Search results for: acetylene hydrogenation

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: 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: S. Sivakumar, Ashwin Bala, S. Prithviraj, K. Panthala Rajakumaran, R. Pradeep, J. Udhayakumar

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Studies reveal that acetylene gas derived from hydrolysis of calcium carbide has similar properties to that of diesel. However, the self-ignition temperature of acetylene gas is higher than that of diesel. Early investigations reveal that acetylene gas could be used as alternative fuel mode. In the present work, acetylene gas of 31/min were inducted and diesel was injected into the combustion chamber of a single cylinder air cooled diesel engine. It was observed that the higher calorific value of acetylene gas improves the brake thermal efficiency at full load conditions. The CO and HC emissions were higher at part load conditions as compared to conventional diesel. The Nox emission level was higher and smoke emission was lower during dual fuel mode under all operating conditions. It is concluded that dual fuel mode of acetylene gas and diesel improves the brake thermal efficiency and reduces smoke in diesel engine.

Keywords: acetylene gas, diesel engine, Nox emission, CO emission, HC emission

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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: 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: 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: 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: Jerzy Ejsmont, Beata Świeczko-Żurek, Grzegorz Ronowski

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Gas cylinders in general and particularly cylinders containing acetylene constitute a great potential danger for fire and rescue services involved in salvage operations. Experiments show that gas cylinders with acetylene, oxygen, hydrogen, CNG, LPG or CO2 may blow after short exposition to heat with very destructive effect as fragments of blown cylinder may fly even several hundred meters. In the case of acetylene, the explosion may occur also several hours after the cylinder is cooled down. One of the possible neutralization procedures that in many cases may be used to prevent explosions is shooting dangerous cylinders by rifle bullets. This technique is used to neutralize acetylene cylinders in a few European countries with great success. In Poland research project 'BLOW' was launched in 2014 with the aim to investigate phenomena related to fire influence on industrial and home used cylinders and to evaluate usefulness of the shooting technique. All together over 100 gas cylinders with different gases were experimentally tested at the military blasting grounds and in shelters. During the experiments cylinder temperature and pressure were recorded. In the case of acetylene that is subjected to thermal decomposition also concentration of hydrogen was monitored. Some of the cylinders were allowed to blow and others were shot by snipers. It was observed that shooting hot cylinders has never created more dangerous situations than letting the cylinders to explode spontaneously. In a great majority of cases cylinders that were punctured by bullets released gas in a more or less violent but relatively safe way. The paper presents detailed information about experiments and presents particularities of behavior of cylinders containing different gases. Extensive research was also done in order to select bullets that may be safely and efficiently used to puncture different cylinders. The paper shows also results of those experiments as well as gives practical information related to techniques that should be used during shooting.

Keywords: fire, gas cylinders, neutralization, shooting

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Authors: Yubo Bi, Xiao Chen, Shouxiang Lu

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A kind of gas-fueled burner, named Burning Rate Emulator, was proposed for the purpose of the emulation of condensed fuel recently. The gaseous fuel can be pure combustible fuel gas or blends of gaseous fuel or inert gas. However, this concept was recently proposed without detailed study on the combustion characteristic of fuel blends. In this study, two kinds of common gaseous fuels were selected, propane and acetylene, to provide the combustion heat as well as a large amount of smoke, which widely exists in liquid and solid fuel burning process. A set of experiments were carried out using a gas-fueled burner with a diameter of 8 cm. The total volume flow rate of propane and acetylene was kept at 3 liters per minute. The volume fraction of propane varied from 0% to 100% at interval of 10%. It is found that the flame height increases with propane volume fraction, which may be caused by the increase of heat release rate, as the energy density of propane is larger than that of acetylene. The dimensionless flame height is correlated against dimensionless heat release rate, which shows a power function relationship. The radiation fraction of the flame does not show a monotonic relationship with propane volume fraction. With the increase of propane volume fraction from 0% to 100%, the value of radiation fraction increases first and reach a maximum value around 0.46 at a propane volume fraction of 10%, and then decreases continuously to a value of 0.25 at the propane volume fraction of 100%. The flame radiation is related to the soot in the flame. The trend of the radiation fraction reflects that there may be a synergistic effect of soot formation between propane and acetylene which can be guessed from the significantly high radiation fraction at a propane volume fraction of 10%. This work provides data for combustion of gaseous fuel blends pool fire and also give reference on the design of Burning Rate Emulator.

Keywords: Burning Rate Emulator, fuel blends pool fire, flame height, radiation fraction

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Authors: Nacira Mecheri, N. Boussid

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A new chemical mechanism designed to study the process of forming the first aromatic ring (benzene) and polycyclic aromatic hydrocarbons (PAH) from a flame of acetylene (C2H2) has been developed. The mechanism developed, contains 50 chemical species involved in 268 reversible elementary reactions. The comparison between the results from modelling and experimental measurements allowed us to test the validity of the postulated mechanism in specific experimental conditions. Kinetic analysis of the flame by calculating the maximum rates for each elementary reaction, allowed us to identify key reactions pathways of consumption and formation of main precursors of soot.

Keywords: benzene, PAH, acetylene, modeling, flame, soot

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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: 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: Moulay Driss Mellaoui, Abdallah Imjjad, Rachid Boutiddar, Haydar Mohammad-Salim, Nivedita Acharjee, Hassan Bourzi, Souad El Issami, Khalid Abbiche, Hanane Zejli

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We have investigated the underlying molecular processes involved in the [3+2] cycloaddition (32CA) reactions between N-methyl-C-(2-furyl) nitrone and three acetylene derivatives: 4b, 5b, and 6b. For this investigation, we utilized molecular electron density theory (MEDT) and density functional theory (DFT) methods at the B3LYP-D3/6 31G (d) computational level. These 32CA reactions, which exhibit a zwitterionic (zw-type) nature, proceed through a one-step mechanism with activation enthalpies ranging from 8.80 to 14.37 kcal mol−1 in acetonitrile and ethanol solvents. When the nitrone reacts with phenyl methyl propiolate (4b), two regioisomeric pathways lead to the formation of two products: P1,5-4b and P1,4-4b. On the other hand, when the nitrone reacts with dimethyl acetylene dicarboxylate (5b) and acetylene dicarboxylic acid (but-2-ynedioic acid) (6b), it results in the formation of a single product. Through topological analysis, we can categorize the nitrone as a zwitterionic three-atom component (TAC). Furthermore, the analysis of conceptual density functional theory (CDFT) indices classifies the 32CA reactions of the nitrone with 4b, 5b, and 6b as forward electron density flux (FEDF) reactions. The study of bond evolution theory (BET) reveals that the formation of new C-C and C-O covalent bonds does not initiate in the transition states, as the intermediate stages of these reactions display pseudoradical centers of the atoms already involved in bonding.

Keywords: 4-isoxazoline, DFT/B3LYP-D3, regioselectivity, cycloaddition reaction, MEDT, ELF

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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: Ravi Prakash

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The effects of Zr addition on kinetics and hydrogen absorption characteristics of BCC alloy 52Ti-12V-36Cr doped with x wt% of Zr (x = 0, 4, 8 & 12) was investigated. The samples have been characterized by X-ray diffraction, and activation study were made at four different temperatures- 100 oC, 200 oC, 300 oC and 400 oC. First hydrogenation kinetics of alloys were studied at 20 bar of hydrogen pressure and room temperature after giving heat treatment at different temperatures for 6 hours. Among the various Zr doped alloys studied, the composition 52Ti-12V-36Cr + 4wt% Zr shows maximum hydrogen storage capacity of 3.6wt%. Small amount of Zr shows advantageous effects on kinetics of alloy. It was also found out that alloys with the higher Zr concentration can be activated by giving heat treatment at lower temperatures. There is reduction in hydrogen storage capacity with increasing Zr content in the alloy primarily due to increasing abundance of secondary phase as established by X-Ray Diffraction and Scanning Electron Microscope results.

Keywords: hydrogen storage, metal hydrides, bcc alloy, heat treatment

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Authors: I. Wiemann, N. Weiß, E. Schlücker, M. Wensing

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A very promising alternative to compression or cryogenics is the chemical storage of hydrogen by liquid organic hydrogen carriers (LOHC). These carriers enable high energy density and allow, at the same time, efficient and safe storage under ambient conditions without leakage losses. Another benefit of this storage medium is the possibility of transporting it using already available infrastructure for the transport of fossil fuels. Efficient use of LOHC is related to precise process control, which requires a number of sensors in order to measure all relevant process parameters, for example, to measure the level of hydrogen loading of the carrier. The degree of loading is relevant for the energy content of the storage carrier and simultaneously represents the modification in the chemical structure of the carrier molecules. This variation can be detected in different physical properties like permittivity, viscosity, or density. E.g., each degree of loading corresponds to different viscosity values. Conventional measurements currently use invasive viscosity measurements or near-line measurements to obtain quantitative information. This study investigates permittivity changes resulting from changes in hydrogenation degree (chemical structure) and temperature. Based on calibration measurements, the degree of loading and temperature of LOHC can thus be determined by comparatively simple permittivity measurements in a cavity resonator. Subsequently, viscosity and density can be calculated. An experimental setup with a heating device and flow test bench was designed. By varying temperature in the range of 293,15 K -393,15 K and flow velocity up to 140 mm/s, corresponding changes in the resonation frequency were determined in the hundredths of the GHz range. This approach allows inline process monitoring of hydrogenation of the liquid organic hydrogen carrier (LOHC).

Keywords: hydrogen loading, LOHC, measurement, permittivity, viscosity

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Authors: Gheorghiţa Mitran, Adriana Urdă, Mihaela Florea, Octavian Dumitru Pavel, Florentina Neaţu

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Oxidative dehydrogenation and hydrogenation reactions of L-malic acid are interesting ways for its transformation into valuable products, including oxaloacetic, pyruvic and malonic acids but also 1,4-butanediol and 1,2,4-butanetriol. Keto acids have a range of applicationsin many chemical syntheses as pharmaceuticals, food additives and cosmetics. 3-Hydroxybutyrolactone and 1,2,4-butanetriol are used for the synthesis of chiral pharmaceuticals and other fine chemicals, while 1,4-butanediol can be used for organic syntheses, such as polybutylene succinate (PBS), polybutylene terephthalate (PBT), and for production of tetrahydrofuran (THF). L-malic acid is a non-toxic and natural organic acid present in fruits, and it is the main component of wine alongside tartaric acid representing about 90% of the wine total acidity. Iron oxides dopped with cobalt (CoxFe3-xO4; x= 0; 0.05; 0.1; 0.15) were studied as catalysts in these reactions. There is no mention in the literature of non-noble transition metal catalysts for these reactions. The method used for catalysts preparation was coprecipitation, whileBET XRD, XPS, FTIR and UV-VIS spectroscopy were used for the physicochemical properties evaluation.TheXRD patterns revealed the presence of α-Fe2O3 rhombohedral hematite structure, with cobalt atoms well dispersed and embedded in this structure. The studied samples are highly crystalline, with a crystallite size ranged from 58 to 65 nm. The optical absorption properties were investigated using UV-Vis spectroscopy, emphasizing the presence of bands that correspond with the reported hematite nanoparticle. Likewise, the presence of bands corresponding to lattice vibration of hexagonal hematite structurehas been evidenced in DRIFT spectra. Oxidative dehydrogenation of malic acid was studied using as solvents for malic acid ethanol or water(2, 5 and 10% malic acid in 5 mL solvent)at room temperature, while the hydrogenation reaction was evaluated in water as solvent (5%), in the presence of 1% catalyst. The oxidation of malic acid into oxaloacetic acid is the first step, after that, oxaloacetic acid is rapidly decarboxylated to malonic acid or pyruvic acid, depending on the active site. The concentration of malic acid in solution, it, in turn, has an influence on conversionthis decreases when the concentration of malic acid in the solution is high. The spent catalysts after the oxidative dehydrogenation of malic acid in ethanol were characterized by DRIFT spectroscopy and the presence of oxaloacetic, pyruvic and malonicacids, along with unreacted malic acidwere observed on the surface. The increase of the ratio of Co/Fe on the surface has an influence on the malic acid conversion and on the pyruvic acid yield, while the yield of malonic acid is influenced by the percentage of iron on the surface (determined from XPS). Oxaloacetic acid yield reaches a maximumat one hour of reaction, being higher when ethanol is used as a solvent, after which it suddenly decreases. The hydrogenation of malic acid occurs by consecutive reactions with the production of 3-hydroxy-butyrolactone, 1,2,4-butanetriol and 1,4-butanediol. Malic acid conversion increases with cobalt loading increasing up to Co/Fe ratio of 0.1, after which it has a slight decrease, while the yield in 1,4-butanediol is directly proportional to the cobalt content.

Keywords: malic acid, oxidative dehydrogenation, hydrogenation, oxaloacetic acid

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Authors: C. Joseph Abou-Fayssal, K. Philippot, R. Poli, E. Manoury, A. Riisager

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The use of soluble polymer-supported metal nanoparticles (MNPs) has received significant attention for the ease of catalyst recovery and recycling. Of particular interest are MNPs that are supported on polymers that are either soluble or form stable colloidal dispersion in water, as this allows to combine of the advantages of the aqueous biphasic protocol with the catalytical performances of MNPs. The objective is to achieve good confinement of the catalyst in the nanoreactor cores and, thus, a better catalyst recovery in order to overcome the previously witnessed MNP extraction. Inspired by previous results, we are interested in the design of polymeric nanoreactors functionalized with ligands able to solidly anchor metallic nanoparticles in order to control the activity and selectivity of the developed nanocatalysts. The nanoreactors are core-crosslinked micelles (CCM) synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. Varying the nature of the core-linked functionalities allows us to get differently stabilized metal nanoparticles and thus compare their performance in the catalyzed aqueous biphasic hydrogenation of model substrates. Particular attention is given to catalyst recyclability.

Keywords: biphasic catalysis, metal nanoparticles, polymeric nanoreactors, catalyst recovery, RAFT polymerization

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Authors: Rajashekar Badam, Vedarajan Raman, Noriyoshi Matsumi

Abstract:

Efficiency of energy converting and storage systems like fuel cells and Li-Air battery principally depended on oxygen reduction reaction (ORR) which occurs at cathode. As the kinetics of the ORR is very slow, it becomes the rate determining step. Exploring carbon substrates for enhancing the dispersion and activity of the metal catalyst and commercially viable simple preparation method is a very crucial area of research in the field of energy materials. Hence, many researchers made large number of carbon-based ORR materials today. But, there are hardly few studies on the effect of interaction between Pt-carbon and carbon-electrolyte on activity. In this work, we have prepared functionalized carbon-based Pt catalyst (Pt-FAB) with enhanced interfacial properties that lead to efficient ORR catalysis. The present work deals with a single-pot method to exfoliate and functionalized acetylene black with enhanced interaction with Pt as well as electrolyte. Acetylene black was functionalized and exfoliated using a facile single pot acid treatment method. The resulted FAB was further decorated with Pt-nano particles (Pt-np). The TEM images of Pt-FAB with uniformly decorated Pt-np of ~3 nm. Further, XPS studies of Pt 4f peak revealed that Pt0 peak was shifted by 0.4 eV in Pt-FAB compared to binding energy of typical Pt⁰ found in Pt/C. The shift can be ascribed to the modulation of electronic state and strong electronic interaction of Pt with carbon. Modulated electronic structure of Pt and strong electronic interaction of Pt with FAB enhances the catalytic activity and durability respectively. To understand the electrode electrolyte interface, electrochemical impedance spectroscopy was carried out. These measurements revealed that the charge transfer resistance of electrode to electrolyte for Pt-FAB is 10 times smaller than that of conventional Pt/C. The interaction with electrolyte helps reduce the interface boundaries, which in turn affects the overall catalytic performance of the electrode. Cyclic voltammetric measurements in 0.1M HClO₄ aq. at a potential scan rate of 50 mVs-1 was employed to evaluate electrochemical surface area (ECSA) of Pt. ECSA of Pt-FAB was found to be as high as 67.2 m²g⁻¹. The three-electrode system showed very high ORR catalytic activity. Mass activity at 0.9 V vs. RHE showed 460 A/g which is much higher than the DOE target values for the year 2020. Further, it showed enhanced performance by showing 723 mW/cm² of highest power density and 1006 mA/cm² of current density at 0.6 V in fuel cell single cell type configuration and 1030 mAhg⁻¹ of rechargeable capacity in Li air battery application. The higher catalytic activity can be ascribed to the improved interaction of FAB with Pt and electrolyte. The aforementioned results evince that Pt-FAB will be a promising cathode material for efficient ORR with significant cyclability for its application in fuel cells and Li-Air batteries. In conclusion, a disordered material was prepared from AB and was systematically characterized. The extremely high ORR activity and ease of preparation make it competent for replacing commercially available ORR materials.

Keywords: functionalized acetylene black, oxygen reduction reaction, fuel cells, Functionalized battery

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Authors: L. M. Ombaka, R. S. Oosthuizen, P. G. Ndungu, V. O. Nyamori

Abstract:

Understanding the role of nitrogen species on the catalytic properties of nitrogen-doped carbon nanotubes (N-CNTs) as catalysts supports is critical as nitrogen species influence the support’s properties. To evaluate the influence of pyrrolic nitrogen on the physicochemical properties and catalytic activity of N-CNTs supported Pd (Pd/N-CNTs); N-CNTs containing varying pyrrolic contents were synthesized. The catalysts were characterised by the use of transmission electron microscope (TEM), scanning electron microscope, X-ray photoelectron spectroscopy (XPS), X-ray diffraction, Fourier transform infrared spectroscopy, and temperature programmed reduction. TEM analysis showed that the Pd nanoparticles were mainly located along the defect sites on N-CNTs. XPS analysis revealed that the abundance of Pd0 decreased while that of Pd2+ increased as the quantity of pyrrolic nitrogen increased. The increase of Pd2+ species was accredited to the formation of stable Pd-N coordination complexes which prevented further reduction of Pd2+ to Pd0 during synthesis. The formed Pd-N complexes increased the stability and dispersion of Pd2+ nanoparticles. The selective hydrogenation of nitrobenzophenone to aminobenzophenone over Pd/N-CNTs was compared to that of Pd on carbon nanotubes (Pd/CNTs). Pd/N-CNTs showed a higher catalytic activity and selectivity compared with Pd/CNTs. Pyrrolic nitrogen functional groups significantly promoted the selectivity towards aminobenzophenone formation.

Keywords: pyrrolic N-CNTs, hydrogenation reactions, chemical vapour deposition technique

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Authors: Rujira Jitrwung, Kuntima Krekkeitsakul, Weerawat Patthaveekongka, Chiraphat Kumpidet, Jarukit Tepkeaw, Krissana Jaikengdee, Anantachai Wannajampa

Abstract:

Flue gas discharging from coal fired or gas combustion power plant contains around 12% Carbon dioxide (CO₂), 6% Oxygen (O₂), and 82% Nitrogen (N₂).CO₂ is a greenhouse gas which has been concerned to the global warming. Carbon Capture, Utilization, and Storage (CCUS) is a topic which is a tool to deal with this CO₂ realization. Flue gas is drawn down from the chimney and filtered, then it is compressed to build up the pressure until 8 bar. This compressed flue gas is sent to three stages Pressure Swing Adsorption (PSA), which is filled with activated carbon. Experiments were showed the optimum adsorption pressure at 7bar, which CO₂ can be adsorbed step by step in 1st, 2nd, and 3rd stage, obtaining CO₂ concentration 29.8, 66.4, and 96.7 %, respectively. The mixed gas concentration from the last step is composed of 96.7% CO₂,2.7% N₂, and 0.6%O₂. This mixed CO₂product gas obtained from 3 stages PSA contained high concentration CO₂, which is ready to use for methanol synthesis. The mixed CO₂ was experimented in 5 Liter/Day of methanol synthesis reactor skid by 3 step processes as followed steam reforming, reverse water gas shift, and then hydrogenation. The result showed that proportional of mixed CO₂ and CH₄ 70/30, 50/50, 30/70 % (v/v), and 10/90 yielded methanol 2.4, 4.3, 5.6, and 6.0 Liter/day and save CO₂ 40, 30, 20, and 5 % respectively. The optimum condition resulted both methanol yield and CO₂ consumption using CO₂/CH₄ ratio 43/57 % (v/v), which yielded 4.8 Liter/day methanol and save CO₂ 27% comparing with traditional methanol production from methane steam reforming (5 Liter/day)and absent CO₂ consumption.

Keywords: carbon capture utilization and storage, pressure swing adsorption, reforming, reverse water gas shift, methanol

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Authors: A. Merzouki, N. Haddaoui

Abstract:

Polymers have a large reputation as electric insulators. These materials are characterized by weak weight, reduced price and a large domain of physical and chemical properties. They conquered new application domains that were until a recent past the exclusivity of metals. In this work, we used some composite materials (polymers/conductive fillers), as electrodes and we try to cover them with metallic lead layers in order to use them as courant collector grids in lead-acid battery plates.

Keywords: electrodeposition, polymer composites, carbon black, acetylene black

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Authors: Magdy G. Asaad

Abstract:

Solitons are among the most beneficial solutions for science and technology for their applicability in physical applications including plasma, energy transport along protein molecules, wave transport along poly-acetylene molecules, ocean waves, constructing optical communication systems, transmission of information through optical fibers and Josephson junctions. In this talk, we will apply the bilinear technique to generate a class of soliton solutions to the (3+1)-dimensional nonlinear soliton equation of Jimbo-Miwa type. Examples of the resulting soliton solutions are computed and a few solutions are plotted.

Keywords: Pfaffian solutions, N-soliton solutions, soliton equations, Jimbo-Miwa

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Authors: Farzaneh Shayeganfar, Ali Ramazani

Abstract:

Exciton (strong electronic interaction of electron-hole) and hot carriers created by surface plasmon polaritons has been demonstrated in nanoscale optoelectronic devices, enhancing the photoresponse of the system. Herein, we employ a quantum framework to consider coupled exciton- hot carriers effects on photovoltaiv energy distribution, scattering process, polarizability and light emission of 2D-semicnductor. We use density functional theory (DFT) to design computationally a semi-functionalized 2D honeycomb silicon boride (SiB) monolayer with H atoms, suitable for photovoltaics. The dynamical stability, electronic and optical properties of SiB and semi-hydrogenated SiB structures were investigated utilizing the Tran-Blaha modified Becke-Johnson (TB-mBJ) potential. The calculated phonon dispersion shows that while an unhydrogenated SiB monolayer is dynamically unstable, surface semi-hydrogenation improves the stability of the structure and leads to a transition from metallic to semiconducting conductivity with a direct band gap of about 1.57 eV, appropriate for photovoltaic applications. The optical conductivity of this H-SiB structure, determined using the random phase approximation (RPA), shows that light adsorption should begin at the boundary of the visible range of light. Additionally, due to hydrogenation, the reflectivity spectrum declines sharply with respect to the unhydrogenated reflectivity spectrum in the IR and visible ranges of light. The energy band gap remains direct, increasing from 0.9 to 1.8 eV, upon increasing the strain from -6% (compressive) to +6% (tensile). Additionally, compressive and tensile strains lead, respectively, to red and blue shifts of optical the conductivity threshold around the visible range of light. Overall, this study suggests that H-SiB monolayers are suitable as two-dimensional solar cell materials.

Keywords: surface plasmon, hot carrier, strain engineering, valley polariton

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Authors: Inom Sh. Normatov, Nurmakhmad Shermatov, Rajabali Barotov, Rano Eshankulova

Abstract:

The results of the studies for the hydrogen production by the application of water electrolysis and plasma-chemical processing of gas condensate-waste of natural gas production methods are presented. Thin coating covers the electrode surfaces in the process of water electrolysis. Therefore, water for electrolysis was first exposed to electrosedimentation. The threshold voltage is shifted to a lower value compared with the use of electrodes made of stainless steel. At electrolysis of electrosedimented water by use of electrodes from stainless steel, a significant amount of hydrogen is formed. Pyrolysis of gas condensates in the atmosphere of a nitrogen was followed by the formation of acetylene (3-7 vol.%), ethylene (4-8 vol.%), and pyrolysis carbon (10-15 wt.%).

Keywords: electrolyze, gascondensate, hydrogen, pyrolysis

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