Search results for: recyclable catalysts

Authors: Ateeq Ur Rehman

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This article deals with the promotional effects of CeO2 on PtPd/CeO2-OMC electrocatalysts. The synthesized catalysts are characterized using different physicochemical techniques and evaluated in a formic acid oxidation fuel cell. N2 adsorption/desorption analysis shows that CeO2 modification increases the surface area of OMC from 1005 m2/g to 1119 m2/g. SEM, XRD and TEM analysis reveal that the presence of CeO2 enhances the active metal(s) dispersion on the CeO2-OMC surface. The average particle size of the dispersed metal decreases with the increase of Pt/Pd ratio on CeO2-OMC support. Cyclic voltametry measurement of Pd/CeO2-OMC gives 12 % higher anodic current activity with 83 mV negative shift of the peak potential as compared to unmodified Pd/OMC. In bimetallic catalysts, the addition of Pt improves the activity and stability of the catalysts significantly. Among the bimetallic samples, Pd3Pt1/CeO2-OMC displays superior current density (74.6 mA/cm2), which is 28.3 times higher than that of Pt/CeO2-OMC. It also shows higher stability in extended period of runs with least indication of CO poisoning effects.

Keywords: CeO2, ordered mesoporous carbon (OMC), nano particles, formic acid fuel cell

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Authors: W. El-Alami, J. Araña, O. González Díaz, J. M. Doña Rodríguez

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The efficiency of the semiconductor TiO₂ needs to be improved to be an effective tool for pollutant removal. To improve the efficiency of this semiconductor, it is necessary to deepen the knowledge of the processes that take place on its surface. In this sense, the deactivation of the catalyst is one of the aspects considered relevant. In order to study this point, the processes of deactivation of TiO₂ during the gas phase degradation of ethanol have been studied. For this, catalysts with only the anatase phase (SA and PC100) and catalysts with anatase and rutile phases (P25 and P90) have been selected. In order to force the deactivation processes, different cycles have been performed, adding ethanol gas but avoiding the degradation of acetates to determine their effect on the process. The surface concentration of fluorine on the catalysts was semi-quantitatively determined by EDAX analysis. The photocatalytic experiments were done with four commercial catalysts (P25, SA, P90, and PC100) and the two fluoride catalysts indicated above. The interaction and photocatalytic degradation of ethanol were followed by Fourier transform infrared spectroscopy (FTIR). EDAX analysis has revealed the presence of sodium on the surface of fluorinated catalysts. In FTIR studies, it has been observed that the acetates adsorbed on the anatase phase in P25 and P90 give rise to electron transfer to surface traps that modify the electronic states of the semiconductor. These deactivation studies have also been carried out with fluorinated P25 and SA catalysts (F-P25 and F-SA) which have observed similar electron transfers but in the opposite direction during illumination. In these materials, it has been observed that the electrons present in the surface traps, as a consequence of the interaction Ti-F, react with the holes, causing a change in the electronic states of the semiconductor. In this way, deactivated states of these materials have been detected by different electron transfer routes. It has been identified that acetates produced from the degradation of ethanol in P25 and P90 are probably hydrated on the surface of the rutile phase. In the catalysts with only the anatase phase (SA and PC100), the deactivation is immediate if the acetates are not removed before adsorbing ethanol again. In F-P25 and F-SA has been observed that the acetates formed react with the sodium ions present on the surface and not with the Ti atoms because they are interacting with the fluorine.

Keywords: photocatalytic degradation, ethanol, TiO₂, deactivation process, F-P25

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Authors: Sony, Ashok N. Bhaskarwar

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Production of hydrogen from a renewable raw material without any co-synthesis of harmful greenhouse gases is the current need for sustainable energy solutions. The sulfur-iodine (SI) thermochemical cycle, using intermediate chemicals, is an efficient process for producing hydrogen at a much lower temperature than that required for the direct splitting of water. No net byproduct forms in the cycle. Hydrogen iodide (HI) decomposition is a crucial reaction in this cycle, as the product, hydrogen, forms only in this step. It is an endothermic, reversible, and equilibrium-limited reaction. The theoretical equilibrium conversion at 550°C is just a meagre of 24%. There is a growing interest, therefore, in enhancing the HI conversion to near-equilibrium values at lower reaction temperatures and by possibly improving the rate. The reaction is relatively slow without a catalyst, and hence catalytic decomposition of HI has gained much significance. Bi-metallic Ni-Co, Ni-Mn, Co-Mn, and tri-metallic Ni-Co-Mn catalysts over zirconia support were tested for HI decomposition reaction. The catalysts were synthesized via a sol-gel process wherein Ni was 3wt% in all the samples, and Co and Mn had equal weight ratios in the Co-Mn catalyst. Powdered X-ray diffraction and Brunauer-Emmett-Teller surface area characterizations indicated the polycrystalline nature and well-developed mesoporous structure of all the samples. The experiments were performed in a vertical laboratory-scale packed bed reactor made of quartz, and HI (55 wt%) was fed along with nitrogen at a WHSV of 12.9 hr⁻¹. Blank experiments at 500°C for HI decomposition suggested conversion of less than 5%. The activities of all the different catalysts were checked at 550°C, and the highest conversion of 23.9% was obtained with the tri-metallic 3Ni-Co-Mn-ZrO₂ catalyst. The decreasing order of the performance of catalysts could be expressed as: 3Ni-Co-Mn-ZrO₂ > 3Ni-2Co-ZrO₂ > 3Ni-2Mn-ZrO₂ > 2.5Co-2.5Mn-ZrO₂. The tri-metallic catalyst remained active till 360 mins at 550°C without any observable drop in its activity/stability. Among the explored catalyst compositions, the tri-metallic catalyst certainly has a better performance for HI conversion when compared to the bi-metallic ones. Owing to their low costs and ease of preparation, these trimetallic catalysts could be used for large-scale hydrogen production.

Keywords: sulfur-iodine cycle, hydrogen production, hydrogen iodide decomposition, bi-, and tri-metallic catalysts

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Authors: Andrea M. Rivas-Castillo, Marlenne Gómez-Ramirez, Isela Rodríguez-Pozos, Norma G. Rojas-Avelizapa

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Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.

Keywords: bioleaching, metal removal, spent catalysts, Acidithiobacillus thiooxidans

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Authors: Xin Zhao. Xuerong Zheng. Andrey L. Rogach

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Using single metal atoms has been considered an efficient way to develop new HER and OER catalysts. MXenes, a class of two-dimensional materials, have attracted tremendous interest as promising substrates for single-atom metal catalysts. However, there is still a lack of systematic investigations on the interaction mechanisms between various MXenes substrates and single atoms. Besides, due to the poor interaction between metal atoms and substrates resulting in low loading and stability, dual-atom MXenes-based catalysts have not been successfully synthesized. We summarized the electrocatalytic enhancement mechanism of three MXenes-based single-atom catalysts through experimental and theoretical results demonstrating the stronger hybridization between Co 3d and surface-terminated O 2p orbitals, optimizing the electronic structure of Co single atoms in the composite. This, in turn, lowers the OER and HER energy barriers and accelerates the catalytic kinetics in the case of the Co@V2CTx composite. The poor interaction between single atoms and substrates can be improved by a surface modification to synthesize dual-atom catalysts. The synergistic electronic structure enhances the stability and electrocatalytic activity of the catalyst. Our study provides guidelines for designing single-atom and dual-atom MXene-based electrocatalysts and sheds light on the origins of the catalytic activity of single-atoms on MXene substrates.

Keywords: dual-atom catalyst, single-atom catalyst, MXene substrates, water splitting

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Authors: Radia Imane Fertout

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In recent years, the reaction of dry reforming of methane (DRM) has attracted much attention due to its environmental and industrial importance. Various catalysts, including Ni-based catalysts, have been investigated for the DRM. Doping Ni/Al₂O₃ by lanthanum and alkaline earth element may strongly influence solid-state reaction and increases the stability of catalysts due to the lower density and high basicity of these oxides. The effect of SrO on the activity and stability of Ni/Al₂O₃-La₂O₃ in dry reforming of methane was investigated. These catalysts have been prepared with the impregnation method, calcined in air at 450 and 650°C, then characterized by BET surface area, X-ray diffraction (XRD), and scanning electron microscopy (SEM) techniques and tested in DRM. The results showed that the addition of strontium to Ni/Al2O₃-La₂O₃ decreased the specific surface area. XRD results revealed the presence of different phases of Al₂O₃, La(OH)₃, La₂O₂CO₃, and SrCO₃. The catalytic evaluation results showed that adding SrO increased the catalytic activity and stability, that explained by the strong basicity of strontium. SEM analysis after the reaction indicates the formation of carbon over the spent catalyst and that the addition of strontium stabilized the surface of the catalyst.

Keywords: dry reforming of methane, Ni/Al₂O₃-La₂O₃ catalyst, strontium, nickel

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Authors: Ali Zazi, Ouiza Cherifi

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The Catalysts materials Ni-SiO₂, Ni-Co-SiO₂ and Ni-Ce-SiO₂ were synthetized by classical method impregnation and supported by silica. This involves combing the silica with an adequate rate of the solution of nickel nitrates, or nickel nitrate and cobalt nitrate, or nickel nitrate and cerium nitrate, mixed, dried and calcined at 700 ° c. These catalysts have been characterized by different physicochemical analysis techniques. The atomic absorption spectrometry indicates that the real contents of nickel, cerium and cobalt are close to the theoretical contents previously assumed, which let's say that the nitrate solutions have impregnated well the silica support. The BET results show that the surface area of the specific surfaces decreases slightly after impregnation with nickel nitrates or Co and Ce metals and a further slight decrease after the reaction. This is likely due to coke deposition. X-ray diffraction shows the presence of the different SiO₂ and NiO phases for all catalysts—theCoO phase for that promoted by Co and the Ce₂O₂ phase for that promoted by Ce. The methane steam reforming reaction was carried out on a quartz reactor in a fixed bed. Reactants and products of the reaction were analyzed by a gas chromatograph. This study shows that the metal addition of Cerium or Cobalt improves the majority of the catalytic performance of Ni for the steam reforming reaction of methane. And we conclude the classification of our Catalysts in order of decreasing activity and catalytic performances as follows: Ni-Ce / SiO₂ >Ni-Co / SiO₂> Ni / SiO₂ .

Keywords: cerium, cobalt, heterogeneous catalysis, hydrogen, methane, steam reforming, synthesis gas

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Authors: Yuri A. Kalvachev, Totka D. Todorova

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Zeolite mordenite has been investigated as a transition metal support for the preparation of efficient catalysts in the oxidation of volatile organic compounds (VOCs). The highly crystalline mordenite samples were treated with hydrofluoric acid and ammonium fluoride to get hierarchical material with secondary porosity. The obtained supports by this method have a high active surface area, good diffusion properties and prevent the extraction of metal components during catalytic reactions. The active metal phases platinum and copper were loaded by impregnation on both mordenite materials (parent and acid treated counterparts). Monometalic Pt and Cu, and bimetallic Pt/Cu catalysts were obtained. The metal phases were fine dispersed as nanoparticles on the functional porous materials. The catalysts synthesized in this way were investigated in the reaction of complete oxidation of propane and benzene. Platinum, copper and platinum/copper were loaded and there catalytic activity was investigated and compared. All samples are characterized by X-ray diffraction analysis, nitrogen adsorption, scanning electron microscopy (SEM), X-ray photoelectron measurements (XPS) and temperature programed reduction (TPR). The catalytic activity of the samples obtained is investigated in the reaction of complete oxidation of propane and benzene by using of Gas Chromatography (GC). The oxidation of three organic molecules was investigated—methane, propane and benzene. The activity of metal loaded mordenite catalysts for methane oxidation is almost the same for parent and treated mordenite as a support. For bigger molecules as propane and benzene, the activity of catalysts based on treated mordenite is higher than those based on parent zeolite.

Keywords: metal loaded catalysts, mordenite, VOCs oxidation, zeolites

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Authors: Adisak Guntida

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Propylene self-metathesis to ethylene and butene was studied over WOx/SiO2 catalysts at 450 °C and atmospheric pressure. The WOx/SiO2 catalysts were prepared by incipient wetness impregnation of ammonium metatungstate aqueous solution. It was found that, adding nano-sized extra supports (SiO2 and TiO2) by physical mixing with the WOx/SiO2 enhanced propylene conversion. The UV-Vis and FT-Raman results revealed that WOx could migrate from the original silica support to the extra support, leading to a better dispersion of WOx. The ICP-OES results also indicate that WOx existed on the extra support. Coke formation was investigated on the catalysts after 10 h time-on-stream by TPO. However, adding nano-sized extra supports led to higher coke formation which may be related to acidity as characterized by NH3-TPD.

Keywords: extra support, nanomaterial, propylene self-metathesis, tungsten oxide

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Authors: Asaolu Olugbenga Stephen, Afolabi Olusegun Temitope

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Lack of proper solid waste management is one of the main causes of environmental pollution and degradation in many cities, especially in developing countries. The aim of this study was to estimate the quantity of waste generated per capita per day, determine the composition and identify the potentials for recycling of waste generated. Characterization of wastes from selected households in the residential areas was done for over a 7 day period. The weight of each sorted category of waste was recorded in a structured database that calculated the proportion of each waste component. The results indicated that 85.4% of the sampled waste characterized was found to be recyclable; with an estimated average waste generated of 1.82kg/capita/day. The various solid waste fractions were organic (64.6%), plastics (15.6%), metals (9.2%), glass materials (1.6%) and unclassified (8.9%). It was concluded from this study that a large proportion of the waste generated from OAU campus residential area was recyclable and that there is a need to enact policy on waste recycling within the university campus.

Keywords: recycling, household wastes, residential, solid waste management

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Authors: Pauline Bredy, Yves Schuurman, David Farrusseng

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To fulfill climate objectives, the production of synthetic e-fuels using CO₂ as a raw material appears as part of the solution. In particular, Power-to-Liquid (PtL) concept combines CO₂ with hydrogen supplied from water electrolysis, powered by renewable sources, which is currently gaining interest as it allows the production of sustainable fossil-free liquid fuels. The proposed process discussed here is an upgrading of the well-known Fischer-Tropsch synthesis. The concept deals with two cascade reactions in one pot, with first the conversion of CO₂ into CO via the reverse water gas shift (RWGS) reaction, which is then followed by the Fischer-Tropsch Synthesis (FTS). Instead of using a Fe-based catalyst, which can carry out both reactions, we have chosen the strategy to decouple the two functions (RWGS and FT) on two different catalysts within the same reactor. The FTS shall shift the equilibrium of the RWGS reaction (which alone would be limited to 15-20% of conversion at 250°C) by converting the CO into hydrocarbons. This strategy shall enable optimization of the catalyst pair and thus lower the temperature of the reaction thanks to the equilibrium shift to gain selectivity in the liquid fraction. The challenge lies in maximizing the activity of the RWGS catalyst but also in the ability of the FT catalyst to be highly selective. Methane production is the main concern as the energetic barrier of CH₄ formation is generally lower than that of the RWGS reaction, so the goal will be to minimize methane selectivity. Here we report the study of different combinations of copper-based RWGS catalysts with different cobalt-based FTS catalysts. We investigated their behaviors under mild process conditions by the use of high-throughput experimentation. Our results show that at 250°C and 20 bars, Cobalt catalysts mainly act as methanation catalysts. Indeed, CH₄ selectivity never drops under 80% despite the addition of various protomers (Nb, K, Pt, Cu) on the catalyst and its coupling with active RWGS catalysts. However, we show that the activity of the RWGS catalyst has an impact and can lead to longer hydrocarbons chains selectivities (C₂⁺) of about 10%. We studied the influence of the reduction temperature on the activity and selectivity of the tandem catalyst system. Similar selectivity and conversion were obtained at reduction temperatures between 250-400°C. This leads to the question of the active phase of the cobalt catalysts, which is currently investigated by magnetic measurements and DRIFTS. Thus, in coupling it with a more selective FT catalyst, better results are expected. This was achieved using a cobalt/iron FTS catalyst. The CH₄ selectivity dropped to 62% at 265°C, 20 bars, and a GHSV of 2500ml/h/gcat. We propose that the conditions used for the cobalt catalysts could have generated this methanation because these catalysts are known to have their best performance around 210°C in classical FTS, whereas the iron catalysts are more flexible but are also known to have an RWGS activity.

Keywords: cobalt-copper catalytic systems, CO₂-hydrogenation, Fischer-Tropsch synthesis, hydrocarbons, low-temperature process

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Authors: Panumard Kaewmora, Thirasak Rirksomboon, Vissanu Meeyoo

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Due to the globally growing demands of petroleum fuel and fossil fuels, the scarcity or even depletion of fossil fuel sources could be inevitable. Alternatively, the utilization of renewable sources, such as biomass, has become attractive to the community. Biomass can be converted into bio-oil by fast pyrolysis. In water phase of bio-oil, acetic acid which is one of its main components can be converted to hydrogen with high selectivity over effective catalysts in steam reforming process. Steam reforming of acetic acid as model compound has been intensively investigated for hydrogen production using various metal oxide supported nickel catalysts and yet they seem to be rapidly deactivated depending on the support utilized. A catalyst support such as Ce1-xZrxO2 mixed oxide was proposed for alleviating this problem with the anticipation of enhancing hydrogen yield. However, catalyst preparation methods play a significant role in catalytic activity and performance of the catalysts. In this work, Ce0.75Zr0.25O2 mixed oxide solid solution support was prepared by urea hydrolysis using microwave as heat source. After that nickel metal was incorporated at 15 wt% by incipient wetness impregnation method. The catalysts were characterized by several techniques including BET, XRD, H2-TPR, XRF, SEM, and TEM as well as tested for the steam reforming of acetic acid at various operating conditions. Preliminary results showed that a hydrogen yield of ca. 32% with a relatively high acetic conversion was attained at 650°C.

Keywords: acetic acid, steam reforming, microwave, nickel, ceria, zirconia

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Authors: Akmuhammet Karayev, Hassam Mazhar, Mamdouh Al Harthi

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Polyethylene terephthalate (PET) recycling stands as a pivotal solution in combating plastic pollution and fostering a circular economy. This study addresses the catalytic glycolysis of PET, a key step in its recycling process, using synthesized catalysts. Our focus lies in elucidating the catalytic mechanism, optimizing reaction kinetics, and enhancing reactor design for efficient PET conversion. We synthesized anionic clays tailored for PET glycolysis and comprehensively characterized them using XRD, FT-IR, BET, DSC, and TGA techniques, confirming their suitability as catalysts. Through systematic parametric studies, we optimized reaction conditions to achieve complete PET conversion to bis hydroxy ethylene terephthalate (BHET) with over 75% yield within 2 hours at 200°C, employing a minimal catalyst concentration of 0.5%. These results underscore the catalysts' exceptional efficiency and sustainability, positioning them as frontrunners in catalyzing PET recycling processes. Furthermore, we demonstrated the recyclability of the obtained BHETs by repolymerizing them back to PET without the need for a catalyst. Heating the BHETs in a distillation unit facilitated their conversion back to PET, highlighting the closed-loop potential of our recycling approach. Our work embodies a significant leap in catalytic glycolysis kinetics, driven by sustainable catalysts, offering rapid and high-impact PET conversion while minimizing environmental footprint. This breakthrough not only sets new benchmarks for efficiency in PET recycling but also exemplifies the pivotal role of catalysis and reaction engineering in advancing sustainable materials management.

Keywords: polymer recycling, catalysis, circular economy, glycolysis

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Authors: Dinda A. Utami, Muhammad N. Alfarizi

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The purpose of this study was to determine the ability of zeolite catalyst for the trans- esterification reaction in biodiesel production from animal fat. The ability of the zeolite as a catalyst is determined by the structure and composition of the zeolite. An important factor that determines the properties of zeolites in catalysis includes adsorption capability to the compound of the reactants. Zeolites with a pore size of specific properties selectively adsorbing molecules. A molecule can be adsorbed by either the zeolite cavities if the size and shape of the molecule in accordance with the size and shape of the cavity in the zeolite. At this time, it is common to use homogeneous catalysts for biodiesel. We know these catalysts have some disadvantages in its use. Such as the difficulty of separation of the product with the catalyst, the generation of waste that is harmful to the environment due to residual catalysts can’t be reused, and the difficulty of handling and storage. But nowadays, solid catalyst developed technically to improve the efficiency of biodiesel production. In this case of study, we used trans-esterification process wherein the triglyceride is reacted with an alcohol with zeolite as a solid catalyst and it will produce biodiesel and glycerol as a byproduct. Development of solid catalyst seems to be the perfect solution to address the problems associated with homogeneous catalysts.

Keywords: biodiesel, animal fat, trans esterification, zeolite catalyst

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Authors: Inalegwu Stephany Akipu

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Before the advent of Colonialists on the shores of Nigeria between the 16th and 17th Centuries, there existed the traditional systems of governance which was successful with Women as active participants. However, the current state of politics in Nigeria reveals an obvious absence of women in the Country’s governance. Being that the economy rests on the quality of leaders and their constructive contribution to the plight of the masses, it becomes pertinent to exhaust all the avenues that may be open to good governance-women inclusive. It is against this backdrop that this paper attempts to compare the machinery that were in place in pre-colonial Nigerian governance that aided the womenfolk to successfully reign or assist in leadership with the seeming lack of interest by women in present times. Factors that militate against the women will also be highlighted. Furthermore, suggestions are made on how to revive these successful traditional systems of governance. The paper concludes by emphasising the role of women as the needed catalysts for this aforementioned rehabilitation of traditional systems and the impact of media in achieving this feat.

Keywords: catalysts, governance, media, rehabilitation

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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: Joy Marie Mora, Mark Daniel De Luna, Tsair-Wang Chung

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Transesterification reaction of soybean oil with methanol was carried out to produce fatty acid methyl esters (FAME) using calcined alkali metal (Na and Li) supported by pumice silica as the solid base catalyst. Pumice silica catalyst was activated by loading alkali metal ions to its surface via an ion-exchange method. Response surface methodology (RSM) in combination with Box-Behnken design (BBD) was used to optimize the operating parameters in biodiesel production, namely: reaction temperature, methanol to oil molar ratio, reaction time, and catalyst concentration. Using the optimized sets of parameters, FAME yields using sodium and lithium silicate catalysts were 98.80% and 98.77%, respectively. A pseudo-first order kinetic equation was applied to evaluate the kinetic parameters of the reaction. The prepared catalysts were characterized by several techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) sorptometer, and scanning electron microscopy (SEM). In addition, the reusability of the catalysts was successfully tested in two subsequent cycles.

Keywords: alkali metal, biodiesel, Box-Behnken design, heterogeneous catalyst, kinetics, optimization, pumice, transesterification

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Authors: Weerachit Pulsawas, Thirasak Rirksomboon

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Due to its abundance from catalytic reforming and thermal cracking of naphtha, toluene could become more value-added compound if it is converted into xylenes, particularly p-xylene, via toluene methylation. Attractively, toluene methylation with methanol is an alternative route to produce xylenes in the absence of other hydrocarbon by-products for which appropriate catalyst would be utilized. In this study, HZSM-5 catalysts with Si/Al molar ratio of 100 were synthesized via hydrothermal treatment and modified by either chemical liquid deposition using tetraethyl-orthosilicate or dealumination with steam. The modified catalysts were characterized by several techniques and tested for their catalytic activity in a continuous down-flow fixed bed reactor. Various operating conditions including WHSV’s of 5 to 20 h-1, reaction temperatures of 400 to 500 °C, and toluene-to-methanol molar ratios (T/M) of 1 to 4 were investigated for attaining possible highest p-xylene selectivity. As a result, the catalytic activity of parent HZSM-5 with temperature of 400 °C, T/M of 4 and WHSV of 24 h-1 showed 65.36% in p-xylene selectivity and 11.90% in toluene conversion as demonstrated for 4 h on stream.

Keywords: toluene methylaion, HZSM-5, silylation, dealumination

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Authors: Ali Zazi, Ouiza Cherifi

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Natural gas currently represents a raw material of choice for the manufacture of a wide range of chemical products via synthesis gas, among the routes of transformation of methane into synthesis gas The reaction of the oxidation of methane by gas vapor 'water. This work focuses on the study of the effect of cerieum on the nickel-based catalyst supported by silica for the methane vapor reforming reaction, with a variation of certain parameters of the reaction. The reaction temperature, the H₂O / CH₄ ratio and the flow rate of the reaction mixture (CH₄-H₂O). Two catalysts were prepared by impregnation of Degussa silica with a solution of nickel nitrates and a solution of cerium nitrates [Ni (NO₃) 2 6H₂O and Ce (NO₃) 3 6H₂O] so as to obtain the 1.5% nickel concentrations. For both catalysts and plus 1% cerium for the second catalyst. These Catalysts have been characterized by physical and chemical analysis techniques: BET technique, Atomic Absorption, IR Spectroscopy, X-ray diffraction. These characterizations indicated that the nitrates had impregnated the silica. And that the NiO and Ce₂O3 phases are present and Ni°(after reaction). The BET surface of the silica decreases without being affected. The catalytic tests carried out on the two catalysts for the steam reforming reactions show that the addition of cerium to the nickel improves the catalytic performances of the nickel. And that these performances also depend on the parameters of the reaction, namely the temperature, the rate of the reaction mixture, and the ratio (H₂O / CH₄).

Keywords: heterogeneous catalysis, steam reforming, Methane, Nickel, Cerium, synthesis gas, hydrogen

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Authors: Tatyana T. Tabakova, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Krasimir I. Ivanov, Yordanka G. Karakirova, Petya Cv. Petrova, Georgi V. Avdeev

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The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH₃OH and (CH₃)₂O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH₃OH conversion at about 60 and 140 ^oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al₂O₃ 1:5 exhibited higher activity for CO and CH₃OH oxidation in comparison with Au on Cu-Ce/γ-Al₂O₃ 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Keywords: CO and VOCs oxidation, copper oxide, Ceria, gold catalysts

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Authors: Ouahiba Bechiri, Mostefa Abbessi

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The color removal from industrial effluents is a major concern in wastewater treatment. The main objective of this work was to study the decolorization of a mixture of Orange G acid (OG) and naphthol blue black dye (NBB) in aqueous solution by hydrogen peroxide using [H1,5Fe1,5P2W12Mo6O61,23H2O] as catalyst. [H1,5Fe1,5P2 W12Mo6O61,23H2O] is a recyclable DAWSON type heteropolyanion. Effects of various experimental parameters of the oxidation reaction of the dye were investigated. The studied parameters were: the initial pH, H2O2 concentration, the catalyst mass and the temperature. The optimum conditions had been determined, and it was found that efficiency of degradation obtained after 15 minutes of reaction was about 100%. The optimal parameters were: initial pH = 3; [H2O2]0 = 0.08 mM; catalyst mass = 0.05g; for a concentration of dyes = 30mg/L.

Keywords: Dawson type heteropolyanion, naphthol blue-black, dye degradation, orange G acid, oxidation, hydrogen peroxide

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Authors: Corazon Virtudazo-Ligaray, Mark Daniel G. de Luna, Meng-Wei Wan, Ming-Chun Lu

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A series of ternary compound catalyst with nanocomposites of ceria, tungsten trioxide and titania (CeO2-WOx-TiO2) with different WOx mole fraction (10, 20, 30, 40) have been synthesized by sol-gel method. These nanocomposite catalysts were used for oxidative extractive desulfurization of model fuel oil, which were composed of dibenzothiophene (DBT) dissolved in toluene. The 30% hydrogen peroxide, H2O2 was used as oxidant and acetonitrile as extractant. These catalysts were characterized by SEM-EDS to determine the morphology. Catalytic oxidation results show that the catalysts have high selectivity in refractory fuel oil with organo sulfur contents. The oxidative removal of DBT increases as the HPW content increases. The nanocomposites CeO2-WOx-TiO2 also shows high selectivity for DBT oxidation in the DBT–toluene acetonitrile system. The catalytic oxidative desulfurization ratio of model fuel reached to 100% with nanocomposites CeO2-WOx-TiO2 (35-30-35) mol percent catalyst nanocomposition under 333 K in 30 minutes.

Keywords: ceria, oxidative desulfurization, titania, phosphotungstic acid

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Authors: Seong Woon Lee, Soo Min Lim, Sung Sik Jeong, Jung Hoon Park

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The atmospheric concentration of greenhouse gas (GHG, Green House Gas) is increasing continuously as a result of the combustion of fossil fuels and industrial development. In response to this trend, many researches have been conducted on the reduction of GHG. Landfill gas (LFG, Land Fill Gas) is one of largest sources of GHG emissions containing the methane (CH₄) as a major constituent and can be considered renewable energy sources as well. In order to use LFG by connecting to the city pipe network, it required a process for removing impurities. In particular, oxygen must be removed because it can cause corrosion of pipes and engines. In this study, methane oxidation was used to eliminate oxygen from LFG and perovskite-type ceramic catalysts of La-Sr-Co-Fe-O composition was selected as a catalyst. Hollow fiber catalysts (HFC, Hollow Fiber Catalysts) have attracted attention as a new concept alternative because they have high specific surface area and mechanical strength compared to other types of catalysts. HFC was prepared by a phase-inversion/sintering technique using commercial La-Sr-Co-Fe-O powder. In order to measure the catalysts' activity, simulated LFG was used for feed gas and complete oxidation reaction of methane was confirmed. Pore structure of the HFC was confirmed by SEM image and perovskite structure of single phase was analyzed by XRD. In addition, TPR analysis was performed to verify the oxygen adsorption mechanism of the HFC. Acknowledgement—The project is supported by the ‘Global Top Environment R&D Program’ in the ‘R&D Center for reduction of Non-CO₂ Greenhouse gases’ (Development and demonstration of oxygen removal technology of landfill gas) funded by Korea Ministry of Environment (ME).

Keywords: complete oxidation, greenhouse gas, hollow fiber catalyst, land fill gas, oxygen removal, perovskite catalyst

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

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Catalytic cracking of butene to propylene was carried out in a continuous-flow fixed-bed reactor over HZSM-5 catalysts modified by nickel and phosphorus. The structure and acidity of catalysts were measured by N2 adsorption, NH3-TPD and XPS. The results revealed that surface area and strong acid sites both decreased with increasing phosphorus loadings. The increment of phosphorus loadings reduced the butene conversion but enhanced the propylene selectivity and catalyst stability.

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

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Authors: Thomas Chinedu Aniokete, Gordian Onyebuchukwu Mbah, Michael Daramola

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A sustainable NaOH integrated hydrothermal protocol was developed for the synthesis of waste-derived hydroxy sodalite catalysts for transesterification of waste animal fat (WAF) with a high per cent free fatty acid (FFA) to biodiesel. In this work, hydroxy sodalite catalyst was synthesized from two complex waste materials namely coal fly ash (CFA) and waste industrial brine (WIB). Measured amounts of South African CFA and WIB obtained from a coal mine field were mixed with NaOH solution at different concentrations contained in secured glass vessels equipped with magnetic stirrers and formed consistent slurries after aging condition at 47 oC for 48 h. The slurries were then subjected to hydrothermal treatments at 140 oC for 48 h, washed thoroughly and separated by the action of a centrifuge on the mixture. The resulting catalysts were calcined in a muffle furnace for 2 h at 200 oC and subsequently characterized for different effects using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and Bennett Emmet Teller (BET) adsorption-desorption techniques. The produced animal fat methyl ester (AFME) was analyzed using the gas chromatography-mass spectrometry (GC-MS) method. Results of the investigation indicate profoundly an enhanced catalyst purity, textural property and desired morphology due to the action of NaOH. Similarly, the performance evaluation with respect to catalyst activity reveals a high catalytic conversion efficiency of 98 % of the high FFA WAF to biodiesel under the following reaction conditions; a methanol-to-WAF ratio of 15:1, amount of SOD catalyst of 3 wt % with a stirring speed of 300-500 rpm, a reaction temperature of 60 oC and a reaction time of 8 h. There was a recovered 96 % stable catalyst after reactions and potentially recyclable, thus contributing to the economic savings to the process that had been a major bottleneck to the production of biodiesel. This NaOH route for synthesizing waste-derived hydroxy sodalite (SOD) catalyst is a sustainable and eco-friendly technology that speaks directly to the global quest for renewable-fossil fuel controversy enforcing sustainable development goal 7.

Keywords: coal fly ash, waste industrial brine, waste-derived hydroxy sodalite catalyst, sodium hydroxide, biodiesel, transesterification, biomass conversion

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Authors: Matthew Ndubuisi Abonyi, Christopher Chiedozie Obi, Joseph Tagbo Nwabanne

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This review focuses on the application of Metal-Organic Frameworks (MOF)-based catalysts in the degradation of organic pollutants in wastewater. The degradation of organic pollutants in wastewater remains a critical environmental challenge, necessitating innovative solutions for effective treatment. MOFs have garnered significant attention as promising catalysts for this purpose, owing to their exceptional surface area, tunable porosity, and diverse chemical functionalities. It explores various catalytic mechanisms, including photocatalysis, Fenton-like reactions, and other advanced oxidation processes facilitated by MOFs. The review also explores the design strategies that enhance the catalytic performance of MOFs, such as structural modifications, composite formation, and post-synthetic modifications. Furthermore, real-world case studies are presented, highlighting the practical applications and environmental impact of MOF-based catalysts in wastewater treatment. Challenges associated with the scalability and stability of these materials are discussed, along with future directions for research and development. This review highlights the significant potential of MOF-based catalysts in addressing the pressing issue of water pollution and advocates for continued innovation to optimize their application in wastewater treatment.

Keywords: metal-organic frameworks (MOFs), catalysis, wastewater treatment, organic pollutant degradation, photocatalysis

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Authors: Francisco Espinosa, Juan Chavarría

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Glycerol is a byproduct of biodiesel production that can be used for aqueous-phase reforming to obtain hydrogen. Iridium is a material that has high activity and hydrogen selectivity for steam phase reforming. Nevertheless, a drawback for the use of iridium in aqueous-phase reforming is the low activity in water-gas shift reaction. Therefore, in this work, it is proposed the use of nickel and copper as a second metal in the catalyst to reach a synergetic effect. Iridium, iridium-nickel and iridium-copper catalysts were prepared by incipient wetness impregnation and evaluated in the aqueous-phase reforming of glycerol using CeO₂ or La₂O₃ as support. The catalysts were characterized by XRD, XPS, and EDX. The reactions were carried out in a fixed bed reactor feeding a solution of glycerol 10 wt% in water at 270°C, and reaction products were analyzed by gas chromatography. It was found that IrNi/CeO₂ reached highest glycerol conversion and hydrogen production, slightly above 70% and 43 vol% respectively. In terms of conversion, iridium is a promising metal, and its activity for hydrogen production can be enhanced when adding a second metal.

Keywords: aqueous-phase reforming, glycerol, hydrogen production, iridium

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Authors: Dorothea Voß, Tobias Esser, Michael Huber, Jakob Albert

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The growing world population and the associated increase in demand for energy and consumer goods, as well as increasing waste production, requires the development of sustainable processes. In addition, the increasing environmental awareness of our society is a driving force for the requirement that processes must be as resource and energy efficient as possible. In this context, the use of polyoxometalate catalysts (POMs) has emerged as a promising approach for the development of green processes. POMs are bifunctional polynuclear metal-oxo-anion cluster characterized by a strong Brønsted acidity, a high proton mobility combined with fast multi-electron transfer and tunable redox potential. In addition, POMs are soluble in many commonly known solvents and exhibit resistance to hydrolytic and oxidative degradation. Due to their structure and excellent physicochemical properties, POMs are efficient acid and oxidation catalysts that have attracted much attention in recent years. Oxidation processes with molecular oxygen are worth mentioning here. However, the fact that the POM catalysts are homogeneous poses a challenge for downstream processing of product solutions and recycling of the catalysts. In this regard, nanofiltration membranes have gained increasing interest in recent years, particularly due to their relative sustainability advantage over other technologies and their unique properties such as increased selectivity towards multivalent ions. In order to establish an efficient downstream process for the highly selective separation of homogeneous POM catalysts from aqueous solutions using nanofiltration membranes, a laboratory-scale membrane system was designed and constructed. By varying various process parameters, a sensitivity analysis was performed on a model system to develop an optimized method for the recovery of POM catalysts. From this, process-relevant key figures such as the rejection of various system components were derived. These results form the basis for further experiments on other systems to test the transferability to serval separation tasks with different POMs and products, as well as for recycling experiments of the catalysts in processes on laboratory scale.

Keywords: downstream processing, nanofiltration, polyoxometalates, homogeneous catalysis, green chemistry

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Authors: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin

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Oxyfuel combustion is a promising method that enables to obtain a CO2 rich stream, with water vapor ( ̴10%), unburned components such as CO and NO, which must be cleaned before the use of CO2. Our objective is then the final treatment of CO and NO by catalysis. Three-way catalysts are well-developed material for simultaneous conversion of NO, CO and hydrocarbons. Pt and/or Rh ensure a quasi-complete removal of NOx, CO and HC and there is also a growing interest in partly replacing Pt with less-expensive Pd. The use of alumina and ceria as support ensures, respectively, the stabilization of such species in active state and discharging or storing oxygen to control the oxidation of CO and HC and the reduction of NOx. In this work, we will compare different metals (Pd, Rh and Pt) supported on Al2O3 and CeO2, for CO2 purification from oxyfuel combustion. The catalyst must reduce NO by CO in an oxidizing environment, in the presence of CO2 rich stream and resistant to water. In this study, Al2O3 and CeO2 were used as support materials of the catalysts. 1wt% M/Support where M = Pd, Rh or Pt catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2], rhodium [Rh(NO3)3] and platinum [Pt(NO2)2(NO3)2]. Materials were characterized by BET surface area, H2 chemisorption, and TEM. Catalytic activity was evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200 mL.min−1, with same GHSV (2.24x104 h-1). The catalytic performances of the samples were investigated with and without water. It shows that the total oxidation of CO occurred over the different materials. This study evidenced an important effect of the nature of the metals, supports and the presence or absence of H2O during the reduction of NO by CO in oxyfuel combustions conditions. Rh based catalysts show that the addition of water has a very positive influence especially on the Rh catalyst on CeO2. Pt based catalysts keep a good activity despite the addition of water on the both supports studied. For the NO reduction, addition of water act as a poison with Pd catalysts. The interesting results of Rh based catalysts with water can be explained by a production of hydrogen through the water gas shift reaction. The produced hydrogen acts as a more effective reductant than CO for NO removal. Furthermore, in TWCs, Rh is the main component responsible for NOx reduction due to its especially high activity for NO dissociation. Moreover, cerium oxide is a promotor for WGSR.

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis

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Authors: Zahra Asgar Pour

Abstract:

Two types of Ti-Al-containing zeolitic beads with an average diameter of 450 to 750 µm and hierarchical porosity were synthesized using a hard template method and tested as heterogeneous catalysts in the epoxidation of cycloalkenes (i.e. cyclohexene and cis-cyclooctene) with aqueous hydrogen peroxide (H₂O₂) or tert-butyl hydroperoxide(TBHP) as the oxidant agent. The first type of zeolitic beads was prepared by hydrothermal treatment of a primarygel (containing the Si, Ti, and Al precursors) in the presence of porous anion-exchange resin beads as the hard shaping template. After calcination, these beads (Ti-Al-Beta-HDT-B) consisted of both crystalline zeolite Beta and an amorphous silicate phase. The second type of zeolitic beads (Ti-Beta-PS-deAl-14.4-B) was obtained by post-synthesis dealumination of Al-containing zeolite Beta beads using 14.4 M HNO₃, followed by Ti grafting (3 wt% per gram of zeolite). The prepared materials were characterised by means of XRD, N2-physisorption, UV-vis, XRF, SEM, and TEM and tested as heterogeneous epoxidation catalysts. This post-synthetically prepared catalyst demonstrated higher activity (cyclohexene conversion of 22.7 % and epoxide selectivity of 33.5 %) after 5 h at60 °C, which emanates from the crystalline structure and higher degrees of hydrophobicity. In addition, the post-synthetically prepared beads were prone to partial Ti leaching in the presence of H₂O₂, whereas they showed to be resistant against Ti leaching using tert-butyl hydroperoxide as the oxidant agent.

Keywords: epoxidation, structured catalysts, hierarchical porosity, bead-shape catalysts

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