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Sample records for propane oxidative dehydrogenation

  1. Kinetic isotopic effects in oxidative dehydrogenation of propane on vanadium oxide catalysts

    SciTech Connect

    Chen, K.; Iglesia, E.; Bell, A.T.

    2000-05-15

    Kinetic isotopic effects (KIEs) for oxidative dehydrogenation of propane were measured on 10 wt% V{sub 2}O{sub 5}/ZrO{sub 2}. Normal KIEs were obtained using CH{sub 3}CH{sub 2}CH{sub 3} and CD{sub 3}CD{sub 2}CD{sub 3} as reactants for primary dehydrogenation (2.8) and combustion (1.9) of propane and for secondary combustion of propene (2.6), suggesting that in all cases C-H bond dissociation is a kinetically relevant step. CH{sub 3}CH{sub 2}CH{sub 3} and CH{sub 3}CD{sub 2}CH{sub 3} reactants led to normal KIEs for dehydrogenation (2.7) and combustion (1.8) of propane, but to a very small KIE (1.1) for propene combustion. These results show that the methylene C-H bond is activated in the rate-determining steps for propane dehydrogenation and combustion reactions. The rate-determining step in secondary propene combustion involves the allylic C-H bond. In each reaction, the weakest C-H bond in the reactant is cleaved in the initial C-H bond activation step. The measured propane oxidative dehydrogenation KIEs are in agreement with theoretical estimates using a sequence of elementary steps, reaction rate expression, and transition state theory. The much smaller KIE for propane oxidative dehydrogenation (2.8) than the maximum KIE (6) expected for propane thermal dehydrogenation indicates the participation of lattice oxygen. The different KIE values for propane primary dehydrogenation and combustion suggest that these two reactions involve different lattice oxygen sites.

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

    PubMed

    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

  3. Site-dependent catalytic activity of graphene oxides towards oxidative dehydrogenation of propane.

    PubMed

    Tang, Shaobin; Cao, Zexing

    2012-12-28

    Graphene oxides (GOs) may offer extraordinary potential in the design of novel catalytic systems due to the presence of various oxygen functional groups and their unique electronic and structural properties. Using first-principles calculations, we explore the plausible mechanisms for the oxidative dehydrogenation (ODH) of propane to propene by GOs and the diffusion of the surface oxygen-containing groups under an external electric field. The present results show that GOs with modified oxygen-containing groups may afford high catalytic activity for the ODH of propane to propene. The presence of hydroxyl groups around the active sites provided by epoxides can remarkably enhance the C-H bond activation of propane and the activity enhancement exhibits strong site dependence. The sites of oxygen functional groups on the GO surface can be easily tuned by the diffusion of these groups under an external electric field, which increases the reactivity of GOs towards ODH of propane. The chemically modified GOs are thus quite promising in the design of metal-free catalysis. PMID:22801590

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

    SciTech Connect

    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

  5. Carbon nanofibers modified with heteroatoms as metal-free catalysts for the oxidative dehydrogenation of propane.

    PubMed

    Marco, Yanila; Roldán, Laura; Muñoz, Edgar; García-Bordejé, Enrique

    2014-09-01

    Carbon nanofibres (CNFs) were modified with B and P by an ex situ approach. In addition, CNFs doped with N were prepared in situ using ethylenediamine as the N and C source. After calcination, the doped CNFs were used as catalysts for the oxidative dehydrogenation of propane. For B-CNFs, the effects of boron loading and calcination temperature on B speciation and catalytic conversion were studied. For the same reaction temperatures and conversions, B- and P-doped CNFs exhibited higher selectivities to propene than pristine CNFs. The N-CNFs were the most active but the least selective of the catalysts tested here. Our results also show that the type of P precursor affects the selectivity to propene and that CNFs modified using triphenylphosphine as the precursor provided the highest selectivity at isoconversion. PMID:25138580

  6. Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

    SciTech Connect

    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.

    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.

  7. Anomalous reactivity of supported V2O5 nanoparticles for propane oxidative dehydrogenation: influence of the vanadium oxide precursor.

    PubMed

    Carrero, Carlos A; Keturakis, Christopher J; Orrego, Andres; Schomäcker, Reinhard; Wachs, Israel E

    2013-09-21

    The oxidative dehydrogenation (ODH) of propane to propylene by supported vanadia catalysts has received much attention in recent years, but different reactivity trends have been reported for this catalytic reaction system. In the present investigation, the origin of these differing trends are investigated with synthesis of supported V/SiO2, V/TiO2, and V/Al2O3 catalysts prepared with three different vanadium oxide precursors (2-propanol/vanadyl triisopropoxide [VO(O-Pri)3] (VTI), oxalic acid/ammonium metavanadate [NH4VO3] (AMV), and toluene/vanadyl acetylacetonate [VO(C5H7O2)2] (VAA)) in order to elucidate the influence of the precursor on supported vanadia phase and propane ODH activity. In situ Raman spectroscopy revealed that the choice of vanadium precursor does not affect the dispersion of the supported vanadium oxide phase below 4 V nm(-2) (0.5 monolayer coverage), where only isolated and oligomeric surface VO4 species are present, and only the AMV precursor favors crystalline V2O5 nanoparticle (NP) formation below monolayer coverage (8 V nm(-2)). The propane ODH specific reactivity trend demonstrated that there is no significant difference in TOF for the isolated and oligomeric surface VO4 sites. Surprisingly, V2O5 NPs in the ∼1-2 nm range exhibit anomalously high propane ODH TOF values for the supported vanadia catalysts. This was found for all supported vanadium oxide catalysts examined. This comparative study with different V-precursors and synthesis methods and oxide supports finally resolves the debate in the catalysis literature about the dependence of TOF on the surface vanadium density that is related to the unusually high reactivity of small V2O5 NPs. PMID:23652298

  8. Stability and catalytic performance of vanadia supported on nanostructured titania catalyst in oxidative dehydrogenation of propane

    NASA Astrophysics Data System (ADS)

    Kootenaei, A. H. Shahbazi; Towfighi, J.; Khodadadi, A.; Mortazavi, Y.

    2014-04-01

    Titanate nanotubes with a high specific surface area were synthesized by the simple hydrothermal method and investigated as support for V2O5 catalyst in oxidative dehydrogenation of propane (ODP). The structures of pristine nanotubes as well as the prepared catalysts were investigated by XRD, Raman, FTIR, HRTEM, SEM, EDS, BET, and XPS techniques. The characterization of the as-synthesized nanotubes showed the synthesis of hydrogen titanate nanotube. The incipient wetness impregnation method was utilized to prepare VTNT-x (x = 5, 10, and 15 wt.% vanadia supported on nanotube) together with VTi5 (5 wt.% vanadia supported on Degussa P25). The anatase phase was developed in VTNT-x catalysts upon calcination along with specific surface area loss. Higher vanadia loading resulted in the lowering of support capacity in maintaining vanadia in dispersed state such that eventually crystalline vanadia appeared. The measured catalyst activity demonstrates that in spite of major support surface area loss in VTNT-5 catalyst, the propylene yield is superior in comparison with VTi5 catalyst. The catalyst activity can be correlated with maximum reduction temperature. Deactivation of VTi5 and VTNT-5 as well as VTNT-15 were studied for 3,000 min time-on-stream. It was found that the activity of VTNT-5 catalyst remain unchanged while a decline in catalytic activity observed in VTi5 and VTNT-15 catalysts. The development of rutile was considered as being a major element in the deactivation of the investigated catalysts which is influenced by the presence of vanadium and reaction atmosphere.

  9. Study on the structure, acidic properties of V-Zr nanocrystal catalysts in oxidative dehydrogenation of propane

    NASA Astrophysics Data System (ADS)

    Chen, Shu; Ma, Fei; Xu, Aixin; Wang, Lina; Chen, Fang; Lu, Weimin

    2014-01-01

    A series of V-doped zirconia nanocrystal (the molar ratio of V/Zr varying from 0.001 to 0.15) were prepared via hydrothermal method and performed in oxidative dehydrogenation of propane. It was found that vanadium was highly dispersed on the surface and in the bulk of ZrO2. The distribution of the vanadium species, the valence states and the aggregation state of V species on the surface, as well as the acid properties of the catalysts including kinds, number and strength were detected by the various characteristic methods. The correlation between the V content and the surroundings of the different V species has been studied. The function of acid properties, especially Brønsted acid in the catalytic performance has been discussed. Oxidative dehydrogenation reactions were carried out in a continuous flow fixed bed reactor and ZrV0.01 catalyst showed good conversion and selectivity with a yield of propylene of 21.3%.

  10. Oxidative dehydrogenation of ethane and propane over Ca-Co-P catalysts

    NASA Astrophysics Data System (ADS)

    Aaddane, A.; Kacimi, M.; Ziyad, M.

    2005-03-01

    Different compositions of calcium-cobalt phosphate Ca{3-x}Cox(PO{4})2 (0≤ x≤ 3) were synthesized by the precipitation method. The X-ray diffraction patterns showed that in the range 0 ≤x≤0.3 the solid displays a whitlockite-type structure which belongs to rhombohedral symmetry with the space group R3c (Z = 6). U.V-visible investigations showed that Co2+ ions occupy the M(5) sites of the phosphate. The same technique revealed that all cobalt cations exist under the +II oxidation state. Pure tricalcium phosphate β -Ca{3}(PO{4})2 was found inactive in the ODH reactions of ethane and propane. An increase of Co2+ concentration in the catalysts improved the performances.

  11. Insertion of porous chromia in {gamma}-zirconium phosphate and its catalytic performance in the oxidative dehydrogenation of propane

    SciTech Connect

    Jimenez-Lopez, A.; Rodriguez-Castellon, E.; Santamaria-Gonzalez, J.; Braos-Garcia, P.; Felici, E.; Marmottini, F.

    2000-04-04

    An expanded phase of acetate-hydroxide of Cr(III) intercalated into {gamma}-zirconium phosphate has been isolated by refluxing a solution formed by chromium(III) acetate-hydroxide and {gamma}-zirconium phosphate, previously dispersed in 1:1 water-acetone solution at 353 K. By calcination of this phase at 623 K under vacuum, an intercalated compound with a basal spacing of 1.73 nm and a surface area of 147 m{sup 2} g{sup {minus}1} was obtained. A temperature-programmed reduction study reveals that this solid contains a little amount of chromium in high oxidation state. However, when the precursor is heated at 673 K, a collapsed structure with a low surface area was obtained. The inserted porous chromia in {gamma}-zirconium phosphate calcined at 623 K is active in the oxidative dehydrogenation of propane at 623 K with 58% conversion and 10% of selectivity to propene. When this material is calcined at 823 K in air, it is also active in this reaction but only at high temperature, 823 K being necessary to attain catalytic properties similar to those observed for the catalyst prepared at low temperature.

  12. Synthesis of Pt–Pd Core–Shell Nanostructures by Atomic Layer Deposition: Application in Propane Oxidative Dehydrogenation to Propylene

    SciTech Connect

    Lei, Yu; Liu, Bin; Lu, Junling; Lobo-Lapidus, Rodrigo J.; Wu, Tianpin; Feng, Hao; Xia, Xiaoxing; Mane, Anil U.; Libera, Joseph A.; Greeley, Jeffrey P.; Miller, Jeffrey T.; Elam, Jeffrey W.

    2012-08-20

    Atomic layer deposition (ALD) was employed to synthesize supported Pt–Pd bimetallic particles in the 1 to 2 nm range. The metal loading and composition of the supported Pt–Pd nanoparticles were controlled by varying the deposition temperature and by applying ALD metal oxide coatings to modify the support surface chemistry. High-resolution scanning transmission electron microscopy images showed monodispersed Pt–Pd nanoparticles on ALD Al2O3- and TiO2-modified SiO2 gel. X-ray absorption spectroscopy revealed that the bimetallic nanoparticles have a stable Pt-core, Pd-shell nanostructure. Density functional theory calculations revealed that the most stable surface configuration for the Pt–Pd alloys in an H2 environment has a Pt-core, Pd-shell nanostructure. Finally, in comparison to their monometallic counterparts, the small Pt–Pd bimetallic core–shell nanoparticles exhibited higher activity in propane oxidative dehydrogenation as compared to their physical mixture.

  13. A practical grinding-assisted dry synthesis of nanocrystalline NiMoO{sub 4} polymorphs for oxidative dehydrogenation of propane

    SciTech Connect

    Chen Miao; Wu Jialing; Liu Yongmei; Cao Yong; Guo Li; He Heyong; Fan Kangnian

    2011-12-15

    A practical two-stage reactive grinding-assisted pathway waste-free and cost-effective for the synthesis of NiMoO{sub 4} has been successfully developed. It was demonstrated that proper design in synthetic strategy for grinding plays a crucial role in determining the ultimate polymorph of NiMoO{sub 4}. Specifically, direct grinding (DG) of MoO{sub 3} and NiO rendered {alpha}-NiMoO{sub 4} after annealing, whereas sequential grinding (SG) of the two independently pre-ground oxides followed by annealing generated {beta}-NiMoO{sub 4} solid solution. Characterizations in terms of Raman and X-ray diffraction suggest the creation of {beta}-NiMoO{sub 4} precursor in the latter alternative is the key aspect for the formation of {beta}-NiMoO{sub 4}. The DG-derived {alpha}-NiMoO{sub 4} tested by oxidative dehydrogenation of propane exhibited superior activity in contrast to its analog synthesized via conventional coprecipitation. It is suggested that the favorable chemical composition facilely obtained via grinding in contrast to that by coprecipitation was essential for achieving a more selective production of propylene. - Graphical Abstract: Grinding-assisted synthesis of NiMoO{sub 4} offers higher and more reproducible activities in contrast to coprecipitation for oxidative dehydrogenation of propane, and both {alpha}- and {beta}-NiMoO{sub 4} can be synthesized. Highlights: Black-Right-Pointing-Pointer NiMoO{sub 4} was prepared through grinding-assisted pathway. Black-Right-Pointing-Pointer Direct/sequential grinding rendered {alpha}-, {beta}-NiMoO{sub 4}, respectively. Black-Right-Pointing-Pointer Grinding-derived {alpha}-NiMoO{sub 4} showed high and reproducible activity for oxidative dehydrogenation of propane.

  14. Oxidative dehydrogenation of propane over vanadia-based catalysts supported on high-surface-area mesoporous MgAl2O4

    SciTech Connect

    Evans, Owen R.; Bell, Alexis T.; Tilley, T. Don

    2004-06-01

    The oxidative dehydrogenation of propane to propene was investigated over a series of novel vanadia-based catalysts supported on high-surface-area magnesium spinel. A mesoporous MgAl2O4 support was synthesized via a low-temperature sol gel process involving the heterobimetallic alkoxide precursor, Mg[Al(O iPr)4]2. A high-purity catalyst support was obtained after calcination at 1173 K under O2 atmosphere and active vanadia catalysts were prepared from the thermolysis of OV(O tBu)3 after grafting onto the spinel support. MgAl2O4-supported catalysts prepared in this manner have BET surface areas of 234 245 m2/g. All of the catalysts were characterized by X-ray powder diffraction, and Raman, solid-state NMR, and diffuse-reflectance UV vis spectroscopy. At all vanadium loadings the vanadia supported on MgAl2O4 exist as a combination of isolated monovanadate and tetrahedral polyvanadate species. As the vanadium surface density increases for these catalysts the ratio of polyvanadate species to isolated monovanadate species increases. In addition, as the vanadium surface density increases for these catalysts, the initial rate of propane ODH per V atom increases and reaches a maximum value at 6 VOx/nm2. Increasing the vanadium surface density past this point results in a decrease in the rate of propane ODH owing to the formation of multilayer species in which subsurface vanadium atoms are essentially rendered catalytically inactive. The initial propene selectivity increases with increasing vanadium surface density and reaches a plateau of {approx}95 percent for the V/MgAl catalysts. Rate coefficients for propane ODH (k1), propane combustion (k2), and propene combustion (k3) were calculated for these catalysts. The value of k1 increases with increasing VOx surface density, reaching a maximum at about 5.5 VOx/nm2. On the other hand, the ratio (k2/k1) for V/MgAl decreases with increasing VOx surface density. The ratio (k3/k1) for both sets of catalysts shows no dependence on

  15. A hybrid sol–gel synthesis of mesostructured SiC with tunable porosity and its application as a support for propane oxidative dehydrogenation.

    PubMed

    Xu, Jie; Liu, Yong-Mei; Xue, Bing; Li, Yong-Xin; Cao, Yong; Fan, Kang-Nian

    2011-06-01

    Porous silicon carbide (SiC) is of great potential as catalyst support in several industrially important reactions because of its unique thermophysical characteristics. Previously porous SiC was mostly obtained by a simple sol–gel or reactive replica technique which can only produce a material with low or medium surface area (< 50 m2 g(−1)). Here we report a new hybrid sol–gel approach to synthesize mesostructured SiC with high surface area (151–345 m2 g(−1)) and tunable porosity. The synthesis route involves a facile co-condensation of TEOS and alkyloxysilane with different alkyl-chain lengths followed by carbothermal reduction of the as-prepared alkyloxysilane precursors at 1350 °C. The resulting materials were investigated by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. A mechanism for the tailored synthesis of mesostructured SiC was tentatively proposed. To demonstrate the catalytic application of these materials, vanadia were loaded on the mesostructured SiC supports, and their catalytic performance in oxidative dehydrogenation of propane was evaluated. Vanadia supported on the mesostructured silicon carbide exhibits higher selectivity to propylene than those on conventional supports such as Al2O3 and SiO2 at the same propane conversion levels, mainly owing to its outstanding thermal conductivity which makes contributions to dissipate the heat generated from reaction thus alleviating the hot spots effect and over-oxidation of propylene. PMID:21739681

  16. ZrO2 -Based Alternatives to Conventional Propane Dehydrogenation Catalysts: Active Sites, Design, and Performance.

    PubMed

    Otroshchenko, Tatyana; Sokolov, Sergey; Stoyanova, Mariana; Kondratenko, Vita A; Rodemerck, Uwe; Linke, David; Kondratenko, Evgenii V

    2015-12-21

    Non-oxidative dehydrogenation of propane to propene is an established large-scale process that, however, faces challenges, particularly in catalyst development; these are the toxicity of chromium compounds, high cost of platinum, and catalyst durability. Herein, we describe the design of unconventional catalysts based on bulk materials with a certain defect structure, for example, ZrO2 promoted with other metal oxides. Comprehensive characterization supports the hypothesis that coordinatively unsaturated Zr cations are the active sites for propane dehydrogenation. Their concentration can be adjusted by varying the kind of ZrO2 promoter and/or supporting tiny amounts of hydrogenation-active metal. Accordingly designed Cu(0.05 wt %)/ZrO2 -La2 O3 showed industrially relevant activity and durability over ca. 240 h on stream in a series of 60 dehydrogenation and oxidative regeneration cycles between 550 and 625 °C. PMID:26566072

  17. Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene.

    PubMed

    Liu, Lei; Deng, Qing-Fang; Agula, Bao; Zhao, Xu; Ren, Tie-Zhen; Yuan, Zhong-Yong

    2011-08-01

    Metal-free ordered mesoporous carbons were demonstrated to be robust catalysts for direct dehydrogenation of propane to propylene, in the absence of any auxiliary steam, exhibiting high activity and selectivity, as well as long catalytic stability, in comparison with nanostructured carbons. PMID:21687889

  18. In Silico Design of Highly Selective Mo-V-Te-Nb-O Mixed Metal Oxide Catalysts for Ammoxidation and Oxidative Dehydrogenation of Propane and Ethane.

    PubMed

    Cheng, Mu-Jeng; Goddard, William A

    2015-10-21

    We used density functional theory quantum mechanics with periodic boundary conditions to determine the atomistic mechanism underlying catalytic activation of propane by the M1 phase of Mo-V-Nb-Te-O mixed metal oxides. We find that propane is activated by Te═O through our recently established reduction-coupled oxo activation mechanism. More importantly, we find that the C-H activation activity of Te═O is controlled by the distribution of nearby V atoms, leading to a range of activation barriers from 34 to 23 kcal/mol. On the basis of the new insight into this mechanism, we propose a synthesis strategy that we expect to form a much more selective single-phase Mo-V-Nb-Te-O catalyst. PMID:26423704

  19. Dehydrogenation of propane over chromia-pillared zirconium phosphate catalysts

    SciTech Connect

    Perez-Reina, F.J.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.

    1999-11-23

    Two series of porous chromia-pillared {alpha}-zirconium phosphate materials, prepared using two different methods of colloidization of the initial phase and with variable chromium contents (CrZrP-Xa and CrZrP-Xb) have been tested in the oxidative and nonoxidative dehydrogenation of propane in a flow reactor at atmospheric pressure. All catalysts are highly selective to propene under nonoxidative conditions at 823 K. In both series of catalysts, the initial activity increases with the chromium content, but generally CrZrP-Xb catalysts are more active than those of series CrZrP-Xa, which is in good agreement with their higher chromium contents and greater dispersions. In all cases, deactivation was detected due to coke formed from undesired reactions. When the reactions were carried out under oxidative conditions at 673 K, the activities were enhanced and the observed deactivation was minimum. The activities found vary between 0.47 and 1.31 {micro}mol of propene g{sup {minus}1} s{sup {minus}1} and are maintained after 200 min of reaction. These activity values were also related to the chromium content, being slightly higher for CrZrP-Xb materials. A parallel study to evaluate the influence of acidity in the obtained results has been carried out. The activities found of these catalysts seem to be related to the presence of Cr(III) centers with vacancies in their coordination sphere. These vacancies, in nonoxidative conditions, can activate the reactive molecules originating propene and hydrogen. On the other hand, in an oxidative atmosphere, Cr(III) species can activate oxygen molecules, through an electronic transference process, yielding propene and water.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

    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.

  2. Preparation of platinum nanoparticle catalyst for propane dehydrogenation.

    PubMed

    Li, Jun; Wang, Jun; Ma, Zhanhua; Sun, Lanyi; Hu, Yangdong

    2014-09-01

    Supported Pt nanoparticle catalysts were prepared by combing a chemical reduction method with an ultrasonic sonication loading method. Several techniques including transmission electron microscopy (TEM), nitrogen sorption technique and pyridine adsorption Fourier-transform infrared (Py-IR) were applied to characterize the physicochemical properties of these catalysts. The catalytic performance of catalysts was evaluated in the dehydrogenation of propane. The influence of the preparation method of Pt nanoparticles, the ratio of Polyvinyl Pyrrolidone (PVP) to Pt, loading method and different supports on the catalytic performance was investigated. PVP is useful for controlling the size of Pt nanoparticles and a PVP/Pt ratio of 15 is favorable to achieve a good catalytic performance. NaBH4 reduction is better than ethanol refluxing in preparing Pt nanoparticles. The ultrasonic sonication is effective to load the Pt nanoparticles onto the support channels. The mesoporous alumina proved to be a good catalyst support due to its high surface area and unique pore structure. PMID:25924358

  3. In situ UV-vis-NIR diffuse reflectance and Raman spectroscopy and catalytic activity studies of propane oxidative dehydrogenation over supported CrO3/ZrO2 catalysts.

    PubMed

    Malleswara Rao, T V; Deo, Goutam; Jehng, Jih-Mirn; Wachs, Israel E

    2004-08-17

    The molecular structures, oxidation states, and reactivity of 3 and 6% CrO3/ZrO2 catalysts prepared by incipient wetness impregnation were examined under different conditions. The in situ Raman spectroscopic studies under dehydrated conditions reveal that the 3 and 6% CrO3/ZrO2 catalysts possess equal amounts of monochromate and polychromate species. Consequently, monolayer coverage on this ZrO2 support is about 3% CrO3. The 6% CrO3/ZrO2 possesses an additional Raman band due to Cr2O3 crystals corresponding to the remaining 3% CrO3. Furthermore, during reaction conditions the polychromate species is preferentially reduced, the monochromate species are slightly affected, and the Cr2O3 crystals are not affected. The in situ UV-vis-NIR diffuse reflectance spectroscopy results reveal that under steady-state reaction conditions the extent of reduction and edge energy position of surface Cr6+ cations increase with an increase in reduction environment for the 3 and 6% CrO3/ZrO2 samples. Propane oxidative dehydrogenation (ODH) studies reveal that the catalytic activity expressed in moles of propane converted per gram catalyst per second is similar for the two catalysts, which is consistent with equal amounts of molecularly dispersed chromia present. The turnover frequency for the 6% CrO3/ZrO2 catalyst is, however, smaller than that for the 3% CrO3/ZrO2 sample due to the presence of Cr2O3 crystals, which are relatively inactive for propane ODH. For this catalytic system and for the experimental conditions used, propene, CO, and CO2 are primary products. Furthermore, the 33-39% propene selectivity is not affected by the C3H8/O2 ratio for both catalysts. Structure-reactivity studies suggest that the molecularly dispersed species are present in equal amounts in the 3 and 6% CrO3/ZrO2 samples as Cr6+ monochromate and polychromate species are the most effective catalytic active sites taking part in the propane ODH reaction. PMID:15301500

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

    SciTech Connect

    Sun, Pingping; Siddiqi, Georges; Vining, William C.; Chi, Miaofang; Bell, Alexis T.

    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.

  5. Carbon dynamics on the molybdenum carbide surface during catalytic propane dehydrogenation.

    PubMed

    Frank, Benjamin; Cotter, Thomas P; Schuster, Manfred E; Schlögl, Robert; Trunschke, Annette

    2013-12-01

    The effect of the gas-phase chemical potential on surface chemistry and reactivity of molybdenum carbide has been investigated in catalytic reactions of propane in oxidizing and reducing reactant mixtures by adding H2, O2, H2O, and CO2 to a C3H8/N2 feed. The balance between surface oxidation state, phase stability, carbon deposition, and the complex reaction network involving dehydrogenation reactions, hydrogenolysis, metathesis, water-gas shift reaction, hydrogenation, and steam reforming is discussed. Raman spectroscopy and a surface-sensitive study by means of in situ X-ray photoelectron spectroscopy evidence that the dynamic formation of surface carbon species under a reducing atmosphere strongly shifts the product spectrum to the C3-alkene at the expense of hydrogenolysis products. A similar response of selectivity, which is accompanied by a boost of activity, is observed by tuning the oxidation state of Mo in the presence of mild oxidants, such as H2O and CO2, in the feed as well as by V doping. The results obtained allow us to draw a picture of the active catalyst surface and to propose a structure-activity correlation as a map for catalyst optimization. PMID:24248701

  6. Effect of ultrasonic irradiation on the catalytic performance of PtSnNa/ZSM-5 catalyst for propane dehydrogenation.

    PubMed

    Liu, Hui; Zhang, Shaobo; Zhou, Yuming; Zhang, Yiwei; Bai, Linyang; Huang, Li

    2011-01-01

    Effects of ultrasonic irradiation on the catalytic performance of PtSnNa/ZSM-5 catalyst for propane dehydrogenation were studied. XRD, TEM and TPDA were used to characterize the catalysts. From the results of XRD, the structure of ZSM-5 was not destroyed by the ultrasound. Ultrasound promoted the dispersion of Pt on the surface of the carrier during impregnation and decreased the size of Pt particles. Compared with the catalyst prepared by conventional impregnation, the supported catalyst prepared by ultrasonic irradiation showed better catalytic activity in propane dehydrogenation. PMID:20452811

  7. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, Harold H.; Chaar, Mohamed A.

    1988-01-01

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M.sub.3 (VO.sub.4).sub.2 and MV.sub.2 O.sub.6, M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  8. Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons

    DOEpatents

    Kung, H.H.; Chaar, M.A.

    1988-10-11

    Oxidative dehydrogenation of alkanes to unsaturated hydrocarbons is carried out over metal vanadate catalysts under oxidizing conditions. The vanadate catalysts are represented by the formulas M[sub 3](VO[sub 4])[sub 2] and MV[sub 2]O[sub 6], M representing Mg, Zn, Ca, Pb, or Cd. The reaction is carried out in the presence of oxygen, but the formation of oxygenate by-products is suppressed.

  9. Selective glycerol oxidation by electrocatalytic dehydrogenation.

    PubMed

    Kim, Hyung Ju; Lee, Jechan; Green, Sara K; Huber, George W; Kim, Won Bae

    2014-04-01

    This study demonstrates that an electrochemical dehydrogenation process can be used to oxidize glycerol to glyceraldehyde and glyceric acid even without using stoichiometric chemical oxidants. A glyceric acid selectivity of 87.0 % at 91.8 % glycerol conversion was obtained in an electrocatalytic batch reactor. A continuous-flow electrocatalytic reactor had over an 80 % high glyceric acid selectivity at 10 % glycerol conversion, as well as greater reaction rates than either an electrocatalytic or a conventional catalytic batch reactor. PMID:24664518

  10. Microchannel apparatus and methods of conducting catalyzed oxidative dehydrogenation

    DOEpatents

    Tonkovich, Anna Lee; Yang, Bin; Perry, Steven T.; Mazanec, Terry; Arora, Ravi; Daly, Francis P.; Long, Richard; Yuschak, Thomas D.; Neagle, Paul W.; Glass, Amanda

    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.

  11. Ultra-dispersed Pt nanoparticles on SAPO-34/γ-Al2O3 support for efficient propane dehydrogenation.

    PubMed

    Chu, Yue; Zhang, Qiang; Wu, Tongwei; Nawaz, Zeeshan; Wang, Yao; Wei, Fei

    2014-09-01

    Ultra-dispersed precious metal nanoparticles with good thermal stability are highly required for heterogeneous catalysis. However, the efficient and effective strategy to disperse ultra-fine precious metal nanoparticles at high reaction temperature is still not fully understood yet. In this contribution, a family of catalysts with ultra-small Pt nanoparticles were prepared using impregnation method by adjusting the zeolite content in the SAPO-34 and γ-Al2O3 mixed support. The effect of Pt nanoparticle size on the catalytic activity, selectivity, and stability was investigated in the propane dehydrogenation reaction. Catalyst with smaller Pt particles exhibits better catalytic performance. Both the highest Pt dispersion and the best catalytic activity can be achieved by using SAPO-34 and γ-Al2O3 mixed support with 70 wt.% of SAPO-34. The size and structure of the Pt nanoparticles on the optimal catalyst were characterized by transmission electron microscopy. Pt nanoparticles with an average size of 1.32 nm were observed. There were stronger metal-support interactions between the oxidized tin species and Pt particles on SAPO-34 support compared to that on γ-Al2O3 catalyst. These lead to high Pt dispersion and consequently good catalytic performance. PMID:25924347

  12. Oxidant-free dehydrogenative coupling reactions via hydrogen evolution.

    PubMed

    He, Ke-Han; Li, Yang

    2014-10-01

    Oxidant-free dehydrogenative coupling reactions: Recently, coupling reactions have followed a novel strategy for the construction of C==C, C==N, C==P, and S==S bonds by dehydrogenation without using any extra oxidant, via H2 evolution. These breakthroughs inspire a new direction in the construction of chemical bonds, towards more sustainable, highly atom-economical, and environmentally benign synthetic methods. PMID:25139249

  13. Oxidative Dehydrogenative Couplings of Pyrazol-5-amines Selectively Forming Azopyrroles

    PubMed Central

    2015-01-01

    New oxidative dehydrogenative couplings of pyrazol-5-amines for the selective synthesis of azopyrrole derivatives have been described. The former reaction simultaneously installs C–I and N–N bonds through iodination and oxidation, whereas the latter involved a copper-catalyzed oxidative coupling process. The resulting iodo-substituted azopyrroles were employed by treatment with various terminal alkynes through Sonogashira cross-coupling leading to new azo compounds. PMID:24731223

  14. Molybdenum Catalyzed Ammonia Borane Dehydrogenation: Oxidation State Specific Mechanisms

    PubMed Central

    2015-01-01

    Though numerous catalysts for the dehydrogenation of ammonia borane (AB) are known, those that release >2 equiv of H2 are uncommon. Herein, we report the synthesis of Mo complexes supported by a para-terphenyl diphosphine ligand, 1, displaying metal–arene interactions. Both a Mo0 N2 complex, 5, and a MoII bis(acetonitrile) complex, 4, exhibit high levels of AB dehydrogenation, releasing over 2.0 equiv of H2. The reaction rate, extent of dehydrogenation, and reaction mechanism vary as a function of the precatalyst oxidation state. Several Mo hydrides (MoII(H)2, [MoII(H)]+, and [MoIV(H)3]+) relevant to AB chemistry were characterized. PMID:25034459

  15. Operando Raman spectroscopy study on the deactivation of Pt/Al2O3 and Pt-Sn/Al2O3 propane dehydrogenation catalysts.

    PubMed

    Sattler, Jesper J H B; Beale, Andrew M; Weckhuysen, Bert M

    2013-08-01

    The deactivation of 0.5 wt% Pt/Al2O3 and 0.5 wt% Pt-1.5 wt% Sn/Al2O3 catalysts has been studied by operando Raman spectroscopy during the dehydrogenation of propane and subsequent regeneration in air for 10 successive dehydrogenation-regeneration cycles. Furthermore, the reaction feed was altered by using different propane/propene/hydrogen ratios. It was found that the addition of hydrogen to the feed increases the catalyst performance and decreases the formation of coke deposits, as was revealed by thermogravimetrical analysis. The positive effect of hydrogen on the catalyst performance is comparable to the addition of Sn, a promoter element which increases both the propane conversion and propene selectivity. Operando Raman spectroscopy showed that hydrogen altered the nature of the coke deposits formed during propane dehydrogenation. Due to this approach it was possible to perform a systematic deconvolution procedure on the Raman spectra. By analysing the related intensity, band position and bandwidth of the different Raman features, it was determined that smaller graphite crystallites, which have less defects, are formed when the partial pressure of hydrogen in the feed was increased. PMID:23615824

  16. Room temperature dehydrogenation of ethane, propane, linear alkanes C4-C8, and some cyclic alkanes by titanium-carbon multiple bonds.

    PubMed

    Crestani, Marco G; Hickey, Anne K; Gao, Xinfeng; Pinter, Balazs; Cavaliere, Vincent N; Ito, Jun-Ichi; Chen, Chun-Hsing; Mindiola, Daniel J

    2013-10-01

    The transient titanium neopentylidyne, [(PNP)Ti≡C(t)Bu] (A; PNP(-)≡N[2-P(i)Pr2-4-methylphenyl]2(-)), dehydrogenates ethane to ethylene at room temperature over 24 h, by sequential 1,2-CH bond addition and β-hydrogen abstraction to afford [(PNP)Ti(η(2)-H2C═CH2)(CH2(t)Bu)] (1). Intermediate A can also dehydrogenate propane to propene, albeit not cleanly, as well as linear and volatile alkanes C4-C6 to form isolable α-olefin complexes of the type, [(PNP)Ti(η(2)-H2C═CHR)(CH2(t)Bu)] (R = CH3 (2), CH2CH3 (3), (n)Pr (4), and (n)Bu (5)). Complexes 1-5 can be independently prepared from [(PNP)Ti═CH(t)Bu(OTf)] and the corresponding alkylating reagents, LiCH2CHR (R = H, CH3(unstable), CH2CH3, (n)Pr, and (n)Bu). Olefin complexes 1 and 3-5 have all been characterized by a diverse array of multinuclear NMR spectroscopic experiments including (1)H-(31)P HOESY, and in the case of the α-olefin adducts 2-5, formation of mixtures of two diastereomers (each with their corresponding pair of enantiomers) has been unequivocally established. The latter has been spectroscopically elucidated by NMR via C-H coupled and decoupled (1)H-(13)C multiplicity edited gHSQC, (1)H-(31)P HMBC, and dqfCOSY experiments. Heavier linear alkanes (C7 and C8) are also dehydrogenated by A to form [(PNP)Ti(η(2)-H2C═CH(n)Pentyl)(CH2(t)Bu)] (6) and [(PNP)Ti(η(2)-H2C═CH(n)Hexyl)(CH2(t)Bu)] (7), respectively, but these species are unstable but can exchange with ethylene (1 atm) to form 1 and the free α-olefin. Complex 1 exchanges with D2C═CD2 with concomitant release of H2C═CH2. In addition, deuterium incorporation is observed in the neopentyl ligand as a result of this process. Cyclohexane and methylcyclohexane can be also dehydrogenated by transient A, and in the case of cyclohexane, ethylene (1 atm) can trap the [(PNP)Ti(CH2(t)Bu)] fragment to form 1. Dehydrogenation of the alkane is not rate-determining since pentane and pentane-d12 can be dehydrogenated to 4 and 4-d12 with comparable

  17. Structure-property relationships of BaCeO perovskites for the oxidative dehydrogenation of alkanes

    SciTech Connect

    Nenoff, T.M.; Jackson, N.B.; Miller, J.E.; Sault, A.G.; Trudell, D.

    1997-12-01

    The oxidative dehydrogenation (ODH) reactions for the formation of two important organic feedstocks ethylene and propylene are of great interest because of the potential in capital and energy savings associated with these reactions. Theoretically, ODH can achieve high conversions of the starting materials (ethane and propane) at lower temperatures than conventional dehydrogenation reactions. The important focus in this study of ODH catalysts is the development of a structure-property relationship for catalyst with respect to selectivity, so as to avoid the more thermodynamically favorable combustion reaction. Catalysts for the ODH reaction generally consist of mixed metal oxides. Since for the most selective catalyst lattice oxygen is known to participate in the reaction, catalysts are sought with surface oxygen atoms that are labile enough to perform dehydrogenation, but not so plentiful or weakly bound as to promote complete combustion. Also, catalysts must be able to replenish surface oxygen by transport from the bulk. Perovskite materials are candidates to fulfill these requirements. The authors are studying BaCeO{sub 3} perovskites doped with elements such as Ca, Mg, and Sr. During the ODH of the alkanes at high temperatures, the perovskite structure is not retained and a mixture of carbonates and oxides is formed, as revealed by XRD. While the Ca doped materials showed enhanced total combustion activity below 600 C, they only showed enhanced alkene production at 700 C. Bulk structural and surface changes, as monitored by powder X-ray diffraction, and X-ray photoelectron spectroscopy are being correlated with activity in order to understand the factors affecting catalyst performance, and to modify catalyst formulations to improve conversion and selectivity.

  18. Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane**

    PubMed Central

    Sattler, Jesper J H B; Gonzalez-Jimenez, Ines D; Luo, Lin; Stears, Brien A; Malek, Andrzej; Barton, David G; Kilos, Beata A; Kaminsky, Mark P; Verhoeven, Tiny W G M; Koers, Eline J; Baldus, Marc; Weckhuysen, Bert M

    2014-01-01

    A novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and 0.25 wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a promoter. PMID:24989975

  19. Pd-Ag Membrane Coupled to a Two-Zone Fluidized Bed Reactor (TZFBR) for Propane Dehydrogenation on a Pt-Sn/MgAl2O4 Catalyst.

    PubMed

    Medrano, José-Antonio; Julián, Ignacio; Herguido, Javier; Menéndez, Miguel

    2013-01-01

    Several reactor configurations have been tested for catalytic propane dehydrogenation employing Pt-Sn/MgAl2O4 as a catalyst. Pd-Ag alloy membranes coupled to the multifunctional Two-Zone Fluidized Bed Reactor (TZFBR) provide an improvement in propane conversion by hydrogen removal from the reaction bed through the inorganic membrane in addition to in situ catalyst regeneration. Twofold process intensification is thereby achieved when compared to the use of traditional fluidized bed reactors (FBR), where coke formation and thermodynamic equilibrium represent important process limitations. Experiments were carried out at 500-575 °C and with catalyst mass to molar flow of fed propane ratios between 15.1 and 35.2 g min mmol-1, employing three different reactor configurations: FBR, TZFBR and TZFBR + Membrane (TZFBR + MB). The results in the FBR showed catalyst deactivation, which was faster at high temperatures. In contrast, by employing the TZFBR with the optimum regenerative agent flow (diluted oxygen), the process activity was sustained throughout the time on stream. The TZFBR + MB showed promising results in catalytic propane dehydrogenation, displacing the reaction towards higher propylene production and giving the best results among the different reactor configurations studied. Furthermore, the results obtained in this study were better than those reported on conventional reactors. PMID:24958620

  20. Pd-Ag Membrane Coupled to a Two-Zone Fluidized Bed Reactor (TZFBR) for Propane Dehydrogenation on a Pt-Sn/MgAl2O4 Catalyst

    PubMed Central

    Medrano, José-Antonio; Julián, Ignacio; Herguido, Javier; Menéndez, Miguel

    2013-01-01

    Several reactor configurations have been tested for catalytic propane dehydrogenation employing Pt-Sn/MgAl2O4 as a catalyst. Pd-Ag alloy membranes coupled to the multifunctional Two-Zone Fluidized Bed Reactor (TZFBR) provide an improvement in propane conversion by hydrogen removal from the reaction bed through the inorganic membrane in addition to in situ catalyst regeneration. Twofold process intensification is thereby achieved when compared to the use of traditional fluidized bed reactors (FBR), where coke formation and thermodynamic equilibrium represent important process limitations. Experiments were carried out at 500–575 °C and with catalyst mass to molar flow of fed propane ratios between 15.1 and 35.2 g min mmol−1, employing three different reactor configurations: FBR, TZFBR and TZFBR + Membrane (TZFBR + MB). The results in the FBR showed catalyst deactivation, which was faster at high temperatures. In contrast, by employing the TZFBR with the optimum regenerative agent flow (diluted oxygen), the process activity was sustained throughout the time on stream. The TZFBR + MB showed promising results in catalytic propane dehydrogenation, displacing the reaction towards higher propylene production and giving the best results among the different reactor configurations studied. Furthermore, the results obtained in this study were better than those reported on conventional reactors. PMID:24958620

  1. Propane dehydrogenation over Pt-Cu bimetallic catalysts: the nature of coke deposition and the role of copper.

    PubMed

    Han, Zhiping; Li, Shuirong; Jiang, Feng; Wang, Tuo; Ma, Xinbin; Gong, Jinlong

    2014-09-01

    This paper describes an investigation of the promotional effect of Cu on the catalytic performance of Pt/Al2O3 catalysts for propane dehydrogenation. We have shown that Pt/Al2O3 catalysts possess higher propylene selectivity and lower deactivation rate as well as enhanced anti-coking ability upon Cu addition. The optimized loading content of Cu is 0.5 wt%, which increases the propylene selectivity to 90.8% with a propylene yield of 36.5%. The origin of the enhanced catalytic performance and anti-coking ability of the Pt-Cu/Al2O3 catalyst is ascribed to the intimate interaction between Pt and Cu, which is confirmed by the change of particle morphology and atomic electronic environment of the catalyst. The Pt-Cu interaction inhibits propylene adsorption and elevates the energy barrier of C-C bond rupture. The inhibited propylene adsorption diminishes the possibility of coke formation and suppresses the cracking reaction towards the formation of lighter hydrocarbons on Pt-Cu/Al2O3, while a higher energy barrier for C-C bond cleavage suppresses the methane formation. PMID:24933477

  2. Propane dehydrogenation over Pt-Cu bimetallic catalysts: the nature of coke deposition and the role of copper

    NASA Astrophysics Data System (ADS)

    Han, Zhiping; Li, Shuirong; Jiang, Feng; Wang, Tuo; Ma, Xinbin; Gong, Jinlong

    2014-08-01

    This paper describes an investigation of the promotional effect of Cu on the catalytic performance of Pt/Al2O3 catalysts for propane dehydrogenation. We have shown that Pt/Al2O3 catalysts possess higher propylene selectivity and lower deactivation rate as well as enhanced anti-coking ability upon Cu addition. The optimized loading content of Cu is 0.5 wt%, which increases the propylene selectivity to 90.8% with a propylene yield of 36.5%. The origin of the enhanced catalytic performance and anti-coking ability of the Pt-Cu/Al2O3 catalyst is ascribed to the intimate interaction between Pt and Cu, which is confirmed by the change of particle morphology and atomic electronic environment of the catalyst. The Pt-Cu interaction inhibits propylene adsorption and elevates the energy barrier of C-C bond rupture. The inhibited propylene adsorption diminishes the possibility of coke formation and suppresses the cracking reaction towards the formation of lighter hydrocarbons on Pt-Cu/Al2O3, while a higher energy barrier for C-C bond cleavage suppresses the methane formation.

  3. Palladium-catalyzed synthesis of dibenzophosphole oxides via intramolecular dehydrogenative cyclization.

    PubMed

    Kuninobu, Yoichiro; Yoshida, Takuya; Takai, Kazuhiko

    2011-09-16

    Dibenzophosphole oxides were obtained from secondary hydrophosphine oxides with a biphenyl group by dehydrogenation via phosphine-hydrogen and carbon-hydrogen bond cleavage in the presence of a catalytic amount of palladium(II) acetate, Pd(OAc)(2). By using this reaction, a ladder-type dibenzophosphole oxide could also be synthesized by double intramolecular dehydrogenative cyclization. PMID:21819045

  4. Oxidative dehydrogenation of ethane on dynamically rearranging supported chloride catalysts.

    PubMed

    Gärtner, Christian A; van Veen, André C; Lercher, Johannes A

    2014-09-10

    Ethane is oxidatively dehydrogenated with a selectivity up to 95% on catalysts comprising a mixed molten alkali chloride supported on a mildly redox-active Dy2O3-doped MgO. The reactive oxyanionic OCl(-) species acting as active sites are catalytically formed by oxidation of Cl(-) at the MgO surface. Under reaction conditions this site is regenerated by O2, dissolving first in the alkali chloride melt, and in the second step dissociating and replenishing the oxygen vacancies on MgO. The oxyanion reactively dehydrogenates ethane at the melt-gas phase interface with nearly ideal selectivity. Thus, the reaction is concluded to proceed via two coupled steps following a Mars-van-Krevelen-mechanism at the solid-liquid and gas-liquid interface. The dissociation of O2 and/or the oxidation of Cl(-) at the melt-solid interface is concluded to have the lowest forward rate constants. The compositions of the oxide core and the molten chloride shell control the catalytic activity via the redox potential of the metal oxide and of the OCl(-). Traces of water may be present in the molten chloride under reaction conditions, but the specific impact of this water is not obvious at present. The spatial separation of oxygen and ethane activation sites and the dynamic rearrangement of the surface anions and cations, preventing the exposure of coordinatively unsaturated cations, are concluded to be the origin of the surprisingly high olefin selectivity. PMID:25118821

  5. Radiolytic oxidation of propane. [Gamma radiation

    SciTech Connect

    Gupta, A.K.

    1983-01-01

    The Co-60 ..gamma.. radiolysis of gaseous propane was studied at 100 torr pressure and 25/sup 0/C, both pure and with 10% added oxygen. In the unscavenged system the major products and their G-values were hydrogen, 4.99; methane, 1.30; ethane, 1.95; iso-butane, 0.61; n-butane, 0.25; i-pentane, 0.42; n-pentane, 0.14; and hexanes, 0.89. Minor products were heptanes, 0.082; octanes, 0.067; nonanes, 0.088, and decanes, 0.033. Small yields of ethylene and propylene were also observed. Yields in the presence of 10% added oxygen were hydrogen, 1.87; methane, 0.83; and ethane, 1.22. Higher saturated hydrocarbons were eliminated. The reaction scheme for formation of major products was examined using computer modeling based on 24 reactions in the unscavenged system and 28 reactions in the propane-oxygen system. Yields could be brought into agreement with the data within experimental error in nearly all cases, but in the pure propane system it was necessary to assume that the molecular hydrogen yield was accompanied by the deposition of polymer on the vessel wall.

  6. Adsorption of propane, isopropyl, and hydrogen on cluster models of the M1 phase of Mo-V-Te-Nb-O mixed metal oxide catalyst

    SciTech Connect

    Govindasamy, Agalya; Muthukumar, Kaliappan; Yu, Junjun; Xu, Ye; Guliants, Vadim V.

    2010-01-01

    The Mo-V-Te-Nb-O mixed metal oxide catalyst possessing the M1 phase structure is uniquely capable of directly converting propane into acrylonitrile. However, the mechanism of this complex eight-electron transformation, which includes a series of oxidative H-abstraction and N-insertion steps, remains poorly understood. We have conducted a density functional theory study of cluster models of the proposed active and selective site for propane ammoxidation, including the adsorption of propane, isopropyl (CH{sub 3}CHCH{sub 3}), and H which are involved in the first step of this transformation, that is, the methylene C-H bond scission in propane, on these active site models. Among the surface oxygen species, the telluryl oxo (Te=O) is found to be the most nucleophilic. Whereas the adsorption of propane is weak regardless of the MO{sub x} species involved, isopropyl and H adsorption exhibits strong preference in the order of Te=O > V=O > bridging oxygens > empty Mo apical site, suggesting the importance of TeO{sub x} species for H abstraction. The adsorption energies of isopropyl and H and consequently the reaction energy of the initial dehydrogenation of propane are strongly dependent on the number of ab planes included in the cluster, which points to the need to employ multilayer cluster models to correctly capture the energetics of surface chemistry on this mixed metal oxide catalyst.

  7. Propane conversion on Ga-HZSM-5: Effect of aging on the dehydrogenating and acid functions using pyridine as an IR probe

    SciTech Connect

    Meriaudeau, P.; Naccache, C. ); Abdul Hamid, S.B. )

    1993-02-01

    Gallium-loaded zeolite (Ga-HZSM-5) catalysts have been extensively studied in the recent past, not only in respect of their interesting catalytic activity in the aromatization of C[sub 3]-C[sub 5] alkanes (Cyclar Process) but also in respect of theoretical considerations. There is clear evidence that in the reaction of alkanes these catalysts behave as bifunctional catalysts, the acid function being provided by the protons and the dehydrogenation function deriving from Ga[sub 2]O[sub 3] or Ga[sup n+] ions in ionic-exchange positions. Ga-HZSM-5 catalysts deactivate with time on-stream. The deactivation can result from poisoning of the acid centers and/or the dehydrogenating sites by coke deposition or from sintering or phase transformation of the dehydrogenating gallium species. The aim of the present study was to investigate the possible modifications of Ga centers and H[sup +] sites which may result from the propane reaction. The active centers were studied by infrared spectroscopy of adsorbed pyridine, pyridine adsorption being used to probe both H[sup +] and Al, Ga Lewis-acid centers. 11 refs., 2 figs., 1 tab.

  8. Moessbauer spectra of ferrite catalysts used in oxidative dehydrogenation

    NASA Technical Reports Server (NTRS)

    Cares, W. R.; Hightower, J. W.

    1971-01-01

    Room temperature Mossbauer spectroscopy was used to examine bulk changes which occur in low surface area CoFe2O4 and CuFe2O4 catalysts as a result of contact with various mixtures of trans-2-butene and O2 during oxidative dehydrogenation reactions at about 420 C. So long as there was at least some O2 in the gas phase, the CoFe2O4 spectrum was essentially unchanged. However, the spectrum changed from a random spinel in the oxidized state to an inverse spinel as it was reduced by oxide ion removal. The steady state catalyst lies very near the fully oxidized state. More dramatic solid state changes occurred as the CuFe2O4 underwent reduction. Under severe reduction, the ferrite was transformed into Cu and Fe3O4, but it could be reversibly recovered by oxidation. An intense doublet located near zero velocity persisted in all spectra of CuFe2O4 regardless of the state of reduction.

  9. Hybrid nanocarbon as a catalyst for direct dehydrogenation of propane: formation of an active and selective core-shell sp2/sp3 nanocomposite structure.

    PubMed

    Wang, Rui; Sun, Xiaoyan; Zhang, Bingsen; Sun, Xiaoying; Su, Dangsheng

    2014-05-19

    Hybrid nanocarbon, comprised of a diamond core and a graphitic shell with a variable sp(2)-/sp(3)-carbon ratio, is controllably obtained through sequential annealing treatment (550-1300 °C) of nanodiamond. The formation of sp(2) carbon increases with annealing temperature and the nanodiamond surface is reconstructed from amorphous into a well-ordered, onion-like carbon structure via an intermediate composite structure--a diamond core covered by a defective, curved graphene outer shell. Direct dehydrogenation of propane shows that the sp(2)-/sp(3)-nanocomposite exhibits superior catalytic performance to that of individual nanodiamond and graphitic nanocarbon. The optimum catalytic activity of the diamond/graphene composite depends on the maximum structural defectiveness and high chemical reactivity of the ketone groups. Ketone-type functional groups anchored on the defects/vacancies are active for propene formation; nevertheless, once the oxygen functional groups are desorbed, the defects/vacancies alone might be active sites responsible for the C-H bond activation of propane. PMID:24740731

  10. Cobalt-promoted Iron Oxide Nanoparticles for the Selective Oxidative Dehydrogenation of Cyclohexane

    NASA Astrophysics Data System (ADS)

    Rutter, Matthew

    Recent work has shown that both cobalt and iron oxide nanoparticles are active for the oxidative dehydrogenation (ODH) of cyclohexane to benzene, the former more active than the latter. Further study has shown that the addition of gold species as a minority component into iron oxide nanocrystals increases the selectivity of the reaction to benzene. Since a primary motivation for this work is the addition of catalysts in jet fuels to facilitate the dehydrogenation and cracking reactions preceding their combustion, a low-cost, sacrificial catalyst is sought after. In this application, catalyst nanoparticles suspended in the fuel stream will dehydrogenate cyclic alkanes (cyclohexane) to their aromatic counterparts (benzene). Alkenes and aromatics have a much higher rate of combustion, which decreases the amount of uncombusted fuel in the exhaust, thereby increasing performance. As these catalysts are not recyclable, there is significant impetus to substitute cheaper base metals for expensive noble metals. In this work, iron oxide nanoparticles are doped with varying levels of cobalt to examine the effect of cobalt content and oxidation state on the selectivity and activity of the iron oxide for the oxidative dehydrogenation of cyclohexane, used as a model cyclic alkane in jet fuel. We have shown previously that small (˜5nm) cobalt oxide nanoparticles favor the production of benzene over the partial dehydrogenation products cyclohexene and cyclohexadiene, or the complete oxidation product carbon dioxide. It is the aim of this work to examine the surface of these cobalt-iron oxide nanoparticles to determine the conditions most favorable for this selective oxidative dehydrogenation. Cobalt-doped iron nanoparticles were prepared by a surfactant-free hydrothermal co-precipitation technique that enabled a high degree of composition control and size control. These samples were characterized via Transmission Electron Microscopy (TEM), powder X-Ray Diffraction (XRD), X

  11. Synthesis and Evaluation of Nanostructured Gold-Iron Oxide Catalysts for the Oxidative Dehydrogenation of Cyclohexane

    NASA Astrophysics Data System (ADS)

    Wu, Peng

    Shape-controlled iron oxide and gold-iron oxide catalysts with a cubic inverse spinel structure were studied in this thesis for the oxidative dehydrogenation of cyclohexane. The structure of iron oxide and gold-iron oxide catalysts has no major impact on their oxidative dehydrogenation activity. However, the product selectivity is influenced. Both cyclohexene and benzene are formed on bare iron oxide nanoshapes, while benzene is the only dehydrogenation product in the presence of gold. The selectivity of benzene over CO2 depends strongly on the stability of the iron oxide support and the gold-support interaction. The highest benzene yield has been observed on gold-iron oxide octahedra. {111}-bound nanooctahedra are highly stable in reaction conditions at 300 °C, while {100}-bound nanocubes start to sinter above 250 °C. The highest benzene yield has been observed on gold-iron oxide nanooctahedra, which are likely to have gold atoms, and few-atom gold clusters strongly-bound on their surface. Cationic gold appears to be the active site for benzene formation. An all-organic method to prepare Au-FeOx nano-catalysts is needed due to the inconvenience of the half-organic, half-inorganic synthesis process discussed above. Several methods from the literature to prepare gold-iron oxide nanocomposites completely in organic solvents were reviewed and followed. FeOx Au synthesis procedures in literatures are initially designed for a Au content of over 70%. This approach was tried here to prepare composites with a much lower Au content (2-5 atom. %). Heat treatment is required to bond Au and FeOx NPs in the organic-phase syntheses. Au-FeOx-4 was obtained as a selective catalyst for the ODH of cyclohexane. A Audelta+ peak is observed in the UV-Vis spectrum of sample Au-FeOx-4. This different Au delta+ form may be cationic Au nano-clusters interacting with the FeOx support. It has been demonstrated that cationic gold is responsible for dehydrogenation behavior. Furthermore, the

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

    PubMed

    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. Catalytic dehydrogenation of propane by carbon dioxide: a medium-temperature thermochemical process for carbon dioxide utilisation.

    PubMed

    Du, X; Yao, B; Gonzalez-Cortes, S; Kuznetsov, V L; AlMegren, Hamid; Xiao, T; Edwards, P P

    2015-01-01

    The dehydrogenation of C3H8 in the presence of CO2 is an attractive catalytic route for C3H6 production. In studying the various possibilities to utilise CO2 to convert hydrocarbons using the sustainable energy source of solar thermal energy, thermodynamic calculations were carried out for the dehydrogenation of C3H8 using CO2for the process operating in the temperature range of 300-500 °C. Importantly, the results highlight the enhanced potential of C3H8 as compared to its lighter and heavier homologues (C2H6 and C4H10, respectively). To be utilised in this CO2 utilisation reaction the Gibbs free energy (ΔrGθm) of each reaction in the modelled, complete reacting system of the dehydrogenation of C3H8 in the presence of CO2 also indicate that further cracking of C3H6 will affect the ultimate yield and selectivity of the final products. In a parallel experimental study, catalytic tests of the dehydrogenation of C3H8 in the presence of CO2 over 5 wt%-Cr2O3/ZrO2 catalysts operating at 500 °C, atmospheric pressure, and for various C3H8 partial pressures and various overall GHSV (Gas Hourly Space Velocity) values. The results showed that an increase in the C3H8 partial pressure produced an inhibition of C3H8 conversion but, importantly, a promising enhancement of C3H6 selectivity. This phenomenon can be attributed to competitive adsorption on the catalyst between the generated C3H6 and inactivated C3H8, which inhibits any further cracking effect on C3H6 to produce by-products. As a comparison, the increase of the overall GHSV can also decrease the C3H8 conversion to a similar extent, but the further cracking of C3H6 cannot be limited. PMID:26392020

  14. The effect of mixed HCl-KCl competitive adsorbate on Pt adsorption and catalytic properties of Pt-Sn/Al2O3 catalysts in propane dehydrogenation

    NASA Astrophysics Data System (ADS)

    Zangeneh, Farnaz Tahriri; Taeb, Abbas; Gholivand, Khodayar; Sahebdelfar, Saeed

    2015-12-01

    The effect of competitive adsorbate concentration and combination on the adsorption of H2PtCl6 onto γ-Al2O3 in the preparation and performance of PtSnK/γ-Al2O3 catalyst for propane dehydrogenation was investigated. The catalysts were prepared by sequential impregnation of Sn and Pt precursors. The effect of competitor concentration on Pt adsorption was studied by using hydrochloric acid (0.1-0.3 M) and the effect of pH was studied by using KCl/HCl mixtures at constant (0.1 M) total chloride ion concentration. The catalysts were characterized by nitrogen adsorption/desorption, XRD, XRF, SEM and CO chemisorption. The catalytic performance tests were carried out in a fixed-bed quartz reactor under kinetic controlled condition for proper catalyst screening. It was found that the corrosive competitor HCl could be partially substituted with KCl without appreciable impact on catalyst performance with the advantage of lower acid attack on the support and reduced leaching of the deposited tin. A model based on initial concentration and uptake of the adsorbates was developed to obtain the adsorption parameters. Values of 890 μmol/g and 600 lit/mol were obtained for adsorption site concentration of the tin-impregnated support and equilibrium constant for Pt adsorption, respectively, for HCl concentration range of 0.1-0.3 M.

  15. Substituent-enabled oxidative dehydrogenative cross-coupling of 1,4-naphthoquinones with alkenes.

    PubMed

    Zhang, Chi; Wang, Meining; Fan, Zhoulong; Sun, Li-Ping; Zhang, Ao

    2014-08-15

    A Rh-catalyzed oxidative dehydrogenative cross-coupling of 1,4-naphthquinones with alkenes was achieved by using a substituent-enabled C(sp(2))-H functionalization (SEF) strategy. The method shows high functional group tolerance, broad substrate scope, and great potential for further functional transformations. PMID:25075553

  16. Study of the Low Temperature Oxidation of Propane

    PubMed Central

    Cord, Maximilien; Husson, Benoit; Huerta, Juan Carlos Lizardo; Herbinet, Olivier; Glaude, Pierre-Alexandre; Fournet, René; Sirjean, Baptiste; Battin-Leclerc, Frédérique; Ruiz-Lopez, Manuel; Wang, Zhandong; Xie, Mingfeng; Cheng, Zhanjun; Qi, Fei

    2013-01-01

    The low-temperature oxidation of propane was investigated using a jet-stirred reactor at atmospheric pressure and two methods of analysis: gas chromatography and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) with direct sampling through a molecular jet. The second method allowed the identification of products, such as molecules with hydroperoxy functions, which are not stable enough to be detected by gas chromatography. Mole fractions of the reactants and reaction products were measured as a function of the temperature (530-730 K), with a particular attention to reaction products involved in the low temperature oxidation, such as cyclic ethers, aldehydes, alcohols, ketones, and hydroperoxides. A new model has been obtained from an automatically generated one, which was used as a starting point, with a large number of re-estimated thermochemical and kinetic data. The kinetic data of the most sensitive reactions, i.e., isomerizations of alkylperoxy radicals and the subsequent decompositions, have been calculated at the CBS-QB3 level of theory. The model allows a satisfactory prediction of the experimental data. A flow rate analysis has allowed highlighting the important reaction channels. PMID:23181456

  17. Parametric study of the partial oxidation of propane over nickel and platinum based catalysts

    NASA Astrophysics Data System (ADS)

    Mukka, Mayuri

    Hydrogen production though the partial oxidation of propane over 1%Pt/CeO 2 and 1%Ni/CeO2 catalysts was studied in a fixed-bed reactor. The purpose of the experiments was to study the pathways, priority and the sequence of reactions which occur over each catalyst system. A temperature of 600°C and O2/C3H8 ratio of 1.78 was used for all the runs. The space velocity was varied by varying the flowrates (100, 200, 300, 400 sccm), and also the catalyst loadings. Seven species were found at the outlet of the reactor (C3H8, O2, H2, CO, CO2, H2O and C3H 6). All the species except H2O were analyzed quantitatively by the gas chromatograph. The following reactions can occur during the process at 600°C: total oxidation, partial oxidation, steam reforming, dry reforming, water gas shift, dehydrogenation and water formation. Of these, a Gaussian elimination process yields four independent reactions. This results in ten sets of possible independent reactions. For each set, a material balance on the six outlet compositions allows the calculation of rates of each of the four reactions in the set. Sets containing negative rates for irreversible reactions are discarded. To confirm the validity of sets containing dry reforming, steam reforming and water gas shift, these reactions were carried out over the catalysts at the experimentally determined outlet conditions for the propane partial oxidation process. For the 1%Ni/CeO2 catalyst, both dry and steam reforming reactions were favorable, but the water gas shift reaction was not favorable. The activities of the 1%Pt/CeO2 catalyst for dry reforming and steam reforming were insignificant. The water gas shift reaction was not conducted over the 1%Pt/CeO2 catalyst as no feasible set contained this reaction. These results, coupled with the effect of weight hourly space velocity, allows us to evaluate the relative importance of each reaction in each allowable set as a function of contact time. The results indicate that the pathways

  18. Porous graphene-based material as an efficient metal free catalyst for the oxidative dehydrogenation of ethylbenzene to styrene.

    PubMed

    Diao, Jiangyong; Liu, Hongyang; Wang, Jia; Feng, Zhenbao; Chen, Tong; Miao, Changxi; Yang, Weimin; Su, Dang Sheng

    2015-02-25

    Reduced porous graphene oxide as a metal free catalyst was selected for the oxidative dehydrogenation of ethylbenzene to styrene. It showed the best catalytic performance compared with other carbon materials (routinely reduced graphene oxide, graphite powder and oxidized carbon nanotubes) and commercial iron oxide. PMID:25625943

  19. Insights into the oxidative dehydrogenation of amines with nanoparticulate iridium oxide.

    PubMed

    Hammond, Ceri; Schümperli, Martin T; Hermans, Ive

    2013-09-23

    The aerobic oxidation of amines offers a promising route towards many versatile chemical compounds. Within this contribution, we extend our previous investigations of iridium oxide-catalyzed alcohol oxidation to amine substrates. In addition to demonstrating the versatility of this catalyst, particular attention is focused on the mechanisms of the reaction. Herein, we demonstrate that although amines are oxidized slower than the corresponding alcohols, the catalyst has a preference for amine substrates, and oxidizes various amines at turnover frequencies greater than other systems found in the open literature. Furthermore, the competition between double amine dehydrogenation, to yield the corresponding nitrile, and amine-imine coupling, to yield the corresponding coupled imine, has been found to arise from a competitive reaction pathway, and stems from an effect of substrate-to-metal ratio. Finally, the mechanism responsible for the formation of N-benzylidene-1-phenylmethanamine was examined, and attributed to the coupling of free benzyl amine substrate and benzaldehyde, formed in situ through hydrolysis of the primary reaction product, benzyl imine. PMID:23939827

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

    PubMed

    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

  1. Visible-Light-Promoted Direct Amination of Phenols via Oxidative Cross-Dehydrogenative Coupling Reaction.

    PubMed

    Zhao, Yating; Huang, Binbin; Yang, Chao; Xia, Wujiong

    2016-07-15

    A transition-metal-free approach was disclosed for intermolecular aryl C-N bonds formation between phenols and cyclic anilines via cross-dehydrogenative coupling (CDC) amination that was mediated by visible light, wherein K2S2O8 served as an external oxidant. The salient features of this protocol include circumventing the requirement for prefunctionalized starting materials and achieving single regioselectivity of amination adducts at room temperature. PMID:27364730

  2. Oxidative dehydrogenation dimerization of propylene over bismuth oxide: kinetic and mechanistic studies

    SciTech Connect

    White, M.G.; Hightower, J.W.

    1983-07-01

    Classical kinetic experiments together with pulse microreactor studies involving deuterium and carbon-13-labeled isotopic tracers were used to investigate the oxidative dehydrogenation dimerization (OXDD) of propylene to 1,5-hexadiene and benzene over bismuth oxide between 748 and 898/sup 0/K. The kinetic data, which indicated that the OXDD reaction is of variable order with respect to oxygen and propylene concentrations, could be fit to rate equations based on either the Langmuir-Hinshelwood model or the Mars-van Krevelen model, although the former gave more linear Arrhenius plots. A significant kinetic isotope effect (k/sub H//k/sub D/ = 1.7 at 873/sup 0/K) shows that the rate-limiting step for the OXDD reaction involves C-H cleavage, and there is only a small amount of H/D scrambling among reactant and product molecules. Analysis of liquid products by infrared spectroscopy indicated that both 1,5-hexadiene and 1,3-cyclohexadiene are stable reaction intermediates; microreactor results involving unlabeled propylene, 1,5-hexadiene, 1,3-cyclohexadiene, and 1,4-cyclohexadiene as reactants confirmed the infrared findings. Pulse microreactor experiments with /sup 13/C-labeled propylene clearly showed that deep oxidation (complete combustion) occurs via a consecutive-parallel network involving the partially oxidized intermediates as well as the starting propylene. Changes in the particle size do not alter the overall activity, although larger particles have lower selectivities for C/sub 6/ products than do smaller particles.

  3. Bulk binary ZrO2-based oxides as highly active alternative-type catalysts for non-oxidative isobutane dehydrogenation.

    PubMed

    Otroshchenko, Tatyana; Radnik, Jörg; Schneider, Matthias; Rodemerck, Uwe; Linke, David; Kondratenko, Evgenii V

    2016-06-21

    Bulk binary ZrO2-based oxides efficiently catalyse non-oxidative dehydrogenation of isobutane to isobutylene. Their activity strongly depends on the kind of second metal oxide. So designed CrZrOx showed superior activity to industrially relevant catalysts with supported Pt or CrOx species. It was also stable under alternating dehydrogenation and oxidative regeneration cycles over ca. 110 h under different reaction conditions between 550 and 600 °C. PMID:27277540

  4. Ethylbenzene oxidative dehydrogenation on MnO{sub x}/SiO{sub 2} catalysts

    SciTech Connect

    Craciun, R.; Dulamita, N.

    1999-04-01

    Supported MnO{sub x} on high surface area SiO{sub 2} (300 m{sup 2}/g) catalysts were successfully used in ethylbenzene oxidative dehydrogenation. X-ray diffraction and X-ray photoelectron spectroscopy were employed to characterize the structure of fresh and used MnO{sub x}/SiO{sub 2} catalysts. The MnO{sub x} catalysts were prepared using the pore volume impregnation method, with MnO{sub 2} loading varying from 0.7 wt % (Mn/Si = 0.005, atomic ratio) to 30 wt % (Mn/Si = 0.14). The changes in the crystalline structure and dispersion of supported MnO{sub x} were related to the precursor/support interaction and the conditions used during catalyst preparation. A possible mechanism for ethylbenzene conversion to styrene on MnO{sub x}/SiO{sub 2} catalysts is proposed, where lattice oxygen from crystalline MnO{sub 2} can be used in the oxidation or oxidative dehydrogenation processes. The high selectivity in styrene (at 723 K, 24% conversion with 76% selectivity in styrene) was related to the high concentration in the MnO{sub 2} phase from the MnO{sub x}/SiO{sub 2} catalysts. The formation of the Mn{sub 3}O{sub 4} phase, observed on the used catalysts, supports the proposed mechanism. These findings are of potential use for industrial applications, particularly in optimization of various oxidative dehydrogenation processes.

  5. Oxidative dehydrogenation of ethane at millisecond contact times: Effect of H{sub 2} addition

    SciTech Connect

    Bodke, A.S.; Henning, D.; Schmidt, L.D.; Bharadwaj, S.S.; Maj, J.J.; Siddall, J.

    2000-04-01

    The oxidative dehydrogenation of ethane using Pt/{alpha}-Al{sub 2}O{sub 3} and various bimetallic catalysts operating at {approximately}1,000 C and very short contact times is examined with H{sub 2} addition to the feed. When H{sub 2} is added with a Pt catalyst, the ethylene selectivity rises from 65 to 72% but ethane conversion drops from 70 to 52%. However, using a Pt-Sn/{alpha}-Al{sub 2}O{sub 3} catalyst, the C{sub 2}H{sub 4} selectivity increases from 70 to greater than 85%, while the conversion remains {approximately}70%. The process also produces approximately as much H{sub 2} as is added to the feed. Effects of other metal promoters, sphere bed and fibermat supports, preheat, pressure, nitrogen dilution, and flow rate are examined in an effort to further elucidate the mechanism. Deactivation of the Pt-Sn catalyst is examined, and a simple method of regenerating the activity on-line is demonstrated. Possible mechanisms to explain high selectivities to ethylene are discussed. Although the process can be regarded as a simple two-step reaction sequence with the exothermic oxidation of hydrogen or ethane driving the endothermic dehydrogenation of ethane to ethylene, the exact contributions of heterogeneous or gas-phase reactions and their spatial variations within the catalyst are yet to be determined.

  6. Chemical kinetic modeling of propane oxidation behind shock waves

    NASA Technical Reports Server (NTRS)

    Mclain, A. G.; Jachimowski, C. J.

    1977-01-01

    The stoichiometric combustion of propane behind incident shock waves was studied experimentally and analytically over a temperature range from 1700 K to 2600 K and a pressure range from 1.2 to 1.9 atm. Measurements of the concentrations of carbon monoxide (CO) and carbon dioxide (CO2) and the product of the oxygen atom and carbon dioxide concentrations (O)(CO) were made after passage of the incident shock wave. A kinetic mechanism was developed which, when used in a computer program for a flowing, reacting gas behind an incident shock wave predicted experimentally measured results quite well. Ignition delay times from the literature were also predicted quite well. The kinetic mechanism consisted of 59 individual kinetic steps.

  7. Phosphate-modified carbon nanotubes in the oxidative dehydrogenation of isopentanes.

    PubMed

    Huang, Rui; Liu, Hong Yang; Zhang, Bing Sen; Sun, Xiao Yan; Liang, Chang Hai; Su, Dang Sheng; Zong, Bao Ning; Rong, Jun Feng

    2014-12-01

    Ketonic/quinonic C=O groups on the surface of a carbon matrix are capable of abstracting hydrogen in C=H bonds from hydrocarbons and enable them to selectively convert into corresponding unsaturated hydrocarbons; this process is the oxidative dehydrogenation (ODH) reaction. However, a variety of inevitable defects or graphene edges and other oxygen-containing groups on the carbon matrix are detrimental to the selective production of alkenes due to their high activity towards overoxidation. Herein, we show that phosphate can not only impede the total oxidation but also cover the selective C=O groups, hence allowing its use as a modulator to defects and oxygen-containing functional groups on the multiwalled carbon nanotubes, regulating the distribution of active sites and related catalytic targets. PMID:25213438

  8. Synthesis of C60-Fused Tetrahydrocarbazole/Dibenzothiophene/Benzothiophene and Dibenzofuran Derivatives via Metal-Free Oxidative Dehydrogenative Carboannulation.

    PubMed

    Liu, Tong-Xin; Ma, Jinliang; Chao, Di; Zhang, Pengling; Ma, Nana; Liu, Qingfeng; Shi, Lei; Zhang, Zhiguo; Zhang, Guisheng

    2016-08-19

    A transition-metal-free oxidative dehydrogenative coupling reaction has been developed for the direct construction of novel C60-fused tetrahydrocarbazoles, dibenzothiophenes, benzothiophenes, and dibenzofurans. This new carboannulation reaction features high atom economy, operational simplicity, broad substrate scope, and excellent functional-group tolerance and provides a convenient access to a scarce class of fullerene derivatives. PMID:27487008

  9. Copper-catalyzed intermolecular dehydrogenative amidation/amination of quinoline N-oxides with lactams/cyclamines.

    PubMed

    Li, Gang; Jia, Chunqi; Sun, Kai

    2013-10-18

    C-H, N-H dehydrogenative coupling of quinoline N-oxides with lactams/cyclamines has been achieved in the presence of the Cu(OAc)2 catalyst to give good to excellent yields. This study provides a new strategy for the construction of a 2-aminoquinoline skeleton via direct functionalization of aryl C-H bonds. PMID:24093556

  10. Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

    PubMed Central

    2015-01-01

    We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)–amidate > Cu(II)–imidate > Cu(II)–benzoate. Consistent with this trend, Cu(II)–amidates and Cu(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

  11. Copper-catalyzed oxidative dehydrogenative carboxylation of unactivated alkanes to allylic esters via alkenes.

    PubMed

    Tran, Ba L; Driess, Matthias; Hartwig, John F

    2014-12-10

    We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV-vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C-H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C-H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper-carboxylate, copper-amidate, and copper-imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)-amidate > Cu(II)-imidate > Cu(II)-benzoate. Consistent with this trend, Cu(II)-amidates and Cu(II)-benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

  12. Oxidative Dehydrogenation on Nanocarbon: Intrinsic Catalytic Activity and Structure-Function Relationships.

    PubMed

    Qi, Wei; Liu, Wei; Guo, Xiaoling; Schlögl, Robert; Su, Dangsheng

    2015-11-01

    Physical and chemical insights into the nature and quantity of the active sites and the intrinsic catalytic activity of nanocarbon materials in alkane oxidative dehydrogenation (ODH) reactions are reported using a novel in situ chemical titration process. A study on the structure-function relationship reveals that the active sites are identical both in nature and function on various nanocarbon catalysts. Additionally, the quantity of the active sites could be used as a metric to normalize the reaction rates, and thus to evaluate the intrinsic activity of nanocarbon catalysts. The morphology of the nanocarbon catalysts at the microscopic scale exhibits a minor influence on their intrinsic ODH catalytic activity. The number of active sites calculated from the titration process indicates the number of catalytic centers that are active (that is, working) under the reaction conditions. PMID:26388451

  13. Gas-phase oxidation of propane in the presence of azaporphin compounds

    SciTech Connect

    Enikobpov, N.S.; Moshkina, R.I.; Nikisha, L.V.; Polyak, S.S.; Promyslova, V.V.

    1985-07-01

    The gas-phase oxidation of an equimolar mixture of propane with oxygen was studied in the presence of various polyphthalocyanins: metal-free PPC and mono- and bimetallic complexes PPC-Fe, PPC-Co, PPC-Cu-Fe, and PPC-Mg-Fe. The inhibition of oxidation increases in the series: PPC-Co < PPC-Fe approx. = PPC-Mg-Fe < PPC < PPC-Cu-Fe. The qualitative and quantitative composition of the products is virtually unchanged in comparison with the untreated reactor.

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

    PubMed

    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

  15. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    NASA Astrophysics Data System (ADS)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-10-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1-xSrxFeyMn1-yO3-d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d and the Fe-K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3-d was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d perovskite oxide.

  16. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    PubMed Central

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

  17. Electrochemical promotion of propane oxidation on Pt deposited on a dense β"-Al2O3 ceramic Ag+ conductor

    NASA Astrophysics Data System (ADS)

    Tsampas, Michail; Kambolis, Anastasios; Obeid, Emil; Lizarraga, Leonardo; Sapountzi, Foteini; Vernoux, Philippe

    2013-08-01

    A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a β"-Al2O3 ceramic Ag+ conductor was developed and evaluated during propane oxidation. It was observed that upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation.

  18. Iodine-Catalyzed Cross Dehydrogenative Coupling Reaction: A Regioselective Sulfenylation of Imidazoheterocycles Using Dimethyl Sulfoxide as an Oxidant.

    PubMed

    Siddaraju, Yogesh; Prabhu, Kandikere Ramaiah

    2016-09-01

    A regioselective formation of C-S bonds has been achieved using a cross dehydrogenative coupling (CDC) protocol using iodine as a catalyst and dimethyl sulfoxide as an oxidant under green chemistry conditions. This strategy employs the reaction of easily available heterocyclic thiols or thiones with imidazoheterocycles. This protocol provides an efficient, mild, and inexpensive method for sulfenylation of imidazoheterocycles with a diverse range of heterocyclic thiols and heterocyclic thiones. PMID:27490357

  19. Oxidative dehydrogenation of isobutane over vanadia catalysts supported by titania nanoshapes

    SciTech Connect

    Kraemer, Shannon K.; Rondinone, Adam Justin; Tsai, Yu-Tung; Schwartz, Viviane; Steven H. Overbury; Idrobo, Juan-Carlos; Wu, Zili

    2015-11-02

    Support plays a complex role in catalysis by supported metal oxides and the exact support effect still remains elusive. One of the approaches to gain fundamental insights into the support effect is to utilize model support systems. In this study, we employed for the first time titania nanoshapes as the model supports and investigated how the variation of surface structure of the support (titania, TiO2) impacts the catalysis of supported oxide (vanadia, VOx). TiO2 truncated rhombi, spheres and rods were synthesized via hydrothermal method and characterized with XRD and TEM. These TiO2 nanoshapes represent different mixtures of surface facets including [1 0 1], [0 1 0] and [0 0 1] and were used to support vanadia. The structure of supported VOx species was characterized in detail with in situ Raman spectroscopy as a function of loading on the three TiO2 nanoshapes. Oxidative dehydrogenation (ODH) of isobutane to isobutene was used as a model reaction to test how the support shape influences the activity, selectivity and activation energy of the surface VOx species. It was shown that the shape of TiO2 support does not pose evident effect on either the structure of surface VOx species or the catalytic performance of surface VOx species in isobutane ODH reaction. Finally, this insignificant support shape effect was ascribed to the small difference in the surface oxygen vacancy formation energy among the different TiO2 surfaces and the multi-faceting nature of the TiO2 nanoshapes.

  20. Oxidative dehydrogenation of isobutane over vanadia catalysts supported by titania nanoshapes

    DOE PAGESBeta

    Kraemer, Shannon K.; Rondinone, Adam Justin; Tsai, Yu-Tung; Schwartz, Viviane; Steven H. Overbury; Idrobo, Juan-Carlos; Wu, Zili

    2015-11-02

    Support plays a complex role in catalysis by supported metal oxides and the exact support effect still remains elusive. One of the approaches to gain fundamental insights into the support effect is to utilize model support systems. In this study, we employed for the first time titania nanoshapes as the model supports and investigated how the variation of surface structure of the support (titania, TiO2) impacts the catalysis of supported oxide (vanadia, VOx). TiO2 truncated rhombi, spheres and rods were synthesized via hydrothermal method and characterized with XRD and TEM. These TiO2 nanoshapes represent different mixtures of surface facets includingmore » [1 0 1], [0 1 0] and [0 0 1] and were used to support vanadia. The structure of supported VOx species was characterized in detail with in situ Raman spectroscopy as a function of loading on the three TiO2 nanoshapes. Oxidative dehydrogenation (ODH) of isobutane to isobutene was used as a model reaction to test how the support shape influences the activity, selectivity and activation energy of the surface VOx species. It was shown that the shape of TiO2 support does not pose evident effect on either the structure of surface VOx species or the catalytic performance of surface VOx species in isobutane ODH reaction. Finally, this insignificant support shape effect was ascribed to the small difference in the surface oxygen vacancy formation energy among the different TiO2 surfaces and the multi-faceting nature of the TiO2 nanoshapes.« less

  1. Copper catalyzed oxidative esterification of aldehydes with alkylbenzenes via cross dehydrogenative coupling.

    PubMed

    Rout, Saroj Kumar; Guin, Srimanta; Ghara, Krishna Kanta; Banerjee, Arghya; Patel, Bhisma K

    2012-08-01

    Copper(II) as the catalyst in a cross dehydrogenative coupling (CDC) reaction has been demonstrated for the synthesis of benzylic esters using aldehydes and alkylbenzenes as coupling partners. PMID:22817825

  2. Palladium-Catalyzed Aerobic Oxidative Dehydrogenation of Cyclohexenes to Substituted Arene Derivatives

    PubMed Central

    Iosub, Andrei V.; Stahl, Shannon S.

    2015-01-01

    A palladium(II) catalyst system has been identified for aerobic dehydrogenation of substituted cyclohexenes to the corresponding arene derivatives. Use of sodium anthraquinone-2-sulfonate (AMS) as a co-catalyst enhances the product yields. A wide range of functional groups are tolerated in the reactions, and the scope and limitations of the method are described. The catalytic dehydrogenation of cyclohexenes is showcased in an efficient route to a phthalimide-based TRPA1 activity modulator. PMID:25734414

  3. Nature of vanadium sites in V/{alpha}-Ti phosphate catalysts for the oxidative dehydrogenation of ethane

    SciTech Connect

    Santamaria-Gonzalez, J.; Martinez-Lara, M.; Rodriguez-Castellon, E.; Jimenez-Lopez, A.; Banares, M.S.; Martinez-Huerta, M.V.; Fierro, J.L.G.

    1999-01-25

    The selective conversion of ethane into ethylene is currently being studied because of the economic impact of using natural gas and LPG`s raw materials to produce chemicals and polymers. The available technology for the production of ethylene is the steam cracking of ethane, although it is a highly energy-intensive process. Several approaches to this problem have been considered, although oxidative dehydrogenation (ODH) remains prominent. The principal reason for this lies in the fact that dehydrogenation in the presence of oxygen is thermodynamically favored and coking side reactions are minimized. The present note reports preliminary results in the performance for the ODH reaction of ethane of a new family of vanadium-loaded {alpha}-Ti phosphate catalyst. Moreover, although these catalysts show modest activity with negligible production of CO{sub 2}, a second objective was to report data on the genesis of surface sites during on-stream operation.

  4. Non-Oxidative Dehydrogenation Pathways for the Conversion of C2 -C4 Alcohols to Carbonyl Compounds.

    PubMed

    Shylesh, Sankaranarayanapillai; Kim, Daeyoup; Ho, Christopher R; Johnson, Gregory R; Wu, Jason; Bell, Alexis T

    2015-12-01

    Gold nanoparticles (NPs) supported on hydrotalcite (Au/HT) are highly active and selective catalysts for the continuous, gas-phase, non-oxidative dehydrogenation of bioderived C2 -C4 alcohols. A sharp increase in turn over frequency (TOF) is noted when the size of Au NPs is less than 5 nm relating to the strong synergy between metallic Au NPs and the acid-base groups on the support surface. It is shown that catalytic activity depends critically on Au NP size, support composition, and support pretreatments. A reaction pathway elucidated from kinetic isotope effects suggests that the abstraction of β-H by Au NPs (C-H activation) is the rate-determining step in the dehydrogenation of bioderived C2 -C4 alcohols. PMID:26493770

  5. Effect of size of catalytically active phases in the dehydrogenation of alcohols and the challenging selective oxidation of hydrocarbons.

    PubMed

    Zhang, Qinghong; Deng, Weiping; Wang, Ye

    2011-09-01

    The size of the active phase is one of the most important factors in determining the catalytic behaviour of a heterogeneous catalyst. This Feature Article focuses on the size effects in two types of reactions, i.e., the metal nanoparticle-catalysed dehydrogenation of alcohols and the metal oxide nanocluster-catalysed selective oxidation of hydrocarbons (including the selective oxidation of methane and ethane and the epoxidation of propylene). For Pd or Au nanoparticle-catalysed oxidative or non-oxidative dehydrogenation of alcohols, the size of metal nanoparticles mainly controls the catalytic activity by affecting the activation of reactants (either alcohol or O(2)). The size of oxidic molybdenum species loaded on SBA-15 determines not only the activity but also the selectivity of oxygenates in the selective oxidation of ethane; highly dispersed molybdenum species are suitable for acetaldehyde formation, while molybdenum oxide nanoparticles exhibit higher formaldehyde selectivity. Cu(II) and Fe(III) isolated on mesoporous silica are highly efficient for the selective oxidation of methane to formaldehyde, while the corresponding oxide clusters mainly catalyse the complete oxidation of methane. The lattice oxygen in iron or copper oxide clusters is responsible for the complete oxidation, while the isolated Cu(I) or Fe(II) generated during the reaction can activate molecular oxygen forming active oxygen species for the selective oxidation of methane. Highly dispersed Cu(I) and Fe(II) species also function for the epoxidation of propylene by O(2) and N(2)O, respectively. Alkali metal ions work as promoters for the epoxidation of propylene by enhancing the dispersion of copper or iron species and weakening the acidity. PMID:21629889

  6. Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir.

    PubMed

    Sheng, Tian; Lin, Wen-Feng; Hardacre, Christopher; Hu, P

    2014-07-14

    In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO2 selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO2 selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using the first principles method. It is found that CH3CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations, are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO2 selectivity and only Rh is able to increase the selectivity of CO2 in DEFCs. PMID:24869778

  7. Operating envelope of a short contact time fuel reformer for propane catalytic partial oxidation

    NASA Astrophysics Data System (ADS)

    Waller, Michael G.; Walluk, Mark R.; Trabold, Thomas A.

    2015-01-01

    Fuel cell technology has yet to realize widespread deployment, in part because of the hydrogen fuel infrastructure required for proton exchange membrane systems. One option to overcome this barrier is to produce hydrogen by reforming propane, which has existing widespread infrastructure, is widely used by the general public, easily transported, and has a high energy density. The present work combines thermodynamic modeling of propane catalytic partial oxidation (cPOx) and experimental performance of a Precision Combustion Inc. (PCI) Microlith® reactor with real-time soot measurement. Much of the reforming research using Microlith-based reactors has focused on fuels such as natural gas, JP-8, diesel, and gasoline, but little research on propane reforming with Microlith-based catalysts can be found in literature. The aim of this study was to determine the optimal operating parameters for the reformer that maximizes efficiency and minimizes solid carbon formation. The primary parameters evaluated were reformate composition, carbon concentration in the effluent, and reforming efficiency as a function of catalyst temperature and O2/C ratio. Including the lower heating values for product hydrogen and carbon monoxide, efficiency of 84% was achieved at an O2/C ratio of 0.53 and a catalyst temperature of 940 °C, resulting in near equilibrium performance. Significant solid carbon formation was observed at much lower catalyst temperatures, and carbon concentration in the effluent was determined to have a negative linear relationship at T < 750 °C. The Microlith reactor displayed good stability during more than 80 experiments with temperature cycling from 360 to 1050 °C.

  8. Main-group compounds selectively oxidize mixtures of methane, ethane, and propane to alcohol esters.

    PubMed

    Hashiguchi, Brian G; Konnick, Michael M; Bischof, Steven M; Gustafson, Samantha J; Devarajan, Deepa; Gunsalus, Niles; Ess, Daniel H; Periana, Roy A

    2014-03-14

    Much of the recent research on homogeneous alkane oxidation has focused on the use of transition metal catalysts. Here, we report that the electrophilic main-group cations thallium(III) and lead(IV) stoichiometrically oxidize methane, ethane, and propane, separately or as a one-pot mixture, to corresponding alcohol esters in trifluoroacetic acid solvent. Esters of methanol, ethanol, ethylene glycol, isopropanol, and propylene glycol are obtained with greater than 95% selectivity in concentrations up to 1.48 molar within 3 hours at 180°C. Experiment and theory support a mechanism involving electrophilic carbon-hydrogen bond activation to generate metal alkyl intermediates. We posit that the comparatively high reactivity of these d(10) main-group cations relative to transition metals stems from facile alkane coordination at vacant sites, enabled by the overall lability of the ligand sphere and the absence of ligand field stabilization energies in systems with filled d-orbitals. PMID:24626925

  9. Oxidative dehydrogenation of cyclohexene on size selected subnanometer cobalt clusters: improved catalytic performance via evolution of cluster-assembled nanostructures.

    PubMed

    Lee, Sungsik; Di Vece, Marcel; Lee, Byeongdu; Seifert, Sönke; Winans, Randall E; Vajda, Stefan

    2012-07-14

    The catalytic activity of oxide-supported metal nanoclusters strongly depends on their size and support. In this study, the origin of morphology transformation and chemical state changes during the oxidative dehydrogenation of cyclohexene was investigated in terms of metal-support interactions. Model catalyst systems were prepared by deposition of size selected subnanometer Co(27±4) clusters on various metal oxide supports (Al(2)O(3), ZnO and TiO(2) and MgO). The oxidation state and reactivity of the supported cobalt clusters were investigated by temperature programmed reaction (TPRx) and in situ grazing incidence X-ray absorption (GIXAS) during oxidative dehydrogenation of cyclohexene, while the sintering resistance monitored with grazing incidence small angle X-ray scattering (GISAXS). The activity and selectivity of cobalt clusters shows strong dependence on the support. GIXAS reveals that metal-support interaction plays a key role in the reaction. The most pronounced support effect is observed for MgO, where during the course of the reaction in its activity, composition and size dynamically evolving nanoassembly is formed from subnanometer cobalt clusters. PMID:22419008

  10. Acceptorless Dehydrogenative Oxidation of Secondary Alcohols Catalysed by Cp*Ir(III) -NHC Complexes.

    PubMed

    Gülcemal, Süleyman; Gülcemal, Derya; Whitehead, George F S; Xiao, Jianliang

    2016-07-18

    A series of new Ir(III) complexes with carbene ligands that contain a range of benzyl wingtip groups have been prepared and fully characterised by NMR spectroscopy, HRMS, elemental analysis and X-ray diffraction. All the complexes were active in the acceptorless dehydrogenation of alcohol substrates in 2,2,2-trifluoroethanol to give the corresponding carbonyl compounds. The most active complex bore an electron-rich carbene ligand; this complex was used to catalyse the highly efficient and chemoselective dehydrogenation of a wide range of secondary alcohols to their respective ketones, with turnover numbers up to 1660. Mechanistic studies suggested that the turnover of the dehydrogenation reaction is limited by the H2 -formation step. PMID:27321021

  11. Identification of Methane, Ethane, and Propane Oxidizing Bacteria at Marine Hydrocarbon Seeps by Stable Isotope Probing

    NASA Astrophysics Data System (ADS)

    Redmond, M.; Ding, H.; Friedrich, M. W.; Valentine, D. L.

    2008-12-01

    Hydrocarbon seeps emit substantial amounts of oil and natural gas into the marine environment, where they can be oxidized by microorganisms in the sediment and water column. Here, we used stable isotope probing of DNA and lipid biomarkers to identify the microorganisms actively consuming 13C-labeled natural gas compounds in seep sediment samples. Surface sediment was collected from the Coal Oil Point seep field (offshore Santa Barbara, California, USA) and incubated under aerobic conditions with 13C labeled methane, ethane, or propane for up to 37 days, with sediment sub-samples taken at 3-4 intermediate time points. DNA was extracted from sediment and separated by CsCl density gradient centrifugation. The microbial community in each fraction was profiled using T-RFLP, and bacterial 16S rRNA gene clone libraries were constructed from un-incubated hydrocarbon seep sediment and selected isotopically 'heavy' (13C) and 'light' (12C) gradient fractions from ethane incubations. All clone libraries were dominated by sequences from members of the family Rhodobacteraceae (>25% of sequences) and a diverse group of Gammaproteobacteria, including sequences related to those of methylotrophs and to those of bacteria known to consume the longer-chain alkanes present in crude oil. After 14 days of incubation, the relative abundance of Rhodobacteraceae was higher in 'heavy' fractions from the 13C-ethane incubation than in 'light' fractions, suggesting incorporation of 13C label. The Rhodobacteraceae are very diverse metabolically, but have often been observed in abundance in oil contaminated seawater. Several members of this group have been shown to oxidize longer chain alkanes (C10 or higher), but none have been previously linked to the consumption of the gaseous alkanes ethane, propane, and butane. For the final time point, 13C content of phospholipid fatty acids (PLFA) were also analyzed, showing substantial incorporation of 13C over 37 days. In the methane incubation

  12. Regiodivergent Cross-Dehydrogenative Coupling of Pyridines and Benzoxazoles: Discovery of Organic Halides as Regio-Switching Oxidants.

    PubMed

    Yamada, Shuya; Murakami, Kei; Itami, Kenichiro

    2016-05-20

    Cross-dehydrogenative coupling (CDC) of two unfunctionalized heteroarenes has been recognized as an ideal transformation to synthesize privileged heterobiaryl scaffolds. However, regioselective activation and transformation of a specific set of two heterocyclic C-H bonds among other bonds have been extremely challenging. Thus, discovering a new controlling element to achieve regio-controlled and regio-divergent heterocyclic CDCs is considered crucial. In this Letter, the unprecedented use of organic halides as an oxidant to achieve the CDC reaction of pyridines and benzoxazoles with palladium catalyst is described. Moreover, the regioselectivity of the pyridine functionalization site can be controlled by the choice of organic halides. PMID:27162109

  13. Methanol Oxidative Dehydrogenation on Oxide Catalysts: Molecular and Dissociative Routes and Hydrogen Addition Energies as Descriptors of Reactivity

    SciTech Connect

    Deshlahra, Prashant; Iglesia, Enrique

    2014-11-13

    The oxidative dehydrogenation (ODH) of alkanols on oxide catalysts is generally described as involving H-abstraction from alkoxy species formed via O–H dissociation. Kinetic and isotopic data cannot discern between such routes and those involving kinetically-relevant H-abstraction from undissociated alkanols. Here, we combine such experiments with theoretical estimates of activation energies and entropies to show that the latter molecular routes prevail over dissociative routes for methanol reactions on polyoxometalate (POM) clusters at all practical reaction temperatures. The stability of the late transition states that mediate H-abstraction depend predominantly on the stability of the O–H bond formed, making H-addition energies (HAE) accurate and single-valued descriptors of reactivity. Density functional theory-derived activation energies depend linearly on HAE values at each O-atom location on clusters with a range of composition (H3PMo12, H4SiMo12, H3PW12, H4PV1Mo11, and H4PV1W11); both barriers and HAE values reflect the lowest unoccupied molecular orbital energy of metal centers that accept the electron and the protonation energy of O-atoms that accept the proton involved in the H-atom transfer. Bridging O-atoms form O–H bonds that are stronger than those of terminal atoms and therefore exhibit more negative HAE values and higher ODH reactivity on all POM clusters. For each cluster composition, ODH turnover rates reflect the reactivity-averaged HAE of all accessible O-atoms, which can be evaluated for each cluster composition to provide a rigorous and accurate predictor of ODH reactivity for catalysts with known structure. These relations together with oxidation reactivity measurements can then be used to estimate HAE values and to infer plausible structures for catalysts with uncertain active site structures.

  14. Surface-inspired molecular vanadium oxide catalysts for the oxidative dehydrogenation of alcohols: evidence for metal cooperation and peroxide intermediates.

    PubMed

    Werncke, C Gunnar; Limberg, Christian; Knispel, Christina; Mebs, Stefan

    2011-10-17

    On the basis that thiacalix[4]arene (H(4)T4A) complex (PPh(4) )(2) [H(2)T4A(VO(2))](2) (Ia) was found to be an adequate functional model for surface species occurring on vanadium oxide based catalysts and itself catalyses the oxidative dehydrogenation (ODH) of alcohols, an analogue containing 2,2'-thiobis(2,4-di-tert-butylphenolate), (S)L(2-), as ligand, namely, (PPh(4))(2)[(S)LVO(2)](2) (II) was investigated in the same context. Despite the apparent similarity of Ia and II, studies on II revealed several novel insights, which are also valuable in connection with surfaces of vanadia catalysts: 1) For Ia and II similar turnover numbers (TONs) were found for the ODH of activated alcohols, which indicates that the additional OH units inherent to Ia do not contribute particularly to the activity of this complex, for instance, through prebinding of the alcohol. 2) On dissolution II enters into an equilibrium with a monomeric form, which is the predominant species in solution; nevertheless, ODH proceeds exclusively at the dimeric form, and this stresses the need for cooperation of two vanadium centres. 3) By omitting O(2) from the system during the oxidation of 9-fluorenol, the reduced form of the catalyst could be isolated and fully characterised (including single-crystal X-ray analysis). The corresponding intermediate had been elusive in case of thiacalixarene system Ia. 4) Reoxidation was found to proceed via a peroxide intermediate that also oxidises one alcohol equivalent. As the peroxide can also perform mono- and dioxygenation of the thioether group in II, after a number of turnovers the active catalyst contains a sulfone group. The reduced form of this ultimate catalyst was also isolated and structurally characterised. Possible implications of 1)-4) for the function of heterogeneous vanadia catalysts are discussed. PMID:21915928

  15. Potassium promotion of iron oxide dehydrogenation catalysts supported on magnesium oxide: 1. Preparation and characterization

    SciTech Connect

    Stobbe, D.E.; Buren, F.R. van ); Dillen, A.J. van; Geus, J.W. )

    1992-06-01

    Catalysts of iron oxide supported on magnesium oxide and promoted with potassium were prepared by incipient wetness impregnation of preshaped magnesium oxide support pellets with a solution of an iron complex, either ammonium iron (III) citrate or ammonium iron (III) EDTA and potassium carbonate. Iron and potassium were applied wither simultaneously or consecutively. As determined using X-ray diffraction, thermogravimetric analysis, and magnetic measurements, calcination above 923 K results in the formation of a mixed oxide of iron and potassium, viz., KFeO[sub 2]. After calcination at 973 K the average crystallite size of the KFeO[sub 2] phase is about 300 [angstrom]. The formation of KFeO[sub 2] appeared to have a strong retarding effect on the reduction of the iron oxide phase to metallic iron. It was found that the KFeO[sub 2] phase is unstable in atomspheric air due to reaction with carbon dioxide and moisture to form potassium (hydrogen) carbonate and (hydrated) iron oxide.

  16. Silylesterification of oxidized multi-wall carbon nanotubes by catalyzed dehydrogenative cross-coupling between carboxylic and hydrosilane functions

    NASA Astrophysics Data System (ADS)

    Seffer, J.-F.; Detriche, S.; Nagy, J. B.; Delhalle, J.; Mekhalif, Z.

    2014-06-01

    Surface modification of oxidized carbon nanotubes (O-CNTs) with silicon based anchoring groups (R-SiR3) is a relatively uncommon approach of the CNTs functionalization. Hydrosilane derivatives constitute an attractive subclass of compounds for silanization reactions on the CNTs surface. In this work, we report on the ZnCl2 catalytically controlled reaction (hydrosilane dehydrogenative cross-coupling, DHCC) of fluorinated hydrosilane probes with the carboxylic functions present on the surface of oxidized multi-wall carbon nanotubes. Carbon nanotubes functionalized with essentially alcohol groups are also used to compare the selectivity of zinc chloride toward carboxylic groups. To assess the efficiency of functionalization, X-ray Photoelectron Spectroscopy is used to determine the qualitative and quantitative composition of the different samples. Solubility tests on the oxidized and silanized MWNTs are also carried out in the framework of the Hansen Solubility Parameters (HSP) theory to apprehend at another scale the effect of DHCC.

  17. Synthesis and Characterization of Nearly Monodisperse Pt Nanoparticles for C1 to C3 Alcohol Oxidation and Dehydrogenation of Dimethylamine-borane (DMAB).

    PubMed

    Erken, Esma; Yildiz, Yunus; Kilbaş, Benan; Sen, Fatih

    2016-06-01

    Highly efficient nearly monodisperse Pt NPs catalyze C1 to C3 alcohol oxidation with very high electrochemical activities and provides one of the highest catalytic activities (TOF = 21.50 h(-1)) in the dehydrogenation of DMAB at room temperature. The exceptional stability towards agglomeration, leaching and CO poisoning for the prepared catalyst allow these particles to be recycled and reused in the catalysis of both DMAB dehydrogenation and C1 to C3 alcohol oxidation. After four subsequent reaction and recovery cycles, catalyst retained ≥ 80% activity towards the complete dehydrogenation of DMAB. The prepared catalyst structures were determined by the X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM) respectively. PMID:27427655

  18. Formation of M2+(O2)(C3H8) species in alkaline-earth-exchanged Y zeolite during propane selective oxidation.

    PubMed

    Xu, Jiang; Mojet, Barbara L; van Ommen, Jan G; Lefferts, Leon

    2005-10-01

    The adsorption of oxygen and d2-propane (CH3CD2CH3) on a series of alkaline-earth-exchanged Y zeolite at room temperature was studied with in situ infrared spectroscopy. Surprisingly at room temperature, oxygen adsorption led to the formation of supercage M2+(O2) species. Further, at low propane coverage, propane was found to adsorb linearly on Mg2+ cations, but a ring-adsorption structure was observed for propane adsorbing on Ca2+, Sr2+, and Ba2+ cations. It is demonstrated that O2 and propane can simultaneously attach to one active center (M2+) to form a M2+(O2)(C3H8) species, which is proposed to be the precursor in thermal propane selective oxidation. Selectivity to acetone in the propane oxidation reaction decreases with increasing temperature and cation size due to the formation of 2-propanol and carboxylate ions. An extended reaction scheme for the selective oxidation of propane over alkaline earth exchanged Y zeolites is proposed. PMID:16853364

  19. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions.

    PubMed

    Burke, Michael P; Goldsmith, C Franklin; Klippenstein, Stephen J; Welz, Oliver; Huang, Haifeng; Antonov, Ivan O; Savee, John D; Osborn, David L; Zádor, Judit; Taatjes, Craig A; Sheps, Leonid

    2015-07-16

    The present paper describes further development of the multiscale informatics approach to kinetic model formulation of Burke et al. (Burke, M. P.; Klippenstein, S. J.; Harding, L. B. Proc. Combust. Inst. 2013, 34, 547-555) that directly incorporates elementary kinetic theories as a means to provide reliable, physics-based extrapolation of kinetic models to unexplored conditions. Here, we extend and generalize the multiscale informatics strategy to treat systems of considerable complexity-involving multiwell reactions, potentially missing reactions, nonstatistical product branching ratios, and non-Boltzmann (i.e., nonthermal) reactant distributions. The methodology is demonstrated here for a subsystem of low-temperature propane oxidation, as a representative system for low-temperature fuel oxidation. A multiscale model is assembled and informed by a wide variety of targets that include ab initio calculations of molecular properties, rate constant measurements of isolated reactions, and complex systems measurements. Active model parameters are chosen to accommodate both "parametric" and "structural" uncertainties. Theoretical parameters (e.g., barrier heights) are included as active model parameters to account for parametric uncertainties in the theoretical treatment; experimental parameters (e.g., initial temperatures) are included to account for parametric uncertainties in the physical models of the experiments. RMG software is used to assess potential structural uncertainties due to missing reactions. Additionally, branching ratios among product channels are included as active model parameters to account for structural uncertainties related to difficulties in modeling sequences of multiple chemically activated steps. The approach is demonstrated here for interpreting time-resolved measurements of OH, HO2, n-propyl, i-propyl, propene, oxetane, and methyloxirane from photolysis-initiated low-temperature oxidation of propane at pressures from 4 to 60 Torr and

  20. Phase transformations of the FePO4 catalyst in the oxidative dehydrogenation to form an alkyl methacrylate

    NASA Astrophysics Data System (ADS)

    Khan, F. B.; Bharuth-Ram, K.; Friedrich, H. B.

    2010-04-01

    A phase specific iron orthophosphate catalyst, FePO4, was synthesized and subjected to oxidative dehydrogenation reactions to form an alkyl methacrylate. The phases of the catalyst, before and after the reactions, were characterized by Mössbauer spectroscopy. The Mössbauer spectra show the change of the catalyst precursor FePO4, tridymite-like phase (tdm), to the reduced form, iron(II) pyrophosphate, Fe2P2O7, and thereafter the phase change is governed by the temperatures of oxidation. X-ray diffraction and Mössbauer measurements on the spent catalyst, after using organic and water co-feeds, show a transformation of the catalyst to a mixture of phases which are condition specific.

  1. A versatile approach to flavones via a one-pot Pd(II)-catalyzed dehydrogenation/oxidative boron-Heck coupling sequence of chromanones.

    PubMed

    Lee, Jun; Yu, Jihyun; Son, Seung Hwan; Heo, Jinyuk; Kim, Taelim; An, Ji-Young; Inn, Kyung-Soo; Kim, Nam-Jung

    2016-01-14

    A variety of flavones were expediently synthesized from readily accessible chromanones via a one-pot sequence involving Pd(II)-catalyzed dehydrogenation and oxidative boron-Heck coupling with arylboronic acid pinacol esters. In particular, the use of arylboronic acid pinacol esters was found to significantly improve the yield of the reaction. PMID:26592753

  2. Chromium and Ruthenium-Doped Zinc Oxide Thin Films for Propane Sensing Applications

    PubMed Central

    Gómez-Pozos, Heberto; González-Vidal, José Luis; Torres, Gonzalo Alberto; Rodríguez-Baez, Jorge; Maldonado, Arturo; de la Luz Olvera, María; Acosta, Dwight Roberto; Avendaño-Alejo, Maximino; Castañeda, Luis

    2013-01-01

    Chromium and ruthenium-doped zinc oxide (ZnO:Cr) and (ZnO:Ru) thin solid films were deposited on soda-lime glass substrates by the sol-gel dip-coating method. A 0.6 M solution of zinc acetate dihydrate dissolved in 2-methoxyethanol and monoethanolamine was used as basic solution. Chromium (III) acetylacetonate and Ruthenium (III) trichloride were used as doping sources. The Ru incorporation and its distribution profile into the films were proved by the SIMS technique. The morphology and structure of the films were studied by SEM microscopy and X-ray diffraction measurements, respectively. The SEM images show porous surfaces covered by small grains with different grain size, depending on the doping element, and the immersions number into the doping solutions. The sensing properties of ZnO:Cr and ZnO:Ru films in a propane (C3H8) atmosphere, as a function of the immersions number in the doping solution, have been studied in the present work. The highest sensitivity values were obtained for films doped from five immersions, 5.8 and 900, for ZnO:Cr and ZnO:Ru films, respectively. In order to evidence the catalytic effect of the chromium (Cr) and ruthenium (Ru), the sensing characteristics of undoped ZnO films are reported as well. PMID:23482091

  3. A rapid compression machine study of the oxidation of propane in the negative temperature coefficient regime

    SciTech Connect

    Gallagher, S.M.; Curran, H.J.; Metcalfe, W.K.; Healy, D.; Simmie, J.M.; Bourque, G.

    2008-04-15

    The oxidation of propane has been studied in the temperature range 680-970 K at compressed gas pressures of 21, 27, and 37 atm and at varying equivalence ratios of 0.5, 1.0, and 2.0. These data are consistent with other experiments presented in the literature for alkane fuels in that, when ignition delay times are plotted as a function of temperature, a characteristic negative coefficient behavior is observed. In addition, these data were simulated using a detailed chemical kinetic model. It was found that qualitatively the model correctly simulated the effect of change in equivalence ratio and pressure, predicting that fuel-rich, high-pressure mixtures ignite fastest, while fuel-lean, low-pressure mixtures ignite slowest. Moreover, reactivity as a function of temperature is well captured, with the model predicting negative temperature coefficient behavior similar to the experiments. Quantitatively the model is faster than experiment for all mixtures at the lowest temperatures (650-750 K) and is also faster than experiment throughout the entire temperature range for fuel-lean mixtures. (author)

  4. Chromium and ruthenium-doped zinc oxide thin films for propane sensing applications.

    PubMed

    Gómez-Pozos, Heberto; González-Vidal, José Luis; Torres, Gonzalo Alberto; Rodríguez-Baez, Jorge; Maldonado, Arturo; Olvera, María de la Luz; Acosta, Dwight Roberto; Avendaño-Alejo, Maximino; Castañeda, Luis

    2013-01-01

    Chromium and ruthenium-doped zinc oxide (ZnO:Cr) and (ZnO:Ru) thin solid films were deposited on soda-lime glass substrates by the sol-gel dip-coating method. A 0.6 M solution of zinc acetate dihydrate dissolved in 2-methoxyethanol and monoethanolamine was used as basic solution. Chromium (III) acetylacetonate and Ruthenium (III) trichloride were used as doping sources. The Ru incorporation and its distribution profile into the films were proved by the SIMS technique. The morphology and structure of the films were studied by SEM microscopy and X-ray diffraction measurements, respectively. The SEM images show porous surfaces covered by small grains with different grain size, depending on the doping element, and the immersions number into the doping solutions. The sensing properties of ZnO:Cr and ZnO:Ru films in a propane (C3H8) atmosphere, as a function of the immersions number in the doping solution, have been studied in the present work. The highest sensitivity values were obtained for films doped from five immersions, 5.8 and 900, for ZnO:Cr and ZnO:Ru films, respectively. In order to evidence the catalytic effect of the chromium (Cr) and ruthenium (Ru), the sensing characteristics of undoped ZnO films are reported as well. PMID:23482091

  5. Propane Basics

    SciTech Connect

    NREL

    2010-03-01

    Propane powers about 190,000 vehicles in the U.S. and more than 14 million worldwide. Propane vehicles are a good choice for many fleet applications including school buses, shuttle buses, taxies and light-duty trucks.

  6. Propane Update.

    ERIC Educational Resources Information Center

    Brantner, Max

    1984-01-01

    Reports on a northern Illinois school bus fleet converted to propane fuel in 1981 and 1982. Includes tables showing, first, total annual fuel costs before and after conversion and, second, fuel efficiency for 16 buses using propane and three using gasoline. Notes precautions for propane use. (MCG)

  7. New insights into low-temperature oxidation of propane from synchrotron photoionization mass spectrometry and multi-scale informatics modeling

    DOE PAGESBeta

    Welz, Oliver; Burke, Michael P.; Antonov, Ivan O.; Goldsmith, C. Franklin; Savee, John David; Osborn, David L.; Taatjes, Craig A.; Klippenstein, Stephen J.; Sheps, Leonid

    2015-04-10

    We studied low-temperature propane oxidation at P = 4 Torr and T = 530, 600, and 670 K by time-resolved multiplexed photoionization mass spectrometry (MPIMS), which probes the reactants, intermediates, and products with isomeric selectivity using tunable synchrotron vacuum UV ionizing radiation. The oxidation is initiated by pulsed laser photolysis of oxalyl chloride, (COCl)2, at 248 nm, which rapidly generates a ~1:1 mixture of 1-propyl (n-propyl) and 2-propyl (i-propyl) radicals via the fast Cl + propane reaction. At all three temperatures, the major stable product species is propene, formed in the propyl + O2 reactions by direct HO2 elimination frommore » both n- and i-propyl peroxy radicals. The experimentally derived propene yields relative to the initial concentration of Cl atoms are (20 ± 4)% at 530 K, (55 ± 11)% at 600 K, and (86 ± 17)% at 670 K at a reaction time of 20 ms. The lower yield of propene at low temperature reflects substantial formation of propyl peroxy radicals, which do not completely decompose on the experimental time scale. In addition, C3H6O isomers methyloxirane, oxetane, acetone, and propanal are detected as minor products. Our measured yields of oxetane and methyloxirane, which are coproducts of OH radicals, suggest a revision of the OH formation pathways in models of low-temperature propane oxidation. The experimental results are modeled and interpreted using a multiscale informatics approach, presented in detail in a separate publication (Burke, M. P.; Goldsmith, C. F.; Klippenstein, S. J.; Welz, O.; Huang H.; Antonov I. O.; Savee J. D.; Osborn D. L.; Zádor, J.; Taatjes, C. A.; Sheps, L. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions. J. Phys. Chem A. 2015, DOI: 10.1021/acs.jpca.5b01003). Additionally, we found that the model predicts the time profiles and yields of the experimentally observed primary products well, and shows satisfactory agreement for products

  8. New insights into low-temperature oxidation of propane from synchrotron photoionization mass spectrometry and multi-scale informatics modeling

    SciTech Connect

    Welz, Oliver; Burke, Michael P.; Antonov, Ivan O.; Goldsmith, C. Franklin; Savee, John David; Osborn, David L.; Taatjes, Craig A.; Klippenstein, Stephen J.; Sheps, Leonid

    2015-04-10

    We studied low-temperature propane oxidation at P = 4 Torr and T = 530, 600, and 670 K by time-resolved multiplexed photoionization mass spectrometry (MPIMS), which probes the reactants, intermediates, and products with isomeric selectivity using tunable synchrotron vacuum UV ionizing radiation. The oxidation is initiated by pulsed laser photolysis of oxalyl chloride, (COCl)2, at 248 nm, which rapidly generates a ~1:1 mixture of 1-propyl (n-propyl) and 2-propyl (i-propyl) radicals via the fast Cl + propane reaction. At all three temperatures, the major stable product species is propene, formed in the propyl + O2 reactions by direct HO2 elimination from both n- and i-propyl peroxy radicals. The experimentally derived propene yields relative to the initial concentration of Cl atoms are (20 ± 4)% at 530 K, (55 ± 11)% at 600 K, and (86 ± 17)% at 670 K at a reaction time of 20 ms. The lower yield of propene at low temperature reflects substantial formation of propyl peroxy radicals, which do not completely decompose on the experimental time scale. In addition, C3H6O isomers methyloxirane, oxetane, acetone, and propanal are detected as minor products. Our measured yields of oxetane and methyloxirane, which are coproducts of OH radicals, suggest a revision of the OH formation pathways in models of low-temperature propane oxidation. The experimental results are modeled and interpreted using a multiscale informatics approach, presented in detail in a separate publication (Burke, M. P.; Goldsmith, C. F.; Klippenstein, S. J.; Welz, O.; Huang H.; Antonov I. O.; Savee J. D.; Osborn D. L.; Zádor, J.; Taatjes, C. A.; Sheps, L. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions. J. Phys. Chem A. 2015, DOI: 10.1021/acs.jpca.5b01003). Additionally, we found that the model predicts the time profiles and yields of the experimentally observed primary products well

  9. Effect of the conditions of preparing mixed oxide catalyst of Mo-V-Te-Nb-O composition on its activity in the oxidative dehydrogenation of ethane

    NASA Astrophysics Data System (ADS)

    Finashina, E. D.; Kucherov, A. V.; Kustov, L. M.

    2013-12-01

    It is shown that catalytic activity of mixed oxide catalyst of Mo-V-Te-Nb-O composition in oxidative dehydrogenation (OD) of ethane is determined to a substantial degree by the Nb-to-(C2O4)2- ratio in niobium-containing precursors. A pH value of 2.8 to 3.0 for a mixture is optimal when conducting the hydrothermal synthesis of a mixed oxide catalyst; this is achieved by using oxaloniobic acid as a niobium-containing precursor. It is determined that substituting antimony for tellurium results in a loss of catalyst activity during the OD of ethane. The optimum Te content in a catalyst is 0.17 mol %.

  10. Reversible catalytic dehydrogenation of alcohols for energy storage

    PubMed Central

    Bonitatibus, Peter J.; Chakraborty, Sumit; Doherty, Mark D.; Siclovan, Oltea; Jones, William D.; Soloveichik, Grigorii L.

    2015-01-01

    Reversibility of a dehydrogenation/hydrogenation catalytic reaction has been an elusive target for homogeneous catalysis. In this report, reversible acceptorless dehydrogenation of secondary alcohols and diols on iron pincer complexes and reversible oxidative dehydrogenation of primary alcohols/reduction of aldehydes with separate transfer of protons and electrons on iridium complexes are shown. This reactivity suggests a strategy for the development of reversible fuel cell electrocatalysts for partial oxidation (dehydrogenation) of hydroxyl-containing fuels. PMID:25588879

  11. Electrochemical promotion of propane oxidation on Pt deposited on a dense β″-Al2O3 ceramic Ag+ conductor

    PubMed Central

    Tsampas, Mihalis N.; Kambolis, Anastasios; Obeid, Emil; Lizarraga, Leonardo; Sapountzi, Foteini M.; Vernoux, Philippe

    2013-01-01

    A new kind of electrochemical catalyst based on a Pt porous catalyst film deposited on a β″-Al2O3 ceramic Ag+ conductor was developed and evaluated during propane oxidation. It was observed that, upon anodic polarization, the rate of propane combustion was significantly electropromoted up to 400%. Moreover, for the first time, exponential increase of the catalytic rate was evidenced during galvanostatic transient experiment in excellent agreement with EPOC equation. PMID:24790942

  12. Propane fear

    SciTech Connect

    Begley, R.

    1992-02-12

    A minor feature of a Congressional energy bill is causing consternation for a number of propane-consuming chemical companies. The firms are fighting the bill`s inclusion of liquefied petroleum gas (LPG) on a list of alternative fuels that can be used to meet its urban fleet vehicles requirements. The firms fear that this added use would drive up the price of propane-an LPG-for homeowners, farmers, and themselves. Speaking for the Propane Consumers Coalition, a Dow Chemical spokesman says 7.7 million households use propane, as does agriculture, and current demand is such that December saw a 23-year low in US inventories. The US depends on imports of propane, he says, and about half the propane sold in the US is derived from the refining of oil, much of which is also imported. Adding demand for vehicle fuel would drive up imports and process, the spokesman says, thereby damaging all users, including the petrochemical industry.

  13. Effects of CeO2 Support Facets on VOx/CeO2 Catalysts in Oxidative Dehydrogenation of Methanol

    SciTech Connect

    Li, Yan; Wei, Zhehao; Gao, Feng; Kovarik, Libor; Peden, Charles HF; Wang, Yong

    2014-05-13

    CeO2 supports with dominating facets, i.e., low index (100), (110) and (111) facets, are prepared. The facet effects on the structure and catalytic performance of supported vanadium oxide catalysts are investigated using oxidative dehydrogenation of methanol as a model reaction. In the presence of mixed facets, Infrared and Raman characterizations demonstrate that surface vanadia species preferentially deposit on CeO2 (100) facets, presumably because of its higher surface energy. At the same surface vanadium densities, VOx species on (100) facets show better dispersion, followed by (110) and (111) facets. The VOx species on CeO2 nanorods with (110) and (100) facets display higher activity and lower apparent activation energies compared to that on CeO2 nanopolyhedras with dominating (111) facets and CeO2 nanocubes with dominating (100) facets. The higher activity for VOx/CeO2(110) might be related to the more abundant oxygen vacancies present on the (110) facets, evidenced from Raman spectroscopic measurements.

  14. Identifying Different Types of Catalysts for CO2 Reduction by Ethane through Dry Reforming and Oxidative Dehydrogenation.

    PubMed

    Porosoff, Marc D; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping; Chen, Jingguang G

    2015-12-14

    The recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2 ) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2 ). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2 C-based materials preserve the CC bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions. PMID:26554872

  15. Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation

    DOE PAGESBeta

    Marc D. Porosoff; Chen, Jingguang G.; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping

    2015-11-10

    In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of thismore » study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.« less

  16. Identifying different types of catalysts for CO2 reduction by ethane through dry reforming and oxidative dehydrogenation

    SciTech Connect

    Marc D. Porosoff; Chen, Jingguang G.; Myint, Myat Noe Zin; Kattel, Shyam; Xie, Zhenhua; Gomez, Elaine; Liu, Ping

    2015-11-10

    In this study, the recent shale gas boom combined with the requirement to reduce atmospheric CO2 have created an opportunity for using both raw materials (shale gas and CO2) in a single process. Shale gas is primarily made up of methane, but ethane comprises about 10 % and reserves are underutilized. Two routes have been investigated by combining ethane decomposition with CO2 reduction to produce products of higher value. The first reaction is ethane dry reforming which produces synthesis gas (CO+H2). The second route is oxidative dehydrogenation which produces ethylene using CO2 as a soft oxidant. The results of this study indicate that the Pt/CeO2 catalyst shows promise for the production of synthesis gas, while Mo2C-based materials preserve the C—C bond of ethane to produce ethylene. These findings are supported by density functional theory (DFT) calculations and X-ray absorption near-edge spectroscopy (XANES) characterization of the catalysts under in situ reaction conditions.

  17. Surface Termination of M1 Phase and Rational Design of Propane Ammoxidation Catalysts

    SciTech Connect

    Guliants, Vadim

    2015-02-16

    This final report describes major accomplishments in this research project which has demonstrated that the M1 phase is the only crystalline phase required for propane ammoxidation to acrylonitrile and that a surface monolayer terminating the ab planes of the M1 phase is responsible for their activity and selectivity in this reaction. Fundamental studies of the topmost surface chemistry and mechanism of propane ammoxidation over the Mo-V-(Te,Sb)-(Nb,Ta)-O M1 and M2 phases resulted in the development of quantitative understanding of the surface molecular structure – reactivity relationships for this unique catalytic system. These oxides possess unique catalytic properties among mixed metal oxides, because they selectively catalyze three alkane transformation reactions, namely propane ammoxidation to acrylonitrile, propane oxidation to acrylic acid and ethane oxidative dehydrogenation, all of considerable economic significance. Therefore, the larger goal of this research was to expand this catalysis to other alkanes of commercial interest, and more broadly, demonstrate successful approaches to rational design of improved catalysts that can be applied to other selective (amm)oxidation processes.

  18. An approach to benzophosphole oxides through silver- or manganese-mediated dehydrogenative annulation involving C-C and C-P bond formation.

    PubMed

    Unoh, Yuto; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

    2013-12-01

    Benzophosphole construction was achieved through the Ag(I) -mediated dehydrogenative annulation of phenylphosphine oxides with internal alkynes in a process involving CC and CP bond formation. A wide range of asymmetrical phenylacetylenes could be employed and the reactions proceeded with perfect regioselectivity. Moreover, the annulation could be conducted even at room temperature when a Mn(III) promoter was used in place of Ag(I) . PMID:24127410

  19. Radical-radical interactions among oxidized guanine bases including guanine radical cation and dehydrogenated guanine radicals.

    PubMed

    Zhao, Jing; Wang, Mei; Yang, Hongfang; Zhang, Meng; Liu, Ping; Bu, Yuxiang

    2013-09-19

    We present here a theoretical investigation of the structural and electronic properties of di-ionized GG base pairs (G(•+)G(•+),G(-H1)(•)G(•+), and G(-H1)(•)G(-H1)(•)) consisting of the guanine cation radical (G(•+)) and/or dehydrogenated guanine radical (G(-H1)(•)) using density functional theory calculations. Different coupling modes (Watson-Crick/WC, Hoogsteen/Hoog, and minor groove/min hydrogen bonding, and π-π stacking modes) are considered. We infer that a series of G(•+)G(•+) complexes can be formed by the high-energy radiation. On the basis of density functional theory and complete active space self-consistent (CASSCF) calculations, we reveal that in the H-bonded and N-N cross-linked modes, (G(•+)G(•+))WC, (G(-H1)(•)G(-H1)(•))WC, (G(-H1)(•)G(-H1)(•))minI, and (G(-H1)(•)G(-H1)(•))minIII have the triplet ground states; (G(•+)G(•+))HoogI, (G(-H1)(•)G(•+))WC, (G(-H1)(•)G(•+))HoogI, (G(-H1)(•)G(•+))minI, (G(-H1)(•)G(•+))minII, and (G(-H1)(•)G(-H1)(•))minII possess open-shell broken-symmetry diradical-characterized singlet ground states; and (G(•+)G(•+))HoogII, (G(•+)G(•+))minI, (G(•+)G(•+))minII, (G(•+)G(•+))minIII, (G(•+)G(•+))HoHo, (G(-H1)(•)G(•+))minIII, (G(-H1)(•)G(•+))HoHo, and (G(-H1)(•)G(-H1)(•))HoHo are the closed-shell systems. For these H-bonded diradical complexes, the magnetic interactions are weak, especially in the diradical G(•+)G(•+) series and G(-H1)(•)G(-H1)(•) series. The magnetic coupling interactions of the diradical systems are controlled by intermolecular interactions (H-bond, electrostatic repulsion, and radical coupling). The radical-radical interaction in the π-π stacked di-ionized GG base pairs ((G(•+)G(•+))ππ, (G(-H1)(•)G(•+))ππ, and (G(-H1)(•)G(-H1)(•))ππ) are also considered, and the magnetic coupling interactions in these π-π stacked base pairs are large. This is the first theoretical prediction that some di

  20. High-temperature catalytic oxidative conversion of propane to propylene and ethylene involving coupling of exothermic and endothermic reactions

    SciTech Connect

    Choudhary, V.R.; Rane, V.H.; Rajput, A.M.

    2000-04-01

    Coupling of the exothermic catalytic oxidative conversion and endothermic thermal cracking (noncatalytic) reactions of propane to propylene and ethylene over the SrO/La{sub 2}O{sub 3}/SA5205 catalyst in the presence of steam and limited oxygen was investigated at different process conditions (temperature, 700--850 C; C{sub 3}H{sub 8}/O{sub 2} ratio in feed, 2.0--8.0; H{sub 2}O/C{sub 3}H{sub 8} ratio, 0.5--2.5; space velocity, 2,000--15,000 cm{sup 3}/g h). In the presence of steam and limited O{sub 2}, the endothermic thermal cracking and exothermic oxidative conversion reactions occur simultaneously and there is no coke formation on the catalyst. Because of the direct coupling of exothermic and endothermic reactions, this process occurs in a most energy efficient and safe manner. The propane conversion, selectivity for propylene, and net heat of reaction ({Delta}H{sub r}) in the process are strongly influenced by the temperature and concentration of O{sub 2} relative to the propane in the feed. The C{sub 3}H{sub 6}/C{sub 2}H{sub 4} product ratio is also strongly influenced by the temperature, C{sub 3}H{sub 8}/O{sub 2} feed ratio, and space velocity. The net heat of reaction can be controlled by manipulating the reaction temperature and C{sub 3}H{sub 8}/O{sub 2} ratio in the feed; the process exothermicity is reduced drastically with increasing the temperature and/or C{sub 3}H{sub 8}/O{sub 2} feed ratio.

  1. Effect of Sodium on the Catalytic Properties of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol

    SciTech Connect

    Li, Yan; Wei, Zhehao; Sun, Junming; Gao, Feng; Peden, Charles HF; Wang, Yong

    2013-03-21

    A series of VOx/CeO2 catalysts with various sodium loadings (Na/V ratio from 0 to 1) has been studied for oxidative dehydrogenation (ODH) of methanol. The effect of sodium on the surface structure, redox properties, and surface acidity/basicity of VOx/CeO2 was investigated using hydrogen temperature-programmed reduction (H2-TPR), Raman spectroscopy, and Diffuse Reflectance Infrared Fourier Transform spectroscopy (DRIFT). The experimental results indicate that the effect of sodium on VOx/CeO2 is highly dependent on the Na/V ratio. At a low Na/V ratio (Na/V<0.25), sodium addition only slightly decreases the redox properties of VOx/CeO2 and has little effect on its activity and selectivity to formaldehyde, even though the Brönsted acidity is almost completely eliminated at a Na/V ratio of 0.25. At a high Na/V ratio (Na/V>0.25), sodium addition greatly alters the nature of the active sites by V-O-Ce bond cleavage and V-O-Na bond formation, leading to significantly reduced activity of the VOx/CeO2 catalysts. At Na/V>0.25, the selectivity to formaldehyde also decreases with increasing Na/V ratio due to: (1) the suppressed reducibility of VOx, and (2) increased basicity leading to increased CO2.

  2. Development of an oxidative dehydrogenation-based fluorescent probe for Cu2+ and its biological imaging in living cells.

    PubMed

    Fan, Jiangli; Liu, Xiaojian; Hu, Mingming; Zhu, Hao; Song, Fengling; Peng, Xiaojun

    2012-07-20

    Based on a boron dipyrromethene (BODIPY) derivative containing an N, O and S tridentate ligand, a Cu(2+) fluorescent probe BTCu was developed. The detection mechanism was verified as Cu(2+)-promoted oxidative dehydrogenation of an amine moiety, leading to a formation of a fluorescent Cu(+)-Schiff base complex. Free BTCu exhibited a maximum absorption wavelength at 496 nm, and a very weak maximum emission at 511 nm. Upon addition of various metals ions, it showed large fluorescence enhancement toward Cu(2+) (417-fold in MeCN and 103-fold in MeCN/HEPES solution, respectively) with high selectivity. The detection limits are as low as 1.74×10(-8) M and 4.96×10(-8) M in the two different solutions, respectively. And BTCu could work in a wide pH range with an extraordinary low pK(a) of 1.21±0.06. Using fluorescence microscopy, the probe was shown to be capable of penetrating into living cells and imaging intracellular Cu(2+) changes. PMID:22713923

  3. A La-doped Mg-Al mixed metal oxide supported copper catalyst with enhanced catalytic performance in transfer dehydrogenation of 1-decanol.

    PubMed

    Zhang, Ming; Zhao, Yajie; Liu, Qian; Yang, Lan; Fan, Guoli; Li, Feng

    2016-01-21

    In the present work, a La-doped Mg-Al mixed metal oxide supported copper catalyst (Cu/La-MgAlO) was synthesized through a layered double hydroxide precursor route. The materials were characterized by powder X-ray diffraction, transmission electron microscopy, CO2-temperature programmed desorption, Fourier transform infrared spectra of CO2 absorption, and X-ray photoelectron spectroscopy. The results revealed that the introduction of a trace amount of La could significantly improve the surface basicity of the Cu/La-MgAlO catalyst, especially strong Lewis basicity. Compared with the undoped supported Cu catalyst, Cu/La-MgAlO exhibited much higher activity and selectivity in the liquid-phase transfer dehydrogenation of 1-decanol with a 1-decanal yield up to 89%. The excellent catalytic efficiency was mainly ascribed to the surface cooperation between the Lewis basic sites and the adjacent Cu(0)/Cu(+) species. That is, basic sites, especially strong-strength basic sites, held the key to the abstraction of protons from the hydroxyl group in 1-decanol, while the adjacent Cu(0) and Cu(+) species were responsible for the hydrogen transfer and the adsorption of styrene in the transfer dehydrogenation and hydrogenation reactions, respectively. This study provides a new method for designing cost-effective supported copper-based catalysts highly efficient for the transfer dehydrogenation of primary aliphatic alcohols by modifying the surface basicity of metal oxide supports. PMID:26659760

  4. Biodegradation of the gasoline oxygenates methyl tert-butyl ether, ethyl tert-butyl ether, and tert-amyl methyl ether by propane-oxidizing bacteria.

    PubMed Central

    Steffan, R J; McClay, K; Vainberg, S; Condee, C W; Zhang, D

    1997-01-01

    Several propane-oxidizing bacteria were tested for their ability to degrade gasoline oxygenates, including methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). Both a laboratory strain and natural isolates were able to degrade each compound after growth on propane. When propane-grown strain ENV425 was incubated with 20 mg of uniformly labeled [14C]MTBE per liter, the strain converted > 60% of the added MTBE to 14CO2 in < 30 h. The initial oxidation of MTBE and ETBE resulted in the production of nearly stoichiometric amounts of tert-butyl alcohol (TBA), while the initial oxidation of TAME resulted in the production of tert-amyl alcohol. The methoxy methyl group of MTBE was oxidized to formaldehyde and ultimately to CO2. TBA was further oxidized to 2-methyl-2-hydroxy-1-propanol and then 2-hydroxy isobutyric acid; however, neither of these degradation products was an effective growth substrate for the propane oxidizers. Analysis of cell extracts of ENV425 and experiments with enzyme inhibitors implicated a soluble P-450 enzyme in the oxidation of both MTBE and TBA. MTBE was oxidized to TBA by camphor-grown Pseudomonas putida CAM, which produces the well-characterized P-450cam, but not by Rhodococcus rhodochrous 116, which produces two P-450 enzymes. Rates of MTBE degradation by propane-oxidizing strains ranged from 3.9 to 9.2 nmol/min/mg of cell protein at 28 degrees C, whereas TBA was oxidized at a rate of only 1.8 to 2.4 nmol/min/mg of cell protein at the same temperature. PMID:9361407

  5. Kinetics of Hydrogen Oxidation Downstream of Lean Propane and Hydrogen Flames

    NASA Technical Reports Server (NTRS)

    Fine, Burton

    1961-01-01

    The decay of hydrogen was measured downstream of lean, flat, premixed hydrogen and propane-air flames seated on cooled porous burners. Experimental variables included temperature, pressure, initial equivalence ratio and diluent. Sampling of burned gas was done through uncooled quartz orifice probes, and the analysis was based on gas chromatography. An approximate treatment of the data in which diffusion was neglected led to the following rate expression for the zone downstream of hydrogen flames d[H (sub 2)] divided by (d times t) equals 1.7 times 10 (sup 10) [H (sub 2)] (sup 3) divided by (sub 2) [O (sub 2)]e (sup (-8100 divided by RT)) moles per liters per second. On the basis of a rate expression of this form, the specific rate constant for the reaction downstream of hydrogen flames was about three times as great as that determined downstream of propane flames. This result was explained on the basis of the existence of a steady state between hydrogen and carbon monoxide in the burned gas downstream of propane flames.

  6. Detailed modeling of low-temperature propane oxidation: 1. The role of the propyl + O(2) reaction.

    PubMed

    Huynh, Lam K; Carstensen, Hans-Heinrich; Dean, Anthony M

    2010-06-24

    Accurate description of reactions between propyl radicals and molecular oxygen is an essential prerequisite for modeling of low-temperature propane oxidation because their multiple reaction pathways either accelerate the oxidation process via chain branching or inhibit it by forming relatively stable products. The CBS-QB3 level of theory was used to construct potential energy surfaces for n-C(3)H(7) + O(2) and i-C(3)H(7) + O(2). High-pressure rate constants were calculated using transition state theory with corrections for tunneling and hindered rotations. These results were used to derive pressure- and temperature-dependent rate constants for the various channels of these reactions under the framework of the Quantum Rice-Ramsperger-Kassel (QRRK) and the modified strong collision (MSC) theories. This procedure resulted in a thermodynamically consistent C(3)H(7) + O(2) submechanism, which was either used directly or as part of a larger extended detailed kinetic mechanism to predict the loss of propyl and the product yields of propylene and HO(2) over a wide range of temperatures, pressures, and residence times. The overall good agreement between predicted and experimental data suggests that this reaction subset is reliable and should be able to properly account for the reactions of propyl radicals with O(2) in propane oxidation. It is also demonstrated that for most conditions of practical interest only a small subset of reactions (e.g., isomerization, concerted elimination of HO(2), and stabilization) controls the oxidation kinetics, which makes it possible to considerably simplify the mechanism. Moreover, we observed strong similarities in the rate coefficients within each reaction class, suggesting the potential for development of relatively simple rate constant estimation rules that could be applied to analogous reactions involving hydrocarbon radicals that are too large to allow accurate detailed electronic structure calculations. PMID:20509639

  7. Deactivation of a mixed oxide catalyst of Mo-V-Te-Nb-O composition in the reaction of oxidative ethane dehydrogenation

    NASA Astrophysics Data System (ADS)

    Mishanin, I. I.; Kalenchuk, A. N.; Maslakov, K. I.; Lunin, V. V.; Koklin, A. E.; Finashina, E. D.; Bogdan, V. I.

    2016-06-01

    The operational stability of a mixed oxide catalyst of Mo-V-Te-Nb-O composition in the oxidative dehydrogenation of ethane (ratio of C2H6: O2 = 3: 1) is studied in a flow reactor at temperatures of 340-400°C, a pressure of 1 atm, and a WHSV of the feed mixture of 800 h-1. It is found that the selectivity toward ethylene is 98% at 340°C, but the conversion of ethane at this temperature is only 6%; when the temperature is raised to 400°C, the conversion of ethane is increased to 37%, while the selectivity toward ethylene is reduced to 85%. Using physical and chemical means (XPS, SEM), it is found that the lack of oxidant in the reaction mixture leads to irreversible changes in the catalyst, i.e., reduced selectivity and activity. Raising the reaction temperature to 400°C allows the reduction of tellurium by ethane, from the +6 oxidation state to the zerovalent state, with its subsequent sublimation and the destruction of the catalytically active and selective phase; in its characteristics, the catalyst becomes similar to the Mo-V-Nb-O system containing no tellurium.

  8. Oxidative dehydrogenation of cyclohexene on size selected subnanometer cobalt clusters: improved catalytic performance via structural fluxionality of cluster-assembled nanostructures.

    SciTech Connect

    Lee, S.; Di Vece, M.; Lee, B.; Seifert, S.; Winans, R. E.; Vajda, S.

    2012-01-01

    The catalytic activity of oxide-supported metal nanoclusters strongly depends on their size and support. In this study, the origin of morphology transformation and chemical state changes during the oxidative dehydrogenation of cyclohexene was investigated in terms of metal-support interactions. Model catalyst systems were prepared by deposition of size selected subnanometer Co{sub 27{+-}4} clusters on various metal oxide supports (Al{sub 2}O{sub 3}, ZnO and TiO{sub 2} and MgO). The oxidation state and reactivity of the supported cobalt clusters were investigated by temperature programmed reaction (TPRx) and in situ grazing incidence X-ray absorption (GIXAS) during oxidative dehydrogenation of cyclohexene, while the sintering resistance monitored with grazing incidence small angle X-ray scattering (GISAXS). The activity and selectivity of cobalt clusters shows strong dependence on the support. GIXAS reveals that metal-support interaction plays a key role in the reaction. The most pronounced support effect is observed for MgO, where during the course of the reaction in its activity, composition and size dynamically evolving nanoassembly is formed from subnanometer cobalt clusters.

  9. Chiral Brønsted Acid Catalyzed Enantioselective Phosphonylation of Allylamine via Oxidative Dehydrogenation Coupling.

    PubMed

    Cheng, Ming-Xing; Ma, Ran-Song; Yang, Qiang; Yang, Shang-Dong

    2016-07-01

    A new strategy for the synthesis of chiral α-amino phosphonates by enantioselective C-H phosphonylation of allylamine with phosphite in the presence of a chiral Brønsted acid catalyst has been developed. This protocol successfully integrates direct C-H oxidation with asymmetric phosphonylation and exhibits high enantioselectivity. PMID:27331612

  10. Niobium phosphates as new highly selective catalysts for the oxidative dehydrogenation of ethane.

    PubMed

    Weng, Weihao; Davies, Mathew; Whiting, Gareth; Solsona, Benjamin; Kiely, Christopher J; Carley, Albert F; Taylor, Stuart H

    2011-10-14

    Several niobium phosphate phases have been prepared, fully characterized and tested as catalysts for the selective oxidation of ethane to ethylene. Three distinct niobium phosphate catalysts were prepared, and each was comprised predominantly of a different bulk phase, namely Nb(2)P(4)O(15), NbOPO(4) and Nb(1.91)P(2.82)O(12). All of the niobium phosphate catalysts showed high selectivity towards ethylene, but the best catalyst was Nb(1.91)P(2.82)O(12), which was produced from the reduction of niobium oxide phosphate (NbOPO(4)) by hydrogen. It was particularly selective for ethylene, giving ca. 95% selectivity at 5% conversion, decreasing to ca. 90% at 15% conversion, and only produced low levels of carbon oxides. It was also determined that the only primary product from ethane oxidation over this catalyst was ethylene. Catalyst activity also increased with time-on-line, and this behaviour was ascribed to an increase of the concentration of the Nb(1.91)P(2.82)O(12) phase, as partially transformed NbOPO(4), formed during preparation, was converted to Nb(1.91)P(2.82)O(12) during use. Catalysts with predominant phases of Nb(2)P(4)O(15) and NbOPO(4) also showed appreciable activity and selectivities to ethylene with values around 75% and 85% respectively at 5% ethane conversion. The presence of phosphorous is required to achieve high ethylene selectivity, as orthorhombic and monoclinic Nb(2)O(5) catalysts showed similar activity, but displayed selectivities to ethylene that were <20% under the same reaction conditions. To the best of our knowledge, this is the first time that niobium phosphates have been shown to be highly selective catalysts for the oxidation of ethane to ethylene, and demonstrates that they are worthy candidates for further study. PMID:21881631

  11. A biomimetic pathway for vanadium-catalyzed aerobic oxidation of alcohols: evidence for a base-assisted dehydrogenation mechanism.

    PubMed

    Wigington, Bethany N; Drummond, Michael L; Cundari, Thomas R; Thorn, David L; Hanson, Susan K; Scott, Susannah L

    2012-11-19

    The first step in the catalytic oxidation of alcohols by molecular O(2), mediated by homogeneous vanadium(V) complexes [LV(V)(O)(OR)], is ligand exchange. The unusual mechanism of the subsequent intramolecular oxidation of benzyl alcoholate ligands in the 8-hydroxyquinolinato (HQ) complexes [(HQ)(2)V(V)(O)(OCH(2)C(6)H(4)-p-X)] involves intermolecular deprotonation. In the presence of triethylamine, complex 3 (X = H) reacts within an hour at room temperature to generate, quantitatively, [(HQ)(2)V(IV)(O)], benzaldehyde (0.5 equivalents), and benzyl alcohol (0.5 equivalents). The base plays a key role in the reaction: in its absence, less than 12% conversion was observed after 72 hours. The reaction is first order in both 3 and NEt(3), with activation parameters ΔH(≠)=(28±4) kJ mol(-1) and ΔS(≠)=(-169±4) J K(-1)  mol(-1). A large kinetic isotope effect, 10.2±0.6, was observed when the benzylic hydrogen atoms were replaced by deuterium atoms. The effect of the para substituent of the benzyl alcoholate ligand on the reaction rate was investigated using a Hammett plot, which was constructed using σ(p). From the slope of the Hammett plot, ρ=+(1.34±0.18), a significant buildup of negative charge on the benzylic carbon atom in the transition state is inferred. These experimental findings, in combination with computational studies, support an unusual bimolecular pathway for the intramolecular redox reaction, in which the rate-limiting step is deprotonation at the benzylic position. This mechanism, that is, base-assisted dehydrogenation (BAD), represents a biomimetic pathway for transition-metal-mediated alcohol oxidations, differing from the previously identified hydride-transfer and radical pathways. It suggests a new way to enhance the activity and selectivity of vanadium catalysts in a wide range of redox reactions, through control of the outer coordination sphere. PMID:23080554

  12. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

    SciTech Connect

    Zhang, Li; Wu, Zili; Nelson, Nicholas; Sadow, Aaron D.; Slowing, Igor I.; Overbury, Steven H.

    2015-09-22

    Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODH reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.

  13. The role of CO2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

    DOE PAGESBeta

    Zhang, Li; Wu, Zili; Nelson, Nicholas; Sadow, Aaron D.; Slowing, Igor I.; Overbury, Steven H.

    2015-09-22

    Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

  14. Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols.

    PubMed

    Gianetti, Thomas L; Annen, Samuel P; Santiso-Quinones, Gustavo; Reiher, Markus; Driess, Matthias; Grützmacher, Hansjörg

    2016-01-26

    The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2 and water are the only by-products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh-H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate. PMID:26693955

  15. The first example of a centro-symmetrical bis(imido)-bridged dinuclear cobalt(III) complex: synthesis via oxidative dehydrogenation and phenoxazinone synthase activity.

    PubMed

    Panja, Anangamohan; Guionneau, Philippe

    2013-04-14

    A bis(imido)-bridged dinuclear cobalt(III) complex, [Co2(amp)2(μ-imp)2Cl2]Cl2·2H2O () [amp = 2-aminomethylpyridine; imp = 2-iminomethylpyridine anion], was synthesized by the reaction of cobalt(II) chloride with 2-aminomethylpyridine in the presence of alkaline hydrogen peroxide at room temperature. X-ray crystallography reveals that both the metal centres in the molecule are related to each other through an inversion centre, and the geometry of each of the Co(III) ions is a distorted octahedral structure having a CoN5Cl coordination environment. The most important feature of the structure is the modification of half of the coordinated amines by the oxidative dehydrogenation process which involves double bridging in the complex cation. To the best of our knowledge, this is the first example of a bis(imido)-bridged dinuclear cobalt(III) complex derived from metal-assisted oxidative dehydrogenation of the coordinated primary amine ligand. Complex was found to be an excellent functional model for the phenoxazinone synthase, catalyzing the oxidative coupling of 2-aminophenol to the corresponding 2-aminophenoxazinone chromophore in dioxygen saturated methanol. The detailed kinetic investigations reveal that the phenoxazinone chromophore is produced via a potential complex-substrate intermediate. PMID:23396321

  16. Mg3(VO4)2-MgO-ZrO2 nano-catalysts for oxidative dehydrogenation of n-butane.

    PubMed

    Lee, Jong Kwon; Seo, Hyun; Hong, Ung Gi; Yoo, Yeonshick; Cho, Young-Jin; Lee, Jinsuk; Park, Gle; Chang, Hosik; Song, In Kyu

    2014-11-01

    A series of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts with different vanadium content (X = 3.3, 5.3, 7.0, 10.2, and 13.4) were prepared by a single-step citric acid-derived sol-gel method for use in the oxidative dehydrogenation of n-butane to n-butene and 1,3-butadiene. The effect of vanadium content of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts on their physicochemical properties and catalytic activities in the oxidative dehydrogenation of n-butane was investigated. Successful formation of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts was confirmed by XRD, Raman spectroscopy, and ICP-AES analyses. The catalytic performance of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts strongly depended on vanadium content. All the X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts showed a stable catalytic performance without catalyst deactivation during the reaction. Among the catalysts tested, 7.0-Mg3(VO4)2-MgO-ZrO2 nano-catalyst showed the best catalytic performance in terms of yield for total dehydrogenation products (TDP, n-butene and 1,3-butadiene). TPRO (temperature-programmed reoxidation) experiments were carried out to measure the oxygen capacity of the catalyst. Experimental results revealed that oxygen capacity of the catalyst was closely related to the catalytic performance. Yield for TDP increased with increasing oxygen capacity of the catalyst. PMID:25958621

  17. Oxidative dehydrogenation of n-butane over magnesium vanadate nano-catalysts supported on magnesia-zirconia: effect of vanadium content.

    PubMed

    Lee, Jong Kwon; Hong, Ung Gi; Yoo, Yeonshick; Cho, Young-Jin; Lee, Jinsuk; Chang, Hosik; Song, In Kyu

    2013-12-01

    Magnesia-zirconia (MgO-ZrO2) support was prepared by a sol-gel method, and magnesium vanadate nano-catalysts supported on magnesia-zirconia (X-Mg3(VO4)2/MgO-ZrO2) were then prepared by a wet impregnation method with a variation of vanadium content (X = 6.6, 9.9, 12.8, 15.2, and 19.1 wt%). X-Mg3(VO4)2/MgO-ZrO2 nano-catalysts were applied to the oxidative dehydrogenation of n-butane to n-butene and 1,3-butadiene. The formation of X-Mg3(VO4)2/MgO-ZrO2 nano-catalysts was well confirmed by XRD, XPS, and ICP-AES analyses. 15.2-Mg3(VO4)2/MgO-ZrO2 and 19.1-Mg3(VO4)2/MgO-ZrO2 catalysts experienced a catalyst deactivation, while the other Mg3(VO4)2/MgO-ZrO2 catalysts showed a stable catalytic performance during the whole reaction time. The effect of oxygen property of X-Mg3(VO4)2/MgO-ZrO2 nano-catalysts on the catalytic performance in the oxidative dehydrogenation of n-butane was investigated. Experimental results revealed that oxygen capacity of the catalyst was closely related to the catalytic performance, while oxygen mobility of the catalyst played an important role in the catalyst stability. Among the catalysts tested, 12.8-Mg3(VO4)2/MgO-ZrO2 catalyst showed the best catalytic performance in terms of yield for TDP (total dehydrogenation products). PMID:24266201

  18. Over-Oxidation as the Key Step in the Mechanism of the MoCl5-Mediated Dehydrogenative Coupling of Arenes.

    PubMed

    Schubert, Moritz; Franzmann, Peter; Wünsche von Leupoldt, Anica; Koszinowski, Konrad; Heinze, Katja; Waldvogel, Siegfried R

    2016-01-18

    Molybdenum pentachloride is an unusually powerful reagent for the dehydrogenative coupling of arenes. Owing to the high reaction rate using MoCl5, several labile moieties are tolerated in this transformation. The mechanistic course of the reaction was controversially discussed although indications for a single electron transfer as the initial step were found recently. Herein, based on a combined study including synthetic investigations, electrochemical measurements, EPR spectroscopy, DFT calculations, and mass spectrometry, we deduct a highly consistent mechanistic scenario: MoCl5 acts as a one-electron oxidant in the absence of TiCl4 and as two-electron oxidant in the presence of TiCl4, but leads to an over-oxidized intermediate in both cases, which protects it from side reactions. In the course of aqueous work-up the reagent waste (Mo(III/IV) species) acts as reducing agent generating the desired organic C-C coupling product. PMID:26473303

  19. Efficient combination of promoter and catalyst for chromic acid oxidation of propan-2-ol to acetone in aqueous acid media at room temperature.

    PubMed

    Mukherjee, Kakali; Saha, Rumpa; Ghosh, Aniruddha; Ghosh, Sumanta K; Saha, Bidyut

    2013-01-15

    Oxidation of propan-2-ol to acetone was carried out in aqueous media at room temperature. The effect of promoter (PA, bpy, phen), micellar catalyst (SDS, CPC, TX-100) and their combination has been studied. The reactions were performed under the condition [Propan-2-ol]T≫[Cr(VI)]T at 30°C. Then kobs and half life of all the reaction were determined to identify which promoter and which combination are the most effective for this oxidation. Among the promoters phen accelerates the reaction most in aqueous media. In absence of promoters anionic surfactant SDS increases the rate more effectively than neutral surfactant TX-100. CPC retards the rate in comparison to aqueous media. The rate of the oxidation is highest in presence of the combination of bpy and SDS. PMID:23123236

  20. An operando Raman study of molecular structure and reactivity of molybdenum(VI) oxide supported on anatase for the oxidative dehydrogenation of ethane.

    PubMed

    Tsilomelekis, George; Boghosian, Soghomon

    2012-02-21

    Supported molybdenum oxide catalysts on TiO(2) (anatase) with surface densities in the range of 1.8-17.0 Mo per nm(2) were studied at temperatures of 410-480 °C for unraveling the configuration and molecular structure of the deposited (MoO(x))(n) species and examining their behavior for the ethane oxidative dehydrogenation (ODH). In situ Raman and in situ FTIR spectra under oxidizing conditions combined with (18)O/(16)O isotope exchange studies provide the first sound evidence for mono-oxo configuration for the deposited (MoO(x))(n) species on anatase. Isolated O=Mo(-O-)(3) tetra-coordinated species in C(3v)-like symmetry prevail at all surface coverages with a low presence of associated (polymeric) species (probably penta-coordinated) evidenced at high coverages, below the approximate monolayer of 6 Mo per nm(2). A mechanistic scenario for (18)O/(16)O isotope exchange and next-nearest-neighbor vibrational isotope effect is proposed at the molecular level to account for the pertinent spectral observations. Catalytic measurements for ethane ODH with simultaneous monitoring of operando Raman spectra were performed. The selectivity to ethylene increases with increasing surface density up to the monolayer coverage, where primary steps of ethane activation follow selective reaction pathways leading to ∼100% C(2)H(4) selectivity. The operando Raman spectra and a quantitative exploitation of the relative normalized Mo=O band intensities for surface densities of 1.8-5.9 Mo per nm(2) and various residence times show that the terminal Mo=O sites are involved in non-selective reaction turnovers. Reaction routes follow primarily non-selective pathways at low coverage and selective pathways at high coverage. Trends in the initial rates of ethane consumption (apparent reactivity per Mo) as a function of Mo surface density are discussed on the basis of several factors. PMID:22143865

  1. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

    PubMed Central

    Xu, Zhen-Feng; Wang, Yixuan

    2011-01-01

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt3Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

  2. Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt(3)M (M=Pt, Ru, Sn, Re, Rh, and Pd).

    PubMed

    Xu, Zhen-Feng; Wang, Yixuan

    2011-10-27

    The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt(3)M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt(3)Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

  3. Mesoporous xEr2O3·CoTiO3 composite oxide catalysts for low temperature dehydrogenation of ethylbenzene to styrene using CO2 as a soft oxidant

    DOE PAGESBeta

    Yue, Yanfeng; Zhang, Li; Chen, Jihua; Hensley, Dale K.; Dai, Sheng; Overbury, Steven H.

    2016-03-29

    A series of mesoporous xEr2O3·CoTiO3 composite oxide catalysts have been prepared using template method and tested as a new type of catalyst for the oxidative dehydrogenation of ethylbenzene to styrene by using CO2 as a soft oxidant. Among the catalysts tested, the 0.25Er2O3 CoTiO3 sample with a ratio of 1:4:4 content and calcined at 600 oC exhibited the highest ethylbenzene conversion (58%) and remarkable styrene selectivity (95%) at low temperature (450 °C).

  4. Atomic-Scale Determination of Active Facets on the MoVTeNb Oxide M1 Phase and Their Intrinsic Catalytic Activity for Ethane Oxidative Dehydrogenation.

    PubMed

    Melzer, Daniel; Xu, Pinghong; Hartmann, Daniela; Zhu, Yuanyuan; Browning, Nigel D; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

    2016-07-25

    Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) has been used to image the basal {001} plane of the catalytically relevant M1 phase in MoVTeNb complex oxides. Facets {010}, {120}, and {210} are identified as the most frequent lateral termination planes of the crystals. Combination of STEM with He ion microscopy (HIM) images, Rietveld analysis, and kinetic tests reveals that the activation of ethane is correlated to the availability of facets {001}, {120}, and {210} at the surface of M1 crystals. The lateral facets {120} and {210} expose crystalline positions related to the typical active centers described for propane oxidation. Conversely, the low activity of the facet {010} is attributed to its configuration, consisting of only stable M6 O21 units connected by a single octahedron. Thus, we quantitatively demonstrated that differences in catalytic activity among M1 samples of equal chemical composition depend primarily on the morphology of the particles, which determines the predominant terminating facets. PMID:26990594

  5. Catalytic oxidative dehydrogenation process

    DOEpatents

    Schmidt, Lanny D.; Huff, Marylin

    2002-01-01

    A process for the production of a mono-olefin from a gaseous paraffinic hydrocarbon having at least two carbon atoms or mixtures thereof comprising reacting said hydrocarbons and molecular oxygen in the presence of a platinum catalyst. The catalyst consist essentially of platinum supported on alumina or zirconia monolith, preferably zirconia and more preferably in the absence of palladium, rhodium and gold.

  6. A study of the effect of cesium loading on the phase transformation of iron in iron phosphate over the oxidative dehydrogenation reactions

    NASA Astrophysics Data System (ADS)

    Khan, Faiza B.; Dasireddy, Venkata D. B. C.; Bharuth-Ram, K.; Masenda, H.; Friedrich, H. B.

    2015-04-01

    A phase specific iron orthophosphate catalyst, FePO4, was synthesized and promoted with cesium. This catalyst was subjected to oxidative dehydrogenation reactions to form an alkyl methacrylate. The phases of the catalyst, before and after the reactions, were studied as a function of different cesium loading. Mössbauer spectra of the catalysts show the change of the catalyst precursor FePO4, to i) the tridymite-like phase, ii) the reduced form, iron(II) pyrophosphate and Fe2 P 2 O 7, and iii) the α-phase of iron phosphate which is governed by the temperatures of oxidation. X-ray diffraction and Mössbauer measurements on the spent catalyst show a transformation of the catalyst to a mixture of phases.

  7. Periodic Density Functional Theory Study of the Oxidative Dehydrogenation of n-butane on the (001) Surface of V2O5

    NASA Astrophysics Data System (ADS)

    Hà, Nguyën Ngoc; Hue, Trán Thành; Tho, Nguyen Minh

    2009-03-01

    The oxidative dehydrogenation (ODH) of light alkanes is an attractive alternative for the production of more valuable alkenes. Considerable research efforts have been made towards the development of catalysts active at low temperature and selective in the formation of alkenes. Most catalysts described in the literature are based on Vanadium oxide as the main component and many studies concerning the reaction mechanism during the ODH of short alkanes have been performed but debates still today exist. The objective of this work is to study in detail theoretically the kinetics of n-butane ODH on the (001) surface of V2O5. The density functional theory using a plane-waves basis set and pseudopotential has been used for this purpose.

  8. Process for para-ethyltoluene dehydrogenation

    SciTech Connect

    Chu, C.C.

    1986-06-03

    A process is described of dehydrogenating para-ethyltoluene to selectively form para-methylstyrene comprising contacting to para-ethyltoluene under dehydrogenation reaction conditions with a catalyst composition comprising: (a) from about 30% to 60% by weight of iron oxide, calculated as ferric oxide; (b) from about 13% to 48% by weight of a potassium compound, calculated as potassium oxide; and (c) from about 0% to 5% by weight of a chromium compound, calculated as chromic oxide. The improvement is described comprising dehydrogenating the para-ethyltoluene with a catalyst composition comprising, in addition to the components (a), (b) and (c), a modifying component (d) capable of rendering the para-methylstyrene-containing dehydrogenation reaction effluent especially resistant to the subsequent formation of popcorn polymers when the dehydrogenation of para-ethyltoluene is conducted over the modified catalyst, the modifying component (d) being a bismuth compound present to the extent of from about 1% to 20% by weight of the catalyst composition, calculated as bismuth trioxide.

  9. Silane-propane ignitor/burner

    DOEpatents

    Hill, Richard W.; Skinner, Dewey F.; Thorsness, Charles B.

    1985-01-01

    A silane propane burner for an underground coal gasification process which is used to ignite the coal and to controllably retract the injection point by cutting the injection pipe. A narrow tube with a burner tip is positioned in the injection pipe through which an oxidant (oxygen or air) is flowed. A charge of silane followed by a supply of fuel, such as propane, is flowed through the tube. The silane spontaneously ignites on contact with oxygen and burns the propane fuel.

  10. Silane-propane ignitor/burner

    DOEpatents

    Hill, R.W.; Skinner, D.F. Jr.; Thorsness, C.B.

    1983-05-26

    A silane propane burner for an underground coal gasification process which is used to ignite the coal and to controllably retract the injection point by cutting the injection pipe. A narrow tube with a burner tip is positioned in the injection pipe through which an oxidant (oxygen or air) is flowed. A charge of silane followed by a supply of fuel, such as propane, is flowed through the tube. The silane spontaneously ignites on contact with oxygen and burns the propane fuel.

  11. Low Temperature Propane Oxidation over Co3O4 based Nano-array Catalysts. Ni Dopant Effect, Reaction Mechanism and Structural Stability

    SciTech Connect

    Ren, Zheng; Wu, Zili; Gao, Puxian; Song, Wenqiao; Xiao, Wen; Guo, Yanbing; Ding, Jun; Suib, Steven L.; Gao, Pu-Xian

    2015-06-09

    Low temperature propane oxidation has been achieved by Co3O4-based nano-array catalysts featuring low catalytic materials loading. The Ni doping into the Co3O4 lattice has led to enhanced reaction kinetics at low temperature by promoting the surface lattice oxygen activity. In situ DRIFTS investigation in tandem with isotopic oxygen exchange reveals that the propane oxidation proceeds via Mars-van Krevelen mechanism where surface lattice oxygen acts as the active site whereas O2 in the reaction feed does not directly participate in CO2 formation. The Ni doping promotes the formation of less stable carbonates on the surface to facilitate the CO2 desorption. The thermal stability of Ni doped Co3O4 decreases with increased Ni concentration while catalytic activity increases. A balance between enhanced activity and compromised thermal stability shall be considered in the Ni doped Co3O4 nano-array catalysts for low temperature hydrocarbon oxidation. This study provides useful and timely guidance for rational catalyst design toward low temperature catalytic oxidation.

  12. Low Temperature Propane Oxidation over Co3O4 based Nano-array Catalysts. Ni Dopant Effect, Reaction Mechanism and Structural Stability

    DOE PAGESBeta

    Ren, Zheng; Wu, Zili; Gao, Puxian; Song, Wenqiao; Xiao, Wen; Guo, Yanbing; Ding, Jun; Suib, Steven L.; Gao, Pu-Xian

    2015-06-09

    Low temperature propane oxidation has been achieved by Co3O4-based nano-array catalysts featuring low catalytic materials loading. The Ni doping into the Co3O4 lattice has led to enhanced reaction kinetics at low temperature by promoting the surface lattice oxygen activity. In situ DRIFTS investigation in tandem with isotopic oxygen exchange reveals that the propane oxidation proceeds via Mars-van Krevelen mechanism where surface lattice oxygen acts as the active site whereas O2 in the reaction feed does not directly participate in CO2 formation. The Ni doping promotes the formation of less stable carbonates on the surface to facilitate the CO2 desorption. Themore » thermal stability of Ni doped Co3O4 decreases with increased Ni concentration while catalytic activity increases. A balance between enhanced activity and compromised thermal stability shall be considered in the Ni doped Co3O4 nano-array catalysts for low temperature hydrocarbon oxidation. This study provides useful and timely guidance for rational catalyst design toward low temperature catalytic oxidation.« less

  13. Synergy between hexavalent chromium ions and TiO2 nanoparticles inside TUD-1 in the photocatalytic oxidation of propane, a spectroscopic study

    NASA Astrophysics Data System (ADS)

    Hamdy, Mohamed S.

    2016-02-01

    Siliceous TUD-1 mesoporous material was bi-functionalized by titanium dioxide nanoparticles and hexavalent chromium ions. The synthesis was carried out by one-pot procedure based on sol-gel technique. The photocatalytic performance of the prepared material was evaluated in the oxidation of propane under the illumination of ultraviolet light (wavelength = 360 nm) and monitored by in situ Fourier transform infrared spectroscopy. The photocatalytic activity of the prepared material exhibited an extra-ordinary activity than the reference samples that contain either hexavalent chromium ions or titanium dioxide nanoparticles only, confirming the true synergy between hexavalent chromium and tetravalent titanium ions of titanium dioxide nanoparticles.

  14. Zinc(II), iron(II/III) and ruthenium(II) complexes of o-phenylenediamine derivatives: oxidative dehydrogenation and photoluminescence.

    PubMed

    Chaudhuri, Satyabrata; Patra, Sarat Chandra; Saha, Pinaki; Saha Roy, Amit; Maity, Suvendu; Bera, Sachinath; Saha Sardar, Pinki; Ghosh, Sanjib; Weyhermüller, Thomas; Ghosh, Prasanta

    2013-11-14

    Reactions of benzoyl pyridine, o-phenylenediamine and anhydrous ZnX2 in methanol afford imine complexes [Zn(L1)X2] (X = Cl, 1; X = Br, 2) in good yields (L1 = (E)-N(1)-(phenyl(pyridin-2-yl)methylene)benzene-1,2-diamine). The reduction of 1 with NaBH4 affords (E)-N(1)-(phenyl(pyridine-2-yl)methylene)benzene-1,2-diamine (L2H). The reaction of L2H with [Ru(II)(PPh3)3Cl2] results in the oxidative dehydrogenation to L1 generating cis-[Ru(II)(L1)(PPh3)Cl2] (3). The reaction of L2H with salicylaldehyde affords (E)-2-(((2-((phenyl(pyridin-2-yl)methyl)amino)phenyl)imino)methyl)phenol (L3H2). The reaction of L3H2 with anhydrous FeCl3 in CH3OH affords cis-[Fe(III)(L3H(-))Cl2] (4). Reaction of L3H2 with [Ru(II)(PPh3)3Cl2] results in the oxidative dehydrogenation to diimine, L4H, affording trans-[Ru(II)(L4(-))(PPh3)2](+), which is isolated as trans-[Ru(II)(L4(-))(PPh3)2]PF6 (5(+)PF6(-)) (L4H = 2-((E)-(2-((E)-phenyl(pyridin-2-yl)methyleneamino)phenylimino)methyl)phenol). The reduction of L3H2 with NaBH4 produces 2-(((2-((phenyl(pyridin-2-yl)methyl)amino)phenyl)amino)methyl)phenol (L5H3). With iron(III) L5H3 undergoes oxidative dehydrogenation to L3H2 affording 4, while with [Ru(II)(PPh3)3Cl2], L5H3 undergoes 4e + 4H(+) transfer giving 5(+). A fluid solution of L3H2 at 298 K exhibits an emission band at 470 nm (λ(ex) = 330 nm, τ1 = 3.70 ns) and a weaker band at 525 nm (λ(ex) = 330, 390 nm, τ1 = 1.1 ns) at higher concentrations due to molecular aggregation, which are temperature dependent. 4 is brightly emissive (λ(ex) = 330 nm, λ(em) = 450 nm, Φ = 0.586, τ1 = 3.70 ns). Time resolved emission spectra (TRES) and lifetime measurements confirm that the lower energy absorption band of L3H2 at 390 nm, which is absent in complex 4, has a larger non-radiative rate constant (k(nr)). The redox innocent Al(III) adduct of L3H2 is fluorescent (λ(ex) = 330 nm, λ(em) = 450 nm, τ1 = 3.70 ns). On the contrary, the cis-[Fe(II)(L3H(-))Cl2](-) and cis-[Co(L3H(-))Cl2](-) analogues are non

  15. Reactions of dioxygen complexes. Oxidative dehydrogenation of 1,6-bis(2-pyridyl)-2,5-diazahexane through cobalt dioxygen complex formation

    SciTech Connect

    Basak, A.K.; Martell, A.E.

    1988-06-01

    The formation constants and oxygenation constants of the cobalt(II) complexes of 1,6-bis(2-pyridyl)-2,5-diazahexane (PYEN) have been determined by potentiometric equilibrium measurements under nitrogen and oxygen. The kinetics of the oxidative degradation of the coordinated ligand in the cobalt dioxygen complex have been measured spectrophotometrically, and the rate constants of two parallel degradation reactions have been determined. Both reactions were found to be second order, first order with respect to the concentration of the dioxygen complex and first order with respect to the hydroxide ion concentration. Kinetics and product analysis reveal that one of the terminal aminomethyl residues of the ligand PYEN undergoes two-electron oxidation to form the corresponding imine, which under the reaction conditions employed is converted to pyridine-2-carboxyaldehyde, identified semiquantitatively as the (2,6-dinitrophenyl)hydrazone. Comparisons of these results with those of systems investigated previously, and the large kinetic deuterium isotope effect for the dehydrogenation reaction, are employed as the basis of a proposed reaction mechanism, which involves deprotonation of an aliphatic amino group in a preequilibrium step. Reaction mechanisms are suggested. 30 references, 10 figures, 3 tables.

  16. Oxidative dehydrogenation of n-butane over vanadium magnesium oxide catalysts supported on nano-structured MgO and ZrO2: effect of oxygen capacity of the catalyst.

    PubMed

    Lee, Howon; Lee, Jong Kwon; Hong, Ung Gi; Song, In Kyu; Yoo, Yeonshick; Cho, Young-Jin; Lee, Jinsuk; Chang, Hosik; Jung, Ji Chul

    2012-07-01

    Vanadium-magnesium oxide catalysts supported on nano-structured MgO and ZrO2 (Mg3(VO4)2/MgO/ZrO2) were prepared by a wet impregnation method with a variation of Mg:Zr ratio (8:1, 4:1, 2:1, and 1:1). For comparison, Mg3(VO4)2/MgO and Mg3(VO4)2/ZrO2 catalysts were also prepared by a wet impregnation method. The prepared catalysts were applied to the oxidative dehydrogenation of n-butane in a continuous flow fixed-bed reactor. Mg3(VO4)2/MgO/ZrO2 (Mg:Zr = 4:1, 2:1, and 1:1) and Mg3(VO4)2/ZrO2 catalysts showed a stable catalytic activity during the whole reaction time, while Mg3(VO4)2/MgO/ZrO2 (8:1) and Mg3(VO4)2/MgO catalysts experienced a severe catalyst deactivation. Deactivation of Mg3(VO4)2/MgO/ZrO2 (8:1) and Mg3(VO4)2/MgO catalysts was due to their low oxygen mobility. Effect of oxygen capacity (the amount of oxygen in the catalyst involved in the reaction) of the supported Mg3(V04)2 catalysts on the catalytic performance in the oxidative dehydrogenation of n-butane was investigated. Experimental results revealed that oxygen capacity of the catalyst was closely related to the catalytic activity in the oxidative dehydrogenation of n-butane. A large oxygen capacity of the catalyst was favorable for obtaining a high catalytic activity in this reaction. Among the catalysts tested, Mg3(VO4)2/MgO/ZrO2 (4:1) catalyst with the largest oxygen capacity showed the best catalytic performance. PMID:22966706

  17. Effect of varying the combustion parameters on the emissions of carbon monoxide and nitrogen oxides in the exhaust gases from propane-fueled vehicles.

    PubMed

    Roberge, B

    2000-05-01

    Propane-fueled forklifts are one source of carbon monoxide (CO) contamination of workplace air. The previous study carried out by the Quebec Occupational Health and Safety Research Institute dealt with worker exposure to CO during forklift use in buildings. It recommends that exhaust gas emissions be kept below a 1 percent concentration. However, this control has not produced a significant reduction in worker exposure to CO, when factors (ventilation, type of work tasks, and management of vehicle fleet) specific to companies are taken into account. Consequently, a reduction in CO emissions below the threshold of 0.3 percent should be considered. The experience acquired with propane-fueled ice resurfacers can be used to determine the effect of combustion parameters on exhaust gas emissions. It is known that a reduction in CO emissions from ice resurfacers resulted in the appearance of nitrogen oxides (NOx) and eventually in nitrogen dioxide (NO2) poisoning. Few publications present NOx results in relation to the CO measured in the exhaust gases of propane-fueled vehicles. The objective of this study is to define the level to which CO emissions can be reduced without increasing NOx concentrations. This real-situation study quantified the CO, NO, and NOx in the exhaust gases of a fleet of propane-fueled forklifts in relation to the mixture ratio. The results show the impact of the motor speed and mixture ratio on the CO, NO, and NO2 concentrations. They confirm an increase in NOx concentrations when CO concentrations are reduced. They also show that proper maintenance of forklifts combined with optimal adjustments can reduce CO and NOx emissions. The study proposes a compromise between CO and NOx emissions by taking into account worker health and safety as well as vehicle performance. Monitoring must be done to control air quality in work areas and worker exposure to CO and NO2. A forklift preventive maintenance program and general building ventilation are the favored

  18. Dehydrogenative Coupling Reactions with Oxidized Guanidino-Functionalized Aromatic Compounds: Novel Options for σ-Bond Activation.

    PubMed

    Wild, Ute; Federle, Stefanie; Wagner, Arne; Kaifer, Elisabeth; Himmel, Hans-Jörg

    2016-08-16

    We present a new option for metal-free σ-bond activation, making use of oxidized, guanidino-functionalized aromatic compounds (GFAs). We demonstrate this new option by the homocoupling reactions of thiols and phosphines. The kinetics and the reaction pathway were studied by a number of experiments (including heterocoupling of thiols and phosphines), supported by quantum-chemical computations. Reaction of the oxidized GFA with p-dihydrobenzoquinone to give p-benzoquinone shows that typical proton-coupled electron-transfer reactions are also possible. PMID:27430589

  19. Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8.

    PubMed

    Wu, Xiao-Nan; Zhao, Hai-Tao; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2014-12-28

    The thermal reactions of [Zn(OH)](+) with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C-H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)](+) serves as active site in the hydride transfer to generate [i-C3H7](+) as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C-H bond results mainly in the formation of water and [Zn(C3,H7)](+). According to computational work, this ionic product corresponds to [HZn(CH3CH=CH2)](+). Attack of the zinc center at a secondary C-H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7](+); (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2=CH2 occurs to produce [HZn(H2O)](+). Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)](+). The combined experimental/computational gas-phase study of C-H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays. PMID:25230924

  20. Hydrogen transport membranes for dehydrogenation reactions

    DOEpatents

    Balachandran; Uthamalingam

    2008-02-12

    A method of converting C.sub.2 and/or higher alkanes to olefins by contacting a feedstock containing C.sub.2 and/or higher alkanes with a first surface of a metal composite membrane of a sintered homogenous mixture of an Al oxide or stabilized or partially stabilized Zr oxide ceramic powder and a metal powder of one or more of Pd, Nb, V, Zr, Ta and/or alloys or mixtures thereof. The alkanes dehydrogenate to olefins by contact with the first surface with substantially only atomic hydrogen from the dehydrogenation of the alkanes passing through the metal composite membrane. Apparatus for effecting the conversion and separation is also disclosed.

  1. Effect of Oxygen Defects on the Catalytic Performance of VOx/CeO2 Catalysts for Oxidative Dehydrogenation of Methanol

    SciTech Connect

    Li, Yan; Wei, Zhehao; Gao, Feng; Kovarik, Libor; Baylon, Rebecca A.; Peden, Charles HF; Wang, Yong

    2015-05-01

    In this work, CeO2 nanocubes with controlled particle size and dominating (100) facets are synthesized as supports for VOx catalysts. Combined TEM, SEM, XRD, and Raman study reveals that the oxygen vacancy density of CeO2 supports can be tuned by tailoring the particle sizes without altering the dominating facets, where smaller particle sizes result in larger oxygen vacancy densities. At the same vanadium coverage, the VOx catalysts supported on small-sized CeO2 supports with higher oxygen defect densities exhibit promoted redox property and lower activation energy for methoxyl group decomposition, as evidenced by H2-TPR and methanol TPD study. These results further confirm that the presence of oxygen vacancies plays an important role in promoting the activity of VOx species in methanol oxidation. We gratefully acknowledge financial support from the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Part of this work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle.

  2. Recent Progress in Dehydro(genative) Diels-Alder Reaction.

    PubMed

    Li, Wenbo; Zhou, Liejin; Zhang, Junliang

    2016-01-26

    In recent years, remarkable progress has been made in dehydro or dehydrogenative Diels-Alder (D-A) reactions. This Minireview gives an overview of the major two strategies for dehydro(genative) Diels-Alder reactions, which differ in dehydrogenation and D-A cyclization sequence. Reactions in which D-A cycloaddition is followed by dehydrogenation are useful methods for the synthesis of various aromatic compounds, whereas advancements in dehydro genative procedures with oxidants or catalysts prior to D-A cycloaddition offer yet further new routes to functionalized cycloadducts. Recent leading findings are highlighted and the current state of the art, scope, and limitations of these processes are discussed in this Minireview. PMID:26786814

  3. Efficiency gain of solid oxide fuel cell systems by using anode offgas recycle - Results for a small scale propane driven unit

    NASA Astrophysics Data System (ADS)

    Dietrich, Ralph-Uwe; Oelze, Jana; Lindermeir, Andreas; Spitta, Christian; Steffen, Michael; Küster, Torben; Chen, Shaofei; Schlitzberger, Christian; Leithner, Reinhard

    The transfer of high electrical efficiencies of solid oxide fuel cells (SOFC) into praxis requires appropriate system concepts. One option is the anode-offgas recycling (AOGR) approach, which is based on the integration of waste heat using the principle of a chemical heat pump. The AOGR concept allows a combined steam- and dry-reforming of hydrocarbon fuel using the fuel cell products steam and carbon dioxide. SOFC fuel gas of higher quantity and quality results. In combination with internal reuse of waste heat the system efficiency increases compared to the usual path of partial oxidation (POX). The demonstration of the AOGR concept with a 300 Wel-SOFC stack running on propane required: a combined reformer/burner-reactor operating in POX (start-up) and AOGR modus; a hotgas-injector for anode-offgas recycling to the reformer; a dynamic process model; a multi-variable process controller; full system operation for experimental proof of the efficiency gain. Experimental results proof an efficiency gain of 18 percentage points (η·POX = 23%, η·AOGR = 41%) under idealized lab conditions. Nevertheless, further improvements of injector performance, stack fuel utilization and additional reduction of reformer reformer O/C ratio and system pressure drop are required to bring this approach into self-sustaining operation.

  4. Aromatization of hydrocarbons by oxidative dehydrogenation catalyzed by the mixed addenda heteropoly acid H sub 5 PMo sub 10 V sub 2 O sub 40

    SciTech Connect

    Neumann, R. ); Lissle, M. )

    1989-09-15

    The mixed addenda heteropoly acid H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} dissolved in 1,2-dichloroethane with tetraglyme, forming the (tetraglyme){sub 3}-H{sub 5}PMo{sub 10}V{sub 2}O{sub 40} complex, catalyzes the aromatization of cyclic dienes at moderate temperatures in the presence of molecular oxygen. Dehydrogenations of exocyclic dienes such as limonene show that dehydrogenation is preceded by isomerization to their endocyclic isomers. Aromatization takes place by successive one-electron transfers and proton abstractions from the organic substrate to the heteropoly acid the latter being reoxidized by dioxygen coupled with the formation of water.

  5. O2 -mediated dehydrogenative amination of phenols.

    PubMed

    Louillat-Habermeyer, Marie-Laure; Jin, Rongwei; Patureau, Frederic W

    2015-03-23

    A method was developed for the direct dehydrogenative construction of CN bonds between unprotected phenols and a series of cyclic anilines without resorting to any kind of metal activation of either substrate and without the use of halides. The resulting process relies on the exclusively organic activation of molecular oxygen and the subsequent oxidation of the aniline substrate. This allows the coupling of ubiquitous phenols, thus furnishing aminophenols through an atom-economical and most sustainable dehydrogenative amination method. This new reactivity, which relies on the intrinsic organic reactivity of cumene in what can be seen as a modified Hock activation process of oxygen, is expected to have a large impact on the formation of CN bonds in organic synthesis. PMID:25655504

  6. Dehydrogenative Diels-Alder reaction.

    PubMed

    Ozawa, Takuya; Kurahashi, Takuya; Matsubara, Seijiro

    2011-10-01

    The dehydrogenative cycloaddition of dieneynes, which possess a diene in the form of a styrene moiety and a dienophile in the form of an alkyne moiety, produces naphthalene derivatives when heated. It was found that a key requirement of this process is the presence of a silyl group attached to the alkyne moiety, which forces a dehydrogenation reaction to occur. PMID:21905638

  7. Selective Alkane Oxidation by Manganese Oxide: Site Isolation of MnOx Chains at the Surface of MnWO4 Nanorods.

    PubMed

    Li, Xuan; Lunkenbein, Thomas; Pfeifer, Verena; Jastak, Mateusz; Nielsen, Pia Kjaer; Girgsdies, Frank; Knop-Gericke, Axel; Rosowski, Frank; Schlögl, Robert; Trunschke, Annette

    2016-03-14

    The electronic and structural properties of vanadium-containing phases govern the formation of isolated active sites at the surface of these catalysts for selective alkane oxidation. This concept is not restricted to vanadium oxide. The deliberate use of hydrothermal techniques can turn the typical combustion catalyst manganese oxide into a selective catalyst for oxidative propane dehydrogenation. Nanostructured, crystalline MnWO4 serves as the support that stabilizes a defect-rich MnOx surface phase. Oxygen defects can be reversibly replenished and depleted at the reaction temperature. Terminating MnOx zigzag chains on the (010) crystal planes are suspected to bear structurally site-isolated oxygen defects that account for the unexpectedly good performance of the catalyst in propane activation. PMID:26913704

  8. Propane Vehicle Demonstration Grant Program

    SciTech Connect

    Jack Mallinger

    2004-08-27

    Project Description: Propane Vehicle Demonstration Grants The Propane Vehicle Demonstration Grants was established to demonstrate the benefits of new propane equipment. The US Department of Energy, the Propane Education & Research Council (PERC) and the Propane Vehicle Council (PVC) partnered in this program. The project impacted ten different states, 179 vehicles, and 15 new propane fueling facilities. Based on estimates provided, this project generated a minimum of 1,441,000 new gallons of propane sold for the vehicle market annually. Additionally, two new off-road engines were brought to the market. Projects originally funded under this project were the City of Portland, Colorado, Kansas City, Impco Technologies, Jasper Engines, Maricopa County, New Jersey State, Port of Houston, Salt Lake City Newspaper, Suburban Propane, Mutual Liquid Propane and Ted Johnson.

  9. Dual Nanoparticle/Substrate Control of Catalytic Dehydrogenation

    SciTech Connect

    Borisevich, Albina Y; Wang, Sanwu; Rashkeev, Sergey; Glazoff, Michael V; Pennycook, Stephen J; Pantelides, Sokrates T

    2007-01-01

    Saturated hydrocarbons, or alkanes (C{sub n}H{sub 2n+2}), are abundant in petroleum and can be converted to alkenes (C{sub n}H{sub 2n}) by dehydrogenation. Alkenes, also known as unsaturated hydrocarbons, are easy to polymerize and are the primary feedstock of the petrochemical industry, especially ethene (n=2) and propene (n = 3). Efficient catalytic dehydrogenation is therefore a major industrial objective. It has been found that oxidative catalytic dehydrogenation, that is, a process assisted by both a solid catalyst and a flow of oxygen gas, is most practical because of higher system longevity. Chromia/alumina catalytic systems have been widely adopted by industry. They have also been the subject of scientific studies seeking understanding that may help optimization of the process.

  10. Study by electrical conductivity measurements of semiconductive and redox properties of M-doped NiO (M = Li, Mg, Al, Ga, Ti, Nb) catalysts for the oxidative dehydrogenation of ethane.

    PubMed

    Popescu, Ionel; Heracleous, Eleni; Skoufa, Zinovia; Lemonidou, Angeliki; Marcu, Ioan-Cezar

    2014-03-14

    Pure and M-doped nickel oxides with M = Li, Mg, Al, Ga, Ti, Nb, catalysts for the oxidative dehydrogenation of ethane into ethylene, were characterized by in situ electrical conductivity measurements. Their electrical conductivity was studied as a function of temperature and oxygen partial pressure and was followed with time during sequential exposures to air, an ethane-air mixture (reaction mixture) and pure ethane under conditions similar to those of catalysis. All the materials appeared to be p-type semiconductors under air with positive holes as the main charge carriers and their electrical conductivity decreased in the following order: Li-NiO > NiO > Mg-NiO > Nb-NiO > Ga-NiO > Al-NiO > Ti-NiO. All the catalysts remained p-type semiconductors in the reaction mixture at 400 °C. Correlations between the p-type semiconductivity and the catalytic properties have been evidenced. The reaction mechanism involves surface lattice O(-) species and can be assimilated to a Mars and van Krevelen mechanism. PMID:24477867

  11. Decarbonylation and dehydrogenation of carbohydrates

    DOEpatents

    Andrews, Mark A.; Klaeren, Stephen A.

    1991-01-01

    Carbohydrates, especially aldose or ketose sugars, including those whose carbonyl group is masked by hemi-acetal or hemi-ketal formation, are decarbonylated by heating the feed carbohydrate together with a transition metal complex in a suitable solvent. Also, primary alcohols, including sugar alditols are simultaneously dehydrogenated and decarbonylated by heating a mixture of rhodium and ruthenium complexes and the alcohol and optionally a hydrogen acceptor in an acceptable solvent. Such defarbonylation and/or dehydrogenation of sugars provides a convenient procedure for the synthesis of certain carbohydrates and may provide a means for the conversion of biomass into useful products.

  12. Elementary steps of the catalytic NOx reduction with NH3: Cluster studies on adsorbate diffusion and dehydrogenation at vanadium oxide substrate

    NASA Astrophysics Data System (ADS)

    Gruber, M.; Hermann, K.

    2013-05-01

    We discuss the details of important steps of the selective catalytic reduction (SCR) of NOx at model V2O5(010) substrate. First, diffusion processes at the substrate surface are considered where hydrogen and ammonium, NH4, are used as examples. Hydrogen diffusion, a prerequisite for water formation involving substrate oxygen, is described by diffusion paths between adjacent surface oxygen sites. Corresponding energy barriers are determined mainly by the flexibility and the amount of distortion of the oxygen atoms which participate in the O-H-O bridge formation at the transition state. Further, diffusion of sub-surface oxygen to fill surface oxygen vacancies of the V2O5(010) substrate has been considered and results in reactive surface sites which have not been discussed so far. NH4 diffusion at the V2O5(010) surface can be described as a combined tumbling and rotation process characterized by quite low diffusion barriers which make the adsorbate rather mobile. Finally, hydrogenation and dehydrogenation of different NHx species at the V2O5(010) substrate surface are studied where special emphasis is given to the influence of surface reduction simulated locally by oxygen vacancies. The results confirm experimental findings of the presence of both NH2 and NH4 species after ammonia adsorption at the V2O5(010) surface.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Mechanism of alkane dehydrogenation catalyzed by acidic zeolites: Ab initio transition path sampling

    NASA Astrophysics Data System (ADS)

    Bučko, Tomáš; Benco, Lubomir; Dubay, Orest; Dellago, Christoph; Hafner, Jürgen

    2009-12-01

    The dehydrogenation of propane over acidic chabazite has been studied using ab initio density-functional simulations in combination with static transition-state searches and dynamic transition path sampling (TPS) methods at elevated temperatures. The acidic zeolite has been modeled both using a small cluster and a large periodic model consisting of two unit cells, the TPS simulations allow to account for the effect of temperature and entropy. In agreement with experimental observations we find propene as the dominant reaction product and that the barrier for the dehydrogenation of a methyl group is higher than that for a methylene group. However, whereas all studies based on small cluster models (including the present one) conclude that the reaction proceeds via the formation of an alkoxy intermediate, our TPS studies based on a large periodic model lead to the conclusion that propene formation occurs via the formation of various forms of propyl cations stabilized by entropy, while the formation of an alkoxy species is a relatively rare event. It was observed only in 15% of the reactive trajectories for methyl dehydrogenation and even in only 8% of the methylene dehydrogenation reactions. Our studies demonstrate the importance of entropic effects and the need to account for the structure and flexibility of the zeolitic framework by using large periodic models.

  15. Selective and Stable Ethylbenzene Dehydrogenation to Styrene over Nanodiamonds under Oxygen-lean Conditions.

    PubMed

    Diao, Jiangyong; Feng, Zhenbao; Huang, Rui; Liu, Hongyang; Hamid, Sharifah Bee Abd; Su, Dang Sheng

    2016-04-01

    For the first time, significant improvement of the catalytic performance of nanodiamonds was achieved for the dehydrogenation of ethylbenzene to styrene under oxygen-lean conditions. We demonstrated that the combination of direct dehydrogenation and oxidative dehydrogenation indeed occurred on the nanodiamond surface throughout the reaction system. It was found that the active sp(2)-sp(3) hybridized nanostructure was well maintained after the long-term test and the active ketonic carbonyl groups could be generated in situ. A high reactivity with 40% ethylbenzene conversion and 92% styrene selectivity was obtained over the nanodiamond catalyst under oxygen-lean conditions even after a 240 h test, demonstrating the potential of this procedure for application as a promising industrial process for the ethylbenzene dehydrogenation to styrene without steam protection. PMID:26871428

  16. Catalysts for Dehydrogenation of ammonia boranes

    SciTech Connect

    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.

  17. Propane-d6 Heterogeneously Hyperpolarized by Parahydrogen

    PubMed Central

    2015-01-01

    Long-lived spin states of hyperpolarized propane-d6 gas were demonstrated following pairwise addition of parahydrogen gas to propene-d6 using heterogeneous parahydrogen-induced polarization (HET-PHIP). Hyperpolarized molecules were synthesized using Rh/TiO2 solid catalyst with 1.6 nm Rh nanoparticles. Hyperpolarized (PH ∼ 1%) propane-d6 was detected at high magnetic field (9.4 T) spectroscopically and by high-resolution 3D gradient-echo MRI (4.7 T) as the gas flowed through the radiofrequency coil with a spatial and temporal resolution of 0.5 × 0.5 × 0.5 mm3 and 17.7 s, respectively. Stopped-flow hyperpolarized propane-d6 gas was also detected at 0.0475 T with an observed nuclear spin polarization of PH ∼ 0.1% and a relatively long lifetime with T1,eff = 6.0 ± 0.3 s. Importantly, it was shown that the hyperpolarized protons of the deuterated product obtained via pairwise parahydrogen addition could be detected directly at low magnetic field. Importantly, the relatively long low-field T1,eff of HP propane-d6 gas is not susceptible to paramagnetic impurities as tested by exposure to ∼0.2 atm oxygen. This long lifetime and nontoxic nature of propane gas could be useful for bioimaging applications including potentially pulmonary low-field MRI. The feasibility of high-resolution low-field 2D gradient-echo MRI was demonstrated with 0.88 × 0.88 mm2 spatial and ∼0.7 s temporal resolution, respectively, at 0.0475 T. PMID:25506406

  18. Dehydrogenation of benzene on Pt(111) surface

    NASA Astrophysics Data System (ADS)

    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.

  19. Dehydration, Dehydrogenation, and Condensation of Alcohols on Supported Oxide Catalysts Based on Cyclic (WO3)3 and (MoO3)3 Clusters

    SciTech Connect

    Rousseau, Roger J.; Dixon, David A.; Kay, Bruce D.; Dohnalek, Zdenek

    2014-01-01

    Supported early transition metal oxides have important applications in numerous catalytic reactions. In this article we review preparation and activity of well-defined model WO3 and MoO3 catalysts prepared via deposition of cyclic gas-phase (WO3)3 and (MoO3)3 clusters generated by sublimation of WO3 and MoO3 powders. Conversion of small aliphatic alcohols to alkenes, aldehydes/ketons, and ethers is employed to probe the structure-activity relationships on model WO3 and MoO3 catalysts ranging from unsupported (WO3)3 and (MoO3)3 clusters embedded in alcohol matrices, to (WO3)3 clusters supported on surfaces of other oxides, and epitaxial and nanoporous WO3 films. Detailed theoretical calculations reveal the underlying reaction mechanisms and provide insight into the origin of the differences in the WO3 and MoO3 reactivity. For the range of interrogated (WO3)3 they further shed light into the role structure and binding of (WO3)3 clusters with the support play in determining their catalytic activity.

  20. Recent advances in copper-catalyzed dehydrogenative functionalization via a single electron transfer (SET) process.

    PubMed

    Zhang, Chun; Tang, Conghui; Jiao, Ning

    2012-05-01

    Copper salts have been developed as versatile catalysts for oxidative coupling reactions in organic synthesis. During these processes, Cu-catalysts are often proposed to serve as a one-electron oxidant to promote the single-electron transfer process. Recently, the transition-metal catalyzed direct dehydrogenative transformation has attracted considerable attention. This tutorial review summarizes the recent advances in the copper-catalyzed dehydrogenative functionalization via a single electron transfer (SET) process achieving C-C, C-N, C-O, C-halogen atoms, C-P, and N-N bond formation. PMID:22349590

  1. Beneficial effect of propane sultone and tris(trimethylsilyl) borate as electrolyte additives on the cycling stability of the lithium rich nickel manganese cobalt (NMC) oxide

    NASA Astrophysics Data System (ADS)

    Birrozzi, Agnese; Laszczynski, Nina; Hekmatfar, Maral; von Zamory, Jan; Giffin, Guinevere A.; Passerini, Stefano

    2016-09-01

    This study reports the investigation of several compounds as electrolyte additives for Li[Li0.2Mn0.56 Ni0.16 Co0.08]O2 (a.k.a lithium rich NMC) cathode material. Among the compounds investigated via electrochemical and ex-situ analytical techniques, i.e. XRD, XPS and RAMAN spectroscopy, only 1,3-propane sultone and tris(trimethylsilyl) borate show a beneficial effect on the capacity retention and coulombic efficiency of the layered cathode. The results suggest that the improved capacity retention of the cells containing the two above-mentioned additives mainly originates from their participation in the formation of the cathode passive layer, which prevents the dissolution of the metals from the cathode material. Additionally, the borate additive reduces the lithium consumption upon the passive layer formation thus leaving a higher amount of lithium available in the electrolyte. Graphite/Li[Li0.2Mn0.56 Ni0.16 Co0.08]O2 cells containing the borate additive in the electrolyte showed 85% capacity retention after 485 cycles, confirming the feasibility of its employment for practical applications.

  2. Position-specific and clumped stable isotope studies: comparison of the Urey and path-integral approaches for carbon dioxide, nitrous oxide, methane, and propane.

    PubMed

    Webb, Michael A; Miller, Thomas F

    2014-01-16

    We combine path-integral Monte Carlo methods with high-quality potential energy surfaces to compute equilibrium isotope effects in a variety of systems relevant to 'clumped' isotope analysis and isotope geochemistry, including CO2, N2O, methane, and propane. Through a systematic study of heavy-atom isotope-exchange reactions, we quantify and analyze errors that arise in the widely used Urey model for predicting equilibrium constants of isotope-exchange reactions using reduced partition function ratios. These results illustrate that the Urey model relies on a nontrivial cancellation of errors that can shift the apparent equilibrium temperature by as much as 35 K for a given distribution of isotopologues. The calculations reported here provide the same level of precision as the best existing analytical instrumentation, resolving the relative enrichment of certain isotopologues to as little as 0.01‰. These findings demonstrate path-integral methods to be a rigorous and viable alternative to more approximate methods for heavy-atom geochemical applications. PMID:24372450

  3. CO2 emission free co-generation of energy and ethylene in hydrocarbon SOFC reactors with a dehydrogenation anode.

    PubMed

    Fu, Xian-Zhu; Lin, Jie-Yuan; Xu, Shihong; Luo, Jing-Li; Chuang, Karl T; Sanger, Alan R; Krzywicki, Andrzej

    2011-11-21

    A dehydrogenation anode is reported for hydrocarbon proton conducting solid oxide fuel cells (SOFCs). A Cu-Cr(2)O(3) nanocomposite is obtained from CuCrO(2) nanoparticles as an inexpensive, efficient, carbon deposition and sintering tolerant anode catalyst. A SOFC reactor is fabricated using a Cu-Cr(2)O(3) composite as a dehydrogenation anode and a doped barium cerate as a proton conducting electrolyte. The protonic membrane SOFC reactor can selectively convert ethane to valuable ethylene, and electricity is simultaneously generated in the electrochemical oxidative dehydrogenation process. While there are no CO(2) emissions, traces of CO are present in the anode exhaust when the SOFC reactor is operated at over 700 °C. A mechanism is proposed for ethane electro-catalytic dehydrogenation over the Cu-Cr(2)O(3) catalyst. The SOFC reactor also has good stability for co-generation of electricity and ethylene at 700 °C. PMID:21984357

  4. Nanoscale platinum and iron-cobalt catalysts deposited in microchannel microreactors for use in hydrogenation and dehydrogenation of cyclohexene, selective oxidation of carbon monoxide and Fischer-Tropsch process to higher alkanes

    NASA Astrophysics Data System (ADS)

    Zhao, Shihuai

    reactions of enormous commercial potential: Fischer-Tropsch (F-T) synthesis, and preferential oxidation of CO in fuel cell. An over 50% conversion of CO and 78% selectivity to propane in F-T synthesis has been achieved. Meanwhile, a 70% conversion of CO and 80% selectivity to CO2 in preferential oxidation is reached in the fuel cell feed gas reaction. Statistical modeling studies were done using a Central Composite Design (CCD) to achieve the optimal condition (temperature 158°C, CO: O2 ratio 1.77 and total flow rate 0.207 sccm) for preferential oxidation of CO in fuel cells.

  5. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts.

    PubMed

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-01-01

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation. PMID:27435112

  6. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts

    PubMed Central

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-01-01

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation. PMID:27435112

  7. Dehydrogenation of Formic Acid by Heterogeneous Catalysts.

    PubMed

    Li, Jun; Zhu, Qi-Long; Xu, Qiang

    2015-01-01

    Formic acid has recently been considered as one of the most promising hydrogen storage materials. The basic concept is briefly discussed and the research progress is detailledly reviewed on the dehydrogenation of aqueous formic acid by heterogeneous catalysts. PMID:26507481

  8. Supported organoiridium catalysts for alkane dehydrogenation

    DOEpatents

    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.

  9. Costs Associated With Propane Vehicle Fueling Infrastructure

    SciTech Connect

    Smith, M.; Gonzales, J.

    2014-08-05

    This document is designed to help fleets understand the cost factors associated with propane vehicle fueling infrastructure. It provides an overview of the equipment and processes necessary to develop a propane fueling station and offers estimated cost ranges.

  10. Costs Associated With Propane Vehicle Fueling Infrastructure

    SciTech Connect

    Smith, M.; Gonzales, J.

    2014-08-01

    This document is designed to help fleets understand the cost factors associated with propane vehicle fueling infrastructure. It provides an overview of the equipment and processes necessary to develop a propane fueling station and offers estimated cost ranges.

  11. 75 FR 14131 - Effect on Propane Consumers of the Propane Education and Research Council's Operations, Market...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-24

    ... comment on whether the operation of the Propane Education and Research Council (PERC), in conjunction with... International Trade Administration Effect on Propane Consumers of the Propane Education and Research Council's... information to fulfill requirements under the Propane Education and Research Act of 1996 that established...

  12. Subnanometer-sized Pt/Sn alloy cluster catalysts for the dehydrogenation of linear alkanes.

    PubMed

    Hauser, Andreas W; Gomes, Joseph; Bajdich, Michal; Head-Gordon, Martin; Bell, Alexis T

    2013-12-21

    The reaction pathways for the dehydrogenation of ethane, propane, and butane, over Pt are analyzed using density functional theory (DFT). Pt nanoparticles are represented by a tetrahedral Pt4 cluster. The objectives of this work were to establish which step is rate limiting and which one controls the selectivity for forming alkenes as opposed to causing further dehydrogenation of adsorbed alkenes to produce precursors responsible for catalyst deactivation due to coking. Further objectives of this work are to identify the role of adsorbed hydrogen, derived from H2 fed together with the alkane, on the reaction pathway, and the role of replacing one of the four Pt atoms by a Sn atom. A comparison of Gibbs free energies shows that in all cases the rate-determining step is cleavage of a C-H bond upon alkane adsorption. The selectivity to alkene formation versus precursors to coking is dictated by the relative magnitudes of the activation energies for alkene desorption and dehydrogenation of the adsorbed alkene. The presence of an adsorbed H atom on the cluster facilitates alkene desorption relative to dehydrogenation of the adsorbed alkene. Substitution of a Sn atom in the cluster to produce a Pt3Sn cluster leads to a downward shift of the potential energy surface for the reaction and causes an increase of the activity of the catalyst as suggested by recent experiments due to the lower net activation barrier for the rate limiting step. However, the introduction of Sn does not alter the relative activation barriers for gas-phase alkene formation versus loss of hydrogen from the adsorbed alkene, the process leading to the formation of coke precursors. PMID:24196250

  13. Dehydrogenative α-oxygenation of ethers with an iron catalyst.

    PubMed

    Gonzalez-de-Castro, Angela; Robertson, Craig M; Xiao, Jianliang

    2014-06-11

    Selective α-oxidation of ethers under aerobic conditions is a long-pursued transformation; however, a green and efficient catalytic version of this reaction remains challenging. Herein, we report a new family of iron catalysts capable of promoting chemoselective α-oxidation of a range of ethers with excellent mass balance and high turnover numbers under 1 atm of O2 with no need for any additives. Unlike metalloenzymes and related biomimetics, the catalyst produces H2 as the only byproduct. Mechanistic investigations provide evidence for an unexpected two-step reaction pathway, which involves dehydrogenative incorporation of O2 into the ether to give a peroxobisether intermediate followed by cleavage of the peroxy bond to form two ester molecules, releasing stoichiometric H2 gas in each step. The operational simplicity and environmental friendliness of this methodology affords a useful alternative for performing oxidation, while the unique ability of the catalyst in oxygenating a substrate via dehydrogenation points to a new direction for understanding metalloenzymes and designing new biomimetic catalysts. PMID:24835531

  14. In situ Raman spectroscopy study of metal-enhanced hydrogenation and dehydrogenation of VO2.

    PubMed

    Wu, Hao; Fu, Qiang; Bao, Xinhe

    2016-11-01

    Vanadium dioxide (VO2) has a phase transition from insulator to metal at 340 K, and this transition can be strongly modified by hydrogenation. In this work, two dimensional (2D) VO2 sheets have been grown on Si(1 1 1) surfaces through chemical vapor deposition, and metal (Au, Pt) thin films were deposited on VO2 surfaces by sputtering. The hydrogenation and dehydrogenation of VO2 and metal-decorated VO2 structures in H2 and in air were in situ studied by Raman. We found that hydrogenation and dehydrogenation temperatures have been significantly decreased with the VO2 surface decorated by Au and Pt. The enhanced hydrogenation and dehydrogenation reactions can be attributed to catalytic dissociation of H2 and O2 molecules on metal surfaces and subsequent spillover of dissociated H and O atoms to the oxide surfaces. PMID:27603090

  15. Dehydrogenation of liquid fuel in microchannel catalytic reactor

    DOEpatents

    Toseland, Bernard Allen; Pez, Guido Peter; Puri, Pushpinder Singh

    2009-02-03

    The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

  16. Dehydrogenation of liquid fuel in microchannel catalytic reactor

    SciTech Connect

    Toseland, Bernard Allen; Pez, Guido Peter; Puri, Pushpinder Singh

    2010-08-03

    The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

  17. Effect of hydrogen injection stability and emissions of an experimental premixed prevaporized propane burner

    NASA Technical Reports Server (NTRS)

    Anderson, D. N.

    1975-01-01

    Hydrogen in quantities up to 5 percent by weight of the total fuel flow was injected into a premixed propane burner. The hydrogen was either premixed with the propane and air upstream of the burner or introduced as a torch at the flameholder. Emissions of total nitrogen oxides, carbon monoxide, and unburned hydrocarbon are reported as are combustion efficiencies and lean blowout limits. To maintain at least 99 percent combustion efficiency at a 700 K inlet mixture temperature with no hydrogen added, it was necessary to burn with a propane equivalence ratio of 0.525. When 4 percent hydrogen was premixed with the propane and air, a combustion efficiency greater than 99 percent was recorded at a propane equivalence ratio of 0.425. The total nitrogen oxides (NOx) emissions corresponding to these two conditions were 0.8 g NO2/kg equivalent propane and 0.44 g NO2/kg equivalent propane, respectively. The hydrogen torch did not reduce NOx emissions.

  18. Influence of Ionic Liquids on an Iron(III) Catalyzed Three-Component Coupling/Hydroarylation/Dehydrogenation Tandem Reaction.

    PubMed

    Muntzeck, Maren; Wilhelm, René

    2016-01-01

    A three-component oxidative dehydrogenation tandem reaction via the coupling and hydroarylation of benzaldehyde, aniline and phenylacetylene to a quinoline derivate was catalyzed by an iron-containing ionic liquid. The reaction was air mediated and could be performed under neat conditions. The iron(III) of the ionic liquid was the oxidizing species. PMID:27258264

  19. Influence of Ionic Liquids on an Iron(III) Catalyzed Three-Component Coupling/Hydroarylation/Dehydrogenation Tandem Reaction

    PubMed Central

    Muntzeck, Maren; Wilhelm, René

    2016-01-01

    A three-component oxidative dehydrogenation tandem reaction via the coupling and hydroarylation of benzaldehyde, aniline and phenylacetylene to a quinoline derivate was catalyzed by an iron-containing ionic liquid. The reaction was air mediated and could be performed under neat conditions. The iron(III) of the ionic liquid was the oxidizing species. PMID:27258264

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

    NASA Astrophysics Data System (ADS)

    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.

  1. Molecular Complexity via C–H Activation: A Dehydrogenative Diels-Alder Reaction

    PubMed Central

    Stang, Erik M.; White, M. Christina

    2011-01-01

    Traditionally, C–H oxidation reactions install oxidized functionality onto a preformed molecular skeleton, resulting in a local molecular change. The use of C–H activation chemistry to construct complex molecular scaffolds is a new area with tremendous potential in synthesis. We report a Pd(II)/bis-sulfoxide catalyzed dehydrogenative Diels-Alder reaction that converts simple terminal olefins into complex cycloadducts in a single operation. PMID:21842902

  2. Marine microbes rapidly adapt to consume ethane, propane, and butane within the dissolved hydrocarbon plume of a natural seep

    NASA Astrophysics Data System (ADS)

    Mendes, Stephanie D.; Redmond, Molly C.; Voigritter, Karl; Perez, Christian; Scarlett, Rachel; Valentine, David L.

    2015-03-01

    Simple hydrocarbon gases containing two to four carbons (ethane, propane, and butane) are among the most abundant compounds present in petroleum reservoirs, and are introduced into the ocean through natural seepage and industrial discharge. Yet little is known about the bacterial consumption of these compounds in ocean waters. To assess the timing by which microbes metabolize these gases, we conducted a three-phase study that tested and applied a radiotracer-based method to quantify the oxidation rates of ethane, propane, and butane in fresh seawater samples. Phase 1 involved the synthesis of tritiated ethane, propane, and butane using Grignard reagents and tritiated water. Phase 2 was a systematic assessment of experimental conditions, wherein the indigenous microbial community was found to rapidly oxidize ethane, propane, and butane. Phase 3 was the application of this tritium method near the Coal Oil Point seeps, offshore California. Spatial and temporal patterns of ethane, propane, and butane oxidation down current from the hydrocarbon seeps demonstrated that >99% of these gases are metabolized within 1.3 days following initial exposure. The oxidation of ethane outpaced oxidation of propane and butane with patterns indicating the microbial community responded to these gases by rapid adaptation or growth. Methane oxidation responded the slowest in plume waters. Estimates based on the observed metabolic rates and carbon mass balance suggest that ethane, propane, and butane-consuming microorganisms may transiently account for a majority of the total microbial community in these impacted waters.

  3. Propane Market Model documentation report

    SciTech Connect

    Not Available

    1993-12-01

    The purpose of this report is to define the objectives of the Propane Market Model (PMM), describe its basic approach, and to provide details on model functions. This report is intended as a reference document for model analysts, users, and the general public. Documentation of the model is in accordance with EIA`s legal obligation to provide adequate documentation in support of its models. The PMM performs a short-term (6- to 9-months) forecast of demand and price for consumer-grad propane in the national US market; it also calculates the end-of-month stock level during the term of the forecast. Another part of the model allows for short-term demand forecasts for certain individual Petroleum Administration for Defense (PAD) districts. The model is used to analyze market behavior assumptions or shocks and to determine the effect on market price, demand, and stock level.

  4. Base metal dehydrogenation of amine-boranes

    DOEpatents

    Blacquiere, Johanna Marie; Keaton, Richard Jeffrey; Baker, Ralph Thomas

    2009-06-09

    A method of dehydrogenating an amine-borane having the formula R.sup.1H.sub.2N--BH.sub.2R.sup.2 using base metal catalyst. The method generates hydrogen and produces at least one of a [R.sup.1HN--BHR.sup.2].sub.m oligomer and a [R.sup.1N--BR.sup.2].sub.n oligomer. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources, such as, but not limited to, fuel cells.

  5. Oxidative conversion of C1-C3 alkanes by vanadium oxide catalysts. DFT results and their accuracy

    NASA Astrophysics Data System (ADS)

    Rozanska, Xavier; Sauer, Joachim

    Elementary steps in the oxidative conversion of methane, ethane, and propane by supported vanadium oxide species are studied by density functional theory, specifically B3LYP. Two models are adopted, namely O dbond V(OH)3 and O dbond VSi7O12H7, which yield similar energy profiles. The initial and rate-determining step is hydrogen abstraction. Within the C1-C3 series, energy barriers and reaction energies follow the same trend as the C bond H bond strength in the different alkanes. For methane, only methanol formation is possible whereas for ethane and propane, oxidative dehydrogenation yields the corresponding alkenes. Single point CCSD(T)/TZVP calculations are used to assess the B3LYP error. For the barrier of the initial hydrogen abstraction the B3LYP error is larger than usual, -40 to -60 kJ/mol. With the non-hybrid BP86 and PBE functionals even larger errors occur and the potential energy surface is qualitatively different.

  6. Partial oxidation catalyst

    DOEpatents

    Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

    2000-01-01

    A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

  7. Better Catalysts through Microscopy: Mesoscale M1/M2 Intergrowth in Molybdenum–Vanadium Based Complex Oxide Catalysts for Propane Ammoxidation

    DOE PAGESBeta

    He, Qian; Woo, Jungwon; Belianinov, Alexei; Guliants, Vadim V.; Borisevich, Albina Y.

    2015-03-06

    Catalysis research has transformed from the predominantly empirical field to one where it is possible to control the catalytic properties via characterization and modification of the atomic-scale active centers. Many phenomena in catalysis, such as synergistic effect, however, transcend the atomic scale and also require the knowledge and control of the mesoscale structure of the specimen to harness. Our paper, we use our discovery of atomic-scale epitaxial interfaces in molybdenum vanadium based complex oxide catalysts systems (i.e., MoVMO, M = Ta, Te, Sb, Nb, etc.) to achieve control of the mesoscale structure of this complex mixture of very different activemore » phases. We can now achieve true epitaxial intergrowth between the catalytically critical M1 and M2 phases in the system that are hypothesized to have synergistic interactions, and demonstrate that the resulting catalyst has improved selectivity in the initial studies. Finally, we highlight the crucial role atomic scale characterization and mesoscale structure control play in uncovering the complex underpinnings of the synergistic effect in catalysis.« less

  8. Better Catalysts through Microscopy: Mesoscale M1/M2 Intergrowth in Molybdenum–Vanadium Based Complex Oxide Catalysts for Propane Ammoxidation

    SciTech Connect

    He, Qian; Woo, Jungwon; Belianinov, Alexei; Guliants, Vadim V.; Borisevich, Albina Y.

    2015-03-06

    Catalysis research has transformed from the predominantly empirical field to one where it is possible to control the catalytic properties via characterization and modification of the atomic-scale active centers. Many phenomena in catalysis, such as synergistic effect, however, transcend the atomic scale and also require the knowledge and control of the mesoscale structure of the specimen to harness. Our paper, we use our discovery of atomic-scale epitaxial interfaces in molybdenum vanadium based complex oxide catalysts systems (i.e., MoVMO, M = Ta, Te, Sb, Nb, etc.) to achieve control of the mesoscale structure of this complex mixture of very different active phases. We can now achieve true epitaxial intergrowth between the catalytically critical M1 and M2 phases in the system that are hypothesized to have synergistic interactions, and demonstrate that the resulting catalyst has improved selectivity in the initial studies. Finally, we highlight the crucial role atomic scale characterization and mesoscale structure control play in uncovering the complex underpinnings of the synergistic effect in catalysis.

  9. Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis

    PubMed Central

    West, Julian G.; Huang, David; Sorensen, Erik J.

    2015-01-01

    The dehydrogenation of unactivated alkanes is an important transformation both in industrial and biological systems. Recent efforts towards this reaction have revolved around high temperature, organometallic C–H activation by noble metal catalysts that produce alkenes and hydrogen gas as the sole products. Conversely, natural desaturase systems proceed through stepwise hydrogen atom transfer at physiological temperature; however, these transformations require a terminal oxidant. Here we show combining tetra-n-butylammonium decatungstate (TBADT) and cobaloxime pyridine chloride (COPC) can catalytically dehydrogenate unactivated alkanes and alcohols under near-UV irradiation at room temperature with hydrogen as the sole by-product. This noble metal-free process follows a nature-inspired pathway of high- and low-energy hydrogen atom abstractions. The hydrogen evolution ability of cobaloximes is leveraged to render the system catalytic, with cooperative turnover numbers up to 48 and yields up to 83%. Our results demonstrate how cooperative base metal catalysis can achieve transformations previously restricted to precious metal catalysts. PMID:26656087

  10. Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis.

    PubMed

    West, Julian G; Huang, David; Sorensen, Erik J

    2015-01-01

    The dehydrogenation of unactivated alkanes is an important transformation both in industrial and biological systems. Recent efforts towards this reaction have revolved around high temperature, organometallic C-H activation by noble metal catalysts that produce alkenes and hydrogen gas as the sole products. Conversely, natural desaturase systems proceed through stepwise hydrogen atom transfer at physiological temperature; however, these transformations require a terminal oxidant. Here we show combining tetra-n-butylammonium decatungstate (TBADT) and cobaloxime pyridine chloride (COPC) can catalytically dehydrogenate unactivated alkanes and alcohols under near-UV irradiation at room temperature with hydrogen as the sole by-product. This noble metal-free process follows a nature-inspired pathway of high- and low-energy hydrogen atom abstractions. The hydrogen evolution ability of cobaloximes is leveraged to render the system catalytic, with cooperative turnover numbers up to 48 and yields up to 83%. Our results demonstrate how cooperative base metal catalysis can achieve transformations previously restricted to precious metal catalysts. PMID:26656087

  11. Effect of Porphyrin Ligands on the Regioselective Dehydrogenation versus Epoxidation of Olefins by Oxoiron(IV) Mimics of Cytochrome P450

    NASA Astrophysics Data System (ADS)

    Kumar, Devesh; Tahsini, Laleh; Visser, Sam P. De; Kang, Hye Yeon; Kim, Soo Jeong; Nam, Wonwoo

    2009-08-01

    The cytochromes P450 are versatile enzymes involved in various catalytic oxidation reactions, such as hydroxylation, epoxidation and dehydrogenation. In this work, we present combined experimental and theoretical studies on the change of regioselectivity in cyclohexadiene oxidation (i.e., epoxidation vs dehydrogenation) by oxoiron(IV) porphyrin complexes bearing different porphyrin ligands. Our experimental results show that meso-substitution of the porphyrin ring with electron-withdrawing substituents leads to a regioselectivity switch from dehydrogenation to epoxidation, affording the formation of epoxide as a major product. In contrast, electron-rich iron porphyrins are shown to produce benzene resulting from the dehydrogenation of cyclohexadiene. Density functional theory (DFT) calculations on the regioselectivity switch of epoxidation vs dehydrogenation have been performed using three oxoiron(IV) porphyrin oxidants with hydrogen atoms, phenyl groups, and pentachlorophenyl (ArCl5) groups on the meso-position. The DFT studies show that the epoxidation reaction by the latter catalyst is stabilized because of favorable interactions of the substrate with halogen atoms of the meso-ligand as well as with pyrrole nitrogen atoms of the porphyrin macrocycle. Hydrogen abstraction transition states, in contrast, have a substrate-binding orientation further away from the porphyrin pyrrole nitrogens, and they are much less stabilized. Finally, the regioselectivity of dehydrogenation versus hydroxylation is rationalized using thermodynamic cycles.

  12. Copper(II)-catalyzed indolizines formation followed by dehydrogenative functionalization cascade to synthesize 1-bromoindolizines.

    PubMed

    Wang, Fuyao; Shen, Yongmiao; Hu, Huayou; Wang, Xiangshan; Wu, Hui; Liu, Yun

    2014-10-17

    A one-pot, three-component cascade reaction between pyridine, α-acylmethylbromide, and maleic anhydride leading to direct access of 1-bromoindolizines in high yields has been developed. This protocol is accomplished via a reaction sequence of 1,3-dipolar cycloaddition of the pyridinium ylide with maleic anhydride, oxidative decarboxylation of the primary cycloadduct, and dehydrogenative bromination of the resulting 1-unsubstituted indolizine. Copper chloride was used as a catalyst and oxygen as the terminal oxidant. This reaction represents the first example of transition-metal-catalyzed direct dehydrogenative bromination of indolizine at the C-1 position. Moreover, the obtained 1-bromoindolizines can be transformed to other 1-substituted indolizines such as 1-arylindolizines via a simple reaction process. PMID:25233481

  13. Modular o-quinone catalyst system for dehydrogenation of tetrahydroquinolines under ambient conditions.

    PubMed

    Wendlandt, Alison E; Stahl, Shannon S

    2014-08-27

    Quinolines are common pharmacophores present in numerous FDA-approved pharmaceuticals and other bioactive compounds. Here, we report the design and development of new o-quinone-based catalysts for the oxidative dehydrogenation of tetrahydroquinolines to afford quinolines. Use of a Co(salophen) cocatalyst allows the reaction to proceed efficiently with ambient air at room temperature. The utility of the catalytic method is demonstrated in the preparation of a number of medicinally relevant quinolines. PMID:25109345

  14. Palladium-catalyzed cross-dehydrogenative functionalization of C(sp(2))-H Bonds.

    PubMed

    Wu, Yinuo; Wang, Jun; Mao, Fei; Kwong, Fuk Yee

    2014-01-01

    The catalytic cross-dehydrogenative coupling (CDC) reaction has received intense attention in recent years. The attractive feature of this coupling process is the formation of a C-C bond from two C-H moieties under oxidative conditions. In this Focus Review, recent advances in the palladium-catalyzed CDC reactions of C(sp(2) )-H bond are summarized, with a focus on the period from 2011 to early 2013. PMID:24123795

  15. Synthesis of cyclic enones via direct palladium-catalyzed aerobic dehydrogenation of ketones.

    PubMed

    Diao, Tianning; Stahl, Shannon S

    2011-09-21

    α,β-Unsaturated carbonyl compounds are versatile intermediates in the synthesis of pharmaceuticals and biologically active compounds. Here, we report the discovery and application of Pd(DMSO)(2)(TFA)(2) as a catalyst for direct dehydrogenation of cyclohexanones and other cyclic ketones to the corresponding enones, using O(2) as the oxidant. The substrate scope includes heterocyclic ketones and several natural-product precursors. PMID:21851123

  16. Synthesis of Cyclic Enones via Direct Palladium-Catalyzed Aerobic Dehydrogenation of Ketones

    PubMed Central

    Diao, Tianning

    2011-01-01

    α,β-Unsaturated carbonyl compounds are versatile intermediates in the synthesis of pharmaceuticals and biologically active compounds. Here, we report the discovery and application of Pd(DMSO)2(TFA)2 as a catalyst for direct dehydrogenation of cyclohexanones and other cyclic ketones to the corresponding enones, using O2 as the oxidant. The substrate scope includes heterocyclic ketones and several natural-product precursors. PMID:21851123

  17. Thermodynamic aspects of dehydrogenation reactions on noble metal surfaces

    SciTech Connect

    Svane, K. L. Hammer, B.

    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.

  18. Thermodynamic aspects of dehydrogenation reactions on noble metal surfaces

    NASA Astrophysics Data System (ADS)

    Svane, K. L.; Hammer, B.

    2014-11-01

    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.

  19. Thermodynamic aspects of dehydrogenation reactions on noble metal surfaces.

    PubMed

    Svane, K L; Hammer, B

    2014-11-01

    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. PMID:25381535

  20. Thermodynamic properties and ideal-gas enthalpies of formation for 2-aminoisobutyric acid (2-methylalanine), acetic acid, (Z)-5-ethylidene-2-norbornene, mesityl oxide (4-methyl-3-penten-2-one), 4-methylpent-1-ene, 2,2{prime}-bis(phenylthio)propane, and glycidyl phenyl ether (1,2-epoxy-3-phenoxypropane)

    SciTech Connect

    Steele, W.V.; Chirico, R.D.; Cowell, A.B.; Knipmeyer, S.E.; Nguyen, A.

    1997-11-01

    The results of a study aimed at improvement of group-contribution methodology for estimation of thermodynamic properties of organic substances are reported. Specific weaknesses where particular group-contribution terms were unknown, or estimated because of lack of experimental data, are addressed by experimental studies of enthalpies of combustion in the condensed phase, vapor-pressure measurements, and differential scanning calorimetric (DSC) heat-capacity measurements. Ideal-gas enthalpies of formation of acetic acid, (Z)-5-ethylidene-2-norbornene, mesityl oxide (4-methyl-3-penten-2-one), 4-methylpent-1-ene, glycidyl phenyl ether (1,2-epoxy-3-phenoxypropane), and 2,2{prime}-bis(phenylthio)propane are reported. An enthalpy of formation of 2-aminoisobutyric acid (2-methylalanine) in the crystalline phase was determined. Using a literature value for the enthalpy of sublimation of 2-aminoisobutyric acid, a value for the ideal-gas enthalpy of formation was derived. An enthalpy of fusion was determined for 2,2{prime}-bis(phenylthio)propane. Two-phase (solid + vapor) or (liquid + vapor) heat capacities were determined from 300 K to the critical region or earlier decomposition temperature for all the compounds except acetic acid. For mesityl oxide and 4-methylpent-1-ene, critical temperatures and critical densities were determined from the DSC results and corresponding critical pressures derived from the fitting procedures. Group-additivity parameters and ring strain energies useful in the application of group-contribution correlations were derived.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

  3. Propane vehicles : status, challenges, and opportunities.

    SciTech Connect

    Rood Werpy, M.; Burnham, A.; Bertram, K.; Energy Systems

    2010-06-17

    Propane as an auto fuel has a high octane value and has key properties required for spark-ignited internal combustion engines. To operate a vehicle on propane as either a dedicated fuel or bi-fuel (i.e., switching between gasoline and propane) vehicle, only a few modifications must be made to the engine. Until recently propane vehicles have commonly used a vapor pressure system that was somewhat similar to a carburetion system, wherein the propane would be vaporized and mixed with combustion air in the intake plenum of the engine. This leads to lower efficiency as more air, rather than fuel, is inducted into the cylinder for combustion (Myers 2009). A newer liquid injection system has become available that injects propane directly into the cylinder, resulting in no mixing penalty because air is not diluted with the gaseous fuel in the intake manifold. Use of a direct propane injection system will improve engine efficiency (Gupta 2009). Other systems include the sequential multi-port fuel injection system and a bi-fuel 'hybrid' sequential propane injection system. Carbureted systems remain in use but mostly for non-road applications. In the United States a closed-loop system is used in after-market conversions. This system incorporates an electronic sensor that provides constant feedback to the fuel controller to allow it to measure precisely the proper air/fuel ratio. A complete conversion system includes a fuel controller, pressure regulator valves, fuel injectors, electronics, fuel tank, and software. A slight power loss is expected in conversion to a vapor pressure system, but power can still be optimized with vehicle modifications of such items as the air/fuel mixture and compression ratios. Cold start issues are eliminated for vapor pressure systems since the air/fuel mixture is gaseous. In light-duty propane vehicles, the fuel tank is typically mounted in the trunk; for medium- and heavy-duty vans and trucks, the tank is located under the body of the vehicle

  4. A Three-Stage Mechanistic Model for Ammonia Borane Dehydrogenation by Shvo's Catalyst.

    PubMed

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

    2012-10-01

    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.The primary mechanism of catalyst deactivation is borazine-mediated hydroboration of the ruthenium species that is the active oxidant in the fast catalysis case. This transition is characterized by a change in the rate law for the reaction and changes in the apparent resting state of the catalyst. Also, in this slow catalysis situation, we see an additional intermediate in the sequence of boron, nitrogen species, aminodiborane. This occurs with concurrent generation of NH(3), which itself does not strongly affect the rate of AB dehydrogenation. PMID:23335832

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

    PubMed Central

    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. The primary mechanism of catalyst deactivation is borazine-mediated hydroboration of the ruthenium species that is the active oxidant in the fast catalysis case. This transition is characterized by a change in the rate law for the reaction and changes in the apparent resting state of the catalyst. Also, in this slow catalysis situation, we see an additional intermediate in the sequence of boron, nitrogen species, aminodiborane. This occurs with concurrent generation of NH3, which itself does not strongly affect the rate of AB dehydrogenation. PMID:23335832

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

    PubMed

    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

  7. Acceptorless Photocatalytic Dehydrogenation for Alcohol Decarbonylation and Imine Synthesis

    SciTech Connect

    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.

  8. Acceptorless photocatalytic dehydrogenation for alcohol decarbonylation and imine synthesis.

    PubMed

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

    2012-08-20

    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 H(2). Methanol, ethanol, benzyl alcohol, and cyclohexanemethanol are readily decarbonylated. The photocatalysts are also active for amine dehydrogenation to give N-alkyl aldimines and H(2). PMID:22847764

  9. Acid-catalyzed dehydrogenation of amine-boranes

    DOEpatents

    Stephens, Frances Helen; Baker, Ralph Thomas

    2010-01-12

    A method of dehydrogenating an amine-borane using an acid-catalyzed reaction. The method generates hydrogen and produces a solid polymeric [R.sup.1R.sup.2B--NR.sup.3R.sup.4].sub.n product. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources.

  10. An unnatural death by propan-1-ol and propan-2-ol.

    PubMed

    Skopp, Gisela; Gutmann, Isabelle; Schwarz, Clara-Sophie; Schmitt, Georg

    2016-07-01

    A fatality of an inpatient ingesting a disinfectant containing ethanol, propan-1-ol, and propan-2-ol is reported. The alleged survival time was about 1 h. Major findings at autopsy were an extended hemorrhagic lung edema, an edematous brain, and shock kidneys. Concentrations of alcohols and acetone, a major metabolite of propan-2-ol, were determined from body fluids (blood from the heart and the femoral vein, urine, gastric contents) and tissues (brain, muscle, liver, kidneys, lungs) by headspace/gas chromatography using 2-methylpropan-2-ol as the internal standard. All samples investigated were positive for propan-1-ol, propan-2-ol, ethanol, and acetone except stomach contents, where acetone was not detectable. The low concentration of acetone compared to propan-2-ol likely supports the short survival time. The concentration ratios estimated from the results are in accordance with the physico-chemical properties of the particular alcohols, their different affinities towards alcohol dehydrogenase as well as their interdependence during biotransformation. Autopsy did not reveal the cause of death. According to the few published data, blood concentrations of 1.44 and 1.70 mg/g of propan-2-ol and propan-1-ol, respectively, are considered sufficient to have caused the death. This case also points to the need to restrict access to antiseptic solutions containing alcohols in wards with patients at risk. PMID:26712504

  11. A reusable unsupported rhenium nanocrystalline catalyst for acceptorless dehydrogenation of alcohols through γ-C-H activation.

    PubMed

    Yi, Jing; Miller, Jeffrey T; Zemlyanov, Dmitry Y; Zhang, Ruihong; Dietrich, Paul J; Ribeiro, Fabio H; Suslov, Sergey; Abu-Omar, Mahdi M

    2014-01-13

    Rhenium nanocrystalline particles (Re NPs), of 2 nm size, were prepared from NH4ReO4 under mild conditions in neat alcohol. The unsupported Re NPs convert secondary and benzylic alcohols to ketones and aldehydes, respectively, through catalytic acceptorless dehydrogenation (AD). The oxidant- and acceptor-free neat dehydrogenation of alcohols to obtain dihydrogen gas is a green and atom-economical process for making carbonyl compounds. Secondary aliphatic alcohols give quantitative conversion and yield. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Re K-edge X-ray absorption near-edge structure (XANES), and X-ray absorption fine structure (EXAFS) data confirmed the characterization of the Re NPs as metallic rhenium with surface oxidation to rhenium(IV) oxide (ReO2). Isotope labeling experiments revealed a novel γ-CH activation mechanism for AD of alcohols. PMID:24282107

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    Krylov, Igor B; Vil’, Vera A

    2015-01-01

    Summary 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

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

    PubMed

    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

  15. Dehydrogenation of dodecahydro-N-ethylcarbazole on Pd/Al2O3 model catalysts.

    PubMed

    Sobota, Marek; Nikiforidis, Ioannis; Amende, Max; Sanmartín Zanón, Beatriz; Staudt, Thorsten; Höfert, Oliver; Lykhach, Yaroslava; Papp, Christian; Hieringer, Wolfgang; Laurin, Mathias; Assenbaum, Daniel; Wasserscheid, Peter; Steinrück, Hans-Peter; Görling, Andreas; Libuda, Jörg

    2011-10-01

    To elucidate the dehydrogenation mechanism of dodecahydro-N-ethylcarbazole (H(12)-NEC) on supported Pd catalysts, we have performed a model study under ultra high vacuum (UHV) conditions. H(12)-NEC and its final dehydrogenation product, N-ethylcarbazole (NEC), were deposited by physical vapor deposition (PVD) at temperatures between 120 K and 520 K onto a supported model catalyst, which consisted of Pd nanoparticles grown on a well-ordered alumina film on NiAl(110). Adsorption and thermally induced surface reactions were followed by infrared reflection absorption spectroscopy (IRAS) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) in combination with density functional theory (DFT) calculations. It was shown that, at 120 K, H(12)-NEC adsorbs molecularly both on the Al(2)O(3)/NiAl(110) support and on the Pd particles. Initial activation of the molecule occurs through C-H bond scission at the 8a- and 9a-positions of the carbazole skeleton at temperatures above 170 K. Dehydrogenation successively proceeds with increasing temperature. Around 350 K, breakage of one C-N bond occurs accompanied by further dehydrogenation of the carbon skeleton. The decomposition intermediates reside on the surface up to 500 K. At higher temperatures, further decay to small fragments and atomic species is observed. These species block most of the absorption sites on the Pd particles, but can be oxidatively removed by heating in oxygen at 600 K, fully restoring the original adsorption properties of the model catalyst. PMID:21953930

  16. CELLULAR LIPIDS OF A NOCARDIA GROWN ON PROPANE AND N-BUTANE.

    PubMed

    DAVIS, J B

    1964-07-01

    Lipid fractions of propane- and n-butane-grown nocardial cells each contain a chloroform-soluble, ether-insoluble polymer not observed previously in liquid n-alkane-grown cells. The polymer in propane-grown cells is poly-beta-hydroxybutyrate. The polymer in n-butane-grown cells apparently contains unsaturation in the molecule, and is identified tentatively as a co-polymer of beta-hydroxybutyric and beta-hydroxybutenoic (specifically 3-hydroxy 2-butenoic) acids. The other major component of the lipid fraction consists of triglycerides containing principally palmitic and stearic acids. There seems to be little qualitative distinction in the glycerides of propane- or n-butane-grown cells. Oxidative assimilation of n-butane is described. PMID:14199017

  17. Auto-ignition and upper explosion limit of rich propane-air mixtures at elevated pressures.

    PubMed

    Norman, F; Van den Schoor, F; Verplaetsen, F

    2006-09-21

    The auto-ignition limits of propane-air mixtures at elevated pressures up to 15 bar and for concentrations from 10 mol% up to 70 mol% are investigated. The experiments are performed in a closed spherical vessel with a volume of 8 dm3. The auto-ignition temperatures decrease from 300 degrees C to 250 degrees C when increasing the pressure from 1 bar to 14.5 bar. It is shown that the fuel concentration most sensitive to auto-ignition depends on initial pressure. A second series of experiments investigates the upper flammability limit of propane-air mixtures at initial temperatures up to 250 degrees C and pressures up to 30 bar near the auto-ignition area. Finally the propane auto-oxidation is modelled using several detailed kinetic reaction mechanisms and these numerical calculations are compared with the experimental results. PMID:16716499

  18. Methanol dehydrogenation by iridium N-heterocyclic carbene complexes.

    PubMed

    Campos, Jesús; Sharninghausen, Liam S; Manas, Michael G; Crabtree, Robert H

    2015-06-01

    A series of homogeneous iridium bis(N-heterocyclic carbene) catalysts are active for three transformations involving dehydrogenative methanol activation: acceptorless dehydrogenation, transfer hydrogenation, and amine monoalkylation. The acceptorless dehydrogenation reaction requires base, yielding formate and carbonate, as well as 2-3 equivalents of H2. Of the few homogeneous systems known for this reaction, our catalysts tolerate air and employ simple ligands. Transfer hydrogenation of ketones and imines from methanol is also possible. Finally, N-monomethylation of anilines occurs through a "borrowing hydrogen" reaction. Notably, this reaction is highly selective for the monomethylated product. PMID:25615426

  19. Propane Clathrate Hydrate Formation Accelerated by Methanol.

    PubMed

    Amtawong, Jaruwan; Guo, Jin; Hale, Jared S; Sengupta, Suvrajit; Fleischer, Everly B; Martin, Rachel W; Janda, Kenneth C

    2016-07-01

    The role of methanol as both an inhibitor and a catalyst for the formation of clathrate hydrates (CHs) has been a topic of intense study. We report a new quantitative study of the kinetics of propane CH formation at 253 K from the reaction of propane gas with <75 μm ice particles that have been doped with varying amounts of methanol. We find that methanol significantly accelerates the formation reaction with quite small doping quantities. Even for only 1 methanol molecule per 10 000 water molecules, the maximum uptake rate of propane into CHs is enhanced and the initiation pressure is reduced. These results enable more efficient production of CHs for gas storage. This remarkable acceleration of the CH formation reaction by small quantities of methanol may place constraints on the mechanism of the inhibition effect observed under other conditions, usually employing much larger quantities of methanol. PMID:27275862

  20. No. 2 heating oil/propane program

    SciTech Connect

    McBrien, J.

    1991-06-01

    During the 1990/91 heating season, the Massachusetts Division of Energy Resources (DOER) participated in a joint data collection program between several state energy offices and the federal Department of Energy's (DOE) Energy Information Administration (EIA). The purpose of the program was to collect and monitor retail and wholesale heating oil and propane prices and inventories from October 1990 through March 1991. This final report begins with an overview of the unique events which had an impact on the reporting period. Next, the report summarizes the results from the residential heating oil and propane price surveys conducted by DOER over the 1990/91 heating season. The report also incorporates the wholesale heating oil and propane prices and inventories collected by the EIA and distributed to the states.

  1. Alkane metathesis by tandem alkane-dehydrogenation-olefin-metathesis catalysis and related chemistry.

    PubMed

    Haibach, Michael C; Kundu, Sabuj; Brookhart, Maurice; Goldman, Alan S

    2012-06-19

    stable solid metal oxides as the olefin-metathesis catalysts. Both the pincer complexes and the alkylidene complexes have been supported on alumina via adsorption through basic para-substituents. This process does not significantly affect catalyst activity, and in some cases it increases both the catalyst lifetime and the compatibility of the co-catalysts. These molecular catalysts are the first systems that effect alkane metathesis with molecular-weight selectivity, particularly for the conversion of C(n)n-alkanes to C(2n-2)n-alkanes plus ethane. This molecular-weight selectivity offers a critical advantage over the few previously reported alkane metathesis systems. We have studied the factors that determine molecular-weight selectivity in depth, including the isomerization of the olefinic intermediates and the regioselectivity of the pincer-iridium catalyst for dehydrogenation at the terminal position of the n-alkane. Our continuing work centers on the development of co-catalysts with improved interoperability, particularly olefin-metathesis catalysts that are more robust at high temperature and dehydrogenation catalysts that are more active at low temperature. We are also designing dehydrogenation catalysts based on metals other than iridium. Our ongoing mechanistic studies are focused on the apparently complex combination of factors that determine molecular-weight selectivity. PMID:22584036

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

    PubMed

    Bebensee, Fabian; Svane, Katrine; Bombis, Christian; Masini, Federico; Klyatskaya, Svetlana; Besenbacher, Flemming; Ruben, Mario; Hammer, Bjørk; Linderoth, Trolle

    2013-10-18

    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. PMID:23999460

  3. . . . While Others Conserve Cash by Converting from Gasoline to Propane.

    ERIC Educational Resources Information Center

    Rasmussen, Scott A.

    1988-01-01

    Since 1983, when the David Douglas Public Schools (Portland, Oregon) converted 30 buses to propane fuel, the district has saved $75,000 in fuel and maintenance costs. Propane is priced consistently lower than gasoline and burns cleaner. Since propane engines do not require a carburetor, there are fewer maintenance problems. (MLH)

  4. Four-electron oxidative dehydrogenation induced by proton-coupled electron transfer in ruthenium(III) complex with 2-(1,4,5,6-tetrahydropyrimidin-2-yl)phenolate.

    PubMed

    Mitsuhashi, Ryoji; Suzuki, Takayoshi; Sunatsuki, Yukinari

    2013-09-01

    New ruthenium(II or III) complexes with general formula [Ru(O-N)(bpy)2](n+) (O-N = unsymmetrical bidentate phenolate ligand; bpy = 2,2'-bipyridine) were synthesized, and their crystal structures and electrochemical properties were characterized. Ru(II) complexes with 2-(2-imidazolinyl)phenolate (Himn(-)) or 2-(1,4,5,6-tetrahydropyrimidin-2-yl)phenolate (Hthp(-)) could be deprotonated by addition of excess KO(t)Bu, although the deprotonated species were easily reprotonated by exposure to air. Unlike these Ru(II) complexes, their Ru(III) analogs showed interesting ligand oxidation reactions upon addition of bases. With [Ru(III)(Himn)(bpy)2](2+), two-electron oxidation of Himn(-) and reduction of the Ru(III) center resulted in conversion of the 2-imidazolinyl group to a 2-imidazolyl group. On the other hand, the corresponding Hthp(-) complex exhibited four-electron oxidation of the ligand to form 2-(2-pyrimidyl)phenolate (pym(-)). These aromatization reactions of imidazolinyl and 1,4,5,6-tetrahydropyrimidyl groups were also achieved by the electrochemically generated Ru(III) complexes. PMID:23967872

  5. Aerobic palladium(II)-catalyzed dehydrogenation of cyclohexene-1-carbonyl indole amides: an indole-directed aromatization.

    PubMed

    Kandukuri, Sandeep R; Oestreich, Martin

    2012-10-01

    A palladium(II)-catalyzed oxidative dehydrogenation of cyclohexene-1-carbonyl indole amides yielding the corresponding benzoylindoles is reported. The new aromatization is also applied to functionalized indoles such as tryptamine and tryptophan. The tethered indole is likely acting as a directing group for allylic C-H bond activation, and there is evidence for a mechanism proceeding through 1,3-diene formation followed by aromatization. PMID:22950832

  6. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in... also known as dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal... manufacturing practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas...

  7. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in... also known as dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal... manufacturing practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas...

  8. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... state. Propane is obtained from natural gas by fractionation following absorption in oil, adsorption to... dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal temperatures and pressures... practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas as...

  9. 21 CFR 184.1655 - Propane.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... in the liquid state. Propane is obtained from natural gas by fractionation following absorption in... also known as dimethylmethane or propyl hydrid. It is a colorless, odorless, flammable gas at normal... manufacturing practice conditions of use: (1) The ingredient is used as a propellant, aerating agent, and gas...

  10. 21 CFR 582.1655 - Propane.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Propane. 582.1655 Section 582.1655 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS SUBSTANCES GENERALLY RECOGNIZED AS SAFE General Purpose Food Additives §...