Search results for: asymmetric hydrogenation

Authors: Littlelet N. Scarlet, Kamaluddin Abdur-Rashid, Paul T. Maragh, Tara Dasgupta

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Aminophosphines are a privileged class of ancillary ligands with emerging importance in homogeneous catalysis. The unique combination of soft phosphorus (P) and hard nitrogen (N) centres affords a variety of transition metal complexes as potential pre-catalysts for synthetically useful reactions. Herein three ligand systems will be reported; two bidentate ligands - (S)-8-(diphenyl-phosphino)-1,2,3,4-tetrahydronaphthalen-1-amine, (S)THNANH2, and (Rc)-1-((Sp)-2-diphenylphosphino) ferrocenylethylamine, (RcSp)PPFNH2 - and a tridentate (Rc)-1-((Sp)-2-diphenylphosphino) ferrocenylimino-pyridine, (RcSp)PPFNNH2 ligand; the latter prepared from the condensation of selected ferrocene aminophosphines with pyridine-2-carboxaldehyde. Suitable combinations of these aminophosphine ligands with ruthenium precursors have afforded highly efficient systems for the asymmetric hydrogenation and transfer hydrogenation of selected ketones in 2-propanol. The Ru-(S)THNANH2 precatalyst was the most efficient in the asymmetric hydrogenation of selected ketones with 100% conversions within 4 hours at a catalyst loading of 0.1 mol%. The Ru-(RcSp)PPFNNH2 precatalyst was the most efficient in the asymmetric transfer hydrogenation of the ketones with conversions as high as 98% with 0.1 mol% catalyst. However, the enantioselectivities were generally low.

Keywords: aminophosphine, asymmetric hydrogenation, homogeneous catalysis, ruthenium (II), transfer hydrogenation

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Authors: Vaclav Heral

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Ideas about the mechanism of heterogeneous catalytic hydrogenation are diverse. The Horiuti-Polanyi mechanism is most often referred to, based on the idea of a semi-hydrogenated state. In our opinion, it does not represent a satisfactory explanation of the hydrogenation mechanism, because, for example: (1) It neglects the fact that the bond of atomic hydrogen to the metal surface is strongly polarized, (2) It does not explain why a surface deprived of atomic hydrogen (by thermal desorption or by alkyne) loses isomerization capabilities, but hydrogenation capabilities remain preserved, (3) It was observed that during the hydrogenation of 1-alkenes, the reaction can be of the 0th order to hydrogen and to the alkene at the same time, which is excluded during the competitive adsorption of both reactants on the catalyst surface. We offer an alternative mechanism that satisfactorily explains many of the ambiguities: It is the idea of an independent course of olefin isomerization, catalyzed by acidic atomic hydrogen bonded on the surface of the catalyst, in addition to the hydrogenation itself, in which a two-layer complex appears on the surface of the catalyst: olefin bound to the surface and molecular hydrogen bound to it in the second layer. The rate-determining step of hydrogenation is the conversion of this complex into the final product. We believe that the Horiuti-Polanyi mechanism is flawed and we naturally think that our two-layer theory better describes the experimental findings.

Keywords: acidity of hydrogenation catalyst, Horiuti-Polanyi, hydrogenation, two-layer hydrogenation

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Authors: Shannen Lorraine, Paul Maragh, Tara Dasgupta, Kamaluddin Abdur-Rashid

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(R)-(4,4',6,6'-tetramethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (R-Ph-Garphos), and (S)-(4,4',6,6'-tetramethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (S-Ph-Garphos) are novel, nucleophilic, chiral atropisomeric ligands. The research explored the synthesis of chiral transition metal complexes containing these ligands and their applications in various asymmetric catalytic transformations. Herein, the transition metal complexes having ruthenium(II), rhodium(I) and iridium(I) metal centres will be discussed. These are air stable complexes and were characterized by CHN analysis, 1H, 13C, and 31P NMR spectroscopy, and polarimetry. Currently, there is an emphasis on 'greener' catalysts and the need for 'green' solvents in asymmetric catalysis. As such, the Ph-Garphos ligands were demethylated thereby introducing hydroxyl moieties unto the ligand scaffold. The facile tunability of the biaryl diphosphines led to the preparation of the (R)-(4,4',6,6'-tetrahydroxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (R-Ph-Garphos-OH), and (S)-(4,4',6,6'-tetrahydroxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (S-Ph-Garphos-OH) ligands. These were successfully characterized by CHN analysis, 1H, 13C, and 31P NMR spectroscopy, and polarimetry. The use of the Ph-Garphos and Ph-Garphos-OH ligands and their transition metal complexes in asymmetric hydrogenations will be reported. Additionally, the scope of the research will highlight the applicability of the Ph-Garphos-OH ligand and its transitional metal complexes as 'green' catalysts.

Keywords: catalysis, asymmetric hydrogenation, diphosphine transition metal complexes, Ph-Garphos ligands

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Authors: Mingchuan Zhou, Haitao Zhang, Hongfang Ma, Weiyong Ying

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Alumina supported platinum and tin catalysts with different loadings of Pt and Sn were prepared and characterized by low temperature N₂ adsorption/desorption, H₂-temperature programed reduction and CO pulse chemisorption. Pt and Sn below 1% loading were suitable for acetic acid hydrogenation. The best performance over 0.75Pt1Sn/Al₂O₃ can reach 87.55% conversion of acetic acid and 47.39% selectivity of ethanol. The operating conditions of acetic acid hydrogenation over 1Pt1Sn/Al₂O₃ were investigated. High reaction temperature can enhance the conversion of acetic acid, but it decreased total selectivity of ethanol and acetyl acetate. High pressure and low weight hourly space velocity were beneficial to both conversion of acetic acid and selectivity to ethanol.

Keywords: acetic acid, hydrogenation, operating condition, PtSn

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Authors: Chia-Ling Li

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The scope of this article includes the production of 10,000 metric tons of non-phthalate per annum. The production process will include hydrogenation, separation, purification, and recycling of unprocessed feedstock. Based on experimental data, conversion and selectivity were chosen as reaction model parameters. The synthesis and separation processes of non-phthalate and phthalate were established by using Aspen Plus software. The article will be divided into six parts: estimation of physical properties, integration of production processes, purification case study, utility consumption, economic feasibility study and identification of bottlenecks. The purities of products was higher than 99.9 wt. %. Process parameters have important guiding significance to the commercialization of hydrogenation of phthalate.

Keywords: economic analysis, hydrogenation, non-phthalate, process simulation

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Authors: Nabilah Ibrahim, Hafiz Mohd Zaini, Wan Fatin Liyana Mutalib

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Ultrasound equipment or machine is capable to scan in two dimensional (2D) areas. However there are some limitations occur during scanning an object. The problem will occur when scanning process that involving the asymmetric object. In this project, the ultrasound probe holder for asymmetric reflector scanning in 3D image is proposed to make easier for scanning the phantom or object that has asymmetric shape. Initially, the constructed asymmetric phantom that construct will be used in 2D scanning. Next, the asymmetric phantom will be interfaced by the movement of ultrasound probe holder using the Arduino software. After that, the performance of the ultrasound probe holder will be evaluated by using the various asymmetric reflector or phantom in constructing a 3D image

Keywords: ultrasound 3D images, axial and lateral resolution, asymmetric reflector, Arduino software

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Authors: Alexander Pesin, Denis Pustovoytov, Mikhail Sverdlik

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Materials with ultrafine-grained structure and unique physical and mechanical properties can be obtained by methods of severe plastic deformation, which include processes of asymmetric rolling (AR). Asymmetric rolling is a very effective way to create ultrafine-grained structures of metals and alloys. Since the asymmetric rolling is a continuous process, it has great potential for industrial production of ultrafine-grained structure sheets. Basic principles of asymmetric rolling are described in detail in scientific literature. In this work finite element modeling of asymmetric rolling and metal forming processes in multiroll gauge was performed. Parameters of the processes which allow achieving significant values of shear strain were defined. The results of the study will be useful for the research of the evolution of ultra-fine metal structure in asymmetric rolling.

Keywords: asymmetric rolling, equivalent strain, FEM, multiroll gauge, profile, severe plastic deformation, shear strain, sheet

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Authors: Faezeh Aghazadeh, Mohammad Javad Sharifi

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The application of neural networks to model a full-scale industrial acetylene hydrogenation in olefin plant has been studied. The operating variables studied are the, input-temperature of the reactor, output-temperature of the reactor, hydrogen ratio of the reactor, [C₂H₂]input, and [C₂H₆]input. The studied operating variables were used as the input to the constructed neural network to predict the [C₂H₆]output at any time as the output or the target. The constructed neural network was found to be highly precise in predicting the quantity of [C₂H₆]output for the new input data, which are kept unaware of the trained neural network showing its applicability to determine the [C₂H₆]output for any operating conditions. The enhancement of [C₂H₆]output as compared with [C₂H₆]input was a consequence of low selective acetylene hydrogenation to ethylene.

Keywords: acetylene hydrogenation, Pd-Ag/Al₂O₃, artificial neural network, modeling, optimal design

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Authors: Gi-Beom Park, Hyong-Gi Park, Seong-Yong Lee, Jaeho Choi, Seok Hong Min, Tae Kwon Ha

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The Nb silicide-based alloy has the excellent high-temperature strength and relatively lower density than the Ni-based superalloy; therefore, it has been receiving a lot of attention for the next generation high-temperature material. To enhance the high temperature creep property and oxidation resistance, Si was added to the Nb-based alloy, resulting in a multi-phase microstructure with metal solid solution and silicide phase. Since the silicide phase has a low machinability due to its brittle nature, it is necessary to fabricate components using the powder metallurgy. However, powder manufacturing techniques for the alloys have not yet been developed. In this study, we tried to fabricate Nb-based alloy powder by the hydrogenation-dehydrogenation reaction. The Nb-based alloy ingot was prepared by vacuum arc melting and it was annealed in the hydrogen atmosphere for the hydrogenation. After annealing, the hydrogen concentration was increased from 0.004wt% to 1.22wt% and Nb metal phase was transformed to Nb hydride phase. The alloy after hydrogenation could be easily pulverized into powder by ball milling due to its brittleness. For dehydrogenation, the alloy powders were annealed in the vacuum atmosphere. After vacuum annealing, the hydrogen concentration was decreased to 0.003wt% and Nb hydride phase was transformed back to Nb metal phase.

Keywords: Nb alloy, Nb metal and silicide composite, powder, hydrogenation-dehydrogenation reaction

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Authors: S. F. H. Tasfy, N. A. M. Zabidi, M. S. Shaharun

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Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO₂ to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO₂ to methanol in microactivity fixed-bed reactor at 250^oC, 2.25 MPa, and H₂/CO₂ ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H₂ and CO₂ and accelerate the CO₂ conversion, resulting in higher methanol production under mild reaction conditions.

Keywords: hydrogenation of carbon dioxide, methanol synthesis, Cu/ZnO-based catalyst, mesoporous silica (SBA-15), metal ratio

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Authors: Farid Habibi Tanha, Hawati Janor, Mojtaba Jahanbazi

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The purpose of this study is to examine the effect of asymmetric information on the composition of capital inflows. This study uses the stock market microstructure to capture the asymmetric information. Such an approach allows one to capture the level and extent of the asymmetric information from a firm’s perspective. This study focuses on the two-dimensional measure of the market microstructure in capturing asymmetric information. The composition of capital inflows is measured by running six models simultaneously. By employing the panel data technique, the main finding of this research shows an increase in the asymmetric information of the stock market, in any of the two dimensions of width and depth. This leads to the reduction of foreign investments in both forms of foreign portfolio investment (FPI) and foreign direct investment (FDI), while the reduction in FPI is higher than that of the FDI. The significant effect of asymmetric information on capital inflows implicitly suggests for policymakers to control the changes of foreign capital inflows through transparency in the level of the market.

Keywords: capital flows composition, asymmetric information, stock market microstructure, foreign portfolio investment, foreign direct investment

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Authors: M. A. Hasnat, M. Amirul Islam, M. A. Rashed, Jamil. Safwan, M. Mahabubul Alam

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Symmetric (Cu–Pt|Nafion|Pt–Cu) and asymmetric(Pt|Nafion|Pt–Cu) assemblies were fabricated to study the nitrate reduction processes at the cathode. The electrocatalytic nitrate reduction reactions were performed in these assemblies in order to investigate the prerequisite for the enhanced catalytic activity, electrochemical cell durability as well as preferable product selectivity resulting from the reduction of nitrate at the cathode. It has been observed for the symmetric assembly that Cu particles were oxidized on the anode surface under an applied potential and the resulting copper ions migrated to the cathode surface through the Nafion membrane, which deposited as copper oxide on the cathode surface. The formation of this copper oxide covering layer on the Pt–Cu cathode surface is attributed as the reason for the deactivation of the cathode that governed the reduced nitrate reduction along with increasing nitrite selectivity. These problems were addressed and resolved with the asymmetric design of the electrocatalytic reactor, where enhanced hydrogen evolution activates the surface by eroding the CuO over layer as well as speeding up the slow rate determining hydrogenation reactions.

Keywords: membrane, nitrate, electrocatalysis, voltammetry, electrolysis

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Authors: Sartaj Singh, Amar Singh, Ashok Sharma, Sandeep Kaur

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With upcoming threats in a digital world, we need to work continuously in the area of security in all aspects, from hardware to software as well as data modelling. The rise in social media activities and hunger for data by various entities leads to cybercrime and more attack on the privacy and security of persons. Cryptography has always been employed to avoid access to important data by using many processes. Symmetric key and asymmetric key cryptography have been used for keeping data secrets at rest as well in transmission mode. Various cryptosystems have evolved from time to time to make the data more secure. In this research article, we are studying various cryptosystems in asymmetric cryptography and their application with usefulness, and much emphasis is given to Elliptic curve cryptography involving algebraic mathematics.

Keywords: cryptography, symmetric key cryptography, asymmetric key cryptography

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Authors: Anatoly A. Kuznetsov, Pavel G. Berezhko, Sergey M. Kunavin, Eugeny V. Zhilkin, Maxim V. Tsarev, Vyacheslav V. Yaroshenko, Valery V. Mokrushin, Olga Y. Yunchina, Sergey A. Mityashin

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The acoustic emission is caused by short-time propagation of elastic waves that are generated as a result of quick energy release from sources localized inside some material. In particular, the acoustic emission phenomenon lies in the generation of acoustic waves resulted from the reconstruction of material internal structures. This phenomenon is observed at various physicochemical transformations, in particular, at those accompanying hydrogenation processes of metals or intermetallic compounds that make it possible to study parameters of these transformations through recording and analyzing the acoustic signals. It has been known that at the interaction between metals or inter metallides with hydrogen the most intensive acoustic signals are generated as a result of cracking or crumbling of an initial compact powder sample as a result of the change of material crystal structure under hydrogenation. This work is dedicated to the study into changes occurring in metallic titanium samples at their interaction with hydrogen and followed by acoustic emission signals. In this work the subjects for investigation were specimens of metallic titanium in two various initial forms: titanium sponge and fine titanium powder made of this sponge. The kinetic of the interaction of these materials with hydrogen, the acoustic emission signals accompanying hydrogenation processes and the structure of the materials before and after hydrogenation were investigated. It was determined that in both cases interaction of metallic titanium and hydrogen is followed by acoustic emission signals of high amplitude generated on reaching some certain value of the atomic ratio [H]/[Ti] in a solid phase because of metal cracking at a macrolevel. The typical sizes of the cracks are comparable with particle sizes of hydrogenated specimens. The reasons for cracking are internal stresses initiated in a sample due to the increasing volume of a solid phase as a result of changes in a material crystal lattice under hydrogenation. When the titanium powder is used, the atomic ratio [H]/[Ti] in a solid phase corresponding to the maximum amplitude of an acoustic emission signal are, as a rule, higher than when titanium sponge is used.

Keywords: acoustic emission signal, cracking, hydrogenation, titanium specimen

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Authors: Rohit Thirumdas, Annapure U. S.

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Low-pressure air plasma is used to investigate the antioxidant properties and fatty acid composition of rice bran at different power levels (40 W and 60 W). We observed partial hydrogenation of rice bran oil after the treatment. The fatty acid composition analysis by gas chromatography showed an increase of 28.2% in palmitic acid and a 29.4% decrease in linoleic acid. FTIR spectrum shows no new peak formation, which confirms negligible amounts of trans-fatty acids. There is a decrease in peroxide value and iodine value, which can be correlated to an increase in saturated fatty acids. The total polyphenolic content was observed to be increased by 20.1% after the treatment. There is an increase in reducing power and DPPH % inhibition of rice bran due to plasma treatment. This study shows cold plasma treatment can be considered an alternative technology for the hydrogenation of oils, replacing traditional toxic processes.

Keywords: cold plasma, rice bran, fatty acid composition, hydrogenation of oils, antioxidant properties

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Authors: Mingchuan Zhou, Haitao Zhang, Hongfang Ma, Weiyong Ying

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Alumina supported PtSn catalysts with cylindrical particles were prepared and characterized by using low temperature N2 adsorption/desorption and X-ray diffraction. Low temperature N2 adsorption/desorption demonstrate that the tableting changed the texture properties of catalysts. XRD pattern indicate that the crystal structure of supports had no change after reaction. The performances over particles of PtSn/Al2O3 catalysts were investigated with regards to reaction temperature, pressure, and H2/AcOH mole ratio. After tableting, the conversion of acetic acid and selectivity of ethanol and acetyl acetate decreased. High reaction temperature and pressure can improve conversion of acetic acid. H2/AcOH mole ratio of 9.36 showed the best performance on acetic acid hydrogenation. High pressure had benefits for the selectivity of ethanol and other two parameters had no obvious effect on selectivity.  

Keywords: acetic acid hydrogenation, cylindrical particles, ethanol, PtSn

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Authors: Farrukh Javed, Krzysztof Podgórski

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We propose a new model that accounts for the asymmetric response of volatility to positive ('good news') and negative ('bad news') shocks in economic time series the so-called leverage effect. In the past, asymmetric powers of errors in the conditionally heteroskedastic models have been used to capture this effect. Our model is using the gamma difference representation of the generalized Laplace distributions that efficiently models the asymmetry. It has one additional natural parameter, the shape, that is used instead of power in the asymmetric power models to capture the strength of a long-lasting effect of shocks. Some fundamental properties of the model are provided including the formula for covariances and an explicit form for the conditional distribution of 'bad' and 'good' news processes given the past the property that is important for the statistical fitting of the model. Relevant features of volatility models are illustrated using S&P 500 historical data.

Keywords: heavy tails, volatility clustering, generalized asymmetric laplace distribution, leverage effect, conditional heteroskedasticity, asymmetric power volatility, GARCH models

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Authors: S. F. H. Tasfy, N. A. M. Zabidi, M.-S. Shaharun

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Utilization of CO2 as a carbon source to produce valuable chemicals is one of the important ways to reduce the global warming caused by increasing CO2 in the atmosphere. Supported metal catalysts are crucial for the production of clean and renewable fuels and chemicals from the stable CO2 molecules. The catalytic conversion of CO2 into methanol is recently under increased scrutiny as an opportunity to be used as a low-cost carbon source. Therefore, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were synthesized via impregnation technique with different total metal loading and tested in the catalytic hydrogenation of CO2 to methanol. The morphological and textural properties of the synthesized catalysts were determined by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and N2-adsorption. The CO2 hydrogenation reaction was performed in microactivity fixed-bed system at 250 °C, 2.25 MPa, and H2/CO2 ratio of 3. Experimental results showed that the catalytic structure and performance was strongly affected by the loading of the active site. Where, the catalytic activity, methanol selectivity as well as the space-time yield increased with increasing the metal loading until it reaches the maximum values at a metal loading of 15 wt% while further addition of metal inhibits the catalytic performance. The higher catalytic activity of 14 % and methanol selectivity of 92 % were obtained over Cu/ZnO-SBA-15 catalyst with total bimetallic loading of 15 wt%. The excellent performance of 15 wt% Cu/ZnO-SBA-15 catalyst is attributed to the presence of well disperses active sites with small particle size, higher Cu surface area, and lower catalytic reducibility.

Keywords: hydrogenation of carbon dioxide, methanol synthesis, metal loading, Cu/ZnO-SBA-15 catalyst

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Authors: Ahtesham Javaid, Costin S. Bildea

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The design and plantwide control of an integrated plant where the endothermic 1,4-butanediol dehydrogenation and the exothermic furfural hydrogenation is simultaneously performed in a single reactor is studied. The reactions can be carried out in an adiabatic reactor using small hydrogen excess and with reduced parameter sensitivity. The plant is robust and flexible enough to allow different production rates of γ-butyrolactone and 2-methyl furan, keeping high product purities. Rigorous steady state and dynamic simulations performed in AspenPlus and AspenDynamics to support the conclusions.

Keywords: dehydrogenation and hydrogenation, reaction coupling, design and control, process integration

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Authors: Huanru Wang, Jianzhun Jiang

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At present, the preparation of the catalyst by carbon carrier is one of the improvement directions of the C₂ pre-hydrogenation catalyst. Carbon materials can be prepared from coal direct liquefaction residues, coconut shells, biomass, etc., and the pore structure of carbon carrier materials can be adjusted through the preparation process; at high temperatures, the carbon carrier itself also shows certain catalytic activity. Therefore, this paper mainly selected typical activated carbon and coconut shell carbon as carbon carrier materials, studied their microstructure and surface properties, prepared a series of carbon-based catalysts loaded with Pd, and investigated the effects of the content of promoter Ag and the concentration of reductant on the structure and performance of the catalyst and its catalytic performance for the pre hydrogenation of C₂. In this paper, the carbon supports from two sources and the catalysts prepared by them were characterized in detail. The results showed that the morphology and structure of different supports and the performance of the catalysts prepared were also obviously different. The catalyst supported on coconut shell carbon has a small specific surface area and large pore diameter. The catalyst supported on activated carbon has a large specific surface area and rich pore structure. The active carbon support is mainly a mixture of amorphous graphite and microcrystalline graphite. For the catalyst prepared with coconut shell carbon as the carrier, the sample is very uneven, and its specific surface area and pore volume are irregular. Compared with coconut shell carbon, activated carbon is more suitable as the carrier of the C₂ hydrogenation catalyst. The conversion of acetylene, methyl acetylene, and butadiene decreased, and the ethylene selectivity increased after Ag was added to the supported Pd catalyst. When the amount of promoter Ag is 0.01-0.015%, the catalyst has relatively good catalytic performance. Ag and Pd form an alloying effect, thus reducing the effective demand for Ag. The Pd Ag ratio is the key factor affecting the catalytic performance. When the addition amount of Ag is 0.01-0.015%, the dispersion of Pd on the carbon support surface can be significantly improved, and the size of active particles can be reduced. The Pd Ag ratio is the main factor in improving the selectivity of the catalyst. When the additional amount of sodium formate is 1%, the catalyst prepared has both high acetylene conversion and high ethylene selectivity.

Keywords: C₂ hydrogenation, activated carbon, Ag promoter, Pd catalysts

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Authors: Mohammad Kousara, Françoise Dumas, Rama Ibrahim, Joëlle Dubois, Joël Raingeaud

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Suberosanes are a small group of marine natural sesquiterpenes discovered since 1996 by Boyd, Sheu and Qi from three gorgonians. Their skeleton was previously found in quadranes produced by the terrestrial fungus Aspergillus terreus. Up to date, eleven suberosanes are described from which (-)-suberosanone and (-)-suberosenol A are reaching the picomolar cytotoxicity level on human solid tumors cell lines. Due to their impressive cytotoxic properties and their limited availability, we undertook an asymmetric synthesis of the most active members of this family in order to get insight into their absolute configurations and their biological properties. The challenge of their synthesis is the regio- and stereoselective elaboration of the compact bridged tricyclic skeleton with up to five all adjacent asymmetric centers, including a central quaternary carbon one. Our strategy is based on an aza-ene-synthesis key step which is regio-and stereo-controlled by the choice of a chiral amine enantiomer. it approach is concise and flexible, the enantiopur ABC tricyclic intermediate that have been synthesized being the common precursor of suberosanes.

Keywords: suberosanes, asymmetric synthesis, sesquiterpenes, quadranes

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Authors: Zia R. Tahir, P. Mandal

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This paper presents the details of a numerical study of buckling and post buckling behaviour of laminated carbon fiber reinforced plastic (CFRP) thin-walled cylindrical shell under axial compression using asymmetric meshing technique (AMT) by ABAQUS. AMT is considered to be a new perturbation method to introduce disturbance without changing geometry, boundary conditions or loading conditions. Asymmetric meshing affects both predicted buckling load and buckling mode shapes. Cylindrical shell having lay-up orientation [0°/+45°/-45°/0°] with radius to thickness ratio (R/t) equal to 265 and length to radius ratio (L/R) equal to 1.5 is analysed numerically. A series of numerical simulations (experiments) are carried out with symmetric and asymmetric meshing to study the effect of asymmetric meshing on predicted buckling behaviour. Asymmetric meshing technique is employed in both axial direction and circumferential direction separately using two different methods, first by changing the shell element size and varying the total number elements, and second by varying the shell element size and keeping total number of elements constant. The results of linear analysis (Eigenvalue analysis) and non-linear analysis (Riks analysis) using symmetric meshing agree well with analytical results. The results of numerical analysis are presented in form of non-dimensional load factor, which is the ratio of buckling load using asymmetric meshing technique to buckling load using symmetric meshing technique. Using AMT, load factor has about 2% variation for linear eigenvalue analysis and about 2% variation for non-linear Riks analysis. The behaviour of load end-shortening curve for pre-buckling is same for both symmetric and asymmetric meshing but for asymmetric meshing curve behaviour in post-buckling becomes extraordinarily complex. The major conclusions are: different methods of AMT have small influence on predicted buckling load and significant influence on load displacement curve behaviour in post buckling; AMT in axial direction and AMT in circumferential direction have different influence on buckling load and load displacement curve in post-buckling.

Keywords: CFRP composite cylindrical shell, asymmetric meshing technique, primary buckling, secondary buckling, linear eigenvalue analysis, non-linear riks analysis

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Authors: Sélima Baccar, Ephraim Clark

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This paper can be considered as a new perspective to analyse credit spreads. A comprehensive empirical analysis of conditional variance of credit spreads indices is performed using various GARCH models. Based on a comparison between traditional and asymmetric GARCH models with alternative functional forms of the conditional density, we intend to identify what macroeconomic and financial factors have driven daily changes in the US Dollar credit spreads in the period from January 2011 through January 2013. The results provide a strong interdependence between credit spreads and the explanatory factors related to the conditions of interest rates, the state of the stock market, the bond market liquidity and the exchange risk. The empirical findings support the use of asymmetric GARCH models. The AGARCH and GJR models outperform the traditional GARCH in credit spreads modelling. We show, also, that the leptokurtic Student-t assumption is better than the Gaussian distribution and improves the quality of the estimates, whatever the rating or maturity.

Keywords: corporate bonds, default risk, credit spreads, asymmetric garch models, student-t distribution

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Authors: Viney Dixit, Rohit R. Shahi, Ashish Bhatnagar, P. Jain, T. P. Yadav, O. N. Srivastava

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Carbons are being widely investigated as hydrogen storage material owing to their light weight, fast hydrogen absorption kinetics and low cost. However, these materials suffer from low hydrogen storage capacity at room temperature. The aim of the present study is to synthesize carbon based material which shows moderate hydrogen storage at room temperature. For this purpose, hydrogenation characteristics of natural precursor coconut kernel is studied in this work. The hydrogen storage measurement reveals that the as-synthesized materials have good hydrogen adsorption and desorption capacity with fast kinetics. The synthesized material absorbs 8 wt.% of hydrogen at liquid nitrogen temperature and 2.3 wt.% at room temperature. This could be due to the presence of certain elements (KCl, Mg, Ca) which are confirmed by TEM.

Keywords: coconut kernel, carbonization, hydrogenation, KCl, Mg, Ca

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Authors: María Victoria Alvarez Magañini, Lautaro Nahuel Rubbi

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According to different theories, the hegemonic war between the United States and the People's Republic of China seems to be imminent. However, nowadays, it is clear that China's conventional military capacity is inferior to that of the United States. Nevertheless, the conditions that in the past were considered to be an indicator of validity in asymmetrical warfare, at present, in a possible asymmetric war scenario, are no longer considered to be taken as such. The military capacity is not the only concept that represents the main indicator of victory. The organisation and the use of forces are also an essential part of it. The present paper aims to analyze the Chinese Defense Strategy in relation to the concept of asymmetric warfare in the face of a possible war with the United States. The starting point will be developed on the basis of application of the theory which corresponds to the concept aforementioned making focus on recent developments of the People’s Republic of China in the field of non-conventional defense. A comparative analysis of the conventional forces of both powers/countries will also be carried out.

Keywords: asymmetric warfare, China, United States, hegemonic warfare

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Authors: Qing Wu, Fei-Yan Li, Heng-Chang Zhang

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Multitask learning support vector machines (SVMs) have recently attracted increasing research attention. Given several related tasks, the single-task learning methods trains each task separately and ignore the inner cross-relationship among tasks. However, multitask learning can capture the correlation information among tasks and achieve better performance by training all tasks simultaneously. In addition, the asymmetric squared loss function can better improve the generalization ability of the models on the most asymmetric distributed data. In this paper, we first make two assumptions on the relatedness among tasks and propose two multitask learning proximal support vector machine algorithms, named MTL-a-PSVM and EMTL-a-PSVM, respectively. MTL-a-PSVM seeks a trade-off between the maximum expectile distance for each task model and the closeness of each task model to the general model. As an extension of the MTL-a-PSVM, EMTL-a-PSVM can select appropriate kernel functions for shared information and private information. Besides, two corresponding special cases named MTL-PSVM and EMTLPSVM are proposed by analyzing the asymmetric squared loss function, which can be easily implemented by solving linear systems. Experimental analysis of three classification datasets demonstrates the effectiveness and superiority of our proposed multitask learning algorithms.

Keywords: multitask learning, asymmetric squared loss, EMTL-a-PSVM, classification

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Authors: R. S. Rajpurohit, N. C. Santhi Srinivas, Vakil Singh

Abstract:

Asymmetric stress cycling leads to accumulation of plastic strain which is called as ratcheting strain. The problem is generally associated with nuclear fuel cladding materials used in nuclear power plants and pressurized pipelines. In the present investigation, asymmetric stress controlled fatigue tests were conducted with three different parameters namely, mean stress, stress amplitude and stress rate (keeping two parameters constant and varying third parameter) to see the plastic strain accumulation and its effect on fatigue life and deformation behavior of Zircaloy-2 at 400°C. The tests were conducted with variable mean stress (45-70 MPa), stress amplitude (95-120 MPa) and stress rate (30-750 MPa/s) and tested specimens were characterized using transmission and scanning electron microscopy. The experimental results show that with the increase in mean stress and stress amplitude, the ratcheting strain accumulation increases with reduction in fatigue life. However, increase in stress rate leads to improvement in fatigue life of the material due to small ratcheting strain accumulation. Fractographs showed a decrease in area fraction of fatigue failed region.

Keywords: asymmetric cyclic loading, ratcheting fatigue, mean stress, stress amplitude, stress rate, plastic strain

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Authors: Hosein Faramarzpour

Abstract:

This work presents the optimum operational conditions for a hydrogen-based micro-scale power source, using a verified mathematical model including fluid dynamics and reaction kinetics. Thereafter the stable operational flame regime is pursued as a key factor in optimizing the design of micro-combustors. The results show that with increasing velocities, four H2 flame regimes develop in the micro-combustor, namely: 1) periodic ignition-extinction regime, 2) steady symmetric regime, 3) pulsating asymmetric regime, and 4) steady asymmetric regime. The first regime that appears in 0.8 m/s inlet velocity is a periodic ignition-extinction regime which is characterized by counter flows and tulip-shape flames. For flow velocity above 0.2 m/s, the flame shifts downstream, and the combustion regime switches to a steady symmetric flame where temperature increases considerably due to the increased rate of incoming energy. Further elevation in flow velocity up to 1 m/s leads to the pulsating asymmetric flame formation, which is associated with pulses in various flame properties such as temperature and species concentration. Further elevation in flow velocity up to 1 m/s leads to the pulsating asymmetric flame formation, which is associated with pulses in various flame properties such as temperature and species concentration. Ultimately, when the inlet velocity reached 1.2 m/s, the last regime was observed, and a steady asymmetric regime appeared.

Keywords: thermophotovoltaic generator, micro combustor, micro power generator, combustion regimes, flame dynamic

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Authors: Sehrish Qayyum

Abstract:

In this age of constant technology, asymmetrical warfare could not be won. Attuned psychometric study confirms that screaming sometimes is more productive than active retaliation against strong adversaries. Asymmetric warfare is a game of nerves and thoughts with least vigorous participation for large anticipated losses. It creates the condition of paraplegia with partial but permanent immobility, which effects the core warfare operations, being screams rather than active retaliation. When one’s own power is doubted, it gives power to one’s own doubt to ruin all planning either done with superlative cost-benefit analysis. Strategically calculated estimation of asymmetric warfare since the early WWI to WWII, WWII-to Cold War, and then to the current era in three chronological periods exposits that courage makes nations win the battle of warriors to battle of comrades. Asymmetric warfare has been most difficult to fight and survive due to unexpectedness and being lethal despite preparations. Thoughts before action may be the best-assumed strategy to mix Regional Security Complex Theory and OODA loop to develop the Paraplegic Resilience Policy Plan (PRPP) to win asymmetric warfare. PRPP may serve to control and halt the ongoing wave of terrorism, guerilla warfare, and insurgencies, etc. PRPP, along with a strategic work plan, is based on psychometric analysis to deal with any possible war condition and tactic to save millions of innocent lives such that lost in Christchurch New Zealand in 2019, November 2015 Paris attacks, and Berlin market attacks in 2016, etc. Getting tangled into self-imposed epistemic dilemmas results in regret that becomes the only option of performance. It is a descriptive psychometric analysis of war conditions with generic application of probability tests to find the best possible options and conditions to develop PRPP for any adverse condition possible so far. Innovation in technology begets innovation in planning and action-plan to serve as a rheostat approach to deal with asymmetric warfare.

Keywords: asymmetric warfare, psychometric analysis, PRPP, security

Procedia PDF Downloads 105

Authors: Hsueh-Cheng Yang

Abstract:

The generation and design of compound involute spur gearings can be used in gear pump. A compound rack cutter with asymmetric involute teeth is presented for determining the mathematical model of compound gear pumps. This paper covers the following topics: (a) generation and geometry of compound rack cutter is presented and used to generate a compound gear and a compound pinion. (b) Based on the developed compound gears, stress analysis was performed for the symmetric gears and the asymmetric gears. Comparing the results of the stress analysis for the asymmetric involute teeth is superior to the symmetric involute teeth. A numerical example that illustrates the developed compound rack cutter is represented.

Keywords: compound, involute teeth, gear pump, rack cutter

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