Search results for: metal loaded catalysts

Authors: Juree Hong, Sanggeun Lee, Jungmok Seo, Taeyoon Lee

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We report a facile synthesis of metal nano particles (NPs) on graphene layer via galvanic displacement reaction between graphene-buffered copper (Cu) and metal ion-containing salts. Diverse metal NPs can be formed on graphene surface and their morphologies can be tailored by controlling the concentration of metal ion-containing salt and immersion time. The obtained metal NP-decorated single-layer graphene (SLG) has been used as hydrogen gas (H2) sensing material and exhibited highly sensitive response upon exposure to 2% of H2.

Keywords: metal nanoparticle, galvanic displacement reaction, graphene, hydrogen sensor

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Shuwen Wu, Zhi LI

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Atomically dispersed Fe‒N₄ catalysts are proven as promising alternatives to commercial Pt/C for the oxygen reduction reaction. Most reported Fe‒N₄ catalysts suffer from inferior O‒O bond-breaking capability due to superoxo-like O₂ adsorption, though the isolated dual-atomic metal sites strategy is extensively adopted. Atomic Fe clusters hold greater promise for promoting O‒O bond cleavage by forming peroxo-like O₂ adsorption. However, the excessively strong binding strength between Fe clusters and oxygenated intermediates sacrifices the activity. Here, we first report a Fex/Cu‒N@CF catalyst with atomic Fe clusters functionalized by adjacent single Cu‒N₄ sites anchoring on a porous carbon nanofiber membrane. The theoretical calculation indicates that the single Cu‒N₄ sites can modulate the electronic configuration of Fe clusters to reduce O₂* protonation reaction free energy, which ultimately enhances the electrocatalytic performance. Particularly, the Cu‒N₄ sites can increase the overlaps between the d orbitals of Fe and p orbitals of O to accelerate O‒O cleavage in OOH*. As a result, this unique atomic catalyst exhibits a half potential (E1/2) of 0.944 V in an alkaline medium exceeding that of commercial Pt/C, whereas acidic performance E1/2 = 0.815 V is comparable to Pt/C. This work shows the great potential of single atoms for improvements in atomic cluster catalysts.

Keywords: Hierarchical porous fibers, atomic Fe clusters, Cu single atoms, oxygen reduction reaction; O-O bond cleavage

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Authors: H. Arceo, S. Rincon, C. Ben-Youssef, J. Rivera, A. Zepeda

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Biodiesel has emerged as a material with great potential as a renewable energy replacement to current petroleum-based diesel. Recently, biodiesel production is focused on the development of more efficient, sustainable process with lower costs of production. In this sense, a “green” approach to biodiesel production has stimulated the use of sustainable heterogeneous acid catalysts, that are better alternatives to conventional processes because of their simplicity and the simultaneous promotion of esterification and transesterification reactions from low-grade, highly-acidic and water containing oils without the formation of soap. The focus of this methodology is the development of new heterogeneous catalysts that under ordinary reaction conditions could reach yields similar to homogeneous catalysis. In recent years, metal organic frameworks (MOF) have attracted much interest for their potential as heterogeneous acid catalysts. They are crystalline porous solids formed by association of transition metal ions or metal–oxo clusters and polydentate organic ligands. This hybridization confers MOFs unique features such as high thermal stability, larger pore size, high specific area, high selectivity and recycling potential. Thus, MOF application could be a way to improve the biodiesel production processes. In this work, we evaluated the catalytic activity of MOF [(4,4-bipyridine)2(O₂CCH₃)2Zn]n (MOF Zn-I) for the synthesis of biodiesel from canola oil. The reaction conditions were optimized using the response surface methodology with a compound design central with 24. The variables studied were: Reaction temperature, amount of catalyst, molar ratio oil: MetOH and reaction time. The preparation MOF Zn-I was performed by mixing 5 mmol 4´4 dipyridine dissolved in 25 mL methanol with 10 mmol Zn(O₂CCH₃)₂ ∙ 2H₂O in 25 mL water. The crystals were obtained by slow evaporation of the solvents at 60°C for 18 h. The prepared catalyst was characterized using X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). The prepared catalyst was characterized using X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). Experiments were performed using commercially available canola oil in ace pressure tube under continuous stirring. The reaction was filtered and vacuum distilled to remove the catalyst and excess alcohol, after which it was centrifuged to separate the obtained biodiesel and glycerol. 1H NMR was used to calculate the process yield. GC-MS was used to quantify the fatty acid methyl ester (FAME). The results of this study show that the acid catalyst MOF Zn-I could be used as catalyst for biodiesel production through heterogeneous transesterification of canola oil with FAME yield 82 %. The optimum operating condition for the catalytic reaction were of 142°C, 0.5% catalyst/oil weight ratio, 1:30 oil:MeOH molar ratio and 5 h reaction time.

Keywords: fatty acid methyl ester, heterogeneous acid catalyst, metal organic framework, transesterification

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Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov

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The development of active and stable catalysts without noble metals for low temperature oxidation of exhaust gases remains a significant challenge. The purpose of this study is to determine the influence of the preparation method on the catalytic activity of the supported copper-manganese mixed oxides in terms of VOCs oxidation. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and acetates and the possibilities for CO, CH3OH and dimethyl ether (DME) oxidation were evaluated using continuous flow equipment with a four-channel isothermal stainless steel reactor. Effect of the support, Cu/Mn mole ratio, heat treatment of the precursor and active component loading were investigated. Highly active alumina supported Cu-Mn catalysts for CO and VOCs oxidation were synthesized. The effect of preparation conditions on the activity behavior of the catalysts was discussed. The synergetic interaction between copper and manganese species increases the activity for complete oxidation over mixed catalysts. Type of support, calcination temperature and active component loading along with catalyst composition are important factors, determining catalytic activity. Cu/Mn molar ratio of 1:5, heat treatment at 450oC and 20 % active component loading are the best compromise for production of active catalyst for simultaneous combustion of CO, CH3OH and DME.

Keywords: copper-manganese catalysts, CO, VOCs oxidation, exhaust gases

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Authors: Nathalie Elia, Samer Aouad, Jane Estephane, Christophe Poupin, Bilal Nsouli, Edmond Abi Aad

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Carbon dioxide is one of the main contributors to greenhouse effect and hence to climate change. As a result, the methanation reaction CO2(g) + 4H2(g) →CH4(g) + 2H2O (ΔH°298 = -165 kJ/mol), also known as Sabatier reaction, has received great interest as a process for the valorization of the greenhouse gas CO2 into methane which is a hydrogen-carrier gas. The methanation of CO2 is an exothermic reaction favored at low temperature and high pressure. However, this reaction requires a high energy input to activate the very stable CO2 molecule, and exhibits serious kinetic limitations. Consequently, the development of active and stable catalysts is essential to overcome these difficulties. Catalytic methanation of CO2 has been studied using catalysts containing Rh, Pd, Ru, Co and Ni on various supports. Among them, the Ni-based catalysts have been extensively investigated under various conditions for their comparable methanation activity with highly improved cost-efficiency. The addition of promoters are common strategies to increase the performance and stability of Ni catalysts. In this work, a small amount of Ru was used as a promoter for Ni catalysts supported on ceria and tested in the CO2 methanation reaction. The nickel loading was 5 wt. % and ruthenium loading is 0.5wt. %. The catalysts were prepared by successive impregnation method using Ni(NO3)2.6H2O and Ru(NO)(NO3)3 as precursors. The calcined support was impregnated with Ni(NO3)2.6H2O, dried, calcined at 600°C for 4h, and afterward, was impregnated with Ru(NO)(NO3)3. The resulting solid was dried and calcined at 600°C for 4 h. Supported monometallic catalysts were prepared likewise. The prepared solids Ru(0.5%)/CeO2, Ni(5%)/CeO2 and Ru(0.5%)-Ni(5%)/CeO2 were then reduced prior to the catalytic test under a flow of 50% H2/Ar (50 ml/min) for 4h at 500°C. Finally, their catalytic performances were evaluated in the CO2 methanation reaction, in the temperature range of 100–350°C by using a gaseous mixture of CO2 (10%) and H2 (40%) in Ar balanced at a total flow rate of 100 mL/min. The effect of pressure on the CO2 methanation was studied by varying the pressure between 1 and 10 bar. The various catalysts showed negligible CO2 conversion at temperatures lower than 250°C. The conversion of CO2 increases with increasing reaction temperature. The addition of Ru as promoter to Ni/CeO2 improved the CO2 methanation. It was shown that the CO2 conversion increases from 15 to 70% at 350°C and 1 bar. The effect of pressure on CO2 conversion was also studied. Increasing the pressure from 1 to 5 bar increases the CO2 conversion from 70% to 87%, while increasing the pressure from 5 to 10 bar increases the CO2 conversion from 87% to 91%. Ru–Ni catalysts showed excellent catalytic performance in the methanation of carbon dioxide with respect to Ni catalysts. Therefore the addition of Ru onto Ni catalysts improved remarkably the catalytic activity of Ni catalysts. It was also found that the pressure plays an important role in improving the CO2 methanation.

Keywords: CO2, methanation, nickel, ruthenium

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Krasimir Ivanov

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The catalytic oxidation of methanol to formaldehyde is an important industrial process in which the waste gas in addition to CO contains methanol and dimethyl ether (DME). Evaluation of the possibility of removing the harmful components from the exhaust gasses needs a more complex investigation. Our previous work indicates that supported Cu-Mn oxide catalysts are promising for effective deep oxidation of these compounds. This work relates to the catalyst, comprising copper-manganese spinel, coated on carrier γ-Al₂O₃. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. Different organometallic compounds on the base of four natural amino acids (Glycine, Alanine, Valine, Leucine) as precursors were used for the preparation of catalysts with Cu/Mn molar ratio 1:5. X-Ray and TEM analysis were performed on the catalyst’s bulk, and surface composition and the specific surface area was determined by BET method. The results obtained show that the activity of the catalysts increase up to 40% although there are some specific features, depending on the nature of the amino acid and the oxidized compound.

Keywords: Cu-Mn/γ-Al₂O₃, CO and VOCs oxidation, heterogeneous catalysis, amino acids

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Authors: Zhanat Shomanova, Ruslan Safarov, Yuri Nosenko, Zheneta Tashmuchambetova, Alima Zharmagambetova

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An effective way of utilization of ferroalloy production wastes is preparing hydrocarbon refining catalysts from them. It is possible due to accordable transition metals containing in the wastes. In the work, we are presenting the results on elemental analysis of sludge samples from Aksu ferroalloy plant (Aksu, Kazakhstan), method of catalysts preparing, results of physical-chemical analysis of obtained catalysts (X-ray analysis, electron microscopy, the BET method etc.), results of using the catalysts in some hydrocarbons refining processes such as hydrocracking of rubber waste, cracking of gasoil, oxidation of cyclohexane. The main results of catalytic activity research are: a) In hydrocracking of rubber waste 64.9% of liquid products were fuel fractions; b) In cracking of gasoil conversion was 51% and selectivity by liquid products was 99%; c) In oxidation of cyclohexane the maximal product yield 87.9% and selectivity by cyclohexanol 93.0% were achieved.

Keywords: catalyst, cyclohexane oxidation, ferroalloy production waste, gasoil cracking

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Authors: Jaibir Sharma, Lee JaeWung, Merugu Srinivas, Navab Singh

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This paper presents thermal annealing dewetting technique for the preparation of porous metal membrane for thin film encapsulation application. Thermal annealing dewetting experimental results reveal that pore size in porous metal membrane depend upon i.e. 1. The substrate on which metal is deposited for formation of porous metal cap membrane, 2. Melting point of metal used for porous metal cap layer membrane formation, 3. Thickness of metal used for cap layer, 4. Temperature used for porous metal membrane formation. Silver (Ag) was used as a metal for preparation of porous metal membrane by annealing the film at different temperature. Pores in porous silver film were analyzed using Scanning Electron Microscope (SEM). In order to check the usefulness of porous metal film for thin film encapsulation application, the porous silver film prepared on amorphous silicon (a-Si) was release using XeF2. Finally, guide line and structures are suggested to use this porous membrane for thin film encapsulation (TFE) application.

Keywords: dewetting, themal annealing, metal, melting point, porous

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Authors: Satya P. Dubey, Hrushikesh A Abhyankar, Veronica Marchante, James L. Brighton, Björn Bergmann

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Aims: To develop a mathematical model that simulates the ROP of PLA taking into account the effect of alternative energy to be implemented in a continuous reactive extrusion production process of PLA. Introduction: The production of large amount of waste is one of the major challenges at the present time, and polymers represent 70% of global waste. PLA has emerged as a promising polymer as it is compostable, biodegradable thermoplastic polymer made from renewable sources. However, the main limitation for the application of PLA is the traces of toxic metal catalyst in the final product. Thus, a safe and efficient production process needs to be developed to avoid the potential hazards and toxicity. It has been found that alternative energy sources (LASER, ultrasounds, microwaves) could be a prominent option to facilitate the ROP of PLA via continuous reactive extrusion. This process may result in complete extraction of the metal catalysts and facilitate less active organic catalysts. Methodology: Initial investigation were performed using the data available in literature for the reaction mechanism of ROP of PLA based on conventional metal catalyst stannous octoate. A mathematical model has been developed by considering significant parameters such as different initial concentration ratio of catalyst, co-catalyst and impurity. Effects of temperature variation and alternative energies have been implemented in the model. Results: The validation of the mathematical model has been made by using data from literature as well as actual experiments. Validation of the model including alternative energies is in progress based on experimental data for partners of the InnoREX project consortium. Conclusion: The model developed reproduces accurately the polymerisation reaction when applying alternative energy. Alternative energies have a great positive effect to increase the conversion and molecular weight of the PLA. This model could be very useful tool to complement Ludovic® software to predict the large scale production process when using reactive extrusion.

Keywords: polymer, poly-lactic acid (PLA), ring opening polymerization (ROP), metal-catalyst, bio-degradable, renewable source, alternative energy (AE)

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Authors: Mithil Pandey, Ragunathan Bala Subramanian

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One of the major conversion technologies in the oil refinery industry is Fluid catalytic cracking (FCC) which produces the majority of the world’s gasoline. Some useful products are generated from the vacuum gas oil, heavy gas oil and residue feedstocks by the FCC unit in an oil refinery. Moreover, Zeolite catalysts (zeo-catalysts) have found widespread applications and have proved to be substantial and paradigmatic in oil refining and petrochemical processes, such as FCC because of their porous features. Several famous zeo-catalysts have been fabricated and applied in industrial processes as milestones in history, and have brought on huge changes in petrochemicals. So far, more than twenty types of zeolites have been industrially applied, and their versatile porous architectures with their essential features have contributed to affect the catalytic efficiency. This poster depicts the evolution of pore models in zeolite catalysts which are accompanied by an increase in environmental and demands. The crucial roles of modulating pore models are outlined for zeo-catalysts for the enhancement of their catalytic performances in various industrial processes. The development of industrial processes for the FCC process, aromatic conversions and olefin production, makes it obvious that the pore architecture plays a very important role in zeo-catalysis processes. By looking at the different necessities of industrial processes, rational construction of the pore model is critically essential. Besides, the pore structure of the zeolite would have a substantial and direct effect on the utilization efficiency of the zeo-catalyst.

Keywords: catalysts, fluid catalytic cracking, industrial processes, zeolite

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Authors: Bhairi Lakshminarayana, Surajit Sarker, Ch. Subrahmanyam

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The present study reports the development of noble metal free nano catalysts for low-temperature CO oxidation and water gas shift reaction. Mn-substituted CeO2 solid solution catalysts were synthesized by co-precipitation, combustion and hydrothermal methods. The formation of solid solution was confirmed by XRD with Rietveld refinement and the percentage of carbon and nitrogen doping was ensured by CHNS analyzer. Raman spectroscopic confirmed the oxygen vacancies. The surface area, pore volume and pore size distribution confirmed by N2 physisorption analysis, whereas, UV-visible diffuse reflectance spectroscopy and XPS data confirmed the oxidation state of the Mn ion. The particle size and morphology (spherical shape) of the material was confirmed using FESEM and HRTEM analysis. Ce0.8Mn0.2O2-δ was calcined at 400 °C, 600 °C and 800 °C. Raman spectroscopy confirmed that the catalyst calcined at 400 °C has the best redox properties. The activity of the designed catalysts for CO oxidation (0.2 vol%), carried out with GHSV of 21,000 h-1 and it has been observed that co-precipitation favored the best active catalyst towards CO oxidation and water gas shift reaction, due to the high surface area, improved reducibility, oxygen mobility and highest quantity of surface oxygen species. The activation energy of low temperature CO oxidation on Ce0.8Mn0.2O2- δ (combustion) was 5.5 kcal.K-1.mole-1. The designed catalysts were tested for water gas shift reaction. The present study demonstrates that Mn ion substituted ceria at 400 °C calcination temperature prepared by co-precipitation method promise to revive a green sustainable energy production approach.

Keywords: Ce0.8Mn0.2O2-ð, CO oxidation, physicochemical characterization, water gas shift reaction (WGS)

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Authors: Vinu Viswanath, Lawrence Dsouza, Ugo Ravon

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Syngas typically and intermediary gas product has a wide range of application of producing various chemical products, such as mixed alcohols, hydrogen, ammonia, Fischer-Tropsch products methanol, ethanol, aldehydes, alcohols, etc. There are several technologies available for the syngas production. An alternative to the conventional processes an attractive route of utilizing carbon dioxide and methane in equimolar ratio to generate syngas of ratio close to one has been developed which is also termed as Dry Reforming of Methane technology. It also gives the privilege to utilize the greenhouse gases like CO2 and CH4. The dry reforming process is highly endothermic, and indeed, ΔG becomes negative if the temperature is higher than 900K and practically, the reaction occurs at 1000-1100K. At this temperature, the sintering of the metal particle is happening that deactivate the catalyst. However, by using this strategy, the methane is just partially oxidized, and some cokes deposition occurs that causing the catalyst deactivation. The current research work was focused to mitigate the main challenges of dry reforming process such coke deposition, and metal sintering at high temperature.To achieve these objectives, we employed three different strategies of catalyst development. 1) Use of bulk catalysts such as olivine and pyrochlore type materials. 2) Use of metal doped support materials, like spinel and clay type material. 3) Use of core-shell model catalyst. In this approach, a thin layer (shell) of redox metal oxide is deposited over the MgAl2O4 /Al2O3 based support material (core). For the core-shell approach, an active metal is been deposited on the surface of the shell. The shell structure formed is a doped metal oxide that can undergo reduction and oxidation reactions (redox), and the core is an alkaline earth aluminate having a high affinity towards carbon dioxide. In the case of metal-doped support catalyst, the enhanced redox properties of doped CeO2 oxide and CO2 affinity property of alkaline earth aluminates collectively helps to overcome coke formation. For all of the mentioned three strategies, a systematic screening of the metals is carried out to optimize the efficiency of the catalyst. To evaluate the performance of them, the activity and stability test were carried out under reaction conditions of temperature ranging from 650 to 850 ̊C and an operating pressure ranging from 1 to 20 bar. The result generated infers that the core-shell model catalyst showed high activity and better stable DR catalysts under atmospheric as well as high-pressure conditions. In this presentation, we will show the results related to the strategy.

Keywords: carbon dioxide, dry reforming, supports, core shell catalyst

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Authors: N. Laosiripojana, P. Tepamatr

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The influence of bismuth on the water gas shift activities of Pt on ceria was studied. The flow reactor was used to study the activity of the catalysts in temperature range 100-400°C. The feed gas composition contains 5%CO, 10% H₂O and balance N₂. The total flow rate was 100 mL/min. The outlet gas was analyzed by on-line gas chromatography with thermal conductivity detector. The catalytic activities of bimetallic 1%Pt1%Bi/CeO₂ catalyst were greatly enhanced when compared with the activities of monometallic 2%Pt/CeO₂ catalyst. The catalysts were characterized by X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR) and surface area analysis. X-ray diffraction pattern of Pt/CeO₂ and PtBi/CeO₂ indicated slightly shift of diffraction angle when compared with pure ceria. This result was due to strong metal-support interaction between platinum and ceria solid solution, causing conversion of Ce⁴⁺ to larger Ce³⁺. The distortions inside ceria lattice structure generated strain into the oxide lattice and facilitated the formation of oxygen vacancies which help to increase water gas shift performance. The H₂-Temperature Programmed Reduction indicated that the reduction peak of surface oxygen of 1%Pt1%Bi/CeO₂ shifts to lower temperature than that of 2%Pt/CeO₂ causing the enhancement of the water gas shift activity of this catalyst. Pt played an important role in catalyzing the surface reduction of ceria and addition of Bi alter the reduction temperature of surface ceria resulting in the improvement of the water gas shift activity of Pt catalyst.

Keywords: bismuth, platinum, water gas shift, ceria

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Authors: Wai Keng Teng, Gek Cheng Ngoh, Rozita Yusoff, Mohamed Kheireddine Aroua

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As a by-product of the biodiesel industries, glycerol has been vastly generated which surpasses the market demand. It is imperative to develop an efficient glycerol valorization processes in minimizing the net energy requirement and intensifying the biodiesel production. In this study, base-catalyzed transesterification of glycerol with dimethyl carbonate using microwave irradiation as heating method to produce glycerol carbonate was conducted by varing grades of glycerol i.e. 70%, 86% and 99% purity that obtained from biodiesel plant. Metal oxide catalysts were used with varying operating parameters including reaction time, DMC/glycerol molar ratio, catalyst weight %, temperature and stirring speed. From the study on the effect of different operating parameters; it was found that the type of catalyst used has the most significant effect on the transesterification reaction. Admist the metal oxide catalysts examined, CaO gave the best performance. This study indicates the feasibility of producing glycerol carbonate using different grade of glycerol in both conventional thermal activation and microwave irradiation with CaO as catalyst. Microwave assisted transesterification (MAT) of glycerol into glycerol carbonate has demostrated itself as an energy efficient route by achieving 94.3% yield of GC at 65°C, 5 minutes reaction time, 1 wt% CaO and DMC/glycerol molar ratio of 2. The advantages of MAT transesterification route has made the direct utilization of bioglycerol from biodiesel production without the need of purification. This has marked a more economical and less-energy intensive glycerol carbonate synthesis route.

Keywords: base-catalyzed transesterification, glycerol, glycerol carbonate, microwave irradiation

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Authors: Shinen B., Bavor J., Dorjkhand B., Suvd B., Maitsetseg B.

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A number of remediation techniques are available for the treatment of soils and sediments contaminated by heavy metals. However, some of these techniques are expensive and environmentally disruptive. Nanomaterials are used in the environment as environmental catalysts to convert toxic substances from water, soil, and sediment into environmentally benign compounds. This study was carried out to scrutinize the feasibility of vivianite nanoparticles for remediation of soils contaminated with heavy metals. Column experiments were performed in the laboratory to examine nanoparticle sequestration of metal in soil amended with vivianite nanoparticle suspension. The effect of environmental parameters such as temperature, pH and redox potential on metal leachability and bioavailability of soil amended with nanoparticle suspension was examined and compared with non-amended soils. The vivianite was effective in reducing the leachability of metals in soils. It is suggested that vivianite nanoparticles could be applied for the remediation of contaminated sites polluted by heavy metals due to mining activities, particularly in Mongolia, where mining industries have been developing rapidly in the last decade.

Keywords: bioavailability, heavy metals, nanoparticles, remediation

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Authors: Zarrin Nasri

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Microwave irradiation is an innovative technology in the petroleum industry. This kind of energy has been considered to convert vacuum residue of oil refineries into useful products. The advantages of microwaves energy are short time, fast heating, high energy efficiency, and precise process control. In this paper, the effects of catalyst type and amount have been investigated on upgrading of vacuum residue using microwave irradiation. The vacuum residue used in this research is from Tehran oil refinery, Iran. Additives include different catalysts, active carbon as sensitizer, and sodium borohydride as a solid hydrogen donor. Various catalysts contain iron, nickel, molybdenum disulfide, iron oxide and copper. The amount of catalysts in two cases of presence and absence of sodium borohydride have been evaluated. The objective parameters include temperature, asphaltene, viscosity, and API. The specifications of vacuum residue are API, 8.79, viscosity, 16391 cSt (60°C), asphaltene, 13.3 wt %. The results show that there is a significant difference between the effects of catalysts. Among the used catalysts, Fe powder is the best catalyst for upgrading vacuum residue using microwave irradiation and resulted in asphaltene reduction, 31.3 %; viscosity reduction, 76.43 %; and 23.43 % in API increase.

Keywords: asphaltene, microwave, upgrading, vacuum residue, viscosity

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Authors: Matthew E. Potter, Daniel J. Stewart, Lindsay M. Armstrong, Pier J. A. Sazio, Robert R. Raja

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Rising CO₂ levels in the atmosphere means that CO₂ is a highly desirable feedstock. This requires specific catalysts to be designed to activate this inert molecule, combining a catalytic site tailored for CO₂ transformations with a support that can readily adsorb CO₂. Metal organic frameworks (MOFs) are regularly used as CO₂ sorbents. The organic nature of the linker molecules, connecting the metal nodes, offers many post-synthesis modifications to introduce catalytic active sites into the frameworks. However, the metal nodes may be coordinatively unsaturated, allowing them to bind to organic moieties. Imidazoles have shown promise catalyzing the formation of cyclic carbonates from epoxides with CO₂. Typically, this synthesis route employs toxic reagents such as phosgene, liberating HCl. Therefore an alternative route with CO₂ is highly appealing. In this work we design active sites for CO₂ activation, by tethering substituted-imidazole organocatalytic species to the available Cr3+ metal nodes of a Cr-MIL-101 MOF, for the first time, to create a tailored species for carbon capture utilization applications. Our tailored design strategy combining a CO₂ sorbent, Cr-MIL-101, with an anchored imidazole results in a highly active and selective multifunctional catalyst, achieving turnover frequencies of over 750 hr-1. These findings demonstrate the synergy between the MOF framework and imidazoles for CO₂ utilization applications. Further, the effect of substrate variation has been explored yielding mechanistic insights into this process. Through characterization, we show that the structural and compositional integrity of the Cr-MIL-101 has been preserved on functionalizing the imidazoles. Further, we show the binding of the imidazoles to the Cr3+ metal nodes. This can be seen through our EPR study, where the distortion of the Cr3+ on binding to the imidazole shows the CO₂ binding site is close to the active imidazole. This has a synergistic effect, improving catalytic performance. We believe the combination of MOF support and organocatalyst allows many possibilities to generate new multifunctional catalysts for CO₂ utilisation. In conclusion, we have validated our design procedure, combining a known CO₂ sorbent, with an active imidazole species to create a unique tailored multifunctional catalyst for CO₂ utilization. This species achieves high activity and selectivity for the formation of cyclic carbonates and offers a sustainable alternative to traditional synthesis methods. This work represents a unique design strategy for CO₂ utilization while offering exciting possibilities for further work in characterization, computational modelling, and post-synthesis modification.

Keywords: carbonate, catalysis, MOF, utilisation

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Authors: Mohammad Reza Ghaani, Michele Catti

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The reduction of CoO/Fe₂O₃ oxides supported on carbon xerogels was studied to elucidate the effect of nano-size distribution of the catalyst in carbon matrices. Resorcinol formaldehyde xerogels were synthesized, impregnated with iron and cobalt nitrates, and subsequently heated to obtain the oxides. The mechanism of oxide reduction to metal was investigated by in-situ synchrotron X-ray diffraction in dynamic, non-isothermal conditions. Kinetic profiles of the reactions were obtained by plotting the diffraction intensities of selected Bragg peaks vs. temperature. The extracted Temperature-Programmed-Reduction (TPR) diagrams were analyzed by appropriate kinetic models, leading to best results with the Avrami-Erofeev model for all reduction reactions considered. The activation energies for the two-step reduction of iron oxide were 65 and 37 kJmol⁻¹, respectively. The average value for the reduction of CoO to Co was found to be around 21 kJ mol⁻¹. Such results may contribute to develop efficient and inexpensive non-noble metal-based catalysts in element form, e.g., Fe, Co, via heterogenization of metal complexes on mesoporous supports.

Keywords: non-isothermal kinetics, carbon aerogel, in-situ synchrotron X-ray diffraction, reduction mechanisms

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Authors: Anoff Anim, Lila Mahmoud, Maria Katsikogianni, Sanjit Nayak

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Sustained and controlled delivery of antimicrobial drugs have been largely studied recently using metal organic frameworks (MOFs)and different polymers. However, much attention has not been given to combining both MOFs and biodegradable polymers, which would be a good strategy in providing a sustained gradual release of the drugs. Herein, we report a comparative study of the sustained and controlled release of widely used antibacterial drugs, cephalexin and metronidazole, from zinc-based MOF-5 incorporated in biodegradable polycaprolactone (PCL) and poly-lactic glycolic acid (PLGA) membranes. Cephalexin and metronidazole were separately incorporated in MOF-5 post-synthetically, followed by their integration into biodegradable PLGA and PCL membranes. The pristine MOF-5 and the loaded MOFs were thoroughly characterized by FT-IR, SEM, TGA and PXRD. Drug release studies were carried out to assess the release rate of the drugs in PBS and distilled water for up to 48 hours using UV-Vis Spectroscopy. Four bacterial strains from both the Gram-positive and Gram-negative types, Staphylococus aureus, Staphylococuss epidermidis, Escherichia coli, Acinetobacter baumanii, were tested against the pristine MOF, pure drugs, loaded MOFs and the drug-loaded MOF-polymer composites. Metronidazole-loaded MOF-5 composite of PLGA (PLGA-Met@MOF-5) was found to show highest efficiency to inhibit the growth of S. epidermidis compared to the other bacteria strains while maintaining a sustained minimum inhibitory concentration (MIC). This study demonstrates that the combination of biodegradable MOF-polymer composites can provide an efficient platform for sustained and controlled release of antimicrobial drugs and can be a potential strategy to integrate them in biomedical devices.

Keywords: antimicrobial resistance, biodegradable polymers, cephalexin, drug release metronidazole, MOF-5, PCL, PLGA

Procedia PDF Downloads 108

Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov, Petya Petrova, Tatyana Tabakova

Abstract:

This work studies the effect of chemical composition on the activity and selectivity of γ–alumina supported CuO/ MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether (DME) and methanol. The catalysts were prepared by impregnation of the support with an aqueous solution of copper nitrate, manganese nitrate and CrO3 under different conditions. Thermal, XRD and TPR analysis were performed. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor. Flow-line equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions that mimic closely the industrial ones was used. The reactant and product gases were analyzed by means of on-line gas chromatographs. On the basis of XRD analysis it can be concluded that the active component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4, Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio. Chemical composition strongly influences catalytic properties, this influence being quite variable with regards to the different processes. The rate of CO oxidation rapidly decrease with increasing of chromium content in the active component while for the DME was observed the reverse trend. It was concluded that the best compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and Mn/Cr molar ratio from 1:3 to 1:4.

Keywords: Cu-Mn-Cr oxide catalysts, volatile organic compounds, deep oxidation, dimethyl ether (DME)

Procedia PDF Downloads 346

Authors: Anoff Anim, Lila A. M. Mahmoud, Maria Katsikogianni, Sanjit Nayak

Abstract:

Sustained and controlled delivery of antimicrobial drugs have been largely studied recently using metal organic frameworks (MOFs)and different polymers. However, much attention has not been given to combining both MOFs and biodegradable polymers, which would be a good strategy in providing a sustained gradual release of the drugs. Herein, we report a comparative study of the sustained and controlled release of widely used antibacterial drugs, cephalexin and metronidazole, from zinc-based MOF-5 incorporated in biodegradable polycaprolactone (PCL) and poly-lactic glycolic acid (PLGA) membranes. Cephalexin and metronidazole were separately incorporated in MOF-5 post-synthetically, followed by their integration into biodegradable PLGA and PCL membranes. The pristine MOF-5 and the loaded MOFs were thoroughly characterized by FT-IR, SEM, TGA and PXRD. Drug release studies were carried out to assess the release rate of the drugs in PBS and distilled water for up to 48 hours using UV-Vis Spectroscopy. Four bacterial strains from both the Gram-positive and Gram-negative types, Staphylococus aureus, Staphylococuss epidermidis, Escherichia coli, Acinetobacter baumanii, were tested against the pristine MOF, pure drugs, loaded MOFs and the drug-loaded MOF-polymer composites. Metronidazole-loaded MOF-5 composite of PLGA (PLGA-Met@MOF-5) was found to show highest efficiency to inhibit the growth of S. epidermidis compared to the other bacteria strains while maintaining a sustained minimum inhibitory concentration (MIC). This study demonstrates that the combination of biodegradable MOF-polymer composites can provide an efficient platform for sustained and controlled release of antimicrobial drugs and can be a potential strategy to integrate them in biomedical devices.

Keywords: antimicrobial resistance, biodegradable polymers, cephalexin, drug release metronidazole, MOF-5, PCL, PLGA

Procedia PDF Downloads 105

Authors: Sanjay P. Gandhi, Sanjay S. Patel

Abstract:

Dry (CO2) reforming of methane (DRM) is both scientific and industrial importance. In recent decades, CO2 utilization has become increasingly important in view of the escalating global warming phenomenon. This reaction produces syngas that can be used to produce a wide range of products, such as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompanied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires operating temperatures of 800–1000 °C to attain high equilibrium conversion of CH4 and CO2 to H2 and CO and to minimize the thermodynamic driving force for carbon deposition. The catalysts used are often composed of transition Methods like Nickel, supported on metallic and non-metallic oxides such as alumina and silica. However, many of these catalysts undergo severe deactivation due to carbon deposition. Noble metals have also been studied and are typically found to be much more resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved in the activation and conversion of CH4 and CO2. CO2 reforming methane over promoted catalyst was studied. The influence of ZrO2, CeO2 and the behavior of Ni-Al2O3 Catalyst, prepare by wet-impregnation and Co-precipitated method was studied. XRD, BET Analysis for different promoted and unprompted Catalyst was studied.

Keywords: CO2 reforming of methane, Ni catalyst, promoted and unprompted catalyst, effect of catalyst preparation

Procedia PDF Downloads 439

Authors: Jian Huang, Weixin Qian, Hongfang Ma, Haitao Zhang, Weiyong Ying

Abstract:

Cobalt catalysts were supported on extruded silica carrier and different-type (SiO₂, γ-Al₂O₃) commercial supports with different shapes and sizes to produce heavy hydrocarbons for Fischer-Tropsch synthesis. The catalysts were characterized by N₂ physisorption and H₂-TPR. The catalytic performance of the catalysts was tested in a fixed bed reactor. The results of Fischer-Tropsch synthesis performance showed that the cobalt catalyst supported on spherical silica supports displayed a higher activity and a higher selectivity to C₅⁺ products, due to the fact that the active components were only distributed in the surface layer of spherical carrier, and the influence of gas diffusion restriction on catalytic performance was weakened. Therefore, it can be concluded that the eggshell cobalt catalyst was superior to precious metals modified catalysts in the synthesis of heavy hydrocarbons.

Keywords: fischer-tropsch synthesis, cobalt catalyst, support shape, heavy hydrocarbons

Procedia PDF Downloads 257

Authors: Huanru Wang, Jianzhun Jiang

Abstract:

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

Procedia PDF Downloads 91

Authors: Anoff Anim, Lila Mahmound, Maria Katsikogianni, Sanjit Nayak

Abstract:

Sustained and controlled delivery of antimicrobial drugs have been largely studied recently using metal organic frameworks (MOFs)and different polymers. However, much attention has not been given to combining both MOFs and biodegradable polymers which would be a good strategy in providing a sustained gradual release of the drugs. Herein, we report a comparative study of the sustained and controlled release of widely used antibacterial drugs, cephalexin and metronidazole, from zinc-based MOF-5 incorporated in biodegradable polycaprolactone (PCL) and poly-lactic glycolic acid (PLGA) membranes. Cephalexin and metronidazole were separately incorporated in MOF-5 post-synthetically, followed by their integration into biodegradable PLGA and PCL membranes. The pristine MOF-5 and the loaded MOFs were thoroughly characterized by FT-IR, SEM, TGA and PXRD. Drug release studies were carried out to assess the release rate of the drugs in PBS and distilled water for up to 48 hours using UV-Vis Spectroscopy. Four bacterial strains from both the Gram-positive and Gram-negative types, Staphylococus aureus, Staphylococuss epidermidis, Escherichia coli, Acinetobacter baumanii, were tested against the pristine MOF, pure drugs, loaded MOFs and the drug-loaded MOF-polymer composites. Metronidazole-loaded MOF-5 composite of PLGA (PLGA-Met@MOF-5) was found to show highest efficiency to inhibit the growth of S. epidermidis compared to the other bacteria strains while maintaining a sustained minimum inhibitory concentration (MIC). This study demonstrates that the combination of biodegradable MOF-polymer composites can provide an efficient platform for sustained and controlled release of antimicrobial drugs, and can be a potential strategy to integrate them in biomedical devices.

Keywords: antimicrobial resistance, biodegradable polymers, cephalexin, drug release metronidazole, MOF-5, PCL, PLGA

Procedia PDF Downloads 55

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

Abstract:

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 226

Authors: Debdut Roy, Vidyasagar Guggilla

Abstract:

In this research, we highlight our exploratory work on modified zeolite based catalysts for catalytic cracking of hydrocarbons for production of light olefin i.e. ethylene and propylene. The work is focused on understanding the catalyst structure and activity correlation. Catalysts are characterized by surface area and pore size distribution analysis, inductively coupled plasma optical emission spectrometry (ICP-OES), Temperature Programmed Desorption (TPD) of ammonia, pyridine Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Thermo-gravimetric Analysis (TGA) and correlated with the catalytic activity. It is observed that the yield of lighter olefins increases with increase of Bronsted acid strength.

Keywords: catalytic cracking, zeolite, propylene, structure-activity correlation

Procedia PDF Downloads 193

Authors: Sisuwan Kaseamsawat, Sivapan Choo-In

Abstract:

A study was conducted in May to July 2013 with the aim of determination of heavy metal concentration in orchard area. 60 samples were collected and analyzed for Cadmium (Cd), Copper (Cu), Lead (Pb), and Zinc (Zn) by Atomic Absorption Spectrophotometer (AAS). The heavy metal concentrations in sediment of orchards, that use chemical for Cd (1.13 ± 0.26 mg/l), Cu (8.00 ± 1.05 mg/l), Pb (13.16 ± 2.01) and Zn (37.41 ± 3.20 mg/l). The heavy metal concentrations in sediment of the orchards, that do not use chemical for Cd (1.28 ± 0.50 mg/l), Cu (7.60 ± 1.20 mg/l), Pb (29.87 ± 4.88) and Zn (21.79 ± 2.98 mg/l). Statistical analysis between heavy metal in sediment from the orchard, that use chemical and the orchard, that not use chemical were difference statistic significant of 0.5 level of significant for Cd and Pb while no statistically difference for Cu and Zn.

Keywords: heavy metal, orchard, pollution and monitoring, sediment

Procedia PDF Downloads 359

Authors: Surajbhan Sevda

Abstract:

Metal containing wastewater is generated in large quintiles due to rapid industrialization. Generally, the metal present in wastewater is not biodegradable and can be accumulated in living animals, humans and plant tissue, causing disorder and diseases. The conventional metal recovery methods include chemical, physical and biological methods, but these are chemical and energy intensive. The recent development in microbial fuel cell (MFC) technology provides a new approach for metal recovery; this technology offers a flexible platform for both reduction and oxidation reaction oriented process. The use of MFCs will be a new platform for more efficient and low energy approach for metal recovery from the wastewater. So far metal recover was extensively studied using chemical, physical and biological methods. The MFCs present a new and efficient approach for removing and recovering metals from different wastewater, suggesting the use of different electrode for metal recovery can be a new efficient and effective approach.

Keywords: metal recovery, microbial fuel cell, wastewater, bioelectricity

Procedia PDF Downloads 191