properties a conclusion was drawn about the nature of synergism observed, which was accounted for by the formation of RhxTcy clusters. 6 refs.; 5 figs.; 1 tab

  10. Dehydrogenation of Methylcyclohexane: Parametric Sensitivity of the Power Law Kinetics

    Arthur A. Garforth; David L. Cresswell; Usman, Muhammad R.

    2013-01-01

    For heterogeneous catalytic reactions, the empirical power law model is a valuable tool that explains variation in the kinetic behavior with changes in operating conditions, and therefore aids in the development of an appropriate and robust kinetic model. In the present work, experiments are performed on 1.0 wt% Pt/Al2O3 catalyst over a wide range of experimental conditions and parametric sensitivity of the power law model to the kinetics of the dehydrogenation of methylcyclohexane is studied...

  11. Synthesis, thermal behavior, and dehydrogenation kinetics study of lithiated ethylenediamine.

    Chen, Juner; Wu, Guotao; Xiong, Zhitao; Wu, Hui; Chua, Yong Shen; Zhou, Wei; Liu, Bin; Ju, Xiaohua; Chen, Ping

    2014-10-13

    The lithiation of ethylenediamine by LiH is a stepwise process to form the partially lithiated intermediates LiN(H)CH2 CH2 NH2 and [LiN(H)CH2 CH2 NH2 ][LiN(H)CH2 CH2 N(H)Li]2 prior to the formation of dilithiated ethylenediamine LiN(H)CH2 CH2 N(H)Li. A reversible phase transformation between the partial and dilithiated species was observed. One dimensional {Lin Nn } ladders and three-dimensional network structures were found in the crystal structures of LiN(H)CH2 CH2 NH2 and LiN(H)CH2 CH2 N(H)Li, respectively. LiN(H)CH2 CH2 N(H)Li undergoes dehydrogenation with an activation energy of 181±8 kJ mol(-1) , whereas the partially lithiated ethylenediamine compounds were polymerized and released ammonia at elevated temperatures. The dynamical dehydrogenation mechanism of the dilithiated ethylenediamine compounds was investigated by using the Johnson-Mehl-Avrami equation. PMID:25164593

  12. Influence of precursor a-Si:H dehydrogenation on the aluminum induced crystallization process

    Duan, Weiyuan, E-mail: weiyuan.duan0924@mail.sim.ac.cn [New Energy Technology Center, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 235 Chengbei Road, Jiading, Shanghai 200050 (China); University of the Chinese Academy of Sciences, Beijing 100039 (China); Qiu, Yu, E-mail: yuqiu@mail.sim.ac.cn [New Energy Technology Center, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 235 Chengbei Road, Jiading, Shanghai 200050 (China); Zhang, Liping; Yu, Jian; Bian, Jiantao; Liu, Zhengxin [New Energy Technology Center, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 235 Chengbei Road, Jiading, Shanghai 200050 (China)

    2014-07-01

    Polycrystalline silicon (poly-Si) thin film grown on low cost substrates such as glass at low temperature is an attractive material for cost-effective solar cells. This work studied the influence of dehydrogenation of a-Si:H precursor on the crystallization behavior by aluminum induced crystallization (AIC) process below the eutectic temperature of 577 °C. The a-Si:H films were deposited by PECVD and aluminum was evaporated in a vacuum evaporation equipment, respectively. Some of the a-Si:H thin films were dehydrogenated in nitrogen atmosphere before aluminum evaporation. It was found that hydrogen content in a-Si:H drops to a stable value after annealing at 480 °C for 1 h. Micro-Raman spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy and scanning electron microscopy measurements were used to investigate the structural characteristics of the a-Si:H and the prepared poly-Si thin films. Our results show that although the dehydrogenation increases AIC temperature and reduces AIC rate, it can improve microstructural quality of poly-Si thin films, leading to less tensile stress, higher crystallinity, smoother and more conformal surface morphology. - Highlights: • The influence of a-Si:H precursor dehydrogenation on AIC process was studied. • Dehydrogenation can improve microstructural quality of poly-Si thin films. • Smoother surface morphology can be observed on dehydrogenation samples after AIC. • The dehydrogenation process is necessary for fabricating high quality solar cells.

  13. Dehydrogenation process of AlH{sub 3} observed by TEM

    Nakagawa, Yuki, E-mail: y-nakagawa@eng.hokudai.ac.jp [Graduate School of Engineering, Hokkaido University, N-13, W-8, Sapporo 060-8278 (Japan); Isobe, Shigehito [Graduate School of Engineering, Hokkaido University, N-13, W-8, Sapporo 060-8278 (Japan); Creative Research Institution, Hokkaido University, N-21, W-10, Sapporo 001-0021 (Japan); Wang, Yongming; Hashimoto, Naoyuki; Ohnuki, Somei [Graduate School of Engineering, Hokkaido University, N-13, W-8, Sapporo 060-8278 (Japan); Zeng, Liang; Liu, Shusheng; Ichikawa, Takayuki; Kojima, Yoshitsugu [Institute for Advanced Materials Research, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8530 (Japan)

    2013-12-15

    Highlights: ► The initial shape of α-AlH{sub 3} particle is cubic and that of γ-AlH{sub 3} is rod-shaped. ► Dehydrogenation kinetics does not depend on Al{sub 2}O{sub 3} thickness in the 4.6–7.8 nm range. ► Milling effect on dehydrogenation kinetics will be larger than doping effect. -- Abstract: Dehydrogenation processes of α- and γ-AlH{sub 3} were investigated by in situ transmission electron microscopy observations. The relationship between Al{sub 2}O{sub 3} thickness and dehydrogenation kinetics was also clarified. The initial shape of α-AlH{sub 3} particle was cubic and that of γ-AlH{sub 3} particle was rod-shaped. The process of γ-AlH{sub 3} was quite similar with α-AlH{sub 3}. The precipitation and growth of Al was observed in both processes. The dehydrogenation kinetics did not depend on Al{sub 2}O{sub 3} thickness. It was found that milling effect on the dehydrogenation kinetics was larger than doping effect. The dehydrogenation process was discussed in terms of both microscopic and kinetic studies.

  14. Propane Dehydrogenation over a Commercial Pt-Sn/Al2O3 Catalyst for Isobutane Dehydrogenation: Optimization of Reaction Conditions

    Farnaz Tahriri Zangeneh; Saeed Sahebdelfar; Mohsen Bahmani

    2013-01-01

    The applicability of a commercial Pt-Sn/Al2O3 isobutane dehydrogenation catalyst in dehydrogenation of propane was studied.Catalyst performance tests were carried out in a fixed-bed quartz reactor under different operating conditions.Generally,as the factors improving propane conversion decrease the propylene selectivity,the optimal operating condition to maximize propylene yield is expected.The optimal condition was obtained by the experimental design method.The investigated parameters were temperature,hydrogen/hydrocarbon (H2/HC) ratio and space velocity,being changed in three levels.Constrains such as the susceptibility of the catalyst components to sintering or phase transformation were also taken into account.Activity,selectivity and stability of the catalyst were considered as the measured response factors,while the space-time-yield (STY) was considered as the variable to be optimized due to its commercial interest.A STY of 16 mol·kg-1·h-1 was achieved under the optimal conditions of T=620 ℃,H2/HC =0.6 and,weight hourly space velocity (WHSV) =2.2 h-1.Single carbon-carbon bond rupture was found to be the main route for the formation of lower hydrocarbon byproducts.

  15. Synthesis of Borohydride and Catalytic Dehydrogenation by Hydrogel Based Catalyst

    Boynuegri, Tugba Akkas; Karabulut, Ahmet F.; Guru, Metin

    2016-08-01

    This paper deals with the synthesis of calcium borohydride (Ca(BH4)2) as hydrogen storage material. Calcium chloride salt (CaCl2), magnesium hydride (MgH2), and boron oxide (B2O3) were used as reactants in the mechanochemical synthesis of Ca(BH4)2. The mechanochemical reaction was carried out by means of Spex type ball milling without applying high pressure and temperature. Parametric studies have been established at different reaction times and for different amounts of reactants at a constant ball to powder ratio (BPR) 4:1. The best combination was determined by Fourier Transform Infrared (FT-IR) analysis. According to the FT-IR analysis, reaction time, the first reaction parameter, was found as 1600 min. After the reaction time was fixed at 1600 min, the difference of the B-H peak areas was dependent on the amount of reactant MgH2 that was investigated. The amount of the reactant (MgH2), the second reaction parameter, was measured to be 2.85 times more than the stoichiometric amount of MgH2. According to our previous studies, BPR was selected as 4:1 for all experiments. Samples were prepared in a glove box under argon atmosphere but the time that elapsed for FT-IR analysis highly affected B-H bonds. B-H peak areas clearly decreased with time because of negative effect of ambient atmosphere. A catalyst was prepared by absorbing cobalt fluoride (CoF2) in poly (acrylamide-co-acrylic acid) hydrogel matrices type and its catalytic dehydrogenation performance that has been characterized by the catalytic reaction of sodium borohydride's known hydrogen capacity in an alkaline medium. The metal amount of hydrogel catalyst was determined as 135.82 mg Co by Atomic Absorption Spectroscopy (AAS). The specific dehydrogenation capacity of the Co active compound in the catalyst thanks to catalytic dehydrogenation of commercial sodium borohydride was measured as 1.66 mL H2/mg Co.

  16. Kinetics with deactivation of methylcyclohexane dehydrogenation for hydrogen energy storage

    Maria, G.; Marin, A.; Wyss, C.; Mueller, S.; Newson, E. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    The methylcyclohexane dehydrogenation step to recycle toluene and release hydrogen is being studied as part of a hydrogen energy storage project. The reaction is performed catalytically in a fixed bed reactor, and the efficiency of this step significantly determines overall system economics. The fresh catalyst kinetics and the deactivation of the catalyst by coke play an important role in the process analysis. The main reaction kinetics were determined from isothermal experiments using a parameter sensitivity analysis for model discrimination. An activation energy for the main reaction of 220{+-}11 kJ/mol was obtained from a two-parameter model. From non-isothermal deactivation in PC-controlled integral reactors, an activation energy for deactivation of 160 kJ/mol was estimated. A model for catalyst coke content of 3-17 weight% was compared with experimental data. (author) 3 figs., 6 refs.

  17. A prolific catalyst for dehydrogenation of neat formic acid.

    Celaje, Jeff Joseph A; Lu, Zhiyao; Kedzie, Elyse A; Terrile, Nicholas J; Lo, Jonathan N; Williams, Travis J

    2016-01-01

    Formic acid is a promising energy carrier for on-demand hydrogen generation. Because the reverse reaction is also feasible, formic acid is a form of stored hydrogen. Here we present a robust, reusable iridium catalyst that enables hydrogen gas release from neat formic acid. This catalysis works under mild conditions in the presence of air, is highly selective and affords millions of turnovers. While many catalysts exist for both formic acid dehydrogenation and carbon dioxide reduction, solutions to date on hydrogen gas release rely on volatile components that reduce the weight content of stored hydrogen and/or introduce fuel cell poisons. These are avoided here. The catalyst utilizes an interesting chemical mechanism, which is described on the basis of kinetic and synthetic experiments. PMID:27076111

  18. Thin Film Models of Magnesium Orthovanadate Catalysts for Oxidative Dehydrogenation

    SAULT,ALLEN G.; MUDD,JASON E.; MILLER,JAMES E.; RUFFNER,JUDITH A.; RODRIGUEZ,MARK A.; TISSOT JR.,RALPH G.

    2001-03-01

    Magnesium vanadates are potentially important catalytic materials for the conversion of alkanes to alkenes via oxidative dehydrogenation. However, little is known about the active sites at which the catalytic reactions take place. It may be possible to obtain a significant increase in the catalytic efficiency if the effects of certain material properties on the surface reactions could be quantified and optimized through the use of appropriate preparation techniques. Given that surface reactivity is often dependent upon surface structure and that the atomic level structure of the active sites in these catalysts is virtually unknown, we desire thin film samples consisting of a single magnesium vanadate phase and a well defined crystallographic orientation in order to reduce complexity and simplify the study of active sites. This report describes the use of reactive RF sputter deposition to fabricate very highly oriented, stoichiometric Mg{sub 3}(VO{sub 4}){sub 2} thin films, and subsequent studies of the reactivity of these films under reaction conditions typically found during oxidative dehydrogenation. We demonstrate that the synthesis methods employed do in fact result in stoichiometric films with the desired crystallographic orientation, and that the chemical behavior of the films closely approximates that of bulk, high surface area Mg{sub 3}(VO{sub 4}){sub 2} powders. We further use these films to demonstrate the effects of oxygen vacancies on chemical behavior, demonstrate that surface composition can vary significantly under reaction conditions, and obtain the first evidence for structure sensitivity in Mg{sub 3}(VO{sub 4}){sub 2} catalysts.

  19. Highly efficient VOx/SBA-15 mesoporous catalysts for oxidative dehydrogenation of propane.

    Liu, Yong-Mie; Cao, Yong; Zhu, Ka-Ke; Yan, Shi-Run; Dai, Wei-Lin; He, He-Yong; Fan, Kang-Nian

    2002-12-01

    Highly dispersed vanadia species on SBA-15 mesoporous silica have been found to exhibit a highly efficient catalytic performance for the oxidative dehydrogenation (ODH) of propane to light olefins (propene + ethylene). PMID:12478769

  20. Calorimetry of dehydrogenation and dangling-bond recombination in several hydrogenated amorphous silicon materials

    Roura Grabulosa, Pere; Farjas Silva, Jordi; Rath, Chandana; Serra-Miralles, J.; Bertrán Serra, Enric; Roca I Cabarrocas, Pere

    2006-01-01

    Differential scanning calorimetry (DSC) was used to study the dehydrogenation processes that take place in three hydrogenated amorphous silicon materials: nanoparticles, polymorphous silicon, and conventional device-quality amorphous silicon. Comparison of DSC thermograms with evolved gas analysis (EGA) has led to the identification of four dehydrogenation processes arising from polymeric chains (A), SiH groups at the surfaces of internal voids (A'), SiH groups at interfaces (B), and in the b...

  1. In situ spectroscopic investigation of oxidative dehydrogenation and disproportionation of benzyl alcohol

    Nowicka, E.; HOFMANN, J.P.; Parker, S. F.; Sankar, M.; Lari, G.M.; Kondrat, S.A.; Knight, D. W.; Bethell, D; Weckhuysen, B.M.; G. J. Hutchings

    2013-01-01

    In the solvent free oxidation of benzyl alcohol, using supported gold–palladium nanoalloys, toluene is often one of major by-products and it is formed by the disproportionation of benzyl alcohol. Gold–palladium catalysts on acidic supports promote both the disproportionation of benzyl alcohol and oxidative dehydrogenation to form benzaldehyde. Basic supports completely switch off disproportionation and the gold–palladium nanoparticles catalyse the oxidative dehydrogenation reaction exclusivel...

  2. Characterization and Dehydrogenation Activity of SBA-15 and HMS Supported Chromia Catalysts

    YUE,Hong-Yong(乐洪咏); ZHENG,Bo(郑波); YUE,Ying-Hong(乐英红); ZHANG,Xue-Zheng(张雪峥); HUA,Wei-Ming(华伟明); GAO,Zi(高滋)

    2002-01-01

    SBA-15 and HMS supported chromia catalysts were prepared and characterized. Chromia is highly dispersed on the mesoporous supports when its loading is ≤7 wt%. The supported catalysts display high activity, selectivity and stability for dehydrogenation of ethyibenzene and propane. ESR measurement of the catalysts before and after reaction shows that the active species for dehydrogenation reaction might be Cr3 + species on the catalyst surface, and the activity of the catalyst is probably correlated with the dispersion of Cr3+ species.

  3. Novel Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation

    Sun, Pingping; Siddiqi, Georges; Vining, William C.; Chi, Miaofang; Bell, Alexis T. (UCB); (ORNL)

    2011-10-28

    Catalysts for the dehydrogenation of light alkanes were prepared by dispersing Pt on the surface of a calcined hydrotalcite-like support containing indium, Mg(In)(Al)O. Upon reduction in H{sub 2} at temperatures above 673 K, bimetallic particles of PtIn are observed by TEM, which have an average diameter of 1 nm. Analysis of Pt LIII-edge extended X-ray absorption fine structure (EXAFS) data shows that the In content of the bimetallic particles increases with increasing bulk In/Pt ratio and reduction temperature. Pt LIII-edge X-ray absorption near edge structure (XANES) indicates that an increasing donation of electronic charge from In to Pt occurs with increasing In content in the PtIn particles. The activity and selectivity of the Pt/Mg(In)(Al)O catalysts for ethane and propane dehydrogenation reactions are strongly dependent on the bulk In/Pt ratio. For both reactants, maximum activity was achieved for a bulk In/Pt ratio of 0.48, and at this In/Pt ratio, the selectivity to alkene was nearly 100%. Coke deposition was observed after catalyst use for either ethane or propane dehydrogenation, and it was observed that the alloying of Pt with In greatly reduced the amount of coke deposited. Characterization of the deposit by Raman spectroscopy indicates that the coke is present as highly disordered graphite particles <30 nm in diameter. While the amount of coke deposited during ethane and propane dehydrogenation are comparable, the effects on activity are dependent on reactant composition. Coke deposition had no effect on ethane dehydrogenation activity, but caused a loss in propane dehydrogenation activity. This difference is attributed to the greater ease with which coke produced on the surface of PtIn nanoparticles migrates to the support during ethane dehydrogenation versus propane dehydrogenation.

  4. Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air

    Poreddy, Raju; Engelbrekt, Christian; Riisager, Anders

    2015-01-01

    The oxidative dehydrogenation of alcohols to carbonyl compounds was studied using CuO nanoparticle catalysts prepared by solution synthesis in buffered media. CuO nanoparticles synthesized in N-cyclohexyl- 3-aminopropanesulfonic acid buffer showed high catalytic activity for the oxidation of...... dehydrogenation of benzyl alcohols to be proposed. The use of CuO as an inexpensive and efficient heterogeneous catalyst under aerobic conditions provides a new noble metal-free and green reaction protocol for carbonyl compound synthesis....

  5. Surface-Modified Carbon Nanotubes Catalyze Oxidative Dehydrogenation of n-Butane

    J. Zhang; Liu, X; Blume, R.; Zhang, A; Schlögl, R.; Su, D.

    2008-01-01

    Butenes and butadiene, which are useful intermediates for the synthesis of polymers and other compounds, are synthesized traditionally by oxidative dehydrogenation (ODH) of n-butane over complex metal oxides. Such catalysts require high O2/butane ratios to maintain the activity, which leads to unwanted product oxidation. We show that carbon nanotubes with modified surface functionality efficiently catalyze the oxidative dehydrogenation of n-butane to butenes, especially butadiene. For low O2/...

  6. Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

    Shan, Junjun; Lucci, Felicia R.; Liu, Jilei; El-Soda, Mostafa; Marcinkowski, Matthew D.; Allard, Lawrence F.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

    2016-08-01

    The non-oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have an excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 °C, and in ultra-high vacuum using model PtCu(111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are more than one order of magnitude higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a reactant in the methanol steam reforming reactions only at higher temperatures over the same metal catalyst.

  7. Dehydrogenation mechanism of LiBH{sub 4} by Poly(methyl methacrylate)

    Huang, Jianmei [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Yan, Yurong [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); Ouyang, Liuzhang, E-mail: meouyang@scut.edu.cn [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Key Laboratory for Fuel Cell Technology in Guangdong Province, South China University of Technology, Guangzhou 510641 (China); Wang, Hui [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China); Zhu, Min, E-mail: memzhu@scut.edu.cn [School of Materials Science and Engineering, and Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, South China University of Technology, Guangzhou 510641 (China); China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou 510641 (China)

    2015-10-05

    Highlights: • LiBH{sub 4} is amorphous after modified with PMMA. • Dehydrogenation temperature of LiBH{sub 4} decreases by 120 °C after modifying with PMMA. • The LiBH{sub 4}@PMMA composite releases 10 wt.% hydrogen at 360 °C within 1 h. • C=O group of PMMA weakens the B−H bonds to lower dehydrogenation temperature. - Abstract: We investigated the dehydrogenation properties and mechanism of Poly(methyl methacrylate) (PMMA) confined LiBH{sub 4}. Thermal stability of LiBH{sub 4} was reduced by PMMA, with a decrease in dehydrogenation temperature by 120 °C. At 360 °C, the composite showed fast dehydrogenation kinetics with 10 wt.% of hydrogen released within 1 h. The improved dehydrogenation performance was mainly attributed to the reaction between LiBH{sub 4} and PMMA forming Li{sub 3}BO{sub 3} as a final product. Furthermore, the presence of electrostatic interaction between B atom of LiBH{sub 4} and O atom in the carbonyl group of PMMA may weaken the B−H bonding of [BH{sub 4}]{sup −} and lower the hydrogen desorption temperature.

  8. Dehydrogenation mechanism of LiBH4 by Poly(methyl methacrylate)

    Highlights: • LiBH4 is amorphous after modified with PMMA. • Dehydrogenation temperature of LiBH4 decreases by 120 °C after modifying with PMMA. • The LiBH4@PMMA composite releases 10 wt.% hydrogen at 360 °C within 1 h. • C=O group of PMMA weakens the B−H bonds to lower dehydrogenation temperature. - Abstract: We investigated the dehydrogenation properties and mechanism of Poly(methyl methacrylate) (PMMA) confined LiBH4. Thermal stability of LiBH4 was reduced by PMMA, with a decrease in dehydrogenation temperature by 120 °C. At 360 °C, the composite showed fast dehydrogenation kinetics with 10 wt.% of hydrogen released within 1 h. The improved dehydrogenation performance was mainly attributed to the reaction between LiBH4 and PMMA forming Li3BO3 as a final product. Furthermore, the presence of electrostatic interaction between B atom of LiBH4 and O atom in the carbonyl group of PMMA may weaken the B−H bonding of [BH4]− and lower the hydrogen desorption temperature

  9. Iron deficiency

    Schou, Morten; Bosselmann, Helle; Gaborit, Freja;

    2015-01-01

    BACKGROUND: Both iron deficiency (ID) and cardiovascular biomarkers are associated with a poor outcome in heart failure (HF). The relationship between different cardiovascular biomarkers and ID is unknown, and the true prevalence of ID in an outpatient HF clinic is probably overlooked. OBJECTIVES...... understand iron metabolism in elderly HF patients....

  10. VLCAD deficiency

    Boneh, A; Andresen, B S; Gregersen, N; Ibrahim, M; Tzanakos, N; Peters, H; Yaplito-Lee, J; Pitt, J J

    2006-01-01

    We diagnosed six newborn babies with very long-chain acyl-CoA dehydrogenase deficiency (VLCADD) through newborn screening in three years in Victoria (prevalence rate: 1:31,500). We identified seven known and two new mutations in our patients (2/6 homozygotes; 4/6 compound heterozygotes). Blood sa...

  11. Aerobic Dehydrogenation of Cyclohexanone to Cyclohexenone Catalyzed by Pd(DMSO)2(TFA)2: Evidence for Ligand-Controlled Chemoselectivity

    Diao, Tianning; Pun, Doris; Stahl, Shannon S.

    2013-01-01

    The dehydrogenation of cyclohexanones affords cyclohexenones or phenols via removal of one or two equivalents of H2, respectively. We recently reported several PdII catalyst systems that effect aerobic dehydrogenation of cyclohexanones with different product selectivities. Pd(DMSO)2(TFA)2 is unique in its high chemoselectivity for the conversion of cyclohexanones to cyclohexenones, without promoting subsequent dehydrogenation of cyclohexenones to phenols. Kinetic and mechanistic studies of th...

  12. Process for alkane group dehydrogenation with organometallic catalyst

    Kaska, William C.; Jensen, Craig M.

    1998-01-01

    An improved process is described for the catalytic dehydrogenation of organic molecules having a ##STR1## group to produce a ##STR2## group. The organic molecules are: ##STR3## wherein: A.sup.1, A.sup.2, A.sup.3, and A.sup.4 are each independently P, As or N: E.sup.2 is independently C or N; E.sup.3 is independently C, Si or Ge; E.sup.4 is independently C, Si, or Ge; and E.sup.5 is independently C, Si or Ge; M.sup.1, M.sup.2, M.sup.3, and M.sup.4 each is a metal atom independently selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum; Q.sup.1, Q.sup.2, Q.sup.3, and Q.sup.4 are each independently a direct bond, --CH.sub.2 --, --CH.sub.2 CH.sub.2 --, or CH.dbd.CH--; in structure I, structure II or structure IV, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.1 and R.sup.2 together and R.sup.3 and R.sup.4 together form a ring structure having from 4 to 10 carbon atoms, or in structure III, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 are each independently selected from alkyl, alkenyl, cycloalkyl, and aryl, or R.sup.5 and R.sup.6 together and R.sup.7 and R.sup.8 together form a ring structure having from 4 to 10 carbon atoms, at a temperature of between about 100.degree. and 250.degree. C. for between about 1 hr and 300 days in the absence of N.sub.2. The surprisingly stable catalyst is a complex of an organic ligand comprising H, C, Si, N, P atoms, and a platinum group metal. The dehydrogenation is performed between about 100 to 200.degree. C., and has increased turnover.

  13. Ruthenium(II)-PNN pincer complex catalyzed dehydrogenation of benzyl alcohol to ester: A DFT study

    Tao, Jingcong; Wen, Li; Lv, Xiaobo; Qi, Yong; Yin, Hailiang

    2016-04-01

    The molecular mechanism of the dehydrogenation of primary alcohol to ester catalyzed by the ruthenium(II)-PNN pincer complex Ru(H)(η2-BH4)(PNN), [PNN: (2-(di-tert-butylphosphinomethyl)-6-(diethlaminomethyl)-pyridine)] has been investigated using density functional theory calculations. The catalytic cycle includes three stages: (stage I) alcohol dehydrogenation to form aldehyde, (stage II) coupling of aldehyde with alcohol to give hemiacetal or ester, and (stage III) hemiacetal dehydrogenation to form ester. Two dehydrogenation reactions occur via the β-H elimination mechanism rather than the bifunctional double hydrogen transfer mechanism, which could be rationalized as the fluxional behavior of the BH4- ligand. At the second stage, the coupling reaction requires alcohol or the ruthenium catalyst as mediator. The formation of hemiacetal through the alcohol-mediated pathway is kinetically favorable than the ruthenium catalyst-mediated one, which may be attributed to the smaller steric hindrance when the aldehyde approaches the alcohol moiety in the reaction system. Our results would be helpful for experimental chemists to design more effective transition metal catalysts for dehydrogenation of alcohols.

  14. A New Homogeneous Catalyst for the Dehydrogenation of Dimethylamine Borane Starting with Ruthenium(III Acetylacetonate

    Ebru Ünel Barın

    2015-06-01

    Full Text Available The catalytic activity of ruthenium(III acetylacetonate was investigated for the first time in the dehydrogenation of dimethylamine borane. During catalytic reaction, a new ruthenium(II species is formed in situ from the reduction of ruthenium(III and characterized using UV-Visible, Fourier transform infrared (FTIR, 1H NMR, and mass spectroscopy. The most likely structure suggested for the ruthenium(II species is mer-[Ru(N2Me43(acacH]. Mercury poisoning experiment indicates that the catalytic dehydrogenation of dimethylamine-borane is homogeneous catalysis. The kinetics of the catalytic dehydrogenation of dimethylamine borane starting with Ru(acac3 were studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Evaluation of the kinetic data provides the activation parameters for the dehydrogenation reaction: the activation energy Ea = 85 ± 2 kJ·mol−1, the enthalpy of activation ∆H# = 82 ± 2 kJ·mol−1 and the entropy of activation; ∆S# = −85 ± 5 J·mol−1·K−1. The ruthenium(II catalyst formed from the reduction of ruthenium(III acetylacetonate provides 1700 turnovers over 100 hours in hydrogen generation from the dehydrogenation of dimethylamine borane before deactivation at 60 °C.

  15. Oxidative dehydrogenation of ethane to ethylene using vanadia based catalysts

    Qiao, Ailing; Kalevaru, V.N. [Univ. Rostock e.V., Rostock (Germany). Leibniz-Inst. fuer Katalyse; Humar, A.S.; Lingaiah, N.; Sai Prasad, P.S.; Martin, A. [Indian Institute of Chemical Technology, Hyderabad (India). Inorganic and Physical Chemistry Div.

    2011-07-01

    In this work, we describe the application of V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalysts for the oxidative dehydrogenation (ODH) of ethane to ethylene. A series of Nb{sub 2}O{sub 5} supported V{sub 2}O{sub 5} catalysts were prepared by impregnation technique. NH{sub 4}VO{sub 3} was used as a precursor for V{sub 2}O{sub 5}. The content of V{sub 2}O{sub 5} is varied in the range from 5 to 20 wt%. Catalytic tests were carried out in a fixed bed quartz reactor in the temperature range from 500 to 600 C. The conversion of ethane has been increased from ca. 20 to 35 % with increase in temperature from 500 to 600 C, while the yield of ethylene is increased from about 5 to 12 % only. CO and CO{sub 2} are the only major by-products of the reaction. The activity tests were performed at low O{sub 2} concentration in the feed and hence low conversions were achieved. Furthermore, the conversion of ethane is found to increase continuously with increase in V{sub 2}O{sub 5} loading while the yield of C{sub 2}H{sub 4} increased only up to 10wt% V{sub 2}O{sub 5} and then decreased. Results revealed that the catalytic activity and selectivity is found to depend on the V{sub 2}O{sub 5} loading. Among all, 10wt% V{sub 2}O{sub 5}/Nb{sub 2}O{sub 5} catalyst has displayed the superior performance. (orig.)

  16. Manipulation of the electronic structure by reversible dehydrogenation of tetra(p-hydroxyphenyl)porphyrin molecules

    Smykalla, Lars; Mende, Carola; Rüffer, Tobias; Lang, Heinrich; Hietschold, Michael

    2014-01-01

    The controlled and reversible interconversion between the free-base and the doubly dehydrogenated form of a 5,10,15,20-tetra(p-hydroxyphenyl)porphyrin molecule in an ordered array is demonstrated. This is achieved through voltage pulses by hydrogen transfer between the center of the porphyrin and the tip of a scanning tunneling microscope (STM). The local dehydrogenation leads to significant shifts in the energetic positions of the molecular orbitals. Density functional theory (DFT) calculations corroborate our conclusions and allow to gain more insight into the different energy level alignment before and after dehydrogenation. Due to the different conductance at a given voltage a clear distinction of both molecular species is possible, which also enables the application as a single-molecular switch.

  17. Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

    Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

    2016-06-01

    We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

  18. Highly Ordered Mesoporous Metal Oxides as Catalysts for Dehydrogenation of Cyclohexanol

    Cyclohexanone is important intermediate for the manufacture of caprolactam which is monomer of nylron. Cyclohexanone is generally produced by dehydrogenation reaction of cyclohexanol. In this study, highly mesoporous metal oxides such as meso-WO3, meso-TiO2, meso-Fe2O3, meso-CuO, meso-SnO2 and meso-NiO were synthesized using mesoporous silica KIT-6 as a hard template via nano-replication method for dehydrogenation of cyclohexanol. The overall conversion of cyclohexanol followed a general order: meso-WO3 >> meso-Fe2O3 > meso-SnO2 > meso-TiO2 > meso-NiO > meso-CuO. In particular, meso-WO3 significantly showed higher activity than the other mesoporous metal oxides. Therefore, the meso-WO3 has wide range of application possibilities for dehydrogenation of cyclohexanol

  19. Dehydrogenation of light alkanes over rhenium catalysts on conventional and mesoporous MFI supports

    Rovik, Anne Krogh; Hagen, Anke; Schmidt, I.;

    2006-01-01

    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...

  20. Theoretical investigation of the mechanism of tritiated methane dehydrogenation reaction using nickel-based catalysts

    Dong, Liang; Li, Jiamao; Deng, Bing; Yang, Yong; Wang, Heyi [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China); Li, Weiyi [School of Physics and Chemistry, Xihua University, Chengdu 610065 (China); Li, Shuo, E-mail: lishuo@cqut.edu.cn [School of Chemical Engineering, Chongqing University of Technology, Chongqing 400054 (China); Tan, Zhaoyi, E-mail: tanzhaoyi@caep.cn [Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621900 (China)

    2015-06-15

    Graphical abstract: - Highlights: • Four-step dehydrogenation of CT{sub 4} catalyzed by Ni to form Ni–C by releasing T{sub 2}. • The process of Ni + CT{sub 4} → NiCT{sub 2} + T{sub 2} is more achievable than that of NiCT{sub 2} → NiC + T{sub 2}. • TNiCT → T{sub 2}NiC step is the RDS with the rate constant of k = 2.8 × 10{sup 13} exp(−313,136/RT). • The hydrogen isotope effect value of k{sub H}/k{sub T} is 2.94, and k{sub D}/k{sub T} is 1.39. • CH{sub 4} and CD{sub 4} dehydrogenations are likely to occur, accompanied by the CT{sub 4} cracking. - Abstract: The mechanism of tritiated methane dehydrogenation reaction catalyzed by nickel-based catalyst was investigated in detail by density functional theory (DFT) at the B3LYP/[6-311++G(d, p), SDD] level. The computational results indicated that the dehydrogenation of tritiated methane is endothermic. The decomposition of tritiated methane catalyzed by Ni to form Ni-based carbon (Ni–C) after a four-step dehydrogenation companied with releasing tritium. After the first and second dehydrogenation steps, Ni + CT{sub 4} formed NiCT{sub 2}. After the third and fourth dehydrogenation steps, NiCT{sub 2} formed NiC. The first and second steps of dehydrogenation occurred on both the singlet and triplet states, and the lowest energy route is Ni + CT{sub 4} → {sup 1}COM → {sup 1}TS1 → {sup 3}IM1 → {sup 3}TS2 → {sup 3}IM2. The third and fourth steps of dehydrogenation occurred on both the singlet and quintet states, and the minimum energy reaction pathway appeared to be IM3 → {sup 1}TS4 → {sup 5}IM4 → {sup 5}TS5 → {sup 5}IM5 → {sup 5}pro + T{sub 2}. The fourth step of dehydrogenation TNiCT → T{sub 2}NiC was the rate-determining step of the entire reaction with the rate constant of k{sub 2} = 2.8 × 10{sup 13} exp(−313,136/RT) (in cm{sup 3} mol{sup −1} s{sup −1}), and its activation energy barrier was calculated to be 51.8 kcal/mol. The Ni-catalyzed CH{sub 4} and CD{sub 4} cracking

  1. Experimental and Theoretical Mechanistic Investigation of the Iridium-Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols

    Olsen, Esben Paul Krogh; Singh, Thishana; Harris, Pernille;

    2015-01-01

    The mechanism for the iridium-BINAP catalyzed dehydrogenative decarbonylation of primary alcohols with the liberation of molecular hydrogen and carbon monoxide was studied experimentally and computationally. The reaction takes place by tandem catalysis through two catalytic cycles involving...... dehydrogenation of the alcohol and decarbonylation of the resulting aldehyde. The square planar complex IrCl(CO)(rac-BINAP) was isolated from the reaction between [Ir(cod)Cl](2), rac-BINAP, and benzyl alcohol. The complex was catalytically active and applied in the study of the individual steps in the catalytic...... cycles. One carbon monoxide ligand was shown to remain coordinated to iridium throughout the reaction, and release of carbon monoxide was suggested to occur from a dicarbonyl complex. IrH2Cl(CO)(rac-BINAP) was also synthesized and detected in the dehydrogenation of benzyl alcohol. In the same experiment...

  2. Iridium‐Catalyzed Dehydrogenative Decarbonylation of Primary Alcohols with the Liberation of Syngas

    Olsen, Esben Paul Krogh; Madsen, Robert

    2012-01-01

    A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe=cyclooct......A new iridium‐catalyzed reaction in which molecular hydrogen and carbon monoxide are cleaved from primary alcohols in the absence of any stoichiometric additives has been developed. The dehydrogenative decarbonylation was achieved with a catalyst generated in situ from [Ir(coe)2Cl]2 (coe......, dehydrogenation of the primary alcohol to the corresponding aldehyde takes place, which is then followed by decarbonylation to the product with one less carbon atom....

  3. Hydrogenation/Dehydrogenation Performances of the MgH2-WS2 Composites

    WANG Jiasheng; ZHANG Wei; CHENG Ying; KE Dandan; HAN Shumin

    2015-01-01

    The hydrogenation/dehydrogenation kinetics and thermodynamic behaviors of the MgH2-WS2 composites were investigated. The TPD (Temperature-Programmed-Desorption) curves showed that the onset dehydrogenation temperature of the MgH2 + 20wt% WS2 composite was 615 K, 58 K lower than that of the pristine MgH2. The kinetic measurements showed that within 21 min, the MgH2 + 20wt% WS2 composite could absorb 2.818wt% at 423 K, and release 4.244 wt% of hydrogen at 623 K, while the hydriding/dehydriding capacity of MgH2 reached only 0.979wt% and 2.319wt% respectively under identical conditions. The improvement of hydrogenation/dehydrogenation performances for the composite was attributed to the co-catalytic effect between the new phases W and MgS which formed during the ball-milling process.

  4. Study on the dehydrogenation kinetics and thermodynamics of Ca(BH4)2

    Ca(BH4)2 is a promising hydrogen storage material due to its high gravimetric hydrogen density of 11.5 wt%. In this work, the dehydrogenation kinetics and thermodynamics of Ca(BH4)2 were systematically investigated by differential thermal analysis (DTA), thermal analysis mass spectrometry (TA/MS), temperature-programmed desorption (TPD), X-ray diffraction (XRD) and pressure, composition, and temperature (PCT) measurements. DTA, TA/MS, TPD and XRD results indicate that the dehydrogenation process of Ca(BH4)2 is a two-step reaction. The dehydriding reaction of Ca(BH4)2 starts at approximately 320 oC, and about 9.6% of hydrogen is desorbed through the two-step reaction. The apparent activation energy (Ea) of about 225.37 and 280.51 kJ/mol for the first-step and second-step dehydrogenation, respectively, were determined by Kissinger's method. The activation energy for the first-step dehydrogenation was further confirmed by the Arrhenius equation. As a result of in-depth kinetic investigations, a geometrical contraction-controlled kinetic mechanism has been identified for the first-step dehydrogenation by analyzing isothermal hydrogen desorption curves with a linear plot method. Finally, the thermodynamic parameters for the dehydrogenation are estimated based on the results of the PCT measurements: enthalpy of reaction ΔH = 87 kJ/mol-H2, and entropy of reaction ΔS = 158 J/K mol-H2. The relatively high activation energy and change in enthalpy indicate that a kinetic and thermodynamic barrier needs to be overcome for Ca(BH4)2 to be suitable as a hydrogen storage material for mobile applications.

  5. Genetics Home Reference: isolated growth hormone deficiency

    ... deficiency dwarfism, pituitary growth hormone deficiency dwarfism isolated GH deficiency isolated HGH deficiency isolated human growth hormone deficiency isolated somatotropin deficiency isolated somatotropin deficiency disorder ...

  6. Mechanistic insights into the oxidative dehydrogenation of amines to nitriles in continuous flow

    Corker, Emily C.; Ruiz-Martínez, Javier; Riisager, Anders;

    2015-01-01

    The oxidative dehydrogenation of various aliphatic amines to their corresponding nitrile compounds using RuO2/Al2O3 catalysts in air was successfully applied to a continuous flow reaction. Conversions of amines (up to >99%) and yields of nitriles (up to 77%) varied depending on reaction conditions...... and the amine utilised. The presence of water was found to be important for the activity and stability of the RuO2/Al2O3 catalyst. The Hammett relationship and in situ infrared spectroscopy were applied to divulge details about the catalytic mechanism of the oxidative dehydrogenation of amines over Ru...

  7. Dehydrogenative Aromatization of Saturated Aromatic Compounds by Graphite Oxide and Molecular Sieves

    张轩; 徐亮; 王希涛; 马宁; 孙菲菲

    2012-01-01

    Graphite oxide (GO) has attracted much attention of material and catalysis chemists recently. Here we describe a combination of GO and molecular sieves for the dehydrogenative aromatization. GO prepared through improved Hummers method showed high oxidative activity in this reaction. Partially or fully saturated aromatic compounds were converted to their corresponding dehydrogenated aromatic products with fair to excellent conversions and selectivities. As both GO and molecular sieves are easily available, cheap, lowly toxic and have good tolerance to various functional groups, this reaction provides a facile approach toward aromatic compounds from their saturated precursors

  8. Development of packed bed membrane reactor for the oxidative dehydrogenation of propane

    Kotanjac, Zeljko

    2009-01-01

    In this research, a reactor concept for the oxidative dehydrogenation of propane was studied. First a literature survey was performed, to investigate which are the best catalyst systems and best operating conditions that result in the largest propylene yield. In the kinetic study of ODHP over a Ga2O

  9. Non-Precious Bimetallic Catalysts for Selective Dehydrogenation of an Organic Chemical Hydride System

    Shaikh Ali, Anaam

    2015-07-06

    Methylcyclohexane (MCH)-Toluene (TOL) chemical hydride cycles as a hydrogen carrier system is successful with the selective dehydrogenation reaction of MCH to TOL, which has been achieved only using precious Pt-based catalysts. Herein, we report improved selectivity using non-precious metal nickel-based bimetallic catalysts, where the second metal occupies the unselective step sites.

  10. A Three-Stage Mechanistic Model for Ammonia Borane Dehydrogenation by Shvo’s Catalyst

    Lu, Zhiyao; Conley, Brian L.; Williams, Travis J.

    2012-01-01

    We propose a mechanistic model for three-stage dehydrogenation of ammonia borane (AB) catalyzed by Shvo’s cyclopentadienone-ligated ruthenium complex. We provide evidence for a plausible mechanism for catalyst deactivation, the transition from fast catalysis to slow catalysis, and relate those findings to the invention of a second-generation catalyst that does not suffer from the same deactivation chemistry.

  11. Study of vanadium based mesoporous silicas for oxidative dehydrogenation of propane and n-butane

    Bulánek, R.; Kalužová, A.; Setnička, M.; Zukal, Arnošt; Čičmanec, P.; Mayerová, Jana

    2012-01-01

    Roč. 179, č. 1 (2012), s. 149-158. ISSN 0920-5861 R&D Projects: GA ČR GAP106/10/0196 Institutional research plan: CEZ:AV0Z40400503 Keywords : vanadium * oxidative dehydrogenation * mesoporous silicas Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.980, year: 2012

  12. The chemical origin and catalytic activity of coinage metals: from oxidation to dehydrogenation.

    Syu, Cih-Ying; Yang, Hao-Wen; Hsu, Fu-Hsing; Wang, Jeng-Han

    2014-04-28

    The high oxidation activity of coinage metals (Cu, Ag and Au) has been widely applied in various important reactions, such as oxidation of carbon monoxide, alkenes or alcohols. The catalytic behavior of those inert metals has mostly been attributable to their size effect, the physical effect. In the present study, the chemical effects on their high oxidation activity have been investigated. We mechanistically examine the direct and oxidative dehydrogenation (partial oxidation) reactions of ethanol to acetaldehyde on a series of transition metals (groups 9, 10 and 11) with identical physical characteristics and varied chemical origins using density functional theory (DFT) calculations and electronic structure analyses at the GGA-PW91 level. The energetic results show that coinage metals have much lower activation energies and higher exothermicities for the oxidative dehydrogenation steps although they have higher energy for the direct dehydrogenation reaction. In the electronic structure analyses, coinage metals with saturated d bands can efficiently donate electrons to O* and OH*, or other electronegative adspecies, and better promote their p bands to higher energy levels. The negatively charged O* and OH* with high-lying p bands are responsible for lowering the energies in oxidative steps. The mechanistic understanding well explains the better oxidation activity of coinage metals and provides valuable information on their utilization in other useful applications, for example, the dehydrogenation process. PMID:24626959

  13. Synthesis and characterization of conventional and mesoporous Ga-MFI for ethane dehydrogenation

    Leth, Karen Thrane; Rovik, Anne Krogh; Holm, Martin Spangsberg;

    2008-01-01

    difference being the morphology of the crystals. The catalytic properties of the samples were tested in ethane dehydrogenation at 823 K and at atmospheric pressure. The two Ga-MFI samples differ greatly in conversion of ethane, as a result of their difference in porosity, and it is found that the conversion...

  14. Structure of alumina supported vanadia catalysts for oxidative dehydrogenation of propane prepared by flame spray pyrolysis

    Høj, Martin; Jensen, Anker Degn; Grunwaldt, Jan-Dierk

    2013-01-01

    A series of five vanadia on alumina catalysts for oxidative dehydrogenation of propane to propene were synthesized by flame spray pyrolysis (FSP) using vanadium(III)acetylacetonate and aluminium(III)acetylacetonate dissolved in toluene as precursors. The vanadium loading was 2, 3, 5, 7.5 and 10wt...

  15. Simultaneous dehydrogenation of organic compounds and hydrogen removal by hydride forming alloys

    Appelman, W.J.T.M.; Kuczynski, M.; Versteeg, G.F.

    1992-01-01

    The applicability of hydrogen-absorbing metals in dehydrogenation reactions was investigated. Based on thermodynamic considerations, operating ranges were defined within which an increase of the reactant conversion can he achieved owing to an in situ hydrogen removal by the alloy. Low plateau pressu

  16. Amino olefin nickel(I) and nickel(0) complexes as dehydrogenation catalysts for amine boranes

    M. Vogt; B. de Bruin; H. Berke; M. Trincado; H. Grützmacher

    2011-01-01

    A rare paramagnetic organometallic nickel(I) olefin complex can be isolated using the ligand bis(5H-dibenzo[a,d]cyclohepten-5-yl)amine. This complex and related nickel(0) hydride complexes show very high catalytic activity in the dehydrogenation of dimethylamino borane with release of one equivalent

  17. Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

    2006-01-01

    Dehydrogenation of ethylbenzene (EB) to styrene (ST) in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift (RWGS), was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process.The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3.Coke deposition and deep reduction of active components are the major causes of catalyst deactivation.CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.

  18. Oxidative dehydrogenation of ethylbenzene to styrene over alumina : effect of calcination

    Nederlof, Christian; Zarubina, Valeriya; Melian-Cabrera, Ignacio; Heeres, Hero Jan (Eric); Kapteijn, Freek; Makkee, Michiel

    2013-01-01

    Commercially available gamma-Al2O3 was calcined at temperatures between 500 and 1200 degrees C and tested for its performance in the oxidative ethylbenzene dehydrogenation (ODH) over a wide range of industrially-relevant conditions. The original gamma-Al2O3, as well as Z- and alpha-Al2O3, were teste

  19. Versatile dehydrogenative alcohol silylation catalyzed by Cu(I)-phosphine complex.

    Ito, Hajime; Watanabe, Akiko; Sawamura, Masaya

    2005-04-28

    [reaction: see text] Cu(I) complexes of xanthane-based diphosphines were versatile catalysts for dehydrogenative alcohol silylation, exhibiting high activity and broad substrate scope. Highly selective silylation of 1-decanol over 2-decanol is possible even with a silylating reagent of small steric demand such as HSiMe(2)Ph or HSiEt(3). PMID:15844927

  20. Iron-Deficiency Anemia

    Full Text Available ... Deficiency Anemia Explore Iron-Deficiency Anemia What Is... CAUSES WHO IS AT RISK SIGNS & SYMPTOMS DIAGNOSIS TREATMENTS ... less hemoglobin than normal. Iron-deficiency anemia can cause fatigue (tiredness), shortness of breath, chest pain, and ...

  1. Spontaneous dehydrogenation of methanol over defect-free MgO(100) thin film deposited on molybdenum

    Song, Zhenjun

    2016-01-01

    The dehydrogenation reaction of methanol on metal supported MgO(100) films has been studied by employing periodic density functional calculations. As far as we know, the dehydrogenation of single methanol molecule over inert oxide insulators such as MgO has never been realized before without the introduction of defects and low coordinated atoms. By depositing the very thin oxide films on Mo substrate we have successfully obtained the dissociative state of methanol. The dehydrogenation reaction is energetically exothermic and nearly barrierless. The metal supported thin oxide films studied here provide a versatile approach to enhance the activity and properties of oxides.

  2. Theoretical Studies on Dehydrogenation Reactions in Mg2(BH4)2(NH2)2 Compounds

    Zheng Chen; Zhe-ning Chen; An-an Wu; Guo-tao Wu; Zhi-tao Xiong; Ping Chen; Xin Xu

    2012-01-01

    Borohydrides have been recently hightlighted as prospective new materials due to their high gravimetric capacities for hydrogen storage.It is,therefore,important to understand the underlying dehydrogenation mechanisms for further development of these materials.We present a systematic theoretical investigation on the dehydrogenation mechanisms of the Mg2(BH4)2(NH2)2 compounds.We found that dehydrogenation takes place most likely via the intermolecular process,which is favorable both kinetically and thermodynamically in comparison with that of the intramolecular process.The dehydrogenation of Mg2(BH4)2(NH2)2 initially takes place via the direct combination of the hydridic H in BH4-and the protic H in NH2-,followed by the formation of Mg-H and subsequent ionic recombination of Mg-Hδ-… Hδ+-N.

  3. Crystal structure change in the dehydrogenation process of the Li-Mg-N-H system

    Highlights: → Structural change in several dehydrogenation stages of p-c isotherm at 523 K. → Mg(NH2)2 and Li3Mg3(NH2)(NH)4 coexist in the plateau region. → Continuous change from Li3Mg3(NH2)(NH)4 to Li2Mg(NH)2 in the sloping region. → The crystal structure Li3+3yMg3(NH2)1-y(NH)4+2y was determined. → The dehydrogenation by the diffusion of Li+ and Mg2+ without N atom diffusion. - Abstract: The Li-Mg-N-H system has the property of reversible reaction with hydrogen between hydrogenation and dehydrogenation (Mg3N2 + 4Li3N + 12H2 ↔ 3Mg(NH2)2 + 12LiH). At the several dehydrogenation stages of p-c isotherm measurement at 523 K, the structural change was investigated using the synchrotron X-ray diffraction. There are two regions in p-c isotherm of the Li-Mg-N-H system, i.e. plateau and sloping region. In the plateau region, Mg(NH2)2 and Li3Mg3(NH2)(NH)4 coexist. In the sloping region, the intermediate phase Li3+3yMg3(NH2)1-y(NH)4+2y changes continuously from Li3Mg3(NH2)(NH)4 to Li2Mg(NH)2. The chemical composition of the intermediate phase was estimated from the amount of desorbed hydrogen by p-c isotherm and the atomic ratio of Mg and N by Rietveld analysis. The crystal structure of the intermediate phase, Li3+3yMg3(NH2)1-y(NH)4+2y (space group: I222), was determined. Because all these intermediate structures are similar to anti-CaF2-type, it is deduced that the dehydrogenation process are caused by the diffusion of Li+ to cation sites of Mg(NH2)2. The analysis of structural change clarified the dehydrogenation process that is accomplished by the diffusion of Li+ and Mg2+ without N atom diffusion.

  4. Elucidating the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts: A density functional theory study

    Wang, Ziyun; Liu, Xinyi; Rooney, D. W.; Hu, P.

    2015-10-01

    The dehydrogenation of cyclohexanol to cyclohexanone is very important in the manufacture of nylon. Copper-based catalysts are the most popular catalysts for this reaction, and on these catalysts the reaction mechanism and active site are in debate. In order to elucidate the mechanism and active site of the cyclohexanol dehydrogenation on copper-based catalysts, density functional theory with dispersion corrections were performed on up to six facets of copper in two different oxidation states: monovalent copper and metallic copper. By calculating the surface energies of these facets, Cu(111) and Cu2O(111) were found to be the most stable facets for metallic copper and for monovalent copper, respectively. On these two facets, all the possible elementary steps in the dehydrogenation pathway of cyclohexanol were calculated, including the adsorption, dehydrogenation, hydrogen coupling and desorption. Two different reaction pathways for dehydrogenation were considered on both surfaces. It was revealed that the dehydrogenation mechanisms are different on these two surfaces: on Cu(111) the hydrogen belonging to the hydroxyl is removed first, then the hydrogen belonging to the carbon is subtracted, while on Cu2O(111) the hydrogen belonging to the carbon is removed followed by the subtraction of the hydrogen in the hydroxyl group. Furthermore, by comparing the energy profiles of these two surfaces, Cu2O(111) was found to be more active for cyclohexanol dehydrogenation than Cu(111). In addition, we found that the coordinatively unsaturated copper sites on Cu2O(111) are the reaction sites for all the steps. Therefore, the coordinatively unsaturated copper site on Cu2O(111) is likely to be the active site for cyclohexanol dehydrogenation on the copper-based catalysts.

  5. Carnitine Deficiency and Pregnancy

    Anouk de Bruyn; Yves Jacquemyn; Kristof Kinget; François Eyskens

    2015-01-01

    We present two cases of carnitine deficiency in pregnancy. In our first case, systematic screening revealed L-carnitine deficiency in the first born of an asymptomatic mother. In the course of her second pregnancy, maternal carnitine levels showed a deficiency as well. In a second case, a mother known with carnitine deficiency under supplementation was followed throughout her pregnancy. Both pregnancies had an uneventful outcome. Because carnitine deficiency can have serious complications, su...

  6. Study on excimer laser irradiation for controlled dehydrogenation and crystallization of boron doped hydrogenated amorphous/nanocrystalline silicon multilayers

    Gontad, F., E-mail: fran_gontad@yahoo.es [Applied Physics Department, University of Vigo, E.I. Industrial, Campus de As Lagoas, Marcosende, E-36310, Vigo (Spain); Conde, J.C. [Applied Physics Department, University of Vigo, E.I. Industrial, Campus de As Lagoas, Marcosende, E-36310, Vigo (Spain); Filonovich, S.; Cerqueira, M.F.; Alpuim, P. [Department of Physics, University of Minho, Campus de Azurém, 4800-058 Guimarães (Portugal); Chiussi, S. [Applied Physics Department, University of Vigo, E.I. Industrial, Campus de As Lagoas, Marcosende, E-36310, Vigo (Spain)

    2013-06-01

    We report on the excimer laser annealing (ELA) induced temperature gradients, allowing controlled crystallization and dehydrogenation of boron-doped a-Si:H/nc-Si:H multilayers. Depth of the dehydrogenation and crystallization process has been studied numerically and experimentally, showing that temperatures below the monohydride decomposition can be used and that significant changes of the doping profile can be avoided. Calculation of temperature profiles has been achieved through numerical modeling of the heat conduction differential equation. Increase in the amount of nano-crystals, but not in their size, has been demonstrated by Raman spectroscopy. Effective dehydrogenation and shape of the boron profile have been studied by time of flight secondary ion mass spectroscopy. The relatively low temperature threshold for dehydrogenation, below the monohydride decomposition temperature, has been attributed to both, the large hydrogen content of the original films and the partial crystallization during the ELA process. The results of this study show that UV-laser irradiation is an effective tool to improve crystallinity and dopant activation in p{sup +}-nc-Si:H films without damaging the substrate. - Highlights: • An efficient dehydrogenation is possible through excimer laser annealing. • 140 mJ/cm{sup 2} is enough for dehydrogenation without significant changes in doping profile. • Fluences up to 300 mJ/cm{sup 2} promote partial crystallization of the amorphous structures.

  7. Experimental Study of Interfacial Friction in NaBH4 Solution in Microchannel Dehydrogenation Reactor

    Sodium borohydride (NaBH4) is considered as a secure metal hydride for hydrogen storage and supply. In this study, the interfacial friction of two-phase flow in the dehydrogenation of aqueous NaBH4 solution in a microchannel with a hydraulic diameter of 461 μm is investigated for designing a dehydrogenation chemical reactor flow passage. Because hydrogen gas is generated by the hydrolysis of NaBH4 in the presence of a ruthenium catalyst, two different flow phases (aqueous NaBH4 solution and hydrogen gas) exist in the channel. For experimental studies, a microchannel was fabricated on a silicon wafer substrate, and 100-nm ruthenium catalyst was deposited on three sides of the channel surface. A bubbly flow pattern was observed. The experimental results indicate that the two-phase multiplier increases linearly with the void fraction, which depends on the initial concentration, reaction rate, and flow residence time

  8. Experimental Study of Interfacial Friction in NaBH{sub 4} Solution in Microchannel Dehydrogenation Reactor

    Choi, Seok Hyun; Hwang, Sueng Sik; Lee, Hee Joon [Kookmin Univ., Seoul (Korea, Republic of)

    2014-02-15

    Sodium borohydride (NaBH{sub 4}) is considered as a secure metal hydride for hydrogen storage and supply. In this study, the interfacial friction of two-phase flow in the dehydrogenation of aqueous NaBH{sub 4} solution in a microchannel with a hydraulic diameter of 461 μm is investigated for designing a dehydrogenation chemical reactor flow passage. Because hydrogen gas is generated by the hydrolysis of NaBH{sub 4} in the presence of a ruthenium catalyst, two different flow phases (aqueous NaBH{sub 4} solution and hydrogen gas) exist in the channel. For experimental studies, a microchannel was fabricated on a silicon wafer substrate, and 100-nm ruthenium catalyst was deposited on three sides of the channel surface. A bubbly flow pattern was observed. The experimental results indicate that the two-phase multiplier increases linearly with the void fraction, which depends on the initial concentration, reaction rate, and flow residence time.

  9. Kinetics of Oxidative Dehydrogenation of Propance over a VMgO Catalyst

    L.Late; E.A.Blekkan

    2002-01-01

    The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550℃ over a VMgO catalyst,Vanadium-magnesium-oxides are among the moste selective and active catalysts for the dehydrogenation of propance to propylene Selectivity to propylene up to about 60% was obtained at 10% conversion ,but the selectivity decreased with increasing conversion.No oxygenates were detected,the only by-products were CO and CO2 ,The reaction rate of propane was found to be first order in propane and close to zero order in oxygen ,which is in agreement with a Mars van Krevelen mechanism with the activation of the hydrocarbon as the rate detemining step.The activation energy,of the conversion of propane was found to be 122±6 kJ/mol.

  10. Oxidative Dehydrogenation of Butane to Butadiene and Butene Using a Novel Inert Membrane Reactor

    2000-01-01

    The oxidative dehydrogenation of butane to butadiene and butene was studied using a conventional fixed-bed ractor (FBR), inert membrane reactor (IMR) and mixed inert membrane reactor (MIMR). When IMR and MIMR were employed, a ceramic membrane modified by partially coating with glaze was used to distribute oxygen to a fixed-bed of 24-V-Mg-O catalyst. The oxygen partial pressure in the catalyst bed could be decreased. The effect of feeding modes and operation conditions were investigated. The selectivity of C4 dehydrogenation products (butene and butadiene) was found to be higher in IMR than in FBR. The feeding mode with 20% of air mixing with butane in MIMR was found to be more efficient than the feeding mode with all air permeating through ceramic membrane. The MIMR gave the most smooth temperature profile along the bed.

  11. Dehydrogenation of n-butane over vanadia catalysts supported on silica gel

    Yuebing Xu; Jiangyin Lu; Mei Zhong; Jide Wang

    2009-01-01

    VOx/SiO2 catalysts prepared by impregnation method were used for catalytic dehydrogenation of n-butane to butenes and characterized by X-ray diffraction,FT-IR,UV-vis,Raman,and BET measurements.The effects of VOx loading and the reaction temperature on the VOx/SiO2 catalysts and their catalytic performances for the dehydrogenation of n-butane were studied.When the VOx loading was 12% g/gcat and reaction temperature was between 590 ℃ and 600 ℃,n-butane conversion and butenes yields reached the highest value under H2 flux of 10 ml/min and n-butane flux of 10 ml/min.Product distribution,such as the ratio of 2-butene to 1-butene and the ratio of cis-2-butene to trans-2-butene,was mainly influenced by the reaction temperature.

  12. Kinetics of the Oxidative Dehydrogenation of Propane over a VMgO Catalyst

    L. L(a)te; E.A. Blekkan

    2002-01-01

    The reaction kinetics of the oxidative dehydrogenation of propane was studied at 475-550℃over a VMgO catalyst. Vanadium-magnesium-oxides are among the most selective and active catalysts forthe dehydrogenation of propane to propylene. Selectivity to propylene up to about 60% was obtained at10% conversion, but the selectivity decreased with increasing conversion. No oxygenates were detected, theonly by-products were CO and CO2. The reaction rate of propane was found to be first order in propaneand close to zero order in oxygen, which is in agreement with a Mars van Krevelen mechanism with theactivation of the hydrocarbon as the rate determining step. The activation energy of the conversion ofpropane was found to be 122±6 kJ/mol.

  13. Incorporation of catalytic dehydrogenation into fischer-tropsch synthesis to significantly reduce carbon dioxide emissions

    Huffman, Gerald P.

    2012-11-13

    A new method of producing liquid transportation fuels from coal and other hydrocarbons that significantly reduces carbon dioxide emissions by combining Fischer-Tropsch synthesis with catalytic dehydrogenation is claimed. Catalytic dehydrogenation (CDH) of the gaseous products (C1-C4) of Fischer-Tropsch synthesis (FTS) can produce large quantities of hydrogen while converting the carbon to multi-walled carbon nanotubes (MWCNT). Incorporation of CDH into a FTS-CDH plant converting coal to liquid fuels can eliminate all or most of the CO.sub.2 emissions from the water-gas shift (WGS) reaction that is currently used to elevate the H.sub.2 level of coal-derived syngas for FTS. Additionally, the FTS-CDH process saves large amounts of water used by the WGS reaction and produces a valuable by-product, MWCNT.

  14. A dehydrogenation mechanism of metal hydrides based on interactions between Hdelta+ and H-.

    Lu, Jun; Fang, Zhigang Zak; Sohn, Hong Yong

    2006-10-16

    This paper describes a reaction mechanism that explains the dehydrogenation reactions of alkali and alkaline-earth metal hydrides. These light metal hydrides, e.g., lithium-based compounds such as LiH, LiAlH4, and LiNH2, are the focus of intense research recently as the most promising candidate materials for on-board hydrogen storage applications. Although several interesting and promising reactions and materials have been reported, most of these reported reactions and materials have been discovered by empirical means because of a general lack of understanding of any underlying principles. This paper describes an understanding of the dehydrogenation reactions on the basis of the interaction between negatively charged hydrogen (H-, electron donor) and positively charged hydrogen (Hdelta+, electron acceptor) and experimental evidence that captures and explains many observations that have been reported to date. This reaction mechanism can be used as a guidance for screening new material systems for hydrogen storage. PMID:17029387

  15. Effects of Al2O3 phase and Cl component on dehydrogenation of propane

    Liu, Jie; Liu, Changcheng; Ma, Aizeng; Rong, Junfeng; Da, Zhijian; Zheng, Aiguo; Qin, Ling

    2016-04-01

    The effects of two Al2O3 phases, γ- and θ-Al2O3, and Cl component on the performances of Pt-Al2O3 catalysts in the dehydrogenation of propane were investigated in this work. The catalysts were systematically characterized by various techniques, such as scanning transmission electron microscopy (STEM), temperature-programmed desorption with ammonia as probe molecules (NH3-TPD) and temperature-programmed oxidation (TPO). The characterizations and catalytic results show that: (i) the pore structures and acid properties of the two Al2O3 phases can change the quantity, location and property of the carbon deposition, (ii) the existence of Cl plays a significant role on the agglomeration of Pt particles and carbon deposition, which further influence the catalytic performances of Pt-Al2O3 catalysts with different support phases for propane dehydrogenation.

  16. Genotypic and phenotypic spectrum of pyridoxine-dependent epilepsy (ALDH7A1 deficiency)

    Mills, Philippa B; Footitt, Emma J; Mills, Kevin A;

    2010-01-01

    Pyridoxine-dependent epilepsy was recently shown to be due to mutations in the ALDH7A1 gene, which encodes antiquitin, an enzyme that catalyses the nicotinamide adenine dinucleotide-dependent dehydrogenation of l-alpha-aminoadipic semialdehyde/L-Delta1-piperideine 6-carboxylate. However, whilst...... normal range, DNA sequencing of the ALDH7A1 gene was performed. Clinicians were asked to complete questionnaires on clinical, biochemical, magnetic resonance imaging and electroencephalography features of patients. The clinical spectrum of antiquitin deficiency extended from ventriculomegaly detected on...

  17. Heterogeneous Rhodium-Catalyzed Aerobic Oxidative Dehydrogenative Cross-Coupling: Nonsymmetrical Biaryl Amines.

    Matsumoto, Kenji; Yoshida, Masahiro; Shindo, Mitsuru

    2016-04-18

    The first heterogeneously catalyzed oxidative dehydrogenative cross-coupling of aryl amines is reported herein. 2-Naphthylamine analogues were reacted with various electron-rich arenes using a heterogeneous Rh/C catalyst under mild aerobic conditions, thus affording nonsymmetrical biaryl amines in excellent yields with high selectivities. This reaction provides a mild, operationally simple, and efficient approach for the synthesis of biaryls which are important to pharmaceutical and materials chemistry. PMID:26996772

  18. Control led sequential dehydrogenation of single molecules by scanning tunneling microscopy

    Sanvito, Stefano

    2010-01-01

    Scanning tunneling microscopy STM is today the most powerful and versatile tool available for imaging and manipulating single molecules on surfaces. Here, we explore its ultimate limit by demonstrating the possibility of controlling sequential di-dehydrogenation of single Co-Salen molecules sublimated on Cu. In particular, we are able to explore the final products of the H 2 dissociation as well as the intermediate state, in which only one H atom is separated from the ...

  19. Cross-dehydrogenative coupling for the intermolecular C–O bond formation

    Igor B. Krylov

    2015-01-01

    Full Text Available The present review summarizes primary publications on the cross-dehydrogenative C–O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C–O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C–O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on and compounds with activated C–H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety. An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C–O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C–H activation processes involving intermolecular C–O bond formation are discussed: acyloxylation reactions with ArI(O2CR2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc..

  20. Alcohol Dehydrogenation with a Dual Site Ruthenium, Boron Catalyst Occurs at Ruthenium

    Denver Guess

    2012-10-01

    Full Text Available The complex [(κ3-(N,N,O-py2B(MeOHRu(NCMe3]+ TfO− (1 is a catalyst for transfer dehydrogenation of alcohols, which was designed to function through a cooperative transition state in which reactivity was split between boron and ruthenium. We show here both stoichiometric and catalytic evidence to support that in the case of alcohol oxidation, the mechanism most likely involves reactivity only at the ruthenium center.

  1. Alcohol Dehydrogenation with a Dual Site Ruthenium, Boron Catalyst Occurs at Ruthenium

    Denver Guess; Williams, Travis J.; Conley, Brian L.; Brock Malinoski; Zhiyao Lu; Ana V. Flores

    2012-01-01

    The complex [(κ3-(N,N,O-py2B(Me)OH)Ru(NCMe)3]+ TfO− (1) is a catalyst for transfer dehydrogenation of alcohols, which was designed to function through a cooperative transition state in which reactivity was split between boron and ruthenium. We show here both stoichiometric and catalytic evidence to support that in the case of alcohol oxidation, the mechanism most likely involves reactivity only at the ruthenium center.

  2. Dehydrogenation in lithium borohydride/conventional metal hydride composite based on a mutual catalysis

    Yu, X.B.; Shi, Qing; Vegge, Tejs;

    2009-01-01

    The dehydrogenation of LiBH4 ball-milled with hydrogenated 40Ti–15Mn–15Cr–30V alloy was investigated. It was found that there is a mutual catalysis between the two hydrides, lowering the temperature of hydrogen release from both hydrides. In the case of 1h milled LiBH4/40Ti–15Mn–15Cr–30V with a...

  3. First-principles calculation of dehydrogenating properties of MgH2-V systems

    ZHOU; Dianwu; PENG; Ping; LIU; Jinshui

    2006-01-01

    Based on experimental results in which VH0.81/MgH2 interface was found during the process of mechanically milling MgH2+5at%V nanocomposite, a VH/MgH2 interface is designed and constituted in this work. A first-principles plane-wave pseudopotential method based on Density Functional Theory (DFT) has been used to investigate the vanadium alloying effects on the dehydrogenating properties of magnesium hydride, i.e., MgH2. A low absolute value of the negative heat of formation of VH/MgH2 interface compared with that of MgH2 indicates that vanadium hydrides befit to improve the dehydrogenating properties of MgH2. Based on the analysis of the density of states (DOS) and the total valence electron density distribution of MgH2 before and after V alloying, it was found that the improvement of the dehydrogenating properties of MgH2 caused by V alloying originates from the increasing of the valence electrons at Fermi level (EF) and the decreasing of the HOMO-LUMO gap (△EH-L) after V alloying. The catalysis effect of V on dehydrogenating kinetics of MgH2 may attribute to a stronger bonding between V and H atoms than that between Mg and H atoms, which leads to nucleation of the α-Mg at the VH/MgH2 interface in the MgH2-V systems easier than that in pure MgH2 phase.

  4. Investigations of VOx/SBA-15 catalytic performance in propane dehydrogenation with CO2

    Ze?czak, Kamila; Michorczyk, Piotr; Ogonowski, Jan

    2011-01-01

    The catalytic activity of V-containing SBA-15 materials wereprepared by incipient wetness method and tested in propane dehydrogenation with carbon dioxide. It has been found that vanadium catalysts show relatively high catalytic activity and selectivity to propene. The highest activity exhibits the sample containing 5 wt. % of V. At temperature 823 K, propane conversion and propene selectivity were 26,7%, while 70 %, respectively.

  5. Cross-dehydrogenative coupling for the intermolecular C-O bond formation.

    Krylov, Igor B; Vil', Vera A; Terent'ev, Alexander O

    2015-01-01

    The present review summarizes primary publications on the cross-dehydrogenative C-O coupling, with special emphasis on the studies published after 2000. The starting compound, which donates a carbon atom for the formation of a new C-O bond, is called the CH-reagent or the C-reagent, and the compound, an oxygen atom of which is involved in the new bond, is called the OH-reagent or the O-reagent. Alcohols and carboxylic acids are most commonly used as O-reagents; hydroxylamine derivatives, hydroperoxides, and sulfonic acids are employed less often. The cross-dehydrogenative C-O coupling reactions are carried out using different C-reagents, such as compounds containing directing functional groups (amide, heteroaromatic, oxime, and so on) and compounds with activated C-H bonds (aldehydes, alcohols, ketones, ethers, amines, amides, compounds containing the benzyl, allyl, or propargyl moiety). An analysis of the published data showed that the principles at the basis of a particular cross-dehydrogenative C-O coupling reaction are dictated mainly by the nature of the C-reagent. Hence, in the present review the data are classified according to the structures of C-reagents, and, in the second place, according to the type of oxidative systems. Besides the typical cross-dehydrogenative coupling reactions of CH- and OH-reagents, closely related C-H activation processes involving intermolecular C-O bond formation are discussed: acyloxylation reactions with ArI(O2CR)2 reagents and generation of O-reagents in situ from C-reagents (methylarenes, aldehydes, etc.). PMID:25670997

  6. Heterogeneous Partial (amm) Oxidation and Oxidative Dehydrogenation Catalysis on Mixed Metal Oxides

    Védrine, Jacques C.

    2016-01-01

    This paper presents an overview of heterogeneous partial (amm)oxidation and oxidative dehydrogenation (ODH) of hydrocarbons. The review has been voluntarily restricted to metal oxide-type catalysts, as the partial oxidation field is very broad and the number of catalysts is quite high. The main factors of solid catalysts for such reactions, designated by Grasselli as the " seven pillars " , and playing a determining role in catalytic properties, are considered to be, namely: isolation of acti...

  7. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst

    M. Toghyani

    2015-07-01

    Full Text Available The Pt/γ-Al2O3 catalyst life time was limited by the formation of coke on the external and internal surfaces of catalyst in dehydrogenation reactors. The kinetics of decoking of dehydrogenation catalyst was studied in a pilot scale fixed bed reactor experimentally. The effects of temperature, oxygen concentration and other operating conditions on decoking process were investigated. A kinetic model was deve-loped to describe the decoking of mentioned catalyst. An objective function was defined as the sum of squares of the deviations among the calculated and plant data. Accordingly the appropriate values were found in order to minimize this function. It was concluded that there was a good agreement between simulation results and experimental data.  © 2015 BCREC UNDIP. All rights reservedReceived: 18th September 2014; Revised: 28th February 2015; Accepted: 9th March 2015How to Cite: Toghyani, M., Rahimi, A., Mamanpoush, M., Kazemian, R., Harandizadeh, A.H. (2015. Experimental Study and Kinetic Modeling of Decoking of Pacol Process Dehydrogenation Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (2: 155-161. (doi:10.9767/bcrec.10.2.7357.155-161 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.7357.155-161  

  8. Dehydration and Dehydrogenation of Ethylene Glycol on Rutile TiO2(110)

    Li, Zhenjun; Kay, Bruce D.; Dohnalek, Zdenek

    2013-08-07

    The interactions of ethylene glycol (EG) with partially reduced rutile TiO2(110) surface have been studied using temperature programmed desorption (TPD). The saturation coverage on the surface Ti rows is determined to be 0.43 monolayer (ML), slightly less than one EG per two Ti sites. Most of the adsorbed ethanol (~80%) undergoes further reactions to other products. Two major channels are observed, dehydration yielding ethylene and water and dehydrogenation yielding acetaldehyde and hydrogen. Hydrogen formation is rather surprising as it has not been observed previously on TiO2(110) from simple organic molecules. The coverage dependent yields of ethylene and acetaldehyde correlate well with that of water and hydrogen, respectively. Dehydration dominates at lower EG coverages (< 0.2 ML) and plateaus as the coverage is increased to saturation. Dehydrogenation is observed primarily at higher EG coverages (>0.2 ML). Our results suggest that the observed dehydration and dehydrogenation reactions proceed via different surface intermediates.

  9. Highly Ordered Mesoporous Metal Oxides as Catalysts for Dehydrogenation of Cyclohexanol

    Lee, Eunok; Jin, Mingshi; Kim, Ji Man [Sungkyunkwan University, Suwon (Korea, Republic of)

    2013-08-15

    Cyclohexanone is important intermediate for the manufacture of caprolactam which is monomer of nylron. Cyclohexanone is generally produced by dehydrogenation reaction of cyclohexanol. In this study, highly mesoporous metal oxides such as meso-WO{sub 3}, meso-TiO{sub 2}, meso-Fe{sub 2}O{sub 3}, meso-CuO, meso-SnO{sub 2} and meso-NiO were synthesized using mesoporous silica KIT-6 as a hard template via nano-replication method for dehydrogenation of cyclohexanol. The overall conversion of cyclohexanol followed a general order: meso-WO{sub 3} >> meso-Fe{sub 2}O{sub 3} > meso-SnO{sub 2} > meso-TiO{sub 2} > meso-NiO > meso-CuO. In particular, meso-WO{sub 3} significantly showed higher activity than the other mesoporous metal oxides. Therefore, the meso-WO{sub 3} has wide range of application possibilities for dehydrogenation of cyclohexanol.

  10. Chemically Modified Activated Carbons as Catalysts of Oxidative Dehydrogenation of n-Butane

    Commercial availability and low price of light alkanes make them very attractive in many branches of industry. Potentially interesting is their use in the process of oxidative dehydrogenation leading to production of olefins. This study was undertaken to characterise the oxidative dehydrogenation of n-butane to 1,3-butadiene (important substrate in production of synthetic rubber and polyamides) taking place over the modified carbon catalysts obtained from peach stones precursor. The catalytic tests were performed in the temperature range 250-450oC at oxygen/n-butane ratio of 1:1. For the majority of the activated carbon samples studied at the lowest temperature the only product was CO2. At 300oC the products of dehydrogenation of n-butane and side products appeared. With increasing temperature the amount of compounds generated increased and in the group of C4 hydrocarbons the dominant were 1-butene and 1,3-butadiene. The most effective catalyst was the sample oxidised with air, the least effective was the sample modified with ammonium peroxydisulphate. (authors)

  11. An experimental survey of additives for improving dehydrogenation properties of magnesium hydride

    Zhou, Chengshang; Fang, Zhigang Zak; Sun, Pei

    2015-03-01

    The use of a wide range of additives has been known as an important method for improving hydrogen storage properties of MgH2. There is a lack of a standard methodology, however, that can be used to select or compare the effectiveness of different additives. A systematic experimental survey was carried out in this study to compare a wide range of additives including transitions metals, transition metal oxides, hydrides, intermetallic compounds, and carbon materials, with respect to their effects on dehydrogenation properties of MgH2. MgH2 with various additives were prepared by using a high-energy-high-pressure planetary ball milling method and characterized by using thermogravimetric analysis (TGA) techniques. The results showed that additives such as Ti and V-based metals, hydride, and certain intermetallic compounds have strong catalytic effects. Additives such as Al, In, Sn, Si showed minor effects on the kinetics of the dehydrogenation of MgH2, while exhibiting moderate thermodynamic destabilizing effects. In combination, MgH2 with both kinetic and thermodynamic additives, such as the MgH2-In-TiMn2 system, exhibited a drastically decreased dehydrogenation temperature.

  12. In situ synchrotron X-ray diffraction study on the dehydrogenation behavior of LiAlH4–MgH2 composites

    Highlights: • The dehydrogenation behavior of LiAlH4–MgH2 composites was investigated. • LiAlH4 and MgH2 exhibited mutual catalytic effects in their dehydrogenation reaction. • Composition dependent dehydrogenation behavior was observed. • Dehydrogenation reaction steps and products were identified. - Abstract: Dehydrogenation behavior of LiAlH4–MgH2 composites was investigated by using thermal gravimetric analysis (TGA) and in situ synchrotron X-ray diffraction (XRD) technique. The experimental results showed that MgH2 could play a catalytic role in lowing the initial dehydrogenation temperature of LiAlH4. Besides, MgH2 could be destabilized by the dehydrogenation reaction products of LiAlH4. The initial dehydrogenation temperature of LiAlH4–MgH2 composites was as low as 145 °C and MgH2 could decompose below 300 °C. The compounds such as LiMgAlH6, Al3Mg2, Al12Mg17 and Li0.92Mg4.08 formed during dehydrogenation process suggested some mutual reactions proceeded between LiAlH4 and MgH2

  13. In situ synchrotron X-ray diffraction study on the dehydrogenation behavior of LiAlH{sub 4}–MgH{sub 2} composites

    Hsu, Wei-Che; Yang, Cheng-Hsien; Tan, Chia-Yen [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Tsai, Wen-Ta, E-mail: wttsai@mail.ncku.edu.tw [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan (China); Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan, Taiwan (China)

    2014-06-25

    Highlights: • The dehydrogenation behavior of LiAlH{sub 4}–MgH{sub 2} composites was investigated. • LiAlH{sub 4} and MgH{sub 2} exhibited mutual catalytic effects in their dehydrogenation reaction. • Composition dependent dehydrogenation behavior was observed. • Dehydrogenation reaction steps and products were identified. - Abstract: Dehydrogenation behavior of LiAlH{sub 4}–MgH{sub 2} composites was investigated by using thermal gravimetric analysis (TGA) and in situ synchrotron X-ray diffraction (XRD) technique. The experimental results showed that MgH{sub 2} could play a catalytic role in lowing the initial dehydrogenation temperature of LiAlH{sub 4}. Besides, MgH{sub 2} could be destabilized by the dehydrogenation reaction products of LiAlH{sub 4}. The initial dehydrogenation temperature of LiAlH{sub 4}–MgH{sub 2} composites was as low as 145 °C and MgH{sub 2} could decompose below 300 °C. The compounds such as LiMgAlH{sub 6}, Al{sub 3}Mg{sub 2}, Al{sub 12}Mg{sub 17} and Li{sub 0.92}Mg{sub 4.08} formed during dehydrogenation process suggested some mutual reactions proceeded between LiAlH{sub 4} and MgH{sub 2}.

  14. Folate-deficiency anemia

    ... medlineplus.gov/ency/article/000551.htm Folate-deficiency anemia To use the sharing features on this page, please enable JavaScript. Folate-deficiency anemia is a decrease in red blood cells (anemia) ...

  15. Leukocyte Adhesion Deficiency (LAD)

    ... Content Marketing Share this: Main Content Area Leukocyte Adhesion Deficiency (LAD) LAD is an immune deficiency in ... are slow to heal also may have LAD. Treatment and Research Doctors prescribe antibiotics to prevent and ...

  16. Iron-Deficiency Anemia

    Full Text Available ... Deficiency Anemia What Is... CAUSES WHO IS AT RISK SIGNS & SYMPTOMS DIAGNOSIS TREATMENTS PREVENTION LIVING WITH CLINICAL ... and women are the two groups at highest risk for iron-deficiency anemia. Outlook Doctors usually can ...

  17. Factor V deficiency

    Factor V deficiency is a condition that is passed down through families, which affects the ability of the blood ... These proteins are called blood coagulation factors. Factor V deficiency is caused by a lack of Factor ...

  18. Iron-Deficiency Anemia

    Full Text Available ... and women are the two groups at highest risk for iron-deficiency anemia. Outlook Doctors usually can successfully ... With and Managing Iron-Deficiency Anemia 05/18/2011 This video— ...

  19. Iron-Deficiency Anemia

    Full Text Available ... This Content: NEXT >> Featured Video Living With and Managing Iron-Deficiency Anemia 05/18/2011 This video— ... treatment. For more information about living with and managing iron-deficiency anemia, go to the Health Topics ...

  20. Familial lipoprotein lipase deficiency

    ... medlineplus.gov/ency/article/000408.htm Familial lipoprotein lipase deficiency To use the sharing features on this page, please enable JavaScript. Familial lipoprotein lipase deficiency is a group of rare genetic disorders ...

  1. Factor VII deficiency

    ... page: //medlineplus.gov/ency/article/000548.htm Factor VII deficiency To use the sharing features on this page, please enable JavaScript. Factor VII (seven) deficiency is a disorder caused by a ...

  2. Iron deficiency and cognition

    Hulthén, Lena

    2003-01-01

    Iron deficiency is the most prevalent nutritional disorder in the world. One of the most worrying consequences of iron deficiency in children is the alteration of behaviour and cognitive performance. In iron-deficient children, striking behavioural changes are observed, such as reduced attention span, reduced emotional responsiveness and low scores on tests of intelligence. Animal studies on nutritional iron deficiency show effects on learning ability that parallel the human studies. Despite ...

  3. Iron-Deficiency Anemia

    Full Text Available ... page from the NHLBI on Twitter. What Is Iron-Deficiency Anemia? Español Iron-deficiency anemia is a ... Content: NEXT >> Featured Video Living With and Managing Iron-Deficiency Anemia 05/18/2011 This video—presented ...

  4. Iron-Deficiency Anemia

    Full Text Available ... the NHLBI on Twitter. What Is Iron-Deficiency Anemia? Español Iron-deficiency anemia is a common, easily ... Featured Video Living With and Managing Iron-Deficiency Anemia 05/18/2011 This video—presented by the ...

  5. Iron-Deficiency Anemia

    ... the NHLBI on Twitter. What Is Iron-Deficiency Anemia? Español Iron-deficiency anemia is a common, easily ... Featured Video Living With and Managing Iron-Deficiency Anemia 05/18/2011 This video—presented by the ...

  6. Thermal dehydrogenation of amorphous silicon deposited on c-Si: Effect of the substrate temperature during deposition

    De Calheiros Velozo, A. [Dept. de Fisica, Instituto Superior Tecnico (UTL), Av. Rovisco Pais 1, 1049-001 Lisboa (Portugal); Lavareda, G. [Dept. de Ciencia dos Materiais, Faculdade de Ciencias e Tecnologia (UNL), 2825-114 Caparica (Portugal); Centro de Tecnologias e Sistemas, Faculdade de Ciencias e Tecnologia (UNL), 2825-114 Caparica (Portugal); Nunes de Carvalho, C. [Dept. de Ciencia dos Materiais, Faculdade de Ciencias e Tecnologia (UNL), 2825-114 Caparica (Portugal); Inst. Ciencia e Eng. de Materiais e Superficies, Instituto Superior Tecnico (UTL), Av. Rovisco Pais 1, 1049-001 Lisboa (Portugal); Amaral, A. [Dept. de Fisica, Instituto Superior Tecnico (UTL), Av. Rovisco Pais 1, 1049-001 Lisboa (Portugal); Inst. Ciencia e Eng. de Materiais e Superficies, Instituto Superior Tecnico (UTL), Av. Rovisco Pais 1, 1049-001 Lisboa (Portugal)

    2012-10-15

    Samples of doped and undoped a-Si:H were deposited at temperatures ranging from 100 C to 350 C and then submitted to different dehydrogenation temperatures (from 350 C to 550 C) and times (from 1 h to 4 h). a-Si:H films were characterised after deposition through the measurements of specific material parameters such as: the optical gap, the conductivity at 25 C, the thermal activation energy of conductivity and its hydrogen content. Hydrogen content was measured after each thermal treatment. Substrate dopant contamination from phosphorus-doped a-Si thin films was evaluated by SIMS after complete dehydrogenation and a junction depth of 0.1 mm was obtained. Dehydrogenation results show a strong dependence of the hydrogen content of the as-deposited film on the deposition temperature. Nevertheless, the dehydrogenation temperature seems to determine the final H content in a way almost independent from the initial content in the sample. H richer films dehydrogenate faster than films with lower hydrogen concentration (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  7. Crystal structure change in the dehydrogenation process of the Li-Mg-N-H system

    Noritake, T., E-mail: e0553@mosk.tytlabs.co.jp [Toyota Central R and D Labs., Inc., Nagakute, Aichi 480-1192 (Japan); Aoki, M.; Matsumoto, M.; Miwa, K.; Towata, S. [Toyota Central R and D Labs., Inc., Nagakute, Aichi 480-1192 (Japan); Li, H.-W.; Orimo, S. [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

    2011-07-14

    Highlights: > Structural change in several dehydrogenation stages of p-c isotherm at 523 K. > Mg(NH{sub 2}){sub 2} and Li{sub 3}Mg{sub 3}(NH{sub 2})(NH){sub 4} coexist in the plateau region. > Continuous change from Li{sub 3}Mg{sub 3}(NH{sub 2})(NH){sub 4} to Li{sub 2}Mg(NH){sub 2} in the sloping region. > The crystal structure Li{sub 3+3y}Mg{sub 3}(NH{sub 2}){sub 1-y}(NH){sub 4+2y} was determined. > The dehydrogenation by the diffusion of Li{sup +} and Mg{sup 2+} without N atom diffusion. - Abstract: The Li-Mg-N-H system has the property of reversible reaction with hydrogen between hydrogenation and dehydrogenation (Mg{sub 3}N{sub 2} + 4Li{sub 3}N + 12H{sub 2} {r_reversible} 3Mg(NH{sub 2}){sub 2} + 12LiH). At the several dehydrogenation stages of p-c isotherm measurement at 523 K, the structural change was investigated using the synchrotron X-ray diffraction. There are two regions in p-c isotherm of the Li-Mg-N-H system, i.e. plateau and sloping region. In the plateau region, Mg(NH{sub 2}){sub 2} and Li{sub 3}Mg{sub 3}(NH{sub 2})(NH){sub 4} coexist. In the sloping region, the intermediate phase Li{sub 3+3y}Mg{sub 3}(NH{sub 2}){sub 1-y}(NH){sub 4+2y} changes continuously from Li{sub 3}Mg{sub 3}(NH{sub 2})(NH){sub 4} to Li{sub 2}Mg(NH){sub 2}. The chemical composition of the intermediate phase was estimated from the amount of desorbed hydrogen by p-c isotherm and the atomic ratio of Mg and N by Rietveld analysis. The crystal structure of the intermediate phase, Li{sub 3+3y}Mg{sub 3}(NH{sub 2}){sub 1-y}(NH){sub 4+2y} (space group: I222), was determined. Because all these intermediate structures are similar to anti-CaF{sub 2}-type, it is deduced that the dehydrogenation process are caused by the diffusion of Li{sup +} to cation sites of Mg(NH{sub 2}){sub 2}. The analysis of structural change clarified the dehydrogenation process that is accomplished by the diffusion of Li{sup +} and Mg{sup 2+} without N atom diffusion.

  8. Heterogeneous catalytic oxidative dehydrogenation of ethylbenzene to styrene with carbon dioxide

    Badstube, T.; Papp, H. [Leipzig Univ. (Germany). Inst. fuer Technische Chemie; Kustrowski, P.; Dziembaj, R. [Jagiellonian Univ., Crakow (Poland). Faculty of Chemistry

    1998-12-31

    Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large excess of CO{sub 2} (CO{sub 2}/EB>10) was harmful for the styrene yield. The most favorable molar ratio of CO{sub 2} to EB was 10:1. No correlation between the molar ratios of reactants and the amount of deposited coke on the surface of catalysts was observed. The highest catalytic activity showed iron loaded D-90 catalysts which were promoted with alkali metals in a molar ratio of 1:10. Iron, nickel and cobalt loaded carbonized PPAN, PC, inorganic supports like Al{sub 2}O{sub 3}, SiO{sub 2}/ZrO{sub 2} or TiO{sub 2} respectively and commercial iron catalysts applied for styrene production did not show comparable catalytic activity in similar conditions. (orig.)

  9. Dehydrogenation of propane in the presence of carbon dioxide over chromium and gallium oxides catalysts

    Lapidus, A.L.; Agafonov, Yu.A.; Gaidai, N.A.; Nekrasov, N.V.; Menshova, M.V.; Kunusova, R.M. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2011-07-01

    Effective chromium and gallium oxides supported catalysts were prepared and tested in longduration experiments for propane dehydrogenation in the presence of CO{sub 2}. The optimal concentrations of active metals were found. It was shown that the activity, selectivity and stability of chromium oxides catalysts were higher than these parameters for gallium ones. Mechanism of propane oxidative dehydrogenation was studied over both catalysts using unstationary and spectroscopic methods. The employment of these methods allowed to establish the differences in process mechanism. It was shown that surface hydroxides took participation in propene formation over Cr-catalysts and hydrides - over Ga-ones. Propane and carbon dioxide participated in the reaction from the adsorbed state over both catalysts but they were differed by the adsorption capacity of the reaction components: CO2 was tied more firmly than C{sub 3}H{sub 6} over both catalysts, CO{sub 2} and C{sub 3}H{sub 6} were tied more strongly with Cr-catalysts than with Ga-ones. It was shown that CO{sub 2} took active participation in reverse watergas shift reaction and in oxidation of catalyst surface over chromium oxides catalysts. The main role of CO{sub 2} in propane dehydrogenation over gallium catalysts consisted in a decrease of coke formation. Step-schemes of propene and cracking products formation were proposed on the basis of literature and obtained data: via the redox mechanism over Cr-catalysts and through a heterolytic dissociation reaction pathway over Ga-ones. (orig.)

  10. Dehydrogenation properties and crystal structure analysis of Mg(BH4)(NH2)

    Highlights: •The thermal properties of Mg(BH4)(NH2) was clarified. •Mg(BH4)(NH2) is crystallized at 453 K and then is stable at 300 K. •The crystal structure of Mg(BH4)(NH2) at 300 K was determined. -- Abstract: Dehydrogenation properties and crystal structure of the double anion complex hydride Mg(BH4)(NH2) were studied by thermal analyses and synchrotron X-ray diffraction. The stoichiometric mixture of Mg(BH4)2 and Mg(NH2)2 were ball-milled and then heated to 453 K to form Mg(BH4)(NH2) crystal. The dehydrogenation of Mg(BH4)(NH2) occurs in two-stage at 513 K and 688 K. The following reaction sequence is suggested by the results of thermal analyses; Mg(BH4)(NH2) → MgH2 + BN + 2H2 (7.3 mass% weight loss) → Mg + BN + 3H2 (11.0 mass% weight loss in total). The dehydrogenation temperature of Mg(BH4)(NH2) is approximately 50 K lower than that of the other double anion complex Li2(BH4)(NH2). The crystal structure of Mg(BH4)(NH2) was determined by the measurement at 300 K (crystal system: tetragonal, space group: I41 (No. 80), lattice constants: a = 5.792(1), c = 20.632(4) Å at 300 K). In the crystal of Mg(BH4)(NH2), the cation (Mg2+) and the anions (BH4- and NH2-) are stacked alternately along the c-axis direction. The Mg2+ cation is tetrahedrally coordinated with two BH4- anions and two NH2- anions

  11. Effect of catalyst structure on oxidative dehydrogenation of ethane and propane on alumina-supported vanadia

    Argyle, Morris D.; Chen, Kaidong; Bell, Alexis T.; Iglesia, Enrique

    2001-09-11

    The catalytic properties of Al2O3-supported vanadia with a wide range of VOx surface density (1.4-34.2 V/nm2) and structure were examined for the oxidative dehydrogenation of ethane and propane. UV-visible and Raman spectra showed that vanadia is dispersed predominantly as isolated monovanadate species below {approx}2.3 V/nm2. As surface densities increase, two-dimensional polyvanadates appear (2.3-7.0 V/nm2) along with increasing amounts of V2O5 crystallites at surface densities above 7.0 V/nm2. The rate constant for oxidative dehydrogenation (k1) and its ratio with alkane and alkene combustion (k2/k1 and k3/k1, respectively) were compared for both alkane reactants as a function of vanadia surface density. Propene formation rates (per V-atom) are {approx}8 times higher than ethene formation rates at a given reaction temperature, but the apparent ODH activation energies (E1) are similar for the two reactants and relatively insensitive to vanadia surface density. Ethene and propene formation rates (per V-atom) are strongly influenced by vanadia surface density and reach a maximum value at intermediate surface densities ({approx}8 V/nm2). The ratio of k2/k1 depends weakly on reaction temperature, indicating that activation energies for alkane combustion and ODH reactions are similar. The ratio of k2/k1 is independent of surface density for ethane, but increase slightly with vanadia surface density for propane, suggesting that isolated structures prevalent at low surface densities are slightly more selective for alkane dehydrogenation reactions. The ratio of k3/k1 decreases markedly with increasing reaction temperature for both ethane and propane ODH. Thus, the apparent activation energy for alkene combustion (E3) is much lower than that for alkane dehydrogenation (E1) and the difference between these two activation energies decreases with increasing surface density. The lower alkene selectivities observed at high vanadia surface densities are attributed to an

  12. Oxygen Assisted Dehydrogenation of Ethane over Alumina Supported Pt-Sn Catalysts

    Radstake, Paul B.

    2012-01-01

    The oxygen-assisted dehydrogenation of ethane (ODE) over supported Pt-Sn catalysts seems to be a promising alternative for the conventional steam cracking of ethane for the production of ethylene. However, despite the fact that much research has been performed on this catalytic system during the last years, little is known about the precise role of the Pt-Sn catalyst on the overall product distribution.The focus of this research work lay therefore on gaining a better understanding of the role...

  13. Oxidative Dehydrogenation of Ethane to Ethylene over LiCI/MnOx/PC Catalysts

    葛庆杰; 李文钊; 于春英; 徐恒泳

    2001-01-01

    The caalytic stability of LiCl/MnOx/PC catalyst have been investigated, the deactivation mechanism was discussed. Tne experimental results show that ethane conversion decreases and etihylene selectivotu keeps about 90% as reaction time increases. The main deactivation reasons LiCI/MnOx/PCcatalyst for oxidative dehydrogenation of ethane (ODHE) to ethylene are the transiton of active species Mn2O3 TO MnOspecies and the loss of active component Cl in catalyst. Instead of ethane with FCC tailed-gas, the stability of LiCl/MnOx/PC catalyst has been largely improved.

  14. A STUDY ON MEMBRANE PROCESS WITH γ-ALUMINA MEMBRANE REACTOR FOR ETHYLBENZENE DEHYDROGENATION TO STYRENE

    Chen Qingling; Xu Zhongqiang

    2001-01-01

    The membrane reaction of ethylbenzene(EB) dehydrogenation to styrene(ST) has been studied by using K2O/Fe2O3 industrial catalyst and γ-alumina ceramic membrane developed by our institute. In comparison with the packed bed reactor (that is, plug flow reactor, abbr. PFR) in industrial practice, the yield of styrene was increased by 5%~10% in the membrane reactor. Furthermore, mathematical modeling of membrane reaction has been studied to display the principle of optimal match between the catalytic activity and the membrane permeability.

  15. Kinetics of dehydrogenation of MgH{sub 2} and AlH{sub 3}

    Gabis, I., E-mail: igor.gabis@gmail.com [Physics Department of St. Petersburg State University, St. Petersburg (Russian Federation); Dobrotvorskiy, M.; Evard, E.; Voyt, A. [Physics Department of St. Petersburg State University, St. Petersburg (Russian Federation)

    2011-09-15

    Kinetics of dehydrogenation was studied using isothermal barometry, TDS and SEM methods. Two stages of the decomposition process are considered: incubation preceding the formation of metallic nuclei on the surface of the particle and hydrogen evolution via these metallic regions serving as facilitating channels for desorption. Duration of the first stage depends on the temperature of the sample. Relationship with material's electronic band structure is discussed. Kinetics of the second stage is controlled by two reactions: desorption of the hydrogen molecules from the surface and shift of the metal-hydride interphase in the bulk. Physical mechanisms of decomposition with detailed reaction kinetics are proposed and kinetic parameters are evaluated.

  16. Formation and Decay of the Dehydrogenated Parent Anion upon Electron Attachment to Dialanine

    Gschliesser, David; Vizcaino, Violaine; Probst, Michael; Scheier, Paul; Denifl, Stephan

    2012-01-01

    Abstract The dehydrogenated parent anion [M−H]− is one of the most dominant anions formed in dissociative electron attachment to various small biomolecules like nucleobases and single amino acids. In the present study, we investigate the [M−H]− channel for the dipeptide dialanine by utilizing an electron monochromator and a two-sector-field mass spectrometer. At electron energies below 2 eV, the measured high-resolution ion-efficiency curve has a different shape to that for the single amino a...

  17. Dynamic Structure of Mo-O Species in Ag-Mo-P-O Catalyst for Oxidative Dehydrogenation of Propane

    2002-01-01

    The dynamic structure of Mo-O species in Ag-Mo-P-O catalyst was studied by in situ confocal microprobe laser Raman spectroscopy (LRS) and catalytic test. The results indicate Mo-O species of MoO3 transformed to Mo-O species of AgMoO2PO4 in C3H8/O2/N2 (3/1/4) flow at 773 K. This behavior is closely relative to oxidative dehydrogenation of propane and intrinsic properties of Mo-O species. The Mo-O species of AgMoO2PO4 may be active species for oxidative dehydrogenation of propane.

  18. A DFT study on the Cu (1 1 1) surface for ethyl acetate synthesis from ethanol dehydrogenation

    Li Ruzhen; Zhang Minhua [Key Laboratory for Green Chemical Technology of Ministry of Education, Tianjin University R and D Center for Petrochemical Technology, Tianjin (China); Yu Yingzhe, E-mail: lrz1699@126.com [Key Laboratory for Green Chemical Technology of Ministry of Education, Tianjin University R and D Center for Petrochemical Technology, Tianjin (China)

    2012-07-01

    Copper-based catalysts have shown excellent catalytic performances. Despite extensive studies in the field, the microscopic mechanism of ethanol dehydrogenation to ethyl acetate (EA) on Cu-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Cu, density functional theory (DFT) calculations have been performed to study the elementary reactions involved in ethanol dehydrogenation to EA on Cu surfaces. In this work, the adsorption properties of ethanol, ethoxy, acetaldehyde, acetyl and EA on the Cu (1 1 1) catalyst surface were investigated. Based on two pathways, many transition states involved are located. The results show that the route proposed by Colley is more likely to happen.

  19. Oxidative dehydrogenation of ethane on rare-earth oxide-based catalysts

    Buyevskaya, O.; Baerns, M. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany)

    1998-12-31

    Results on the oxidative dehydrogenation of ethane on rare-earth oxide (REO) based catalysts (Na-P-Sm-O, Sm-Sr(Ca)-O, La-Sr-O and Nd-Sr-O) are described. Oxygen adsorption was found to be a key factor which determines the activity of this type of catalysts. Continuous flow experiments in the presence of catalysts which reveal strong oxygen adsorption showed that the reaction mixture is ignited resulting in an enhanced heat generation at the reactor inlet. The heat produced by the oxidative reactions was sufficient under the conditions chosen for the endothermic thermal pyrolysis which takes place preferentially in the gas phase. Ignition of the reaction mixture is an important catalyst function. Contrary to non-catalytic oxidative dehydrogenation, reaction temperatures above 700 C could be achieved without significant external heat input. Ethylene yields of up to 34-45% (S=66-73%) were obtained on REO-based catalysts under non-isothermal conditions (T{sub max}=810-865 C) at contact times in the order of 30 to 40 ms. (orig.)

  20. Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures

    Ojeda, Manuel; Iglesia, Enrique

    2008-11-24

    Formic acid (HCOOH) is a convenient hydrogen carrier in fuel cells designed for portable use. Recent studies have shown that HCOOH decomposition is catalyzed with Ru-based complexes in the aqueous phase at near-ambient temperatures. HCOOH decomposition reactions are used frequently to probe the effects of alloying and cluster size and of geometric and electronic factors in catalysis. These studies have concluded that Pt is the most active metal for HCOOH decomposition, at least as large crystallites and extended surfaces. The identity and oxidation state of surface metal atoms influence the relative rates of dehydrogenation (HCOOH {yields} H{sub 2} + CO{sub 2}) and dehydration (HCOOH {yields} H{sub 2}O + CO) routes, a selectivity requirement for the synthesis of CO-free H{sub 2} streams for low-temperature fuel cells. Group Ib and Group VIII noble metals catalyze dehydrogenation selectively, while base metals and metal oxides catalyze both routes, either directly or indirectly via subsequent water-gas shift (WGS) reactions.

  1. Characterization of Metal Dispersion of Some Naphtha Reforming Catalysts by Methylcyclohexane Dehydrogenation Reaction

    Ameel Mohammed Rahman

    2009-01-01

    Full Text Available The dispersion of supported Pt and Pt–Ir reforming catalysts have been studied, after treatment with oxidative and reducing atmosphere. Methylcyclohexane dehydrogenation reaction in the absence of hydrogen was used as a test reaction. An attempt was made to relate the behavior of the catalysts upon subject to reaction, to the dispersion of the same type of catalysts upon treatment with similar atmosphere and temperatures which appeared in literature. The total conversion of reaction can be explained by a change in metal dispersion. Thus, methylcyclohexane dehydrogenation reaction appears to be a really “structure sensitive” reaction. The toluene yield increases as the oxidation temperature increases over the studied catalyst RG-402, RG-412, RG-422 and RG-432 respectively and reached a maximum value at 550°C. Above 550 the conversion decreases due to the effect of catalyst sintering. No significant change were observed for reduction temperature range 400-600°C for the above studied catalysts.The selectivity order for the studied catalysts and for reduction treatment experiments arranged as follows:RG-422> RG-432> RG-412> RG-402

  2. Rate Parameter Distributions for Isobutane Dehydrogenation and Isobutene Dimerization and Desorption over HZSM-5

    Trevor C. Brown

    2013-11-01

    Full Text Available Deconvolution of the evolved isobutene data obtained from temperature-programmed, low-pressure steady-state conversion of isobutane over HZSM-5 has yielded apparent activation energies for isobutane dehydrogenation, isobutene dimerization and desorption. Intrinsic activation energies and associated isobutane collision frequencies are also estimated. A combination of wavelet shrinkage denoising, followed by time-varying flexible least squares of the evolved mass-spectral abundance data over the temperature range 150 to 450 °C, provides accurate, temperature-dependent, apparent rate parameters. Intrinsic activation energies for isobutane dehydrogenation range from 86 to 235.2 kJ mol−1 (average = 150 ± 42 kJ mol−1 for isobutene dimerization from 48.3 to 267 kJ mol−1 (average = 112 ± 74 kJ mol−1 and for isobutene desorption from 64.4 to 97.8 kJ mol−1 (average = 77 ± 12 kJ mol−1. These wide ranges reflect the heterogeneity and acidity of the zeolite surface and structure. Seven distinct locations and sites, including Lewis and Brønsted acid sites can be identified in the profiles. Isobutane collision frequencies range from 10−0.4 to 1022.2 s−1 and are proportional to the accessibility of active sites, within the HZSM-5 micropores or on the external surface.

  3. Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

    Luma M. Ahmed

    2014-01-01

    Full Text Available Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100. The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR, X-ray diffraction (XRD, atomic force microscopy (AFM, and UV-visible diffuse spectrophotometry (UV-Vis. XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

  4. Theoretical Study on the Dehydrogenation Reaction of H2S by VS+ (3∑-)

    2005-01-01

    The dehydrogenation reaction of H2S by the 3∑- ground state of VS+: VS+ + H2S → VS2+ + H2 has been studied by using Density Functional Theory (DFT) at the B3LYP/DZVP level. It is found that the reaction proceeds along two possible pathways (A and B) yielding two isomer dehydrogenation products VS2+-1 (3B2) and VS2+-2 (3A1), respectively. For both pathways,the reaction has a two-step-reaction mechanism that involves the migration of two hydrogen atoms from S2 to V+, respectively. The migration of the second hydrogen via TS3 and that of the first via TS4 are the rate-determining steps for pathways A and B, respectively. The activation energy is 17.4 kcal/mol for pathway A and 22.8 kcal/mol for pathway B relative to the reactants. The calculated reaction heat of 9.9 kcal/mol indicates the endothermicity of pathway A and that of -11.9 kcal/mol suggests the exothermicity of pathway B.

  5. Novel dehydrogenation properties derived from nanoscale LiBH{sub 4}

    Wan Xuefei [Department of Chemical, Materials and Biomolecular Engineering, University of Connecticut, Storrs, CT (United States); Shaw, Leon L., E-mail: leon.shaw@uconn.edu [Department of Chemical, Materials and Biomolecular Engineering, University of Connecticut, Storrs, CT (United States)

    2011-06-15

    Graphical abstract: The nanoscale LiBH{sub 4}: (a) exhibits the largest H{sub 2} release, whereas the bulk LiBH{sub 4}, (c) has the smallest H{sub 2} release with the partially oxidized nanoscale LiBH{sub 4} and (b) showing the intermediate behavior. - Abstract: Nanoscale, amorphous LiBH{sub 4} powder with sizes from 20 to 50 nm is synthesized via a solvent evaporation process without the aid of nanoscaffolds. The nanoscale LiBH{sub 4} starts to release H{sub 2} at {approx}32 deg. C and forms Li{sub 2}B{sub 12}H{sub 12} at 265 deg. C or lower. The amount of H{sub 2} released in the solid state from 25 to 265 deg. C reaches 3.5 wt.%, which is substantially higher than 0.75 wt.% H{sub 2} released by bulk LiBH{sub 4}. These novel dehydrogenation properties have been discussed based on the observed improvements in both the thermodynamic driving force and reaction kinetics. The nanoscale LiBH{sub 4} not only enhances the dehydrogenation kinetics, but also alters the rate-limiting step.

  6. ENHANCEMENT OF EQUILIBRIUMSHIFT IN DEHYDROGENATION REACTIONS USING A NOVEL MEMBRANE REACTOR; FINAL

    With the advances in new inorganic materials and processing techniques, there has been renewed interest in exploiting the benefits of membranes in many industrial applications. Inorganic and composite membranes are being considered as potential candidates for use in membrane-reactor configuration for effectively increasing reaction rate, selectivity and yield of equilibrium limited reactions. To investigate the usefulness of a palladium-ceramic composite membrane in a membrane reactor-separator configuration, we investigated the dehydrogenation of cyclohexane by equilibrium shift. A two-dimensional pseudo-homogeneous reactor model was developed to study the dehydrogenation of cyclohexane by equilibrium shift in a tubular membrane reactor. Radial diffusion was considered to account for the concentration gradient in the radial direction due to permeation through the membrane. For a dehydrogenation reaction, the feed stream to the reaction side contained cyclohexane and argon, while the separation side used argon as the sweep gas. Equilibrium conversion for dehydrogenation of cyclohexane is 18.7%. The present study showed that 100% conversion could be achieved by equilibrium shift using Pd-ceramic membrane reactor. For a feed containing cyclohexane and argon of 1.64 x 10(sup -6) and 1.0 x 10(sup -3) mol/s, over 98% conversion could be readily achieved. The dehydrogenation of cyclohexane was also experimentally investigated in a palladium-ceramic membrane reactor. The Pd-ceramic membrane was fabricated by electroless deposition of palladium on ceramic substrate. The performance of Pd-ceramic membrane was compared with a commercially available hydrogen-selective ceramic membrane. From limited experimental data it was observed that by appropriate choice of feed flow rate and sweep gas rate, the conversion of cyclohexane to benzene and hydrogen can increased to 56% at atmospheric pressure and 200 C in a Pd-ceramic membrane reactor. In the commercial ceramic membrane

  7. Muscle phosphorylase kinase deficiency

    Preisler, N; Orngreen, M C; Echaniz-Laguna, A; Laforet, P; Lonsdorfer-Wolf, E; Doutreleau, S; Geny, B; Akman, H O; Dimauro, S; Vissing, J

    2012-01-01

    To examine metabolism during exercise in 2 patients with muscle phosphorylase kinase (PHK) deficiency and to further define the phenotype of this rare glycogen storage disease (GSD).......To examine metabolism during exercise in 2 patients with muscle phosphorylase kinase (PHK) deficiency and to further define the phenotype of this rare glycogen storage disease (GSD)....

  8. Iron deficiency anemia

    Anemia - iron deficiency ... iron from old red blood cells. Iron deficiency anemia develops when your body's iron stores run low. ... You may have no symptoms if the anemia is mild. Most of the time, ... slowly. Symptoms may include: Feeling weak or tired more often ...

  9. Nutritional iron deficiency

    Zimmermann, M.B.; Hurrell, R.F.

    2007-01-01

    Iron deficiency is one of the leading risk factors for disability and death worldwide, affecting an estimated 2 billion people. Nutritional iron deficiency arises when physiological requirements cannot be met by iron absorption from diet. Dietary iron bioavailability is low in populations consuming

  10. Lipoprotein lipase deficiency.

    Shankar K; Bava H; Shetty J; Joshi M

    1997-01-01

    A rare case of a 3 month old child with lipoprotein lipase deficiency who presented with bronchopneumonia is reported. After noticing lipaemic serum and lipaemia retinalis, a diagnosis of hyperlipoproteinaemia was considered. Lipoprotein lipase deficiency was confirmed with post heparin lipoprotein lipase enzyme activity estimation.

  11. G6PD Deficiency

    Glucose-6-phosphate dehydrogenase (G6PD) deficiency is a genetic disorder that is most common in males. About 1 in 10 African American males in the United States has it. G6PD deficiency mainly affects red blood cells, which carry oxygen ...

  12. Deficiently Extremal Gorenstein Algebras

    Pavinder Singh

    2011-08-01

    The aim of this article is to study the homological properties of deficiently extremal Gorenstein algebras. We prove that if / is an odd deficiently extremal Gorenstein algebra with pure minimal free resolution, then the codimension of / must be odd. As an application, the structure of pure minimal free resolution of a nearly extremal Gorenstein algebra is obtained.

  13. Vitamin deficiencies and excesses

    Vitamins are essential nutrients that must be supplied exogenously either as part of a well balanced diet or as supplements. Deficiency states are uncommon in developed countries except, perhaps, among some food insecure families. In contrast, deficiency states are quite common in many developing ...

  14. Iron-Deficiency Anemia

    Full Text Available ... Blood Tests Blood Transfusion Restless Legs Syndrome Send a link to NHLBI to someone by E-MAIL | ... Iron-Deficiency Anemia? Español Iron-deficiency anemia is a common, easily treated condition that occurs if you ...

  15. Tailored Formation of N-Doped Nanoarchitectures by Diffusion-Controlled on-Surface (Cyclo)-Dehydrogenation of Heteroaromatics

    Pinardi, A. L.; Otero-Irurueta, G.; Palacio, I.; Martinez, J. I.; Sánchez-Sánchez, C.; Tello, M.; Rogero, C.; Cossaro, A.; Preobrajenski, A.; Gomez-Lor, B.; Jančařík, Andrej; Stará, Irena G.; Starý, Ivo; Lopez, M. F.; Méndez, J.; Martin-Gago, J. A.

    2013-01-01

    Roč. 7, č. 4 (2013), s. 3676-3684. ISSN 1936-0851 R&D Projects: GA ČR(CZ) GAP207/10/2207 Institutional support: RVO:61388963 Keywords : surface-assisted dehydrogenation * dibenzo[5]helicene * N-doped nanographene * heteroaromatic polymer Subject RIV: CC - Organic Chemistry Impact factor: 12.033, year: 2013

  16. Facile synthesis of TiN decorated graphene and its enhanced catalytic effects on dehydrogenation performance of magnesium hydride.

    Wang, Ying; Li, Li; An, Cuihua; Wang, Yijing; Chen, Chengcheng; Jiao, Lifang; Yuan, Huatang

    2014-06-21

    TiN@rGO nanohybrids were successfully synthesized by a simple "urea glass" technique. Experimental results demonstrated that TiN nanocrystals, with an average particle size of 20 nm, were uniformly anchored onto highly reduced graphene nanosheets. The as-synthesized TiN@rGO nanohybrids showed a porous planar-like structure, which had a large surface area of 177 m(2) g(-1). More importantly, the as-prepared TiN@rGO hybrids showed enhanced catalytic effects on the dehydrogenation of MgH2. The dehydrogenation thermodynamics and kinetics of the MgH2-TiN@rGO composites were systematically investigated and some significant improvements were confirmed. It was found that the 10 wt% TiN@rGO doped MgH2 sample started to release hydrogen at about 167 °C, and roughly 6.0 wt% hydrogen was released within 18 min when isothermally heated to 300 °C. In contrast, the onset dehydrogenation temperature of the pure MgH2 sample was about 307 °C, and only 3.5 wt% hydrogen was released even after 120 min of heating under identical conditions. In addition, the catalytic mechanism of TiN@rGO on the dehydrogenation of MgH2 was discussed using the Johnson-Mehl-Avrami (JMA) model and X-ray diffraction equipment. PMID:24817573

  17. Catalytic effect of Ti and Ni on dehydrogenation of AlH{sub 3}: A first principles investigation

    Yu, H.Z.; Dai, J.H.; Song, Y., E-mail: sy@hitwh.edu.cn

    2015-08-30

    Graphical abstract: - Highlights: • Ni doped in bulk and on the surface of AlH{sub 3} are unfavourable comparing to Ti. • Ti and Ni prefer to substitute for Al atom in both the bulk and surface doped systems. • Ti improves the dissociation properties of AlH{sub 3} by weakening the interactions between Al and H atoms, but the catalytic effect is weaker if Ti substitutes for Al than its interstitial doping. - Abstract: Ab initio calculations were performed for the M-doped (M = Ti or Ni) AlH{sub 3} to investigate influence of dopants Ti and Ni on the dehydrogenation properties of AlH{sub 3}. It was found that Ti and Ni prefer to substitute for Al atom in both the bulk phase and the slab surface. However a large amount of energy was needed for Ni to dope into AlH{sub 3} making that Ni might not a suitable catalyst for AlH{sub 3}. Mechanisms that Ti improved the dehydrogenation properties of AlH{sub 3} were clarified. Ti greatly decreased the dehydrogenation energy of AlH{sub 3} by weakening the interaction between Al and H atoms, its influence on the dehydrogenation of AlH3 was however sensitive to the occupation behavior. The calculations indicated that the catalytic effect of Ti was weaker if Ti substitutes for Al than its interstitial occupation.

  18. Dehydrogenative Synthesis of Imines from Alcohols and Amines Catalyzed by a Ruthenium N-Heterocyclic Carbene Complex

    Maggi, Agnese; Madsen, Robert

    2012-01-01

    applied to a variety of primary alcohols and amines and can be combined with a subsequent addition reaction. A deuterium labeling experiment indicates that the catalytically active species is a ruthenium dihydride. The reaction is believed to proceed by initial dehydrogenation of the alcohol to the...

  19. Combined oxidative and non-oxidative dehydrogenation of n-butane over VOX species supported on HMS

    Setnička, Michal; Čičmanec, Pavel; Tvarůžková, Eva; Bulánek, Roman

    2013-01-01

    The combination of oxidative and non-oxidative dehydrogenation of n-butane as an attractive possibility for production of C4 olefins was studied over VOX based catalyst. Long-term activity and selectivity to desired products could be achieved over the catalysts with well dispersed monomeric vanadium oxide species supported on mesoporous silica support.

  20. The mechanism of pyridine hydrogenolysis on molybdenum-containing catalysts : III. Cracking, hydrocracking, dehydrogenation and disproportionation of pentylamine

    Sonnemans, J.; Mars, P.

    1974-01-01

    The conversion of pentylamine on a MoO3-Al2O3 catalyst was studied between 250 and 350 °C, at various hydrogen pressures. The reactions observed were cracking to pentene and ammonia, hydrocracking to pentane and ammonia, dehydrogenation to pentanimine and butylcarbonitrile, and disproportionation to

  1. Catalytic effect of Ti and Ni on dehydrogenation of AlH3: A first principles investigation

    Graphical abstract: - Highlights: • Ni doped in bulk and on the surface of AlH3 are unfavourable comparing to Ti. • Ti and Ni prefer to substitute for Al atom in both the bulk and surface doped systems. • Ti improves the dissociation properties of AlH3 by weakening the interactions between Al and H atoms, but the catalytic effect is weaker if Ti substitutes for Al than its interstitial doping. - Abstract: Ab initio calculations were performed for the M-doped (M = Ti or Ni) AlH3 to investigate influence of dopants Ti and Ni on the dehydrogenation properties of AlH3. It was found that Ti and Ni prefer to substitute for Al atom in both the bulk phase and the slab surface. However a large amount of energy was needed for Ni to dope into AlH3 making that Ni might not a suitable catalyst for AlH3. Mechanisms that Ti improved the dehydrogenation properties of AlH3 were clarified. Ti greatly decreased the dehydrogenation energy of AlH3 by weakening the interaction between Al and H atoms, its influence on the dehydrogenation of AlH3 was however sensitive to the occupation behavior. The calculations indicated that the catalytic effect of Ti was weaker if Ti substitutes for Al than its interstitial occupation

  2. Theoretical study on the structure and dehydrogenation mechanism of mixed metal amidoborane, Na[Li(NH{sub 2}BH{sub 3})]{sub 2}

    Wang, Kun; Zhang, Jian-Guo, E-mail: zjgbit@bit.edu.cn; He, Piao

    2013-12-25

    Highlights: •The systematic study of its structure and electronic structure in gas and solid phase. •The gas phase structures indicate that Li{sup +} cation and Na{sup +} cation acts as very different roles in the dehydrogenation. •Potential energy curves of dehydrogenation were obtained by CCSD(T) method. •Obtained the dehydrogenation rates similar to the experimental values. -- Abstract: This study is based on the synthesis of a mixed metal amidoborane, Na[Li(NH{sub 2}BH{sub 3})]{sub 2} (SLAB), the first example of an inorganic sodium–lithium compound. This paper is the first systematic study of its structure and dehydrogenation mechanism, and the results obtained were consistent with the experimental results. The first principle method was used to study the structure of SLAB in solid phase, while the second Moller–Plesset Perturbation Theory was used for gas-phase kinetic studies. Potential energy curves were obtained by CCSD(T) method. Three mechanistic pathways were designed to study its dehydrogenation, which include A pathway (without the cleavage of N–B bond (S and S′ pathways)), B pathway (with the cleavage of the intramolecular N–B bond before dehydrogenation), and D pathway (with the formation of direct dihydrogen bonds). Na{sup +} cation movement was proved to play a very important role in the hydrogen-transfer process. Finally, a possible dissociation pathway (A pathway) was confirmed and dehydrogenation rates similar to the experimental values were obtained.

  3. In situ synchrotron X-ray diffraction study on the improved dehydrogenation performance of NaAlH4–Mg(AlH4)2 mixture

    Highlights: •The dehydrogenation reactions of NaAlH4–Mg(AlH4)2 mixture were explored by in situ XRD. •NaAlH4–Mg(AlH4)2 mixture exhibited multiple-step dehydrogenation processes. •The mutual catalytic roles of NaAlH4 and Mg(AlH4)2 in the mixture were investigated. •NaAlH4–Mg(AlH4)2 mixture release 5.35 wt% H2 at an initial temperature of 120 °C. -- Abstract: The dehydrogenation performance and mechanism of the synthesized NaAlH4–Mg(AlH4)2 powders were investigated by performing thermogravimetric analysis and in situ synchrotron X-ray diffraction analysis. NaAlH4 not only facilitates the first step dehydrogenation of Mg(AlH4)2 in lowering its initial dehydrogenation temperature but also increases the total amount of H2 released. Besides, MgH2 and/or Al phases, the products of the first step dehydrogenation reaction, play a catalytic role in lowering the initial dehydrogenation temperature of NaAlH4. The synthesized NaAlH4–Mg(AlH4)2 mixture has an initial dehydrogenation temperature as low as 120 °C, and is able to release 5.35 wt% H2 below 350 °C. The self-catalytic dehydrogenation behavior of the NaAlH4–Mg(AlH4)2 mixture was elaborated in this work with the aid of in situ synchrotron XRD

  4. Catalytic dehydrogenation of isobutane in the presence of hydrogen over Cs-modified Ni2P supported on active carbon

    Graphical abstract: - Highlights: • Ni2P catalyst is tested in dehydrogenation of isobutane for the first time. • The effects of Cs promoter on catalytic performance of Ni2P/AC were investigated. • Cs-Ni2P/AC exhibits high activity and selectivity for isobutane dehydrogenation. - Abstract: In this article, an environmentally friendly non-noble-metal class of Cs-Ni2P/active carbon (AC) catalyst was prepared and demonstrated to exhibit enhanced catalytic performance in isobutane dehydrogenation. The results of activity tests reveal that Ni/AC catalyst was highly active for isobutane cracking, which led to the formation of abundant methane and coke. After the introduction of phosphorus through impregnation with ammonium di-hydrogen phosphate and H2-temperature programmed reduction, undesired cracking reactions were effectively inhibited, and the selectivity to isobutene and stability of catalyst increased remarkably. The characterization results indicate that, after the addition of phosphorous, the improvement of dehydrogenation selectivity is ascribed to the partial positive charges carried on Ni surface in Ni2P particles, which decreases the strength of Ni-C bond between Ni and carbonium-ion intermediates and the possibility of excessive dehydrogenation. In addition, Cs-modified Ni2P/AC catalysts display much higher catalytic performance as compared to Ni2P/AC catalyst. Cs-Ni2P-6.5 catalyst has the highest catalytic performance, and the selectivity to isobutene higher than 93% can be obtained even after 4 h reaction. The enhancement in catalytic performance of the Cs-modified catalysts is mainly attributed to the function of Cs to improve the dispersion of Ni2P particles, transfer electron from Cs to Ni, and decrease acid site number and strength

  5. Isolated FeII on Silica As a Selective Propane Dehydrogenation Catalyst

    Hu, Bo; Schweitzer, Neil M.; Zhang, Guanghui; Kraft, Steven J.; Childers, David J.; Lanci, Michael P.; Miller, Jeffrey T.; Hock, Adam S.

    2015-04-17

    ABSTRACT: We report a comparative study of isolated FeII, iron oxide particles, and metallic nanoparticles on silica for non-oxidative propane dehydrogenation. It was found that the most selective catalyst was an isolated FeII species on silica prepared by grafting the open cyclopentadienide iron complex, bis(2,4-dimethyl-1,3-pentadienide) iron(II) or Fe(oCp)2. The grafting and evolution of the surface species was elucidated by 1H NMR, diffuse reflectance infrared Fourier transform spectroscopy and X-ray absorption spectroscopies. The oxidation state and local structure of surface Fe were characterized by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure. The initial grafting of iron proceeds by one surface hydroxyl Si-OH reacting with Fe(oCp)2 to release one diene ligand (oCpH), generating a SiO2-bound FeII(oCp) species, 1-FeoCp. Subsequent treatment with H2 at 400 °C leads to loss of the remaining diene ligand and formation of nanosized iron oxide clusters, 1-C. Dispersion of these Fe oxide clusters occurs at 650 °C, forming an isolated, ligand-free FeII on silica, 1-FeII, which is catalytically active and highly selective (~99%) for propane dehydrogenation to propene. Under reaction conditions, there is no evidence of metallic Fe by in situ XANES. For comparison, metallic Fe nanoparticles, 2-NP-Fe0, were independently prepared by grafting Fe[N(SiMe3)2]2 onto silica, 2-FeN*, and reducing it at 650 °C in H2. The Fe NPs were highly active for propane conversion but showed poor selectivity (~14%) to propene. Independently prepared Fe oxide clusters on silica display a low activity. The sum of these results suggests that selective propane dehydrogenation occurs at isolated FeII sites.

  6. Dehydrogenation properties and crystal structure analysis of Mg(BH{sub 4})(NH{sub 2})

    Noritake, Tatsuo, E-mail: e0553@mosk.tytlabs.co.jp [Toyota Central R and D Labs., Inc., Nagakute, Aichi 480-1192 (Japan); Miwa, Kazutoshi; Aoki, Masakazu; Matsumoto, Mitsuru; Towata, Shin-ichi [Toyota Central R and D Labs., Inc., Nagakute, Aichi 480-1192 (Japan); Li, Hai-Wen [International Research Center for Hydrogen Energy, Kyushu University, Fukuoka 819-0395 (Japan); Orimo, Shin-ichi [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan)

    2013-12-15

    Highlights: •The thermal properties of Mg(BH{sub 4})(NH{sub 2}) was clarified. •Mg(BH{sub 4})(NH{sub 2}) is crystallized at 453 K and then is stable at 300 K. •The crystal structure of Mg(BH{sub 4})(NH{sub 2}) at 300 K was determined. -- Abstract: Dehydrogenation properties and crystal structure of the double anion complex hydride Mg(BH{sub 4})(NH{sub 2}) were studied by thermal analyses and synchrotron X-ray diffraction. The stoichiometric mixture of Mg(BH{sub 4}){sub 2} and Mg(NH{sub 2}){sub 2} were ball-milled and then heated to 453 K to form Mg(BH{sub 4})(NH{sub 2}) crystal. The dehydrogenation of Mg(BH{sub 4})(NH{sub 2}) occurs in two-stage at 513 K and 688 K. The following reaction sequence is suggested by the results of thermal analyses; Mg(BH{sub 4})(NH{sub 2}) → MgH{sub 2} + BN + 2H{sub 2} (7.3 mass% weight loss) → Mg + BN + 3H{sub 2} (11.0 mass% weight loss in total). The dehydrogenation temperature of Mg(BH{sub 4})(NH{sub 2}) is approximately 50 K lower than that of the other double anion complex Li{sub 2}(BH{sub 4})(NH{sub 2}). The crystal structure of Mg(BH{sub 4})(NH{sub 2}) was determined by the measurement at 300 K (crystal system: tetragonal, space group: I4{sub 1} (No. 80), lattice constants: a = 5.792(1), c = 20.632(4) Å at 300 K). In the crystal of Mg(BH{sub 4})(NH{sub 2}), the cation (Mg{sup 2+}) and the anions (BH{sub 4}{sup -} and NH{sub 2}{sup -}) are stacked alternately along the c-axis direction. The Mg{sup 2+} cation is tetrahedrally coordinated with two BH{sub 4}{sup -} anions and two NH{sub 2}{sup -} anions.

  7. A First Principles Study of Mass Transport in the Dehydrogenation of Lithium Amides and Lithium Alanates

    Rolih, Biljana

    The pursuit of competitive alternatives to energy derived from the combustion of fossil fuels, has led to a great variety of new technologies. Exceptional develop- ments in electrochemical storage and production promise to lead to clean burning passenger vehicles. The high chemical density of a hydrogen fuel cell enables it to meet current standards for driving range and weight required of vehicles, making it an excellent candidate for universal application in the automotive industry. One of the biggest obstacles the fuel cell industry has yet to overcome is the means of practical hydrogen storage. Solid state metal hydrides are a class of materials that show potential for both economic and practical hydrogen storage. The search for the ideal metal hydride is defined by thermodynamic and kinetic constraints, since the requirements for a viable system are a rapid release of hydrogen in the temperature range of -40°C, to 80°C. First-principles density functional theory is an excellent method for gaining insight into the kinetics and thermodynamics of metal hydride solid state reactions. In the work presented here, density functional theory is used to explore formation energies, concentrations and migration barriers of metal hydrides. In particular, the following systems were analyzed: • Li - N - H It is well known that the reactive hydride composite LiNH 2 + LiH reversibly releases a large amount of hydrogen gas, with more favorable thermodynamics than LiNH2 alone. Kinetics of mass transport during the dehydrogenation of LiNH2 + LiH are investigated. A model is developed for determining activation energies of native defects in bulk crystals. In order to establish whether mass transport is the rate-limiting step in the dehydrogenation reaction, results are compared to experimental values. • Li - Al - H Kinetics of mass transport during the dehydrogenation of the metal hydride LiAlH2 are investigated. It is known that LiAlH4 endothermically decomposes via a two

  8. Thiamine deficiency and delirium.

    Osiezagha, Kenneth; Ali, Shahid; Freeman, C; Barker, Narviar C; Jabeen, Shagufta; Maitra, Sarbani; Olagbemiro, Yetunde; Richie, William; Bailey, Rahn K

    2013-04-01

    Thiamine is an essential vitamin that plays an important role in cellular production of energy from ingested food and enhances normal neuronal actives. Deficiency of this vitamin leads to a very serious clinical condition known as delirium. Studies performed in the United States and other parts of the world have established the link between thiamine deficiency and delirium. This literature review examines the physiology, pathophysiology, predisposing factors, clinical manifestations (e.g., Wernicke's encephalopathy, Wernicke-Korsakoff syndrome, structural and functional brain injuries) and diagnosis of thiamine deficiency and delirium. Current treatment practices are also discussed that may improve patient outcome, which ultimately may result in a reduction in healthcare costs. PMID:23696956

  9. Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane

    Zhu, Haibo

    2015-03-05

    The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400°C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300°C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90% of their original intrinsic activity was retained after 50h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane.

  10. Compensation Effect in the Hydrogenation/Dehydrogenation Kinetics of Metal Hydrides

    Andreasen, A.; Vegge, T.; Pedersen, Allan Schrøder

    2005-01-01

    The possible existence of a compensation effect, i.e. concurrent changes in activation energy and prefactor, is investigated for the hydrogenation and dehydrogenation kinetics of metal hydrides, by analyzing a series of reported kinetic studies on Mg and LaNi5 based hydrides. For these systems, we...... find a clear linear relation between apparent prefactors and apparent activation energies, as obtained from an Arrhenius analysis, indicating the existence of a compensation effect. Large changes in apparent activation energies in the case of Mg based hydrides are rationalized in terms of a dependency...... of observed apparent activation energy on the degree of surface oxidation, i.e., a physical effect. On the other hand, we find the large concurrent changes in apparent prefactors to be a direct result of the Arrhenius analysis. Thus, we find the observed compensation effect to be an artifact of the data...

  11. High speed laser activated membrane introduction mass spectrometric evaluation of bulk methylcyclohexane dehydrogenation catalysts

    Laser activated membrane introduction mass spectrometry (LAMIMS) is a modification of membrane introduction mass spectrometry where a silicone membrane serves as a separator between an analyte stream and the vacuum of a quadrupole mass spectrometer. Carbon paper, commonly used as a fuel cell gas diffusion layer, has been overlaid upon the silicone membrane to serve as a support for catalyst array libraries that are heated by a CO2 laser during evaluation. The LAMIMS reactor is a closed environment permitting steady state exposure of the catalyst library to the reactant stream. In this work, Pt/Al2O3 catalysts for the dehydrogenation of methylcyclohexane (MCH) to toluene have been ranked by LAMIMS. Spot-to-spot evaluation times (after preconditioning) are 1 min in this study. The data suggests that by optimization of signal-to-noise and spot-to-spot dwell times, ranking can be conducted at substantially under a minute per array spot candidate

  12. Metal oxides modified NiO catalysts for oxidative dehydrogenation of ethane to ethylene

    Zhu, Haibo

    2014-06-01

    The sol-gel method was applied to the synthesis of Zr, Ti, Mo, W, and V modified NiO based catalysts for the ethane oxidative dehydrogenation reaction. The synthesized catalysts were characterized by XRD, N2 adsorption, SEM and TPR techniques. The results showed that the doping metals could be highly dispersed into NiO domains without the formation of large amount of other bulk metal oxide. The modified NiO materials have small particle size, larger surface area, and higher reduction temperature in contrast to pure NiO. The introduction of group IV, V and VI transition metals into NiO decreases the catalytic activity in ethane ODH. However, the ethylene selectivity is enhanced with the highest level for the Ni-W-O and Ni-Ti-O catalysts. As a result, these two catalysts show improved efficiency of ethylene production in the ethane ODH reaction. © 2014 Elsevier B.V. All rights reserved.

  13. Highly selective oxidative dehydrogenation of ethane with supported molten chloride catalysts

    Gaertner, C.A.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen (Germany). Catalysis Research Center

    2011-07-01

    Ethene production is one of the most important transformations in chemical industry, given that C{sub 2}H{sub 4} serves as building block for many mass-market products. Besides conventional thermal processes like steam cracking of ethane, ethane can be produced selectively by catalytic processes. One of the classes of catalysts that have been reported in literature as active and highly selective for the oxidative dehydrogenation of ethane is that of supported molten chloride catalysts, containing an alkali chloride overlayer on a solid support. This work deals with fundamental aspects of the catalytic action in latter class of catalysts. Results from kinetic reaction studies are related to observations in detailed characterization and lead to a comprehensive mechanistic understanding. Of fundamental importance towards mechanistic insights is the oxygen storage capacity of the catalysts that has been determined by transient step experiments. (orig.)

  14. Minor dehydrogenated and cleavaged dammarane-type saponins from the steamed roots of Panax notoginseng.

    Gu, Cheng-Zhen; Lv, Jun-Jiang; Zhang, Xiao-Xia; Yan, Hui; Zhu, Hong-Tao; Luo, Huai-Rong; Wang, Dong; Yang, Chong-Ren; Xu, Min; Zhang, Ying-Jun

    2015-06-01

    Nine new minor dehydrogenated and cleavaged dammarane-type triterpenoid saponins, namely notoginsenosides ST6-ST14 (1-9) were isolated from the steamed roots of Panax notoginseng, together with 14 known ones. Among them, 5-7 and 21-22 were protopanaxadiol type and the left 18 compounds, including 1-4, 8-20, and 23 were protopanaxatriol type saponins. Their structures were identified by extensive analysis of MS, 1D and 2D NMR spectra, and acidic hydrolysis. Resulted from the side chain cleavage, the new saponins 1 and 2 featured in a ketone group at C-25, and 3-5 had an aldehyde unit at C-23. The known saponins 12, 16 and 18 displayed the enhancing potential of neurite outgrowth of NGF-mediated PC12 cells at a concentration of 10 μM, while 20 exhibited acetyl cholinesterase inhibitory activity, with IC50 value of 13.97 μM. PMID:25797537

  15. Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces.

    Beste, Ariana; Overbury, Steven H

    2016-04-21

    We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed product selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors. PMID:27005883

  16. Influence of promoters and oxidants on propane dehydrogenation over chromium-oxide catalysts

    Lapidus, A.L.; Agafonov, Yu.A.; Shaporeva, N.Yu.; Trushin, D.V.; Gaidai, N.A.; Nekrasov, N.V. [Russian Academy of Sciences, Moscow (Russian Federation). N.D. Zelinsky Inst. of Organic Chemistry

    2010-12-30

    Possibilities for increasing the efficiency of supported on SiO{sub 2} chromium-oxide catalysts in propane oxidative dehydrogenation in CO{sub 2} presence are investigated: the introduction of Li, Na, K, Ca in catalysts and the addition of O{sub 2} in the reaction mixture. It was been found that the positive role of K - the increase of the selectivity to propene and stability of catalysts at long-duration tests - appeared at the relation of Cr:K=20. It was shown that the presence of little amount of O{sub 2} (2%) in the reaction mixtures of propane and carbon dioxide resulted in the increase of propene yield and catalyst stability. (orig.)

  17. Concept and progress in coupling of dehydrogenation and hydrogenation reactions through catalysts

    C V Pramod; C Raghavendra; K Hari Prasad Reddy; G V Ramesh Babu; K S Rama Rao; B David Raju

    2014-03-01

    This review focuses on the importance of coupling of catalytic reactions which involves dehydrogenation and hydrogenation simultaneously and the study of catalytic materials that are designed, adopted and/or modified for these reactions. The special features of these reactions are minimization of H2 utilization and reduction in production cost. Structural and textural properties also play a decisive role in this kind of coupled reactions. This particular review although not comprehensive discusses the significant progress made in the area of coupled reactions and also helps future researchers or engineers to find out the improvements required in areas such as advancements in catalytic material preparation, design of the new reactors and the application of new technologies.

  18. Iron-Deficiency Anemia

    Full Text Available ... Digg. Share this page from the NHLBI on Facebook. Add this link to the NHLBI to my ... such as tiredness, poor skin tone, dizziness, and depression. After her doctor diagnosed her with iron-deficiency ...

  19. Iron-Deficiency Anemia

    Full Text Available ... Topics Anemia Blood Tests Blood Transfusion Restless Legs Syndrome Send a link to NHLBI to someone by ... symptoms. Severe iron-deficiency anemia can lead to heart problems, infections, problems with growth and development in ...

  20. Iron-Deficiency Anemia

    Full Text Available ... symptoms. Severe iron-deficiency anemia can lead to heart problems, infections, problems with growth and development in ... 18/2011 This video—presented by the National Heart, Lung, and Blood Institute, part of the National ...

  1. Iron-Deficiency Anemia

    Full Text Available ... Entire Site Health Topics News & Resources Intramural Research Public Health Topics Education & Awareness Resources Contact The Health ... Severe iron-deficiency anemia can lead to heart problems, infections, problems with growth and development in children, ...

  2. Folate-deficiency anemia

    Folate-deficiency anemia is a decrease in red blood cells (anemia) due to a lack of folate. Folate is a type ... B vitamin. It is also called folic acid. Anemia is a condition in which the body does ...

  3. Sleep Deprivation and Deficiency

    ... page from the NHLBI on Twitter. What Are Sleep Deprivation and Deficiency? Sleep deprivation (DEP-rih-VA- ... Rate This Content: NEXT >> Updated: February 22, 2012 Sleep Infographic Sleep Disorders & Insufficient Sleep: Improving Health through ...

  4. Iron-Deficiency Anemia

    Full Text Available ... Health Topics Education & Awareness Resources Contact The Health Information Center Health Professionals Systematic Evidence Reviews & Clinical Practice ... and see the benefits of treatment. For more information about living with and managing iron-deficiency anemia, ...

  5. Iron-Deficiency Anemia

    Full Text Available ... intravenous iron therapy. Rate This Content: NEXT >> Featured Video Living With and Managing Iron-Deficiency Anemia 05/18/2011 This video—presented by the National Heart, Lung, and Blood ...

  6. Iron-Deficiency Anemia

    Full Text Available ... iron-rich protein that carries oxygen from the lungs to the rest of the body. Iron-deficiency ... 2011 This video—presented by the National Heart, Lung, and Blood Institute, part of the National Institutes ...

  7. Iron-Deficiency Anemia

    Full Text Available ... Alerts E-Newsletters About NHLBI Organization NHLBI Director Budget, Planning, & Legislative Advisory Committees Contact Us FAQs Home » ... severity of the condition. Treatments may include dietary changes, medicines, and surgery. Severe iron-deficiency anemia may ...

  8. Iron-Deficiency Anemia

    Full Text Available ... CAUSES WHO IS AT RISK SIGNS & SYMPTOMS DIAGNOSIS TREATMENTS PREVENTION LIVING WITH CLINICAL TRIALS LINKS Related Topics ... Doctors usually can successfully treat iron-deficiency anemia. Treatment will depend on the cause and severity of ...

  9. Clinical significance of complement deficiencies.

    Pettigrew, H David; Teuber, Suzanne S; Gershwin, M Eric

    2009-09-01

    The complement system is composed of more than 30 serum and membrane-bound proteins, all of which are needed for normal function of complement in innate and adaptive immunity. Historically, deficiencies within the complement system have been suspected when young children have had recurrent and difficult-to-control infections. As our understanding of the complement system has increased, many other diseases have been attributed to deficiencies within the complement system. Generally, complement deficiencies within the classical pathway lead to increased susceptibility to encapsulated bacterial infections as well as a syndrome resembling systemic lupus erythematosus. Complement deficiencies within the mannose-binding lectin pathway generally lead to increased bacterial infections, and deficiencies within the alternative pathway usually lead to an increased frequency of Neisseria infections. However, factor H deficiency can lead to membranoproliferative glomerulonephritis and hemolytic uremic syndrome. Finally, deficiencies within the terminal complement pathway lead to an increased incidence of Neisseria infections. Two other notable complement-associated deficiencies are complement receptor 3 and 4 deficiency, which result from a deficiency of CD18, a disease known as leukocyte adhesion deficiency type 1, and CD59 deficiency, which causes paroxysmal nocturnal hemoglobinuria. Most inherited deficiencies of the complement system are autosomal recessive, but properidin deficiency is X-linked recessive, deficiency of C1 inhibitor is autosomal dominant, and mannose-binding lectin and factor I deficiencies are autosomal co-dominant. The diversity of clinical manifestations of complement deficiencies reflects the complexity of the complement system. PMID:19758139

  10. Adult growth hormone deficiency

    Vishal Gupta

    2011-01-01

    Adult growth hormone deficiency (AGHD) is being recognized increasingly and has been thought to be associated with premature mortality. Pituitary tumors are the commonest cause for AGHD. Growth hormone deficiency (GHD) has been associated with neuropsychiatric-cognitive, cardiovascular, neuromuscular, metabolic, and skeletal abnormalities. Most of these can be reversed with growth hormone therapy. The insulin tolerance test still remains the gold standard dynamic test to diagnose AGHD. Growth...

  11. Iron deficiency anemia Review

    Yıldız, İnci

    2009-01-01

    Iron deficiency anemia is the most frequent and widespread anemia around the world Its prevalence is increased in infants and adolescent girls The etiologic factors may vary but anemia is essentially related to iron deficient nutrition blood loss and malabsorption Children may have paleness cardiovascular and neurologic impacts of anemia pica epithelial changes as koilonychia glossitis angular stomatitis Treatment is by oral or parenteral supplementation of iron Turk Arch Ped 2009; 44 Suppl: ...

  12. Ethylbenzene dehydrogenation over binary FeOx–MeOy/Mg(Al)O catalysts derived from hydrotalcites

    Balasamy, Rabindran J.

    2010-12-20

    A series of FeOx-MeOy/Mg(Al)O catalysts were prepared from hydrotalcite-like compounds as precursors and were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The hydrotalcite-like precursors of the metal compositions of Mg3Fe 0.25Me0.25Al0.5 (Me = Cu, Zn, Cr, Mn, Fe, Co and Ni) were coprecipitated from the nitrates of metal components and calcined to mixed oxides at 550 °C. After the calcination, the mixed oxides showed high surface area of 150-200 m2 gcat -1, and were mainly composed of (MgMe)(Fe3+Al)O periclase in the bulk, whereas the surface was enriched by (MgMe)(Fe3+Al)2O 4 pinel. Among the Me species tested, Co2+ was the most effective, followed by Ni2+. Co2+ addition increased the activity of original FeOx/Mg(Al)O catalyst, whereas Ni2+ increased the activity at the beginning of reaction, but deactivated the catalyst during the reaction. The other metals formed isolated MeOx species in the catalyst, resulting in a decrease in the activity compared to the original FeOx/Mg(Al)O catalyst. The active Fe species exists as metastable Fe3+ on the FeOx/Mg(Al)O catalyst. By the addition of Co2+, the reduction-oxidation between Fe3+ and Fe2+ was facilitated and, moreover, the active Fe3+ species was stabilized. It is likely that the dehydrogenation proceeds on the active Fe3+ species via its reduction-oxidation assisted by Co 2+. © 2010 Elsevier B.V.

  13. A study of the isobutane dehydrogenation in a porous membrane catalytic reactor: design, use and modelling

    Casanave, D.

    1996-01-26

    The aim of this study was to set up and model a catalytic fixed-bed membrane reactor for the isobutane dehydrogenation. The catalyst, developed at Catalysis Research Institute (IRC), was a silicalite-supported Pt-based catalyst. Their catalytic performances (activity, selectivity, stability) where found better adapted to the membrane reactor, when compared with commercial Pt or Cr based catalysts. The kinetic study of the reaction has been performed in a differential reactor and led to the determination of a kinetic law, suitable when the catalyst is used near thermodynamic equilibrium. The mass transfer mechanisms were determined in meso-porous and microporous membranes through both permeability and gas mixtures (iC{sub 4}/H{sub 2}/N{sub 2}) separation measurements. For the meso-porous {gamma}-alumina, the mass transfer is ensured by a Knudsen diffusion mechanism which can compete with surface diffusion for condensable gas like isobutane. The resulting permselectivity H{sub 2}/iC4 of this membrane is low ({approx} 4). For the microporous zeolite membrane, molecular sieving occurs due to steric hindrance, leading to higher permselectivity {approx}14. Catalyst/membrane associations were compared in terms of isobutane dehydrogenation performances, for both types of membranes (meso-porous and microporous) and for two different reactor configurations (co-current and counter-current sweep gas flow). The best experimental results were obtained with the zeolite membrane, when sweeping the outer compartment in a co-current flow. The equilibrium displacement observed with the {gamma}-alumina membrane was lower and mainly due to a dilution effect of the reaction mixture by the sweep gas. A mathematical model was developed, which correctly describes all the experimental results obtained with the zeolite membrane, when the co-current mode is used. (Abstract Truncated)

  14. Kinetics modeling of ethylbenzene dehydrogenation to styrene over a mesoporous alumina supported iron catalyst

    Hossain, Mohammad M.

    2012-10-01

    The kinetics of ethylbenzene (EB) dehydrogenation over a FeO x-meso-Al 2O 3 catalyst is studied. The models were developed based on physicochemical characterization and a CREC fluidized Riser Simulator data. N 2 adsorption shows that the synthesized FeO x-meso-Al 2O 3 catalyst is mesoporous with pore size between 9 and 35nm. TPR profile indicates that iron on meso-Al 2O 3 forms easily reducible nanostructured crystals which is confirmed by TEM image. NH 3- and CO-TPD analysis, respectively reveals the availability of both acidic and basic sites. The dehydrogenation of ethylbenzene on FeO x-meso-Al 2O 3 catalyst mainly gives styrene (∼99%) while a small amount of benzene, toluene and coke are also detected. Based on the experimental observations two Langmuir-Hinshelwood type kinetics models are formulated. The possible catalyst deactivation is expressed as function of EB conversion. Parameters are estimated by fitting of the experimental data implemented in MATLAB. Results show that one type site Langmuir-Hinshelwood model appropriately describes the experimental data, with adequate statistical fitting indicators and also satisfied the physical constraints. The activation energy for the formation of styrene (80kJ/mol) found to be significantly lower than that of the undesired products benzene (144kJ/mol) and toluene (164kJ/mol). The estimated heat of adsorptions of EB and ST are found to be 55kJ/mol and 19kJ/mol, respectively. © 2012 Elsevier B.V.

  15. Iron deficiency in Europe.

    Hercberg, S; Preziosi, P; Galan, P

    2001-04-01

    In Europe, iron deficiency is considered to be one of the main nutritional deficiency disorders affecting large fractions of the population, particularly such physiological groups as children, menstruating women and pregnant women. Some factors such as type of contraception in women, blood donation or minor pathological blood loss (haemorrhoids, gynaecological bleeding...) considerably increase the difficulty of covering iron needs. Moreover, women, especially adolescents consuming low-energy diets, vegetarians and vegans are at high risk of iron deficiency. Although there is no evidence that an absence of iron stores has any adverse consequences, it does indicate that iron nutrition is borderline, since any further reduction in body iron is associated with a decrease in the level of functional compounds such as haemoglobin. The prevalence of iron-deficient anaemia has slightly decreased in infants and menstruating women. Some positive factors may have contributed to reducing the prevalence of iron-deficiency anaemia in some groups of population: the use of iron-fortified formulas and iron-fortified cereals; the use of oral contraceptives and increased enrichment of iron in several countries; and the use of iron supplements during pregnancy in some European countries. It is possible to prevent and control iron deficiency by counseling individuals and families about sound iron nutrition during infancy and beyond, and about iron supplementation during pregnancy, by screening persons on the basis of their risk for iron deficiency, and by treating and following up persons with presumptive iron deficiency. This may help to reduce manifestations of iron deficiency and thus improve public health. Evidence linking iron status with risk of cardiovascular disease or cancer is unconvincing and does not justify changes in food fortification or medical practice, particularly because the benefits of assuring adequate iron intake during growth and development are well established

  16. Glucose-6-phosphate dehydrogenase deficiency

    G-6-PD deficiency; Hemolytic anemia due to G6PD deficiency; Anemia - hemolytic due to G6PD deficiency ... G6PD deficiency occurs when a person is missing or doesn't have enough of an enzyme called glucose- ...

  17. Influence of Vanadium Oxidation States on the Performance of V-Mg-Al Mixed-Oxide Catalysts for the Oxidative Dehydrogenation of Propane

    Leticia Schacht; Juan Navarrete; Persi Schacht; Ramírez, Marco A.

    2010-01-01

    V-Mg-Al mixed-oxide catalysts for oxidative dehydrogenation of propane were prepared by thermal decomposition of Mg-Al-layered double hydroxides with vanadium interlayer doping. The obtained catalysts were tested for the oxidative dehydrogenation of propane, obtaining good results in catalytic activity (conversion 16.55 % and selectivity 99.97 %). Results indicated that catalytic performance of these materials depends on how vanadium is integrated in the layered structure, which is determined...

  18. Dehydrogenation of N{sub 2}H{sub X} (X = 2 − 4) by nitrogen atoms: Thermochemical and kinetics

    Spada, Rene Felipe Keidel; Araujo Ferrão, Luiz Fernando de [Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos 12.228-900, São Paulo (Brazil); Departamento de Física, Instituto Tecnológico de Aeronáutica, São José dos Campos 12.228-900, São Paulo (Brazil); Roberto-Neto, Orlando [Divisão de Aerotermodinâmica e Hipersônica, Instituto de Estudos Avançados, São José dos Campos 12.229-840, São Paulo (Brazil); Machado, Francisco Bolivar Correto, E-mail: fmachado@ita.br [Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos 12.228-900, São Paulo (Brazil)

    2013-11-21

    Thermochemical and kinetics of sequential hydrogen abstraction reactions from hydrazine by nitrogen atoms were studied. The dehydrogenation was divided in three steps, N{sub 2}H{sub 4} + N, N{sub 2}H{sub 3} + N, and N{sub 2}H{sub 2} + N. The thermal rate constants were calculated within the framework of canonical variational theory, with zero and small curvature multidimensional tunnelling corrections. The reaction paths were computed with the BB1K/aug-cc-pVTZ method and the thermochemical properties were improved with the CCSD(T)/CBS//BB1K/aug-cc-pVTZ approach. The first dehydrogenation step presents the lowest rate constants, equal to 1.22 × 10{sup −20} cm{sup 3} molecule{sup −1} s{sup −1} at 298 K.

  19. Antepartum ornithine transcarbamylase deficiency.

    Nakajima, Hitoshi; Sasaki, Yosuke; Maeda, Tadashi; Takeda, Masako; Hara, Noriko; Nakanishi, Kazushige; Urita, Yoshihisa; Hattori, Risa; Miura, Ken; Taniguchi, Tomoko

    2014-01-01

    Ornithine transcarbamylase deficiency (OTCD) is the most common type urea cycle enzyme deficiencies. This syndrome results from a deficiency of the mitochondrial enzyme ornithine transcarbamylase, which catalyzes the conversion of ornithine and carbamoyl phosphate to citrullin. Our case was a 28-year-old female diagnosed with OTCD following neurocognitive deficit during her first pregnancy. Although hyperammonemia was suspected as the cause of the patient's mental changes, there was no evidence of chronic liver disease. Plasma amino acid and urine organic acid analysis revealed OTCD. After combined modality treatment with arginine, sodium benzoate and hemodialysis, the patient's plasma ammonia level stabilized and her mental status returned to normal. At last she recovered without any damage left. PMID:25759629

  20. Catalytic mechanism of the dehydrogenation of ethylbenzene over Fe–Co/Mg(Al)O derived from hydrotalcites

    Tope, Balkrishna B.

    2011-11-01

    Catalytic mechanism of ethylbenzene dehydrogenation over Fe-Co/Mg(Al)O derived from hydrotalcites has been studied based on the XAFS and XPS catalyst characterization and the FTIR measurements of adsorbed species. Fe-Co/Mg(Al)O showed synergy, whereas Fe-Ni/Mg(Al)O showed no synergy, in the dehydrogenation of ethylbenzene. Ni species were stably incorporated as Ni2+ in the regular sites in periclase and spinel structure in the Fe-Ni/Mg(Al)O. Contrarily, Co species exists as a mixture of Co3+/Co2+ in the Fe-Co/Mg(Al)O and was partially isolated from the regular sites in the structures with increasing the Co content. Co addition enhanced Lewis acidity of Fe3+ active sites by forming Fe3+-O-Co 3+/2+(1/1) bond, resulting in an increase in the activity. FTIR of ethylbenzene adsorbed on the Fe-Co/Mg(Al)O clearly showed formations of C-O bond and π-adsorbed aromatic ring. This suggests that ethylbenzene was strongly adsorbed on the Fe3+ acid sites via π-bonding and the dehydrogenation was initiated by α-H+ abstraction from ethyl group on Mg2+-O2- basic sites, followed by C-O-Mg bond formation. The α-H+ abstraction by O2-(-Mg 2+) was likely followed by β-H abstraction, leading to the formations of styrene and H2. Such catalytic mechanism by the Fe 3+ acid-O2-(-Mg2+) base couple and the Fe 3+/Fe2+ reduction-oxidation cycle was further assisted by Co3+/Co2+, leading to a good catalytic activity for the dehydrogenation of ethylbenzene. © 2011 Elsevier B.V. All rights reserved.

  1. Characterization of Industrial Pt-Sn/Al2O3 Catalyst and Transient Product Formations during Propane Dehydrogenation

    Kah Sing Ho; Joanna Jo Ean Chye; Sim Yee Chin; Chin Kui Cheng

    2013-01-01

    The major problem plaguing propane dehydrogenation process is the coke formation on the Pt-Sn/Al2O3 catalyst which leads to catalyst deactivation. Due to information paucity, the physicochemical characteristics of the commercially obtained regenerated Pt-Sn/Al2O3 catalyst (operated in moving bed reactor) and coke formation at different temperatures of reaction were discussed. The physicochemical characterization of regenerated catalyst gave a BET surface area of 104.0 m2/g with graphitic carb...

  2. Chemical, Structural, and Morphological Changes of a MoVTeNb Catalyst during Oxidative Dehydrogenation of Ethane

    Valente, Jaime S.; Armendariz-Herrera, Héctor; Quintana-Solorzano, Roberto; Del Angel, Paz; Nava, Noel; Masso Ramírez, Amada; López Nieto, José Manuel

    2014-01-01

    MoVTeNb mixed oxide, a highly active and selective catalyst for the oxidative dehydrogenation of ethane to produce ethylene, exhibits the so-called M1 and M2 crystalline phases. The thermal stability of the MoVTeNb catalytic system was assessed under varying reaction conditions; to this end, the catalyst was exposed to several reaction temperatures spanning from 440 to 550 °C. Both the pristine and spent materials were analyzed by several characterization techniques. The ...

  3. Making coke a more efficient catalyst in the oxidative dehydrogenation of ethylbenzene using wide-pore transitional aluminas

    Zarubina, V.; Nederlof, C.; B. VAN DER LINDEN; F. Kapteijn; Heeres, H. J.; Makkee, M.; Melián-Cabrera, I.

    2014-01-01

    The thermal activation of a silica-stabilized gamma-alumina impacts positively on the oxidative dehydrogenation of ethylbenzene (EB) to styrene (ST). A systematic thermal study reveals that the transition from gamma-alumina into transitional phases at 1050 degrees C leads to an optimal enhancement of both conversion and selectivity under pseudo-steady state conditions; where active and selective coke have been deposited. The effect is observed in the reaction temperature range of 450-475 degr...

  4. Role of Sn in the Regeneration of Pt/γ-Al2O3 Light Alkane Dehydrogenation Catalysts

    Pham, Hien N.; Sattler, Jesper J. H. B.; Weckhuysen, Bert M.; Datye, Abhaya K.

    2016-01-01

    Alumina-supported Pt is one of the major industrial catalysts for light alkane dehydrogenation. This catalyst loses activity during reaction, with coke formation often considered as the reason for deactivation. As we show in this study, the amount and nature of carbon deposits do not directly correlate with the loss of activity. Rather, it is the transformation of subnanometer Pt species into larger Pt nanoparticles that appears to be responsible for the loss of catalytic activity. Surprising...

  5. Mechanistic understanding and kinetic studies of highly selective oxidative dehydrogenation of ethane over novel supported molten chloride catalysts

    Gaertner, C.; Veen, A.C. van; Lercher, J.A. [Technische Univ. Muenchen, Garching (Germany). Dept. of Chemistry

    2012-07-01

    Ethene is one of the most important feedstocks for chemical industry, nowadays mainly produced via steam cracking. However, oxidative dehydrogenation becomes a more important process route, allowing to produce ethene selectively and at lower temperatures. Supported alkali chloride catalysts are promising materials. However, the ODH mechanism of this class of catalysts is not well investigated so far. The investigation of the reaction mechanism is thus the aim of this contribution. (orig.)

  6. Study of the performance of vanadium based catalysts prepared by grafting in the oxidative dehydrogenation of propane

    Santacesaria, E.; Carotenuto, G.; Tesser, R.; Di Serio, M. [Naples Univ. (Italy). Dept. of Chemistry

    2011-07-01

    The oxidative dehydrogenation (ODH) of propane has been investigated by using many different vanadia based catalysts, prepared by grafting technique and containing variable amounts of active phase supported on SiO{sub 2} previously coated, by grafting in three different steps, with multilayer of TiO{sub 2}. A depth catalytic screening, conducted in a temperature range of 400-600 C, at atmospheric pressure and in a range of residence time W/F=0.08-0.33 ghmol{sub -1}, has shown that the vanadium oxide catalysts on TiO{sub 2}-SiO{sub 2} support, prepared by grafting have good performances in the ODH of propane. In particular, a preliminary study has demonstrated that higher selectivities can be obtained employing catalysts having a well dispersed active phase that can be achieved with a V{sub 2}O{sub 5} content lower than 10%{sub w}t. It is well known that, in the case of redox catalysts, an increase of the selectivity can be achieved not only by using an adequate catalytic system but also via engineering routes like decoupling catalytic steps of reduction and re-oxidation. In fact it has been observed that by operating in dehydrogenating mode, on the same catalysts, a higher selectivity is obtained although the catalyst is poisoned by the formation of coke on the surface. As consequence of the results obtained in dehydrogenation, in this work has been explored the possibility to feed low amounts of oxygen, below the stoichiometric level with the aim to keep clean the surface from coke but maintaining high the selectivity, because, dehydrogenation reaction prevails. In this work, the behavior of catalysts containing different amounts of V2O5 has been studied in the propane-propene reaction by using different ratios C{sub 3}H{sub 8}/O{sub 2} included in the range 0-2. (orig.)

  7. Adsorption and dehydrogenation mechanism of methane on clean and oxygen-covered Pd (1 0 0) surfaces: A DFT study

    Highlights: • Adsorption and dehydrogenation mechanisms of methane on Pd (1 0 0) surface were studied using DFT calculations. • The optimized structures and adsorption energies were obtained. The energy barriers and reaction energies were calculated. • The presence of oxygen atom inhibited the dissociation of CHx except for CH3 group. - Abstract: Using density functional theory (DFT) together with periodic slab models, the adsorption and dehydrogenation mechanisms of methane on clean and oxygen-covered Pd (1 0 0) surfaces have been studied systematically. Different adsorption geometries were investigated for CH4 and related intermediates (CH3, CH2, CH, C, H, O and OH). It was found that CH4 and CH3 prefer to adsorb on the top site, CH2 and OH are favorable on the bridge site, while CH, C, O and H species adsorb preferentially on the hollow site. In addition, this work identified the stable co-adsorption configurations for the relevant co-adsorption groups. It was concluded that the effect of co-adsorbed oxygen atom tends to weaken the adsorbate–substrate interaction on the Pd (1 0 0) surface. Finally, transition states, energy barriers and reaction energies were determined to confirm the mechanism of dehydrogenation of CH4 on clean and oxygen-covered Pd (1 0 0) surfaces. The existence of oxygen atom increases the energy barriers obviously and inhibits the dissociation of CHx (x = 1, 2 and 4) except for CH3 group

  8. Microbial transformations of steroids--IV. 6,7-Dehydrogenation; a new class of fungal steroid transformation product.

    Smith, K E; Latif, S; Kirk, D N; White, K A

    1989-08-01

    Microbial steroid dehydrogenation is quite common. The reaction seems to occur mainly in bacteria and usually results in hydrogen abstraction from positions C(1)-C(2) and/or C(4)-C(5) with occasional aromatisation of ring A. We have screened large numbers of fungal cultures for their ability to monohydroxylate steroids at unusual sites and in the course of our investigations we have identified seven fungal strains capable of dehydrogenating ring B of progesterone and androstenedione at positions C(6)-C(7). Microbiological dehydrogenation at this site seems not to have been reported previously. The structures of the metabolites isolated from progesterone, and the producing fungi, are: 6-dehydroprogesterone (Botryodiplodia theobromae), 11 alpha-hydroxy-6-dehydroprogesterone (Botryosphaerica obtusa, Mucor racemosus and Nigrospora sphaerica), 12 alpha-, 15 beta- and 16 alpha-hydroxy-6-dehydroprogesterones (B. obtusa) and 14 alpha-hydroxy-6-dehydroprogesterone (Apiocrea chrysosperma) [1]. From androstenedione we isolated 6-dehydroandrostenedione (Absidia coerulea and Curvularia lunata) and 6-dehydrotestosterone (C. lunata). PMID:2770300

  9. Towards understanding a mechanism for reversible hydrogen storage: theoretical study of transition metal catalysed dehydrogenation of sodium alanate.

    Ljubić, Ivan; Clary, David C

    2010-04-28

    On the basis of density functional theory and coupled-cluster CCSD(T) calculations we propose a mechanism of the dehydrogenation of transition metal doped sodium alanate. Insertion of two early 3d-transition metals, scandium and titanium, both of which are promising catalysts for reversible hydrogen storage in light metal hydrides, is compared. The mechanism is deduced from studies on the decomposition of a model system consisting of one transition metal atom and two NaAlH(4) units. Subsequently, the significance of such minimal cluster model systems to the real materials is tested by embedding the systems into the surface of the NaAlH(4) crystal. It is found that the dehydrogenation proceeds via breaking of the bridge H-Al bond and consequent formation of intermediate coordination compounds in which the H(2) molecule is side-on (eta(2)-) bonded to the transition metal centre. The total barrier to the H(2) release is thus dependent upon both the strength of the Al-H bond to be broken and the depth of the coordinative potential. The analogous mechanism applies for the recognized three successive dehydrogenation steps. The gas-phase model structures embedded into the surface of the NaAlH(4) crystal exhibit an unambiguous kinetic stability and their general geometric features remain largely unchanged. PMID:20379493

  10. The role of molecular oxygen in the iron(III)-promoted oxidative dehydrogenation of amines.

    Saucedo-Vázquez, Juan Pablo; Kroneck, Peter M H; Sosa-Torres, Martha Elena

    2015-03-28

    A mechanistic study is presented of the oxidative dehydrogenation of the iron(III) complex [Fe(III)L(3)](3+), 1, (L(3) = 1,9-bis(2'-pyridyl)-5-[(ethoxy-2''-pyridyl)methyl]-2,5,8-triazanonane) in ethanol in the presence of molecular oxygen. The product of the reaction was identified by NMR spectroscopy and X-ray crystallography as the identical monoimine complex [Fe(II)L(4)](2+), 2, (L(4) = 1,9-bis(2'-pyridyl)-5-[(ethoxy-2''-pyridyl)methyl]-2,5,8-triazanon-1-ene) also formed under an inert nitrogen atmosphere. Molecular oxygen is an active player in the oxidative dehydrogenation of iron(III) complex 1. Reduced oxygen species, e.g., superoxide, (O2˙(-)) and peroxide (O2(2-)), are formed and undergo single electron transfer reactions with ligand-based radical intermediates. The experimental rate law can be described by the third order rate equation, -d[(Fe(III)L(3))(3+)]/dt = kOD[(Fe(III)L(3))(3+)][EtO(-)][O2], with kOD = 3.80 ± 0.09 × 10(7) M(-2) s(-1) (60 °C, μ = 0.01 M). The reduction O2 → O2˙(-) represents the rate determining step, with superoxide becoming further reduced to peroxide as shown by a coupled heme catalase assay. In an independent study, with H2O2, replacing O2 as the oxidant, the experimental rate law depended on [H2O2]: -d[(Fe(III)L(3))(3+)]/dt = kH2O2[(Fe(III)L(3))(3+)][H2O2]), with kH2O2 = 6.25 ± 0.02 × 10(-3) M(-1) s(-1). In contrast to the reaction performed under N2, no kinetic isotope effect (KIE) or general base catalysis was found for the reaction of iron(III) complex 1 with O2. Under N2, two consecutive one-electron oxidation steps of the ligand coupled to proton removal produced the iron(II)-monoimine complex [Fe(II)L(4)](2+) and the iron(II)-amine complex [Fe(II)L(3)](2+) in a 1 : 1 ratio (disproportionation), with the amine deprotonation being the rate determining step. Notably, the reaction is almost one order of magnitude faster in the presence of O2, with kEtO(-) = 3.02 ± 0.09 × 10(5) M(-1) s(-1) (O2) compared to k

  11. Alpha1-antitrypsin deficiency

    Stolk, Jan; Seersholm, Niels; Kalsheker, Noor

    2006-01-01

    biennially to exchange views and research findings. The fourth biennial meeting was held in Copenhagen, Denmark, on 2-3 June 2005. This review covers the wide range of AAT deficiency-related topics that were addressed encompassing advances in genetic characterization, risk factor identification, clinical...... epidemiology, inflammatory and signalling processes, therapeutic advances, and lung imaging techniques....

  12. MCAD deficiency in Denmark

    Andresen, Brage Storstein; Lund, Allan Meldgaard; Hougaard, David Michael; Christensen, Ernst; Gahrn, Birthe; Christensen, Mette; Bross, Peter; Vested, Anne; Simonsen, Henrik; Skogstrand, Kristin; Olpin, Simon; Brandt, Niels Jacob; Skovby, Flemming; Nørgaard-Pedersen, Bent; Gregersen, Niels

    2012-01-01

    Medium-chain acyl-CoA dehydrogenase deficiency (MCADD) is the most common defect of fatty acid oxidation. Many countries have introduced newborn screening for MCADD, because characteristic acylcarnitines can easily be identified in filter paper blood spot samples by tandem mass spectrometry (MS/M...

  13. Iron-Deficiency Anemia

    Full Text Available ... the body. Iron-deficiency anemia usually develops over time if your body doesn't have enough iron ... Institutes of Health—shows how Susan, a full-time worker and student, has coped with having iron- ...

  14. Iron-Deficiency Anemia

    Full Text Available ... body. Low iron levels usually are due to blood loss, poor diet, or an inability to absorb enough iron from food. Overview Iron-deficiency anemia is a common type of anemia . The term "anemia" usually refers to ...

  15. Control of Reactivity and Regioselectivity for On-Surface Dehydrogenative Aryl-Aryl Bond Formation.

    Kocić, Nemanja; Liu, Xunshan; Chen, Songjie; Decurtins, Silvio; Krejčí, Ondřej; Jelínek, Pavel; Repp, Jascha; Liu, Shi-Xia

    2016-05-01

    Regioselectivity is of fundamental importance in chemical synthesis. Although many concepts for site-selective reactions are well established for solution chemistry, it is not a priori clear whether they can easily be transferred to reactions taking place on a metal surface. A metal will fix the chemical potential of the electrons and perturb the electronic states of the reactants because of hybridization. Additionally, techniques to characterize chemical reactions in solution are generally not applicable to on-surface reactions. Only recent developments in resolving chemical structures by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) paved the way for identifying individual reaction products on surfaces. Here we exploit a combined STM/AFM technique to demonstrate the on-surface formation of complex molecular architectures built up from a heteroaromatic precursor, the tetracyclic pyrazino[2,3-f][4,7]phenanthroline (pap) molecule. Selective intermolecular aryl-aryl coupling via dehydrogenative C-H activation occurs on Au(111) upon thermal annealing under ultrahigh vacuum (UHV) conditions. A full atomistic description of the different reaction products based on an unambiguous discrimination between pyrazine and pyridine moieties is presented. Our work not only elucidates that ortho-hydrogen atoms of the pyrazine rings are preferentially activated over their pyridine equivalents, but also sheds new light onto the participation of substrate atoms in metal-organic coordination bonding during covalent C-C bond formation. PMID:27059121

  16. OXIDATIVE DEHYDROGENATION OF PROPANE BY RARE EARTH PHOSPHATES SUPPORTED ON AL-PILC

    Carolina De Los Santos

    2012-12-01

    Full Text Available Catalytic activity in propane oxidative dehydrogenation of rare earth phosphates LnPO4 (where Ln = La, Ce, Pr, Nd, Sm and of the same supported by an aluminum pillared clay, of high specific surface area, is presented. The solids were characterized by TGA, XRD, nitrogen adsorption and immediate analysis after reaction in order to determine eventual carbon formation. Catalytic assays were performed at temperatures in the range 400oC-600oC, the reaction mixture was C3H8/O2/Ar = 10/10/80. All the catalysts were active. The reaction products were H2, CO, CO2, CH4, C2H4 and C3H6 and there were no organic oxygenated compounds detected. Although all the investigated systems were active, the Al-PILC supported catalysts presented a higher activity than the bulk materials. In this context, the samarium supported catalyst showed a propene yield increase from 4% to 10% compared with bulk samarium phosphate at 600°C. This effect was attributed to the increase in the specific surface area.

  17. Upgrading Lignocellulosic Products to Drop-In Biofuels via Dehydrogenative Cross-Coupling and Hydrodeoxygenation Sequence.

    Sreekumar, Sanil; Balakrishnan, Madhesan; Goulas, Konstantinos; Gunbas, Gorkem; Gokhale, Amit A; Louie, Lin; Grippo, Adam; Scown, Corinne D; Bell, Alexis T; Toste, F Dean

    2015-08-24

    Life-cycle analysis (LCA) allows the scientific community to identify the sources of greenhouse gas (GHG) emissions of novel routes to produce renewable fuels. Herein, we integrate LCA into our investigations of a new route to produce drop-in diesel/jet fuel by combining furfural, obtained from the catalytic dehydration of lignocellulosic pentose sugars, with alcohols that can be derived from a variety of bio- or petroleum-based feedstocks. As a key innovation, we developed recyclable transition-metal-free hydrotalcite catalysts to promote the dehydrogenative cross-coupling reaction of furfural and alcohols to give high molecular weight adducts via a transfer hydrogenation-aldol condensation pathway. Subsequent hydrodeoxygenation of adducts over Pt/NbOPO4 yields alkanes. Implemented in a Brazilian sugarcane biorefinery such a process could result in a 53-79% reduction in life-cycle GHG emissions relative to conventional petroleum fuels and provide a sustainable source of low carbon diesel/jet fuel. PMID:26216783

  18. Synthesis, spectral and catalytic dehydrogenation studies of ruthenium complexes containing NO bidentate ligands

    Shoair, A. F.; El-Bindary, A. A.

    2014-10-01

    The synthesis and characterization of ruthenium mononuclear complexes containing NO bidentate ligands are reported. The complexes cis-[RuII(bpy)2L](PF6)n (1a-c), [RuIIICl(L)2(H2O)] (2a-b) and [RuIIICl2(L)2]Cl (2c) were prepared by the reaction of cis-[RuIICl2(bpy)2]·2H2O (bpy = 2,2";-bipyridine) and/or RuCl3·nH2O with the Ligands: 2-aminophenol (2-aph), 8-hydroxyquinoline (8-hq) and 4-aminoantipyrine (4-apy). These complexes were characterized by elemental analysis, spectroscopic (IR, UV-Vis, 1H NMR, ESR) and magnetic susceptibility measurements. The ligand field parameters, Δo (splitting parameter), B (Racah parameter of interelectronic repulsion), and β (nephelauxetic ratio) were calculated. The redox properties were also investigated electrochemically by cyclic voltammetry. The complexes cis-[RuII(bpy)2(8-hq)](PF6)2 (1b) and [RuIIICl(8-hq)2(H2O)] (2b) have been investigated in conjunction with N-methylmorpholine-N-oxide (NMO) as co-oxidant for the catalytic dehydrogenation of benzyl amine, p-methyl benzylamine and p-nitrobenzylamine to their respective nitriles.

  19. Interaction of methanol and its dehydrogenation species with Pt-alloy surfaces

    Cahyanto, Wahyu Tri; Widanarto, Wahyu; Effendi, Mukhtar; Hamdi, Muhammad Raihan; Kasai, Hideaki

    2016-02-01

    Adsorption of sequential single methanol dehydrogenation intermediate species on Pt-, PtRu-, and PtRuMo-surfaces is investigated by using density functional theory (DFT). This work is a part of our efforts in understanding the methanol oxidation reaction (MOR) on Pt-alloy surfaces for further possible prediction of decomposition processes. Particularly, effects of Ru and Mo impurity to the pure Pt surface to form PtRu and PtRuMo surfaces as possible candidates for promising catalysts of direct methanol fuel cells (DMFCs) are given. However, the study is limited to the scientific point of view, i.e., fundamental interactions between adsorbates and surfaces, in correspondence with adsorption mechanism using charge transfer analysis. The trend in the increase of adsorption energy and charge transfer by alloying Ru and Mo to the Pt surface is observed. Moreover, the increase of the d-orbital vacancy caused by alloying Ru and Mo possessing lesser filled d-orbital is suggested to responsible for the increase of surface-adsorbate interaction strength.

  20. Spectroscopic Characterization of Lanthanum-Mediated Dehydrogenation and C-C Bond Coupling of Ethylene.

    Kumari, Sudesh; Cao, Wenjin; Zhang, Yuchen; Roudjane, Mourad; Yang, Dong-Sheng

    2016-07-01

    La(C2H2) and La(C4H6) are observed from the reaction of laser-vaporized La atoms with ethylene molecules by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. La(C2H2) is identified as a metallacyclopropene and La(C4H6) as a metallacyclopentene. The three-membered ring is formed by concerted H2 elimination and the five-membered cycle by dehydrogenation and C-C bond coupling. Both metallacycles prefer a doublet ground state with a La 6s-based unpaired electron. Ionization of the neutral doublet state of either complex produces a singlet ion state by removing the La-based electron. The ionization allows accurate measurements of the adiabatic ionization energy of the neutral doublet state and metal-ligand and ligand-based vibrational frequencies of the neutral and ionic states. Although the La atom is in a formal oxidation state of +2, the ionization energies of these metal-hydrocarbon cycles are lower than that of the neutral La atom. Deuteration has a small effect on the ionization energies of the two cyclic radicals but distinctive effects on their vibrational frequencies. PMID:27322131

  1. Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

    Tan, Shuai; Gil, Laura Briones; Subramanian, Nachal; Sholl, David S.; Nair, Sankar; Jones, Christopher W.; Moore, Jason S.; Liu, Yujun; Dixit, Ravindra S.; Pendergast, John G. (Dow); (GIT)

    2015-08-26

    We have investigated the catalytic performance of novel In₂O₃–Ga₂O₃ mixed oxides synthesized by the alcoholic-coprecipitation method for propane dehydrogenation (PDH). Reactivity measurements reveal that the activities of In₂O₃–Ga₂O₃ catalysts are 1–3-fold (on an active metal basis) and 12–28-fold (on a surface area basis) higher than an In₂O₃–Al₂O₃ catalyst in terms of C₃H₈ conversion. The structure, composition, and surface properties of the In₂O₃–Ga₂O₃ catalysts are thoroughly characterized. NH₃-TPD shows that the binary oxide system generates more acid sites than the corresponding single-component catalysts. Raman spectroscopy suggests that catalysts that produce coke of a more graphitic nature suppress cracking reactions, leading to higher C₃H₆ selectivity. Lower reaction temperature also leads to higher C₃H₆ selectivity by slowing down the rate of side reactions. XRD, XPS, and XANES measurements, strongly suggest that metallic indium and In₂O₃ clusters are formed on the catalyst surface during the reaction. The agglomeration of In₂O₃ domains and formation of a metallic indium phase are found to be irreversible under O₂ or H₂ treatment conditions used here, and may be responsible for loss of activity with increasing time on stream.

  2. Study of the hydrogenation/dehydrogenation process in the Mg–Ni–C–Al system

    Palumbo, O. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Research Center Hydro-Eco, Sapienza University of Rome, Via A. Scarpa 14, 00161 Roma (Italy); Trequattrini, F. [Physics Department, Sapienza University of Rome, Piazzale A. Moro 5, 00185 Roma (Italy); Vitucci, F.M. [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Bianchin, A. [MBN Nanomaterialia S.p.A., Via G. Bortolan 42, 31040 Vascon di Carbonera-TV (Italy); Paolone, A., E-mail: annalisa.paolone@roma1.infn.it [CNR-ISC, U.O.S. La Sapienza, Piazzale A. Moro 5, 00185 Roma (Italy); Research Center Hydro-Eco, Sapienza University of Rome, Via A. Scarpa 14, 00161 Roma (Italy)

    2015-10-05

    Highlights: • A Mg–Ni–C–Al mixture synthesized for application as pellets in a tank is studied. • It is the combination of a hydrogen storing composite with a binding phase. • The storage properties are studied by PCI curves, TGA–DSC and XRD. • The hydrogen absorbtion/desorption occurs in two steps. • The thermodynamics of the first more massive step is improved compared to MgH{sub 2}. - Abstract: In this work we present a detailed study of the hydrogenation and dehydrogenation processes of a nanostructured Mg–Ni–C–Al mixture. The sample has been characterized by means of X-ray diffraction, concomitant thermogravimetric and differential scanning calorimetry measurements and pressure-composition isothermal analyses. The hydrogenation takes place in two steps and is compatible with the formation of MgH{sub 2} and Mg{sub 2}NiH{sub 4}. The enthalpy and the activation energy measured for the main hydrogen desorption are lower than those ones reported for magnesium hydride.

  3. Incorporation of catalytic dehydrogenation into Fischer-Tropsch synthesis to lower carbon dioxide emissions

    Huffman, Gerald P

    2012-09-18

    A method for producing liquid fuels includes the steps of gasifying a starting material selected from a group consisting of coal, biomass, carbon nanotubes and mixtures thereof to produce a syngas, subjecting that syngas to Fischer-Tropsch synthesis (FTS) to produce a hyrdrocarbon product stream, separating that hydrocarbon product stream into C1-C4 hydrocarbons and C5+ hydrocarbons to be used as liquid fuels and subjecting the C1-C4 hydrocarbons to catalytic dehydrogenation (CDH) to produce hydrogen and carbon nanotubes. The hydrogen produced by CDH is recycled to be mixed with the syngas incident to the FTS reactor in order to raise the hydrogen to carbon monoxide ratio of the syngas to values of 2 or higher, which is required to produce liquid hydrocarbon fuels. This is accomplished with little or no production of carbon dioxide, a greenhouse gas. The carbon is captured in the form of a potentially valuable by-product, multi-walled carbon nanotubes (MWNT), while huge emissions of carbon dioxide are avoided and very large quantities of water employed for the water-gas shift in traditional FTS systems are saved.

  4. Oxidative dehydrogenation of isobutyl alcohol over different structure type of zeolites

    Full text: Partial heterogen-catalytic of aliphatic alcohols is perspective method for production of important oxygen-containing compounds. Numerous of the literature data testify that the different mixed oxides of metals show the relatively high catalytic activity in the reactions of oxidation of aliphatic alcohols. Until recently however little attention had been given to the possibility of using of the modified zeolites for promoting these reactions. The present paper is devoted to oxidative dehydrogenation of isobutyl alcohol in the presence of molecular oxygen over different structure type of synthetical (A, X, Y, ZSM-5) and natural zeolites modified by cations of transition elements (Cu2+, Sn2+, Ni2+, Co2+, Fe2+ and Pd2+) for the purpose of selection of an active catalyst for production of corresponding aldehyde. For making of active catalyst on the first stage the study was carried out ever mono- and on the second stage over bimethalzeolite catalysts. It has been established that for each of zeolite has there optimum concentration of transition element cation in the dependence of structure of zeolites. It has been found that, the mono metallic catalysts on the basis of synthetical zeolites more active in this reaction than catalysts on the basis of natural zeolites. Introduction of second metal cation (Pd2+) into structure of mono metallic catalyst leaded considerable increasing of conversion of alcohol and selectivity of the process and stability of operation of catalysts

  5. Oxidative Dehydrogenation of Methanol on Chromium Oxide/Montmorillonite K10 Catalysts

    Methanol conversion was carried out on one of meso porous materials, Chromia I Montmorillonite K10 (MK10) in a pulse micro catalytic system. Methanol was converted to formaldehyde and ethylene by two different mechanisms. Methanol dehydrogenation increases by reaction temperature (300-400 degree C) and as chromia loading decrease. In contradiction, the dehydration of methanol takes place at higher temperature (400-500 degree C) and as chromia loading increase, 3-18% Cr. Redox and exposed non-redox Cr3+ are responsible for HCHO formation. There is relationship between increasing of C2H4 production and the increase of Cr+6 phase (from TPR and UV-Vis) according to the acidity of chromia catalysts 34 and 76 μL tert-Butylamine /gram catalyst for 3% Cr and 18% Cr, respectively. Formaldehyde formation is diffusional controlled at high temperature (400-500 degree C) and kinetically controlled at lower reaction temperature (300-400 degree C) while methanol dehydration to ethylene is surface reaction controlled at 400-500 degree C

  6. Glucose-6-phosphate dehydrogenase deficiency

    ... this page: //medlineplus.gov/ency/article/000528.htm Glucose-6-phosphate dehydrogenase deficiency To use the sharing features on this page, please enable JavaScript. Glucose-6-phosphate dehydrogenase (G6PD) deficiency is a condition ...

  7. Transient partial growth hormone deficiency due to zinc deficiency.

    Nishi, Y; Hatano, S; Aihara, K; Fujie, A; Kihara, M

    1989-04-01

    We present here a 13-year-old boy with partial growth hormone deficiency due to chronic mild zinc deficiency. When zinc administration was started, his growth rate, growth hormone levels, and plasma zinc concentrations increased significantly. His poor dietary intake resulted in chronic mild zinc deficiency, which in turn could be the cause of a further loss of appetite and growth retardation. There was also a possibility of renal zinc wasting which may have contributed to zinc deficiency. Zinc deficiency should be carefully ruled out in patients with growth retardation. PMID:2708733

  8. Iron deficiency and cognitive functions

    Jáuregui-Lobera I

    2014-11-01

    Full Text Available Ignacio Jáuregui-Lobera Department of Nutrition and Bromatology, Pablo de Olavide University, Seville, Spain Abstract: Micronutrient deficiencies, especially those related to iodine and iron, are linked to different cognitive impairments, as well as to potential long-term behavioral changes. Among the cognitive impairments caused by iron deficiency, those referring to attention span, intelligence, and sensory perception functions are mainly cited, as well as those associated with emotions and behavior, often directly related to the presence of iron deficiency anemia. In addition, iron deficiency without anemia may cause cognitive disturbances. At present, the prevalence of iron deficiency and iron deficiency anemia is 2%–6% among European children. Given the importance of iron deficiency relative to proper cognitive development and the alterations that can persist through adulthood as a result of this deficiency, the objective of this study was to review the current state of knowledge about this health problem. The relevance of iron deficiency and iron deficiency anemia, the distinction between the cognitive consequences of iron deficiency and those affecting specifically cognitive development, and the debate about the utility of iron supplements are the most relevant and controversial topics. Despite there being methodological differences among studies, there is some evidence that iron supplementation improves cognitive functions. Nevertheless, this must be confirmed by means of adequate follow-up studies among different groups. Keywords: iron deficiency, anemia, cognitive functions, supplementation

  9. Biotin and biotinidase deficiency

    Zempleni, Janos; Hassan, Yousef I.; Wijeratne, Subhashinee SK

    2008-01-01

    Biotin is a water-soluble vitamin that serves as an essential coenzyme for five carboxylases in mammals. Biotin-dependent carboxylases catalyze the fixation of bicarbonate in organic acids and play crucial roles in the metabolism of fatty acids, amino acids and glucose. Carboxylase activities decrease substantially in response to biotin deficiency. Biotin is also covalently attached to histones; biotinylated histones are enriched in repeat regions in the human genome and appear to play a role...

  10. Iron Deficiency Anemia

    Hassan Ahari

    1965-01-01

    Full Text Available The object of this paper is to draw attention to iron deficiency anemia which is the most common nutritional disturbance in infants and children. Iron deficiency anemia constitutes the most prevalent form of anemia in this age group. The records of infants and children admitted to the Pediatric Department of Tehran University Puhlavi Hospital for various ailments during a one year period (Mnrch l!l63 - HHi-t were analyzed. 262 infants and children out of a total number of an5, or 7t•/., showed iron deficiency anemia detect cd by blood film studies and hemoglobin determination, The majority, 123 or 4{.!t•/., of these patients were infants and children between six months and two years of age. The etiology indicates that faulty feeding is the main cause. Infections, parnsitcs, and hemorrhage were among other causes observed. ,'('itll regard to treatment, parenteral iron was preferred because cf its ef., Icctivcncss in short periods of hospital stay. In conclusion, the routine study of blood films and hemoglobin determiualion, especially in the low socio _ economic group of medically less organized countries is advised