Search results for: dehydrogenation and hydrogenation

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: 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

Procedia PDF Downloads 309

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: 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

Procedia PDF Downloads 243

Authors: Anıl Dinçer, Dilek Duranoğlu

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Ketones, which are widely used as solvent and chemical intermediates in chemical process industry, are commercially produced by using catalytic dehydrogenation of secondary alcohols at higher temperature (300-500ºC), and pressure (1-5 bar). Although it is possible to obtain high conversion values (60-87%) via gas phase catalytic dehydrogenation, working high temperature and pressure can result in side reactions and shorten the catalyst life. In order to overcome these challenges, catalytic dehydrogenation in the presence of an appropriate liquid solvent has been started to use. Hence, secondary alcohols can be converted to respective ketones at relatively low temperature (150-200ºC) under atmospheric pressure. In this study, methyl ethyl ketone and acetone was produced via catalytic dehydrogenation of appropriate secondary alcohols (isopropyl alcohol and sec-butyl alcohol) in the presence of liquid solvent at 160-190ºC. Obtained methyl ethyl ketone and acetone were analyzed by using FTIR and GC spectrometer. Effects of temperature, amount of catalyst and solvent on conversion and reaction rate were investigated. Optimum process conditions, which gave high conversion and reaction rate, were determined. According to GC results, 70% of secondary butyl alcohol and 42% of isopropyl alcohol was converted to related ketone (methyl ethyl ketone and acetone, respectively) at optimum process conditions. After distillation, 99.13% methyl ethyl ketone and 99.20% acetone was obtained. Consequently, liquid phase dehydrogenation process, which can compete with commercial gas phase process, was developed.

Keywords: dehydrogenation, liquid phase, methyl ethyl ketone, secondary alcohol

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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

Procedia PDF Downloads 240

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

Procedia PDF Downloads 222

Authors: Napat Hataivichian

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The effect of transition metal doping on Pt/Al2O3 catalyst used in propane dehydrogenation reaction at 500˚C was studied. The preparation methods investigated were sequential impregnation (Pt followed by the 2nd metal or the 2nd metal followed by Pt) and co-impregnation. The metal contents of these catalysts were fixed as the weight ratio of Pt per the 2nd metal of around 0.075. These catalysts were characterized by N2-physisorption, TPR, CO-chemisorption and NH3-TPD. It was found that the impregnated 2nd metal had an effect upon reducibility of Pt due to its interaction with transition metal-containing structure. This was in agreement with the CO-chemisorption result that the presence of Pt metal, which is a result from Pt species reduction, was decreased. The total acidity of bimetallic catalysts is decreased but the strong acidity is slightly increased. It was found that the stability of bimetallic catalysts prepared by co-impregnation and sequential impregnation where the 2nd metal was impregnated before Pt were better than that of monometallic catalyst (undoped Pt one) due to the forming of Pt sites located on the transition metal-oxide modified surface. Among all preparation methods, the sequential impregnation method- having Pt impregnated before the 2nd metal gave the worst stability because this catalyst lacked the modified Pt sites and some fraction of Pt sites was covered by the 2nd metal.

Keywords: alumina, dehydrogenation, platinum, transition metal

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Authors: S. Assylbekova, D. Zolotareva, A. Dauletbakov, Ye. Belyankova, S. Bayazit, A. Basharimova, A. Zazybin, A. Isimberlenova, A. Kakim, M. Aydemir, A. Kairullinova

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Transfer hydrogenation (TH) is a key process in organic chemistry, especially in pharmaceutical and agrochemical synthesis, offering a safer and more sustainable approach compared to traditional methods. This work is devoted to the synthesis and use of ruthenium catalysts containing phosphinite ligands in TH reactions. Ruthenium complexes are particularly noteworthy for their effectiveness in asymmetric TH. Their stability and adaptability to different reaction environments make them ideal for both laboratory-scale and industrial applications. Phosphinite ligands (P(OR)R'2) are used in the synthesis of complexes to improve their properties. These ligands are known for their ability to finely tune the electronic and steric properties of metal centers. The electron-donating nature of the phosphorus atom, combined with the variability in the R and R' groups, allows for significant customization of the catalyst's properties. The purpose and difference of the work is to study the incorporation of a hydrophilic ionic liquid into the composition of a phosphinite ligand, which will then be converted into a catalyst. The technique involves the synthesis of a phosphinite ligand with an ionic liquid at room temperature under an inert atmosphere and then a ruthenium complex. Next, the TH reactions of acetophenone and its derivatives are carried out using the resulting catalyst. The conversion of ketone to alcohol is analyzed using a gas chromatograph. This study contributes to the understanding of the influence of catalyst chemical properties on transfer hydrogenation results.

Keywords: transfer hydrogenation, ruthenium, catalysts, phosphinite ligands

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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: Ayman Hijazi, Witold Kwapinski, J. J. Leahy

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Finding a sustainable alternative energy to fossil fuel is an urgent need as various environmental challenges in the world arise. Therefore, formic acid (FA) decomposition has been an attractive field that lies at the center of biomass platform, comprising a potential pool of hydrogen energy that stands as a new energy vector. Liquid FA features considerable volumetric energy density of 6.4 MJ/L and a specific energy density of 5.3 MJ/Kg that qualifies it in the prime seat as an energy source for transportation infrastructure. Additionally, the increasing research interest in FA decomposition is driven by the need of in-situ H2 production, which plays a key role in the hydrogenation reactions of biomass into higher value components. It is reported elsewhere in literature that catalytic decomposition of FA is usually performed in poorly designed setup using simple glassware under magnetic stirring, thus demanding further energy investment to retain the used catalyst. it work suggests an approach that integrates designing a novel catalyst featuring magnetic property with a robust setup that minimizes experimental & measurement discrepancies. One of the most prominent active species for dehydrogenation/hydrogenation of biomass compounds is palladium. Accordingly, we investigate the potential of engrafting palladium metal onto functionalized magnetic nanoparticles as a heterogeneous catalyst to favor the production of CO-free H2 gas from FA. Using ordinary magnet to collect the spent catalyst renders core-shell magnetic nanoparticles as the backbone of the process. Catalytic experiments were performed in a jacketed batch reactor equipped with an overhead stirrer under inert medium. Through a novel approach, FA is charged into the reactor via high-pressure positive displacement pump at steady state conditions. The produced gas (H2+CO2) was measured by connecting the gas outlet to a measuring system based on the amount of the displaced water. The novelty of this work lies in designing a very responsive catalyst, pumping consistent amount of FA into a sealed reactor running at steady state mild temperatures, and continuous gas measurement, along with collecting the used catalyst without the need for centrifugation. Catalyst characterization using TEM, XRD, SEM, and CHN elemental analyzer provided us with details of catalyst preparation and facilitated new venues to alter the nanostructure of the catalyst framework. Consequently, the introduction of amine groups has led to appreciable improvements in terms of dispersion of the doped metals and eventually attaining nearly complete conversion (100%) of FA after 7 hours. The relative importance of the process parameters such as temperature (35-85°C), stirring speed (150-450rpm), catalyst loading (50-200mgr.), and Pd doping ratio (0.75-1.80wt.%) on gas yield was assessed by a Taguchi design-of-experiment based model. Experimental results showed that operating at lower temperature range (35-50°C) yielded more gas while the catalyst loading and Pd doping wt.% were found to be the most significant factors with a P-values 0.026 & 0.031, respectively.

Keywords: formic acid decomposition, green catalysis, hydrogen, mesoporous silica, process optimization, nanoparticles

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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: M. Sneha Reddy, M. Arun Kumar, V. Kameswara Rao

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Chromites are binary transition metal oxides with a general formula of ACr₂O₄, where A = Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, and Cu²⁺. Chromites have a normal-type spinel structure with interesting applications in the areas of applied physics, material sciences, and geophysics. They have attracted great consideration because of their unique physicochemical properties and tremendous technological applications in nanodevices, sensor elements, and high-temperature ceramics with useful optical properties. Copper chromite is one of the most efficient spinel oxides, having pronounced commercial application as a catalyst in various chemical reactions like oxidation, hydrogenation, alkylation, dehydrogenation, decomposition of organic compounds, and hydrogen production. Apart from its usage in chemical industries, CuCr₂O₄ finds its major application as a burn rate modifier in solid propellant processing for space launch vehicles globally. Herein we synthesized the nanoparticles of copper chromite using the co-precipitation method. The synthesized nanoparticles were characterized by XRD, TEM, SEM, BET, and TG-DTA. The synthesized nanoparticles of copper chromites were used as a catalyst for the thermal decomposition of various high-energy materials.

Keywords: copper chromite, coprecipitation method, high energy materials, catalytic thermal decomposition

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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: 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: Chongsutthamani Sitthiwet, Praphatsorn Plerdsranoy, Palmarin Dansirima, Priew Eiamlamai, Oliver Utke, Rapee Utke

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Hydrogen storage tank containing compacted LiNH2-LiH is developed by doping with TiF₄ and multi-walled nanotubes (MWCNTs) to study kinetic properties. Transition metal-based catalyst (TiF₄) provides the catalytic effect on hydrogen dissociation/recombination, while MWCNTs benefit thermal conductivity and hydrogen permeability during de/rehydrogenation process. The Enhancement of dehydrogenation kinetics is observed from the single-step reaction at a narrower and lower temperature range of 150-350 ºC (100 ºC lower than the compacted LiNH₂-LiH without additives) as well as long plateau temperature and constant hydrogen flow rate (50 SCCM) up to 30 min during desorption. Besides, Hydrogen contents de/absorbed during 5-6 cycles increase from 1.90-2.40 to 3.10-4.70 wt. % H₂ (from 29 to up to 80 % of theoretical capacity). In the process, Li₅TiN₃ is detected upon cycling probably absorbs NH₃ to form Li₅TiN₃(NH₃)x, which is favoring hydrogen sorption properties of the LiNH₂-LiH system. Importantly, the homogeneous reaction mechanisms and performances are found at all positions inside the tank of compacted LiNH₂-LiH doped with TiF₄ and MWCNTs.

Keywords: carbon, hydride, kinetics, dehydrogenation

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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: Yaxin Tang, Mingao Hou, Qian He, Guangfu Luo

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Bimetallic nanoparticles serve as a promising class of catalysts with tunable properties suitable for diverse catalytic reactions, yet a comprehensive understanding of their actual structures under operating conditions and the optimal design principles remains largely elusive. In this study, we unveil a prevalent surface segregation phenomenon in nearly 100 platinum-group-element-based bimetallic nanoparticles through first principles-based molecular dynamics simulations. Our findings highlight that two components in a nanoparticle with relatively lower surface energy tend to segregate to the surface. Motivated by this discovery, we propose a deliberate exploitation of surface segregation in designing bimetallic nanoparticle catalysts, aiming for heightened stability and reduced consumption of precious metals. To validate this strategy, we further investigate 36 platinum-based bimetallic nanoparticles for propane dehydrogenation catalysis. Through a systematic examination of catalytic sites on nanoparticles, we identify several systems as top candidates with Pt-enriched surfaces, remarkable thermal stability, and superior catalytic activity for propane dehydrogenation. The insights gained garnered from this study are anticipated to provide a valuable framework for the optimal design of other bimetallic nanoparticles.

Keywords: bimetallic nanoparticles, platinum-group element, catalysis, surface segregation, first-principles calculations

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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: Ayman Hijazi, Witold Kwapinski, J. J. Leahy

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Finding a sustainable alternative energy to fossil fuel is an urgent need as various environmental challenges in the world arise. Therefore, formic acid (FA) decomposition has been an attractive field that lies at the center of the biomass platform, comprising a potential pool of hydrogen energy that stands as a distinct energy vector. Liquid FA features considerable volumetric energy density of 6.4 MJ/L and a specific energy density of 5.3 MJ/Kg that qualifies it in the prime seat as an energy source for transportation infrastructure. Additionally, the increasing research interest in FA decomposition is driven by the need for in-situ H₂ production, which plays a key role in the hydrogenation reactions of biomass into higher-value components. It is reported elsewhere in the literature that catalytic decomposition of FA is usually performed in poorly designed setups using simple glassware under magnetic stirring, thus demanding further energy investment to retain the used catalyst. Our work suggests an approach that integrates designing a distinct catalyst featuring magnetic properties with a robust setup that minimizes experimental & measurement discrepancies. One of the most prominent active species for the dehydrogenation/hydrogenation of biomass compounds is palladium. Accordingly, we investigate the potential of engrafting palladium metal onto functionalized magnetic nanoparticles as a heterogeneous catalyst to favor the production of CO-free H₂ gas from FA. Using an ordinary magnet to collect the spent catalyst renders core-shell magnetic nanoparticles as the backbone of the process. Catalytic experiments were performed in a jacketed batch reactor equipped with an overhead stirrer under an inert medium. Through a distinct approach, FA is charged into the reactor via a high-pressure positive displacement pump at steady-state conditions. The produced gas (H₂+CO₂) was measured by connecting the gas outlet to a measuring system based on the amount of the displaced water. The uniqueness of this work lies in designing a very responsive catalyst, pumping a consistent amount of FA into a sealed reactor running at steady-state mild temperatures, and continuous gas measurement, along with collecting the used catalyst without the need for centrifugation. Catalyst characterization using TEM, XRD, SEM, and CHN elemental analyzer provided us with details of catalyst preparation and facilitated new venues to alter the nanostructure of the catalyst framework. Consequently, the introduction of amine groups has led to appreciable improvements in terms of dispersion of the doped metals and eventually attaining nearly complete conversion (100%) of FA after 7 hours. The relative importance of the process parameters such as temperature (35-85°C), stirring speed (150-450rpm), catalyst loading (50-200mgr.), and Pd doping ratio (0.75-1.80wt.%) on gas yield was assessed by a Taguchi design-of-experiment based model. Experimental results showed that operating at a lower temperature range (35-50°C) yielded more gas, while the catalyst loading and Pd doping wt.% were found to be the most significant factors with P-values 0.026 & 0.031, respectively.

Keywords: formic acid decomposition, green catalysis, hydrogen, mesoporous silica, process optimization, nanoparticles

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

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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: Farzaneh Shayeganfar, Ali Ramazani

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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: Paramita Banerjee, K. R. S. Chandrakumar, G. P. Das

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Bulk MgH2 has drawn much attention for the purpose of hydrogen storage because of its high hydrogen storage capacity (~7.7 wt %) as well as low cost and abundant availability. However, its practical usage has been hindered because of its high hydrogen desorption enthalpy (~0.8 eV/H2 molecule), which results in an undesirable desorption temperature of 3000C at 1 bar H2 pressure. To surmount the limitations of bulk MgH2 for the purpose of hydrogen storage, a detailed first-principles density functional theory (DFT) based study on the structure and stability of neutral (Mgm) and positively charged (Mgm+) Mg nanoclusters of different sizes (m = 2, 4, 8 and 12), as well as their interaction with molecular hydrogen (H2), is reported here. It has been found that due to the absence of d-electrons within the Mg atoms, hydrogen remained in molecular form even after its interaction with neutral and charged Mg nanoclusters. Interestingly, the H2 molecules do not enter into the interstitial positions of the nanoclusters. Rather, they remain on the surface by ornamenting these nanoclusters and forming new structures with a gravimetric density higher than 15 wt %. Our observation is that the inclusion of Grimme’s DFT-D3 dispersion correction in this weakly interacting system has a significant effect on binding of the H2 molecules with these nanoclusters. The dispersion corrected interaction energy (IE) values (0.1-0.14 eV/H2 molecule) fall in the right energy window, that is ideal for hydrogen storage. These IE values are further verified by using high-level coupled-cluster calculations with non-iterative triples corrections i.e. CCSD(T), (which has been considered to be a highly accurate quantum chemical method) and thereby confirming the accuracy of our ‘dispersion correction’ incorporated DFT calculations. The significance of the polarization and dispersion energy in binding of the H2 molecules are confirmed by performing energy decomposition analysis (EDA). A total of 16, 24, 32 and 36 H2 molecules can be attached to the neutral and charged nanoclusters of size m = 2, 4, 8 and 12 respectively. Ab-initio molecular dynamics (AIMD) simulation shows that the outermost H2 molecules are desorbed at a rather low temperature viz. 150 K (-1230C) which is expected. However, complete dehydrogenation of these nanoclusters occur at around 1000C. Most importantly, the host nanoclusters remain stable up to ~500 K (2270C). All these results on the adsorption and desorption of molecular hydrogen with neutral and charged Mg nanocluster systems indicate towards the possibility of reducing the dehydrogenation temperature of bulk MgH2 by designing new Mg-based nano materials which will be able to adsorb molecular hydrogen via this weak Mg-H2 interaction, rather than the strong Mg-H bonding. Notwithstanding the fact that in practical applications, these interactions will be further complicated by the effect of substrates as well as interactions with other clusters, the present study has implications on our fundamental understanding to this problem.

Keywords: density functional theory, DFT, hydrogen storage, molecular dynamics, molecular hydrogen adsorption, nanoclusters, physisorption

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