Search results for: acidity of hydrogenation catalyst

Authors: Vaclav Heral

Abstract:

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: 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: 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: 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. 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: 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: Komal Kumar, Sreedevi Upadhyayula

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In this study, a two-stage process was established for the synthesis of HMF esters using ionic liquid acid catalyst. Ionic liquid catalyst with different strength of the Bronsted acidity was prepared in the laboratory and characterized using 1H NMR, FT-IR, and 13C NMR spectroscopy. Solid acid catalyst from the ionic liquid catalyst was prepared using the immobilization method. The acidity of the synthesized acid catalyst was measured using Hammett function and titration method. Catalytic performance was evaluated for the biomass conversion to 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) in methyl isobutyl ketone (MIBK)-water biphasic system. A good yield of 5-HMF and LA was found at the different composition of MIBK: Water. In the case of MIBK: Water ratio 10:1, good yield of 5-HMF was observed at ambient temperature 150˚C. Upgrading of 5-HMF into monoesters from the reaction of 5-HMF and reactants using biomass-derived monoacid were performed. Ionic liquid catalyst with -SO₃H functional group was found to be best efficient in comparative of a solid acid catalyst for the esterification reaction and biomass conversion. A good yield of 5-HMF esters with high 5-HMF conversion was found to be at 105˚C using the best active catalyst. In this process, process A was the hydrothermal conversion of cellulose and monomer into 5-HMF and LA using acid catalyst. And the process B was the esterification followed by using similar acid catalyst. All monoesters of 5-HMF synthesized here can be used in chemical, cross linker for adhesive or coatings and pharmaceutical industry. A theoretical density functional theory (DFT) study for the optimization of the ionic liquid structure was performed using the Gaussian 09 program to find out the minimum energy configuration of ionic liquid catalyst.

Keywords: biomass conversion, 5-HMF, Ionic liquid, HMF ester

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Authors: Shashank Bahri, Divyanshu Arya, Rajni Jain, Sreedevi Upadhyayula

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Petroleum products can be obtained from syngas catalytic conversion using Fischer Tropsch Reaction. The liquid fuels obtained from FTS are sulphur and nitrogen free and thus may easily meet the increasing stringent environment regulations. In the present work we have synthesized Meso porous ZSM-5 supported catalyst. Meso structure were created in H-ZSM-5 crystallites by demetalation via subsequent base and acid treatment. Desilication through base treatment provides H-ZSM-5 with pore size and volumes similar to amorphous SiO2 (Conventional Carrier). Modifying the zeolite texture and surface chemistry by Desilication and acid washing alters its accessibility and interactions with metal phase and consequently the CO adsorption behavior and hydrocarbon product distribution. Increasing the mesoporosity via desilication provides the micro porous zeolite with essential surface area to support optimally sized metal crystallites. This improves the metal dispersion and hence improve the activity of the catalyst. Transition metal (Co) was loaded using wet impregnation method. Synthesized catalysts were characterized by Infrared Spectroscopy, Powdered X-Ray Diffraction, Scanning Electron Microscopy (SEM), BET Method analytical techniques. Acidity of the catalyst which plays an important role in FTS reaction was measured by DRIFT setup pyridine adsorption instead of NH3 Temperature Programmed Desorption. The major difference is that, Pyridine Adsorption can distinguish between Lewis acidity and Bronsted Acidity, thus giving their relative strengths in the catalyst sample, whereas TPD gives total acidity including Lewis and Bronsted ones.

Keywords: mesopourus, fischer tropsch reaction, pyridine adsorrption, drift study

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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: Ji Sun Kim, Jae Ho Baek, Kyeong Ho Kim, Ji Hae Ha, Seong Soo Hong, Jung-Wook Park, Man Sig Lee

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Carbon supported palladium catalysts have been used in many industrial reactions, especially for hydrogenation in the fine chemical industry. Porous carbons had been widely used as catalyst supports due to its higher surface area and larger pore volume. The specific surface area, pore structure and surface chemical functional groups of porous carbon affects metal dispersion and particle size. In this paper, we confirm the effect of support texture on the dispersion of Pd. Pd catalyst supported on activated carbon having various specific surface area were characterized by BET, XRD and FE-TEM. Catalyst activity and dispersion of prepared catalyst were evaluated on the basis of the CO adsorption capacity by CO-chemisorption. As concluding remark to this part of our study, let us note that specific area of carbon play important role on the synthesis of Pd/C catalyst/.

Keywords: carbon, dispersion, Pd/C, specific are, support

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Authors: Abd El-Aziz Said

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In this study, natural silica was used as an active, selective, reusable and eco-friendly catalyst for the liquid phase synthesis of iso-amyl, benzyl and cinnamyl esters. The original and calcined natural silica were characterized by TG-DTA, XRF, XRD, FTIR, SEM, and N2-sorption analysis. The surface acidity of the catalysts was determined using isopropanol dehydration and the strength of available acid sites was measured using chemisorption of pyridine (PY) and dimethyl pyridine (DMPY). The results of acidity specified that the acidic sites are of Brönsted type, while PY-TPD demonstrated that almost of the acidic sites over the surface of natural silica are of weak and intermediate strength. The catalytic activity of natural silica towards esterification of acetic acid with alcohols was extensively studied. The results revealed that natural silica had high catalytic activity with 100% selectivity to all targeted esters. In addition, the yields obtained in batch methods were 83, 81, and 80%, respectively, whereas these yields after simple distillation were improved 97, 99.5, and 90%, respectively.

Keywords: liquid-phase esterification, natural silica, acidity esters, characterization

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Authors: Thidarat Imyen, Paisan Kongkachuichay

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Cu-Zn/core-shell Al-MCM-41 catalyst with various copper species, prepared by a combination of three methods—substitution, ion-exchange, and impregnation, was studied for the selective catalytic reduction (SCR) of NO with NH3 at 300 °C for 150 min. In order to investigate the effects of Zn introduction on the nature of the catalyst, Cu/core-shell Al-MCM-41 and Zn/core-shell Al-MCM-41 catalysts were also studied. The roles of Zn promoter in the acidity and the NOx adsorption properties of the catalysts were investigated by in situ Fourier transform infrared spectroscopy (FTIR) of NH3 and NOx adsorption, and temperature-programmed desorption (TPD) of NH3 and NOx. The results demonstrated that the acidity of the catalyst was enhanced by the Zn introduction, as exchanged Zn(II) cations loosely bonded with Al-O-Si framework could create Brønsted acid sites by interacting with OH groups. Moreover, Zn species also provided the additional sites for NO adsorption in the form of nitrite (NO2–) and nitrate (NO3–) species, which are the key intermediates for SCR reaction. In addition, the effect of Zn on the nature of copper was studied by in situ FTIR of CO adsorption and in situ X-ray adsorption near edge structure (XANES). It was found that Zn species hindered the reduction of Cu(II) to Cu(0), resulting in higher Cu(I) species in the Zn promoted catalyst. The Cu-Zn/core-shell Al-MCM-41 exhibited higher catalytic activity compared with that of the Cu/core-shell Al-MCM-41 for the whole reaction time, as it possesses the highest amount of Cu(I) sites, which are responsible for SCR catalytic activity. The Cu-Zn/core-shell Al-MCM-41 catalyst also reached the maximum NO conversion of 100% with the average NO conversion of 76 %. The catalytic performance of the catalyst was further improved by using Zn promoter in the form of ZnO instead of reduced Zn species. The Cu-ZnO/core-shell Al-MCM-41 catalyst showed better catalytic performance with longer working reaction time, and achieved the average NO conversion of 81%.

Keywords: Al-MCM-41, copper, nitrogen oxide, selective catalytic reduction, zinc

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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: Sarra Boughaba

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The α-aminophosphonates have received considerable attention in organic and medicinal chemistry because of their structural resemblance with α-amino acids. They are used as antitumor agents, anti-inflammatory and antibiotics. As a result, a number of procedures have been developed for their synthesis. However, many of these methods suffer from some disadvantages such as long reaction times, environmental pollution caused by utilization of organic solvents, and expensive catalyst. On the other hand, thiazole components, particularly 2-aminothiazole is an important class of heterocyclic compounds. They appear in the structure of natural products and biologically actives compounds, thiamine (vitamin-B), and some antibiotics drugs (penicillin, micrococcin). In the past few years, heteropolyacids have received great attention as environmentally benign catalysts for organic synthetic processes, they possess unique physicochemical properties, such as super-acidity, high thermal and chemical stability, ability to accept and release electrons and high proton mobility, and the possibility of varying their acidity and oxidizing potential. In this study, an efficient and eco-friendly process has been developed for the synthesis of α-aminophosphonates containing aminothiazole moiety via Kabachnik-Field reaction catalyzed by H₆P₂W₁₈O₆₂.14H₂O as reusable catalyst, by condensation of aromatic aldehydes, 2-aminothiazole and triethylphosphite under free conditions. The X-ray crystallographic data of obtained compounds were provided. The main advantages of our protocol include the absence of solvent in the reaction, easy work-up, short reaction time, atom-economy and reusability of catalyst without significant loss of its activity.

Keywords: aminophosphonates, green synthesis, H₆P₂W₁₈O₆₂.14H₂O catalyst, x-ray study

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Authors: Brenda Cecilia Ledesma, Andrea Beltramone

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This work deals with the bio-waste valorization approach for catalyst development, the use of products derived from biomass as raw material and the obtaining of biofuels. In this research, activated carbons were synthesized from the orange peel using different synthesis conditions. With the activated carbons obtained with the best structure and texture, PtIr bimetallic catalysts were prepared. Carbon activation was carried out through a chemical process with phosphoric acid as an activating agent, varying the acid concentration, the ratio substrate/activating agent and time of contact between them. The best support was obtained using a carbonization time of 1 h, the temperature of carbonization of 470oC, the phosphoric acid concentration of 50 wt.% and a BET area of 1429 m2/g. Subsequently, the metallic nanoparticles were deposited in the activated carbon to use the solid as a catalytic material for the hydrogenation of HMF to 2,5-DMF. The catalyst presented an excellent performance for biofuels generation.

Keywords: orange peel, bio-waste valorization, platinum, iridium, 5-hydroxymethylfurfural

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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: 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: Jianwen Li, Hongfang Ma, Haitao Zhang, Qiwen Sun, Weiyong Ying

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HZSM-5 zeolites modified by iron and phosphorus were applied in catalytic cracking of butene. N2 adsorption and NH3-TPD were employed to measure the structure and acidity of catalysts. The results indicate that increasing phosphorus loading decreased surface area, pore volume and strong acidity of catalysts. The introduction of phosphorus significantly decreased butene conversion and promoted propylene selectivity. The catalytic performance of catalyst was strongly dependent on the reaction conditions. Appropriate reaction conditions could suppress side reactions and enhance propylene selectivity.

Keywords: butene catalytic cracking, HZSM-5, modification, reaction conditions

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

Abstract:

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: Reta

Abstract:

Coffee is widely consumed not only because of its typical taste, but coffee has antioxidant properties because of its polyphenols, and it stimulates brain's performance. The main problem with the consumption of coffee is its content of caffeine. Caffeine, when consumed in excess, can increase muscle tension, stimulate the heart, and increase the secretion of gastric acid. In this research, we applied ohmic-based fermentation technology, which is specially designed to mimic the stomach. We used Arabica coffee, which although cheaper than Luwak coffee, has high acidity, which needs to be reduced. Hence, we applied the ohmic technology, varied the time and temperature of the process and measured the total acidity of the coffee to determine optimum fermentation conditions. Results revealed total acidity of the coffee varied with fermentation conditions; 0.32% at 400C and 12 hr, and 0.52% at 400C and 6 hr. The longer the fermentation, the lower was the acidity. The acidity of the mongoose-fermented (natural fermentation) beans was 2.34%, which is substantially higher than the acidity of the ohmic samples. Ohmic-based fermentation technology, therefore, offers improvements in coffee quality, and this is discussed to highlight the potential of ohmic technology in coffee processing.

Keywords: ohmic technology, fermentation, coffee quality, Arabica coffee

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Authors: Sarra Boughaba

Abstract:

α-aminophosphonates have found a wide range of applications in organic and medicinal chemistry; they are considered as pharmacological agents, anti-inflammatory antitumor agents, and antibiotics. A number of procedures have been developed for their synthesis. However, many of these methods suffer from some disadvantages such as long reaction times, environmental pollution, utilization of organic solvents, and expensive catalysts. In the past few years, heteropolyacids have received great attention as environmentally benign catalysts for organic synthetic processes, they possess unique physicochemical properties, such as super-acidity, high thermal and chemical stability, ability to accept and release electrons and high proton mobility, and the possibility of varying their acidity and oxidizing potential. In this context, an efficient and eco-friendly protocol has been described for the synthesis of α-aminophosphonates via one pot, three component reaction catalyzed by H₆P₂W₁₈O₆₂.14H₂O as reusable catalyst, by condensation of amino acids esters, various aromatic aldehydes and triethylphosphite under solvent-free conditions, the corresponding α-aminophosphonates were formed in good yields as racemic or diastereomericmixture. All the new products were systematically characterized by IR, MS, and ¹H, ¹³C-³¹P-NMR analyses. This method offers advantages such as simplicity workup with the green aspects by avoiding expensive catalysts and toxic solvents, good yields, short reaction times.

Keywords: amino acids esters, α-aminophosphonates, H₆P₂W₁₈O₆₂.14H₂O catalyst, green chemistry

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Authors: Rita Riekstina-Dolge, Zanda Kruma, Daina Karklina, Fredijs Dimins

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Apple juice is the main raw material for cider production. In this study apple juices obtained from 14 dessert and crab variety apples grown in Latvia were investigated. For all samples soluble solids, titratable acidity, pH and sugar content were determined. Crab apples produce more dry matter, total sugar and acid content compared to the dessert apples but it depends on the apple variety. Total sugar content of crab apple juices was 1.3 to 1.8 times larger than in dessert apple juices. Titratable acidity of dessert apple juices is in the range of 4.1g L-1 to 10.83g L-1 and in crab apple juices titratable acidity is from 7.87g L-1 to 19.6g L-1. Fructose was detected as the main sugar whereas glucose level varied depending on the variety. The highest titratable acidity and content of sugars was detected in ‘Cornelia’ apples juice.

Keywords: apple juice, hierarchical cluster analysis, sugars, titratable acidity

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Authors: A. S. Al-Fatesh, A. A. Ibrahim, A. M. AlSharekh, F. S. Alqahtani, S. O. Kasim, A. H. Fakeeha

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Hydrogen is the expected future fuel since it produces energy without any pollution. It can be used as a fuel directly or through the fuel cell. It is also used in chemical and petrochemical industry as reducing agent or in hydrogenation processes. It is produced by different methods such as reforming of hydrocarbon, electrolytic method and methane decomposition. The objective of the present paper is to study the decomposition of methane reaction at 700°C and 800°C. The catalysts were prepared via impregnation method using 20%Fe and different proportions of combined alumina and silica support using the following ratios [100%, 90%, 80%, and 0% Al₂O₃/SiO₂]. The prepared catalysts were calcined and activated at 600 OC and 500 OC respectively. The reaction was carried out in fixed bed reactor at atmospheric pressure using 0.3g of catalyst and feed gas ratio of 1.5/1 CH₄/N₂ with a total flow rate 25 mL/min. Catalyst characterizations (TPR, TGA, BET, XRD, etc.) have been employed to study the behavior of catalysts before and after the reaction. Moreover, a brief description of the weight loss and the CH₄ conversions versus time on stream relating the different support ratios over 20%Fe/Al₂O₃/SiO₂ catalysts has been added as well. The results of TGA analysis provided higher weights losses for catalysts operated at 700°C than 800°C. For the 90% Al₂O₃/SiO₂, the activity decreases with the time on stream using 800°C reaction temperature from 73.9% initial CH₄ conversion to 46.3% for a period of 300min, whereas the activity for the same catalyst increases from 47.1% to 64.8% when 700°C reaction temperature is employed. Likewise, for 80% Al₂O₃/SiO₂ the trend of activity is similar to that of 90% Al₂O₃/SiO₂ but with a different rate of activity variation. It can be inferred from the activity results that the ratio of Al₂O₃ to SiO₂ is crucial and it is directly proportional with the activity. Whenever the Al/Si ratio decreases the activity declines. Indeed, the CH₄ conversion of 100% SiO₂ support was less than 5%.

Keywords: Al₂O₃, SiO₂, CH₄ decomposition, hydrogen, iron

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Authors: Ali Gharib, Leila Vojdanifard, Nader Noroozi Pesyan, Mina Roshani

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We describe an efficient method for oxidation of alcohols to related aldehydes and ketones by hydrogen peroxide as oxidizing agent, under reflux conditions. Nano-graphene oxide (NGO) as a heterogeneous catalyst was used and had their activity compared with other various catalysts. This catalyst was found to be an excellent catalyst for oxidation of alcohols. The effects of various parameters, including catalyst type, nature of the substituent in the alcohols and temperature, on the yield of the carboxylic acids were studied. Nano-graphene oxide was synthesized by the oxidation of graphite powders. This nanocatalyst was found to be highly efficient in this reaction and products were obtained in good to excellent yields. The recovered nano-catalyst was successfully reused for several runs without significant loss in its catalytic activity.

Keywords: nano-graphene oxide, oxidation, aldehyde, ketone, catalyst

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Authors: Sarina Sulaiman, N.Khairudin , P.Jamal, M.Z. Alam, Zaki Zainudin, S. Azmi

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In this study, fish bone waste was used as a new catalyst for biodiesel production. Instead of discarding the fish bone waste, it will be utilized as a source for catalyst that can provide significant benefit to the environment. Also, it can be substitute as a calcium oxide source instead of using eggshell, crab shell and snail shell. The XRD and SEM analysis proved that calcined fish bone contains calcium oxide, calcium phosphate and hydroxyapatite. The catalyst was characterized using Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD).

Keywords: calcinations, fish bone, transesterification, waste catalyst

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Authors: Khaled Alshammari

Abstract:

A facile approach to synthesizing highly active and stable Au/NiO catalysts for the hydrogenation of nitro-aromatics is reported. Preformed gold nanoparticles have been immobilized onto NiO using a colloidal method. In this article, the reduction of 4-nitrophenol with NaBH4 has been used as a model reaction to investigate the catalytic activity of synthesized Au/NiO catalysts. In addition, we report a systematic study of the reduction kinetics and the influence of specific reaction parameters such as (i) temperature, (ii) stirring rate, (iii) sodium borohydride concentration and (iv) substrate/metal molar ratio. The reaction has been performed at a substrate/metal molar ratio of 7.4, a ratio significantly higher than previously reported. The reusability of the catalyst has been examined, with little to no decrease in activity observed over 5 catalytic cycles. Systematic variation of Au loading reveals the successful synthesis of low-cost and efficient Au/NiO catalysts at very low Au content and using high substrate/metal molar ratios.

Keywords: nonochemistry, catalyst, nanoparticles supported, characterization of materials, colloidal nanoparticles

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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

Abstract:

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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