Search results for: rhodium cobalt bimetallic catalyst

Authors: Y. C. Bhattacharyulu, Amit J. Agrawal, Vikram S. Chatake, Ketan S. Desai

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In recent years, the improper disposal of waste polymeric materials like plastics, rubber, liquid containers, daily household materials, etc. is posing a grave problem by polluting the environment. On the other hand fluctuations in the oil market and limited stocks of fossil fuels have diverted the interest of researchers to study the production of fuels and hydrocarbons from alternative sources. Hence, to study the production of fuels from waste plastic is the need of hour at present. Effect of alkali solutions of different concentrations with copper comprising catalyst on depolymerisation reactions was studied here. The present study may become a preliminary method for obtaining valuable hydrocarbons from waste plastics and an effective way for depolymerising or degrading waste plastics for their safe disposal without causing any environmental problems.

Keywords: catalyst, depolymerisation, disposal, hydrocarbon liquids, waste plastic

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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: Flavio A. F. Da Ponte, Jackson Q. Malveira, Monica C. G. Albuquerque

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In recent years a worldwide interest in renewable resources from the biomass has spurred the industry. In this work the chemical structure of oleic acid chains was modified by homogeneous and heterogeneous catalysis in order to produce esters. The homogeneous epoxidation was carried out at H2O2 to oleic acid unsaturation molar ratio of 20:1. The reaction temperature was 338 K and reaction time 16 h. Formic acid was used as catalyst. For heterogeneous catalysis reaction temperature was 343 K and reaction time 24 h. The esters production was carried out by heterogeneous catalysis of the epoxidized oleic acid and butanol using Mg/SBA-15 as catalyst. The resulting products were confirmed by NMR (1H and 13C) and FTIR spectroscopy. The products were characterized before and after each reaction. The catalysts were characterized by X-ray diffraction, X-ray fluorescence, thermogravimetric analysis (TGA) and BET surface areas. The results were satisfactory for the bioproducts formed.

Keywords: acid oleic, bioproduct, esters, epoxidation

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Authors: Francisco Vidal Vázquez, Pekka Simell, Christian Frilund, Matti Reinikainen, Ilkka Hiltunen, Tim Böltken, Benjamin Andris, Paolo Piermartini

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Carbon capture and utilization (CCU) are one of the key topics in mitigation of CO2 emissions. There are many different technologies that are applied for the production of diverse chemicals from CO2 such as synthetic natural gas, Fischer-Tropsch products, methanol and polymers. Power-to-Gas and Power-to-Liquids concepts arise as a synergetic solution for storing energy and producing value added products from the intermittent renewable energy sources and CCU. VTT is a research and technology development company having energy in transition as one of the key focus areas. VTT has extensive experience in piloting and upscaling of new energy and chemical processes. Recently, VTT has developed and commissioned a Mobile Synthesis Unit (MOBSU) in close collaboration with INERATEC, a spin-off company of Karlsruhe Institute of Technology (KIT, Germany). The MOBSU is a multipurpose synthesis unit for CO2 upgrading to energy carriers and chemicals, which can be transported on-site where CO2 emission and renewable energy are available. The MOBSU is initially used for production of fuel compounds and chemical intermediates by combination of two consecutive processes: reverse Water-Gas Shift (rWGS) and Fischer-Tropsch synthesis (FT). First, CO2 is converted to CO by high-pressure rWGS and then, the CO and H2 rich effluent is used as feed for FT using an intensified reactor technology developed and designed by INERATEC. Chemical equilibrium of rWGS reaction is not affected by pressure. Nevertheless, compression would be required in between rWGS and FT in the case when rWGS is operated at atmospheric pressure. This would also require cooling of rWGS effluent, water removal and reheating. For that reason, rWGS is operated using precious metal catalyst in the MOBSU at similar pressure as FT to simplify the process. However, operating rWGS at high pressures has also some disadvantages such as methane and carbon formation, and more demanding specifications for materials. The main parts of FT module are an intensified reactor, a hot trap to condense the FT wax products, and a cold trap to condense the FT liquid products. The FT synthesis is performed using cobalt catalyst in a novel compact reactor technology with integrated highly-efficient water evaporation cooling cycle. The MOBSU started operation in November 2016. First, the FT module is tested using as feedstock H2 and CO. Subsequently, rWGS and FT modules are operated together using CO2 and H2 as feedstock of ca. 5 Nm3/hr total flowrate. On spring 2017, The MOBSU unit will be integrated together with a direct air capture (DAC) of CO2 unit, and a PEM electrolyser unit at Lappeenranta University of Technology (LUT) premises for demonstration of the SoletAir concept. This would be the first time when synthetic fuels are produced by combination of DAC unit and electrolyser unit which uses solar power for H2 production.

Keywords: CO2 utilization, demonstration, Fischer-Tropsch synthesis, intensified reactors, reverse water-gas shift

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Authors: Ratna Dewi Kusumaningtyas, Riris Pristiyani, Heny Dewajani

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Biodiesel is commonly produced via the two main routes, i.e. the transesterification of triglycerides and the esterification of free fatty acid (FFA) using short-chain alcohols. Both the two routes have drawback in term of the side product yielded during the reaction. Transesterification reaction of triglyceride results in glycerol as side product. On the other hand, FFA esterification brings in water as side product. Both glycerol and water in the biodiesel production are managed as waste. Hence, a separation process is necessary to obtain a high purity biodiesel. Meanwhile, separation processes is generally the most capital and energy intensive part in industrial process. Therefore, to reduce the separation process, it is essential to produce biodiesel via an alternative route eliminating glycerol or water side-products. In this work, biodiesel synthesis was performed using a glycerol-free process through chemical interesterification of jatropha oil with ethyl acetate in the presence on sodium acetate catalyst. By using this method, triacetine, which is known as fuel bio-additive, is yielded instead of glycerol. This research studied the effects of catalyst concentration on the jatropha oil interesterification process in the range of 0.5 – 1.25% w/w oil. The reaction temperature and molar ratio of oil to ethyl acetate were varied at 50, 60, and 70°C, and 1:6, 1:9, 1:15, 1:30, and 1:60, respectively. The reaction time was evaluated from 0 to 8 hours. It was revealed that the best yield was obtained with the catalyst concentration of 0.5%, reaction temperature of 70 °C, molar ratio of oil to ethyl acetate at 1:60, at 6 hours reaction time.

Keywords: biodiesel, interesterification, glycerol-free, triacetine, jatropha oil

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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: F. A. F. da Ponte, J. Q. Malveira, I. A. Maciel, M. C. G. Albuquerque

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In this work aviation, biofuel production was studied by fatty acids (C6 to C16) esterification. The process variables in heterogeneous catalysis were evaluated using an experimental design. Temperature and reaction time were the studied parameters, and the methyl esters content was the response of the experimental design. An ion exchange resin was used as a heterogeneous catalyst. The process optimization was carried out using response surface methodology (RSM) and polynomial model of second order. Results show that the most influential variables on the linear coefficient of each effect studied were temperature and reaction time. The best result of methyl esters conversion in the experimental design was under the conditions: 10% wt of catalyst; 100 °C and 4 hours of reaction. The best-achieved conversion was 96.5% wt of biofuel.

Keywords: esterification, ion-exchange resins, response surface methodology, biofuel

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Authors: Ratna Siti Khodijah, Mirzam Abdurrachman

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Gold is recovered from gold ores. Within the ores, there are not only gold but also several types of precious metals. Copper, silver, and platinum group elements (ruthenium, rhodium, palladium, rhenium, osmium, and iridium) are metals commonly found in the ores. These metals combine to form an ore because they have the same properties. It is due to their position in periodic-system-of-elements are near to gold. However, the presence of mercury in every gold ore has not been mentioned, even though it is located right next to gold in the periodic-system-of-elements and they are located in the same block, d-block. Thus, it is possible that mercury is contained in the ores. Moreover, the elements of the same group with mercury—zinc and cadmium—sometimes can be found in the ores. It is suspected that mercury can not be detected because the processing of gold ores usually using fire assay method. Before the ores melting, mercury would evaporate because it has the lowest boiling point of all precious metal in the ores. Therefore, it suggested doing research on the presence of mercury in gold ores by CVAAS method. The results of this study would obtain the amount of mercury in gold ores that should be purified. So it can be produced economically if possible.

Keywords: boiling point, d-block, fire assay, precious metal

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Authors: Istijabatul Aliyah, Bambang Setioko, Rara Sugiarti

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Surakarta is one of the cities which are formed with the concept of Javanese cosmology. As a traditional town of Java, Surakarta is known as ‘the paradise’ of traditional markets. Since its establishment, Surakarta is formed with Catur Gatra Tunggal or Four Single-Slot concept (palace, square, mosques, and markets). Current development in Surakarta downtown today indicates that traditional markets have improved themselves in both physical and non-physical aspects. The efforts start from the market façade revitalization, restoration and the overall development of market; up to social activities, competition between traders or large celebrations in the neighbourhood market. This research was conducted in Surakarta, which is aimed at: identifying the role of traditional market revitalization efforts in the development of a city. This study employs several methods of analysis, namely: 1) Spatial analysis for mapping the distribution of traditional markets in the city constellation, 2) Category-Based Analysis (CBA) to classify the revitalization of traditional markets that has an influence in the development of the city, and 3) Interactive Method of Analysis. The results of this research indicate that the presence of a constellation of traditional markets in Surakarta is dominated by the presence of Gede Market, not only as the oldest traditional market, but also as a center of economic and socio-cultural activities of the community. The role of traditional market revitalization in the development of a town is as an Urban Catalyst towards a MICE city in the sense that the revitalization effort, even done in a relatively short time and not yet covering the overall objects, is able to establish brand image of Surakarta as a city of culture which is friendly and ready to be MICE tourism city.

Keywords: traditional market revitalization, urban catalyst, MICE tourism, Surakarta

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Authors: O. P. Yadav

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Nano-size Ag-N co-doped ZnO/CuO composite photo-catalyst has been synthesized by chemical method and characterized using XRD, TEM, FTIR, AAS and UV-Vis spectroscopic techniques. Photo-catalytic activity of as-synthesized nanomaterial has been studied using degradation of methyl orange as a probe under UV as well as visible radiations. Ag-N co-doped ZnO/CuO composite showed higher photo-catalytic activity than Ag- or N-doped ZnO and undoped ZnO-CuO composite photo-catalysts. The observed highest activity of Ag-N co-doped ZnO-CuO among the studied photo-catalysts is attributed to the cumulative effects of lowering of band-gap energy and decrease of recombination rate of photo-generated electrons and holes owing to doped N and Ag, respectively. Effects of photo-catalyst load, pH and substrate initial concentration on degradation of methyl orange have also been studied. Photo-catalytic degradation of methyl orange follows pseudo first order kinetics.

Keywords: degradation, nanocomposite, photocatalyst, spectroscopy, XRD

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Authors: Kritsada Pipitthapan

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WO3/SiO2 catalysts were modified by an ion exchange method with sodium hydroxide or potassium hydroxide solution. The performance of the modified catalysts was tested in the metathesis of ethylene and trans-2-butene to propylene. During ion exchange, sodium and potassium ions played different roles. Sodium modified catalysts revealed constant trans-2-butene conversion and propylene selectivity when the concentrations of sodium in the solution were varied. In contrast, potassium modified catalysts showed reduction of the conversion and increase of the selectivity. From these results, potassium hydroxide may affect the transformation of tungsten oxide active species, resulting in the decrease in conversion whereas sodium hydroxide did not. Moreover, the modification of catalysts by this method improved the catalyst stability by lowering the amount of coke deposited on the catalyst surface.

Keywords: acid sites, alkali metal, isomerization, metathesis

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Authors: Ene Rosemary Ndidiamaka, Nwangwu Florence Chinyere

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The physiochemical properties of the melon seed oil was studied to determine its potentials as viable feed stock for biodisel production. The melon seed was extracted by solvent extraction using n-hexane as the extracting solvent. In this research, methanol was the alcohol used in the production of biodiesel, although alcohols like ethanol, propanol may also be used. Sodium hydroxide was employed for the catalysis. The melon seed oil was characterized for specific gravity, pH, ash content, iodine value, acid value, saponification value, peroxide value, free fatty acid value, flash point, viscosity, and refractive index using standard methods. The melon seed oil had very high oil content. Specific gravity and flash point of the oil is satisfactory. However, moisture content of the oil exceeded the stipulated ASRTM standard for biodiesel production. The overall results indicates that the melon seed oil is suitable for single-stage transesterification process to biodiesel production.

Keywords: biodiesel, catalyst, melon seed, transesterification

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Authors: Saimatun Nisa

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Walnut is an important export product from the Union Territory of Jammy and Kashmir. After extraction of the kernel, the walnut shell forms a solid waste that needs to be managed. Pyrolysis is one interesting option for the utilization of this walnut waste. In this study microwave pyrolysis reactor is used to convert the walnut shell biomass into its value-added products. Catalytic and non-catalytic conversion of walnut shell waste to oil, gas and char was evaluated using a Co-based catalyst. The catalyst was characterized using XPS and SEM analysis. Pyrolysis temperature, reaction time, particle size and sweeping gas (N₂) flow rate were set in the ranges of 400–600 °C, 40 min, <0.6mm to < 4.75mm and 300 ml min−1, respectively. The heating rate was fixed at 40 °C min−1. Maximum gas yield was obtained at 600 °C, 40 min, particle size range 1.18-2.36, 0.5 molar catalytic as 45.2%. The liquid product catalytic and non-catalytic was characterized by GC–MS analyses. In addition, the solid product was analyzed by means of FTIR & SEM.

Keywords: walnut shell, biooil, biochar, microwave pyrolysis

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Authors: H. Boucheloukh, N. Aoun, S. Rouissa, T. Sehili, F. Parrino, V. Loddo

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Photocatalysis has made a revolution in wastewater treatment and the elimination of persistent organic pollutants. This process is based on the use of semiconductors as photocatalysts. In this study, nickel ferrite spinel (NiFe2O4) nanoparticles were successfully synthesized by the sol-gel route. The structural, morphological, elemental composition, chemical state, particle size, optical and electrochemical characterizations using powder X-ray diffraction (P-XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy(SEM), energy-dispersive X-ray spectroscopy (EDAX ). We tested the prepared NiFe2O4(NPS)by monitoring the degradation of Rose Bengal (RB) dye in an aqueous solution under direct sunlight irradiation. The effects of catalyst dosage and dye concentration were also considered for the effective degradation of RB dye. The optimum catalyst dosage and concentration of dye were found to be 1 g/L and 10 μM, respectively. A maximum of 80% photocatalytic degradation efficiency (DE%) was achieved at 120 min of direct sunlight irradiation.

Keywords: Rose Bengal, Nickelate, photocatalysis, irradiation

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Authors: Abhishek Sraw, Amit Sobti, Yamini Pandey, R. K. Wanchoo, Amrit Pal Toor

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Monocrotophos (MCP) is a widely used pesticide in India, which belong to an extremely toxic organophosphorus family, is persistent in nature and its toxicity is widely reported in all environmental segments in the country. Advanced Oxidation Process (AOP) is a promising solution to the problem of water pollution. TiO₂ is being widely used as a photocatalyst because of its many advantages, but it has a large band gap, due to which it is modified using metal and nonmetal dopant to make it active under sunlight and visible light. The use of nanosized powdered catalysts makes the recovery process extremely complicated. Hence the aim is to use low cost, easily available, eco-friendly clay material in form of bead as the support for the immobilization of catalyst, to solve the problem of post-separation of suspended catalyst from treated water. A recirculation type photocatalytic reactor (RTPR), using ultraviolet light emitting source (blue black lamp) was designed which work effectively for both suspended catalysts and catalyst coated clay beads. The bare, TiO₂ and W-TiO₂ coated clay beads were characterized by scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS) and N₂ adsorption–desorption measurements techniques (BET) for their structural, textural and electronic properties. The study involved variation of different parameters like light conditions, recirculation rate, light intensity and initial MCP concentration under UV and sunlight for the degradation of MCP. The degradation and mineralization studies of the insecticide solution were performed using UV-Visible spectrophotometer, and COD vario-photometer and GC-MS analysis respectively. The main focus of the work lies in checking the recyclability of the immobilized TiO₂ over clay beads in the developed RTPR up to 30 continuous cycles without reactivation of catalyst. The results demonstrated the economic feasibility of the utilization of developed RTPR for the efficient purification of pesticide polluted water. The prepared TiO₂ clay beads delivered 75.78% degradation of MCP under UV light with negligible catalyst loss. Application of W-TiO₂ coated clay beads filled RTPR for the degradation of MCP under sunlight, however, shows 32% higher degradation of MCP than the same system based on undoped TiO₂. The COD measurements of TiO₂ coated beads led to 73.75% COD reduction while W-TiO₂ resulted in 87.89% COD reduction. The GC-MS analysis confirms the efficient breakdown of complex MCP molecules into simpler hydrocarbons. This supports the promising application of clay beads as a support for the photocatalyst and proves its eco-friendly nature, excellent recyclability, catalyst holding capacity, and economic viability.

Keywords: immobilized clay beads, monocrotophos, recirculation type photocatalytic reactor, TiO₂

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Authors: Medhanie Gebremedhin Gebru, Alex Schechter

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Dimethyl ether (DME) possesses several advantages over other small organic molecules such as methanol, ethanol, and ammonia in terms of providing higher energy density, being less toxic, and having lower Nafion membrane crossover. However, the absence of an active and stable catalyst has been the bottleneck that hindered the commercialization of direct DME fuel cells. A Vulcan XC72 carbon-supported ternary metal catalyst, Pt₃Pd₃Sn₂/C is reported to have yielded the highest specific power density (90 mW mg-¹PGM) as compared to other catalysts tested fordirect DME fuel cell (DDMEFC). However, the micropores and sulfur groups present in Vulcan XC72 hinder the fuel utilization by causing Pt agglomeration and sulfur poisoning. Vulcan XC72 having a high carbon sp³ hybridization content, is also prone to corrosion. Therefore, carbon supports such as multi-walled carbon nanotube (MWCNT), black pearl 2000 (BP2000), and their cold N2 plasma-treated counterpartswere tested to further enhance the activity of the catalyst, and the outputs with these carbons were compared with the originally used support. Detailed characterization of the pristine and carbon supports was conducted. Electrochemical measurements in three-electrode cells and laboratory prototype fuel cells were conducted.Pt₃Pd₃Sn₂/BP2000 exhibited excellent performance in terms of electrochemical active surface area (ECSA), peak current density (jp), and DME oxidation charge (Qoxi). The effect of the plasma activation on the activity improvement was observed only in the case of MWCNT while having little or no effect on the other carbons. A Pt₃Pd₃Sn₂ supported on the optimized mixture of carbons containing 75% plasma-activated MWCNT and 25% BP2000 (Pt₃Pd₃Sn₂/75M25B) provided the highest reported power density of 117 mW mg-1PGM using an anode loading of1.55 mgPGMcm⁻².

Keywords: DME, DDMEFC, ternary metal catalyst, carbon support, plasma activation

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Authors: Seyed Mohamad Rasool Mirkarimi, David Chiaramonti, Samir Bensaid

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Catalytic methane decomposition (CMD, reaction 4) is a one-step process for hydrogen production where carbon in the methane molecule is sequestered in the form of stable and higher-value carbon materials. Metallic catalysts and carbon-based catalysts are two major types of catalysts utilized for the CDM process. Although carbon-based catalysts have lower activity compared to metallic ones, they are less expensive and offer high thermal stability and strong resistance to chemical impurities such as sulfur. Also, it would require less costly separation methods as some of the carbon-based catalysts may not have an active metal component in them. Since the regeneration of metallic catalysts requires burning of the C on their surfaces, which emits CO/CO2, in some cases, using carbon-based catalysts would be recommended because regeneration can be completely avoided, and the catalyst can be directly used in other processes. This work focuses on the effect of biochar as a carbon-based catalyst for the conversion of methane into hydrogen and carbon. Biochar produced from the pyrolysis of poplar wood and activated biochar are used as catalysts for this process. In order to observe the impact of carbon-based catalysts on methane conversion, methane cracking in the absence and presence of catalysts for a gas stream with different levels of methane concentration should be performed. The results of these experiments prove conversion of methane in the absence of catalysts at 900 °C is negligible, whereas in the presence of biochar and activated biochar, significant growth has been observed. Comparing the results of the tests related to using char and activated char shows the enhancement obtained in BET surface area of the catalyst through activation leads to more than 10 vol.% methane conversion.

Keywords: hydrogen production, catalytic methane decomposition, biochar, activated biochar, carbon-based catalyts

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Authors: Aryan Azad, Sun Jae Kim

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Cotton fabric is particularly prone to wrinkling. BTCA has been confirmed as the most effective reagent with sodium hypophosphite (SHP) as catalyst for decreasing the wrinkle issue. Using nano TiO2 as aco-catalyst could improve the catalytic reaction of the BTCA as well. In this study, the effect of dying process using reactive/disperse on the cotton/polyester blended fabric (65/35%) which is previously treated by nano TiO2 and BTCA, were investigated. Results were compared by samples which were not treated by nano TiO2 and BTCA by scanning electronic microscopy (SEM). Results showed, samples which were treated by mixing nano TiO2 and BTCA have not absorbed dye as much as untreated samples.

Keywords: cotton/polyester, dyeing process, nano titanium dioxide (TiO2), sodium hypophosphite (SHP), Tetra carboxylic acid (BTCA)

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: M. Nuhu, M. S. Amina, A. H. Aminu, A. J. Abbas, N. Salahudeen, A. Z. Yusuf

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Transesterification of jatropha methyl ester (JME) with the common polyol, trimethylolpropane (TMP) produced the TMP based ester which exhibits improved temperature properties. This paper discusses the physic-chemical properties of jatropha bio-lubricant base oil applicable for ISO VG32 and VG46 requirement. The catalyst employed for the JME was CaO synthesized in National Research Institute for Chemical Technology (NARICT) that gives 100% conversion. The molar ratio of JME to TMP was 3.5:1 and the catalyst (NaOCH3) loading were found to be 0.8% of the weight of the total reactants. The final fractionated jatropha bio-lubricant base was found to contain 11.95% monoesters, 43.89% diesters and 44.16% triesters (desired product). In addition, it was found that the bio-lubricant base oil produced is comparable to the ISO VG46 commercial standards for light and industrial gears applications and other plant based bio-lubricant.

Keywords: biodegradability, methyl ester, pour point, transesterification, viscosity index

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Authors: Abdoulaye Maihatchi Ahamed, Zubin Arora, Benjamin Swobada, Jean-yves Lansot, Alexandre Chagnes

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Lithium-ion battery (LiB) is the technology of choice in the development of electric vehicles. But there are still many challenges, including the development of positive electrode materials exhibiting high cycle ability, high energy density, and low environmental impact. For this latter, LiBs must be manufactured in a circular approach by developing the appropriate strategies to reuse and recycle them. Presently, the recycling of LiBs is carried out by the pyrometallurgical route, but more and more processes implement or will implement the hydrometallurgical route or a combination of pyrometallurgical and hydrometallurgical operations. After producing the black mass by mineral processing, the hydrometallurgical process consists in leaching the black mass in order to uptake the metals contained in the cathodic material. Then, these metals are extracted selectively by liquid-liquid extraction, solid-liquid extraction, and/or precipitation stages. However, liquid-liquid extraction combined with precipitation/crystallization steps is the most implemented operation in the LiB recycling process to selectively extract copper, aluminum, cobalt, nickel, manganese, and lithium from the leaching solution and precipitate these metals as high-grade sulfate or carbonate salts. Liquid-liquid extraction consists in contacting an organic solvent and an aqueous feed solution containing several metals, including the targeted metal(s) to extract. The organic phase is non-miscible with the aqueous phase. It is composed of an extractant to extract the target metals and a diluent, which is usually aliphatic kerosene produced from the petroleum industry. Sometimes, a phase modifier is added in the formulation of the extraction solvent to avoid the third phase formation. The extraction properties of the diluent do not depend only on the chemical structure of the extractant, but it may also depend on the nature of the diluent. Indeed, the interactions between the diluent can influence more or less the interactions between extractant molecules besides the extractant-diluent interactions. Only a few studies in the literature addressed the influence of the diluent on the extraction properties, while many studies focused on the effect of the extractants. Recently, new low-carbon footprint aliphatic diluents were produced by catalytic dearomatisation and distillation of bio-based oil. This study aims at investigating the influence of the nature of the diluent on the extraction properties of three extractants towards cobalt, nickel, manganese, copper, aluminum, and lithium: Cyanex®272 for nickel-cobalt separation, DEHPA for manganese extraction, and Acorga M5640 for copper extraction. The diluents used in the formulation of the extraction solvents are (i) low-odor aliphatic kerosene produced from the petroleum industry (ELIXORE 180, ELIXORE 230, ELIXORE 205, and ISANE IP 175) and (ii) bio-sourced aliphatic diluents (DEV 2138, DEV 2139, DEV 1763, DEV 2160, DEV 2161 and DEV 2063). After discussing the effect of the diluents on the extraction properties, this conference will address the development of a low carbon footprint process based on the use of the best bio-sourced diluent for the production of high-grade cobalt sulfate, nickel sulfate, manganese sulfate, and lithium carbonate, as well as metal copper.

Keywords: diluent, hydrometallurgy, lithium-ion battery, recycling

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Authors: Mukul R. Gupta, Rajkumar Gandhi, Rajitha Sachan, Naveen K. Khare

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The field of glycoscience has burgeoned in the last several decades, leading to the identification of many glycosides which could serve critical roles in a wide range of biological processes. This has prompted a resurgence in synthetic interest, with a particular focus on new approaches to construct the selective glycosidic bond. Despite the numerous elegant strategies and methods developed for the formation of glycosidic bonds, stereoselective construction of glycosides remains challenging. Here, we have recently developed the novel Hexafluoroisopropanol (HFIP) catalyzed stereoselective glycosylation methods by using KDN imidate glycosyl donor and a variety of alcohols in excellent yield. This method is broadly applicable to a wide range of substrates and with excellent selectivity of glycoside. Also, herein we are reporting the functionalization of the unbiased side of newly formed glycosides by dual-catalytic transition metal systems (Ru- or Fe-). We are using the innovative Reverse & Catalyst strategy, i.e., a reversible activation reaction by one catalyst with a functionalization reaction by another catalyst, together with enabling functionalization of substrates at their inherently unreactive sites. As well, we are targeting the diSia derivative synthesis by Wittig reaction. This synthetic method is applicable in mild conditions, functional group tolerance of the dual-catalytic systems and also highlights the potential of the multicatalytic approach to address challenging transformations to avoid multistep procedures in carbohydrate synthesis.

Keywords: KDN, stereoselective glycosylation, dual-catalytic functionalization, Wittig reaction

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Authors: S. Shanthi

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Catalyzed oxidation processes show extraordinary guarantee for application in numerous wastewater treatment ranges. Advanced oxidation processes are emerging innovation that might be utilized for particular objectives in wastewater treatment. This research work provides a solution for removal a refractory organic compound 2,4-dichlorophenoxyaceticacid a common water pollutant. All studies were done in batch mode in a constantly stirred reactor. Alternative ozonation processes catalysed by transition metals or granular activated carbon have been investigated for degradation of organics. Catalytic ozonation under study are homogeneous catalytic ozonation, which is based on ozone activation by transition metal ions present in aqueous solution, and secondly as heterogeneous catalytic ozonation in the presence of Granular Activated Carbon (GAC). The present studies reveal that heterogeneous catalytic ozonation using GAC favour the ozonation of 2,4-dichlorophenoxyaceticacid by increasing the rate of ozonation and a much higher degradation of substrates were obtained in a given time. Be that it may, Fe2+and Fe3+ ions decreased the rate of degradation of 2,4-dichlorophenoxyaceticacid indicating that it acts as a negative catalyst. In case of heterogeneous catalytic ozonation using GAC catalyst it was found that during the initial 5 minutes of contact solution concentration decreased significantly as the pollutants were adsorbed initially. Thereafter the substrate started getting oxidized and ozonation became a dominates the treatment process. The exhausted GAC was found to be regenerated in situ. The percentage reduction of the substrate was maximum achieved in minimum possible time when GAC catalyst is employed.

Keywords: ozonation, homogeneous catalysis, heterogeneous catalysis, granular activated carbon

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Authors: Kateryna Zhdanova, Evelyn Szeinbaum, Michelle Lo, Yeonjae Jo, Abel E. Navarro

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Alginate hydrogel beads (AB), spent peppermint leaf (PM), and a hybrid adsorbent of these two materials (ABPM) were studied as potential biosorbents of Cobalt (II) ions from aqueous solutions. Cobalt ion is a commonly underestimated pollutant that is responsible for several health problems. Discontinuous batch experiments were conducted at room temperature to evaluate the effect of solution acidity, mass of adsorbent on the adsorption of Co(II) ions. The interfering effect of salinity, the presence of surfactants, an organic dye, and Pb(II) ions were also studied to resemble the application of these adsorbents in real wastewater. Equilibrium results indicate that Co(II) uptake is maximized at pH values higher than 5, with adsorbent doses of 200 mg, 200 mg, and 120 mg for AB, PM, and ABPM, respectively. Co(II) adsorption followed the trend AB > ABPM > PM with Adsorption percentages of 77%, 71% and 64%, respectively. Salts had a strong negative effect on the adsorption due to the increase of the ionic strength and the competition for adsorption sites. The presence of Pb(II) ions, surfactant, and dye BY57 had a slightly negative effect on the adsorption, apparently due to their interaction with different adsorption sites that do not interfere with the removal of Co(II). A polar-electrostatic adsorption mechanism is proposed based on the experimental results. Scanning electron microscopy indicates that adsorbent has appropriate morphological and textural properties, and also that ABPM encapsulated most of the PM inside of the hydrogel beads. These experimental results revealed that AB, PM, and ABPM are promising adsorbents for the elimination of Co(II) ions from aqueous solutions under different experimental conditions. These biopolymers are proposed as eco-friendly alternatives for the removal of heavy metal ions at lower costs than the conventional techniques.

Keywords: adsorption, Co(II) ions, alginate hydrogel beads, spent peppermint leaf, pH

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Authors: Muhammad Saeed, Sheeba Khalid

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Aqueous pollution due to the textile industry is an important issue. Photocatalysis using metal oxides as catalysts is one of the methods used for eradication of dyes from textile industrial effluents. In this study, the synthesis, characterization, and evaluation of photocatalytic activity of Ag-TiO₂ are reported. TiO₂ catalysts with 2, 4, 6 and 8% loading of Ag were prepared by green methods using Azadrachea indica leaves' extract as reducing agent and titanium dioxide and silver nitrate as precursor materials. The 4% Ag-TiO₂ exhibited the best catalytic activity for degradation of dyes. Prepared catalyst was characterized by advanced techniques. Catalytic degradation of methylene blue and rhodamine B were carried out in Pyrex glass batch reactor. Deposition of Ag greatly enhanced the catalytic efficiency of TiO₂ towards degradation of dyes. Irradiation of catalyst excites electrons from conduction band of catalyst to valence band yielding an electron-hole pair. These photoexcited electrons and positive hole undergo secondary reaction and produce OH radicals. These active radicals take part in the degradation of dyes. More than 90% of dyes were degraded in 120 minutes. It was found that there was no loss catalytic efficiency of prepared Ag-TiO₂ after recycling it for two times. Photocatalytic degradation of methylene blue and rhodamine B followed Eley-Rideal mechanism which states that dye reacts in fluid phase with adsorbed oxygen. 27 kJ/mol and 20 kJ/mol were found as activation energy for photodegradation of methylene blue and rhodamine B dye respectively.

Keywords: TiO₂, Ag-TiO₂, methylene blue, Rhodamine B., photo degradation

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Authors: M. Al Zallouha, Y. Landkocz, J. Brunet, R. Cousin, J. M. Halket, E. Genty, P. J. Martin, A. Verdin, D. Courcot, S. Siffert, P. Shirali, S. Billet

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Toluene is one of the most used Volatile Organic Compounds (VOCs) in the industry. Amongst VOCs, Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) emitted into the atmosphere have a major and direct impact on human health. It is, therefore, necessary to minimize emissions directly at source. Catalytic oxidation is an industrial technique which provides remediation efficiency in the treatment of these organic compounds. However, during operation, the catalysts can release some compounds, called byproducts, more toxic than the original VOCs. The catalytic oxidation of a gas stream containing 1000ppm of toluene on Pd/α-Al2O3 can release a few ppm of benzene, according to the operating temperature of the catalyst. The development of new catalysts must, therefore, include chemical and toxicological validation phases. In this project, A549 human lung cells were exposed in air/liquid interface (Vitrocell®) to gas mixtures derived from the oxidation of toluene with a catalyst of Pd/α-Al2O3. Both exposure concentrations (i.e. 10 and 100% of catalytic emission) resulted in increased gene expression of Xenobiotics Metabolising Enzymes (XME) (CYP2E1 CYP2S1, CYP1A1, CYP1B1, EPHX1, and NQO1). Some of these XMEs are known to be induced by polycyclic organic compounds conventionally not searched during the development of catalysts for VOCs degradation. The increase in gene expression suggests the presence of undetected compounds whose toxicity must be assessed before the adoption of new catalyst. This enhances the relevance of toxicological validation of such systems before scaling-up and marketing.

Keywords: BTEX toxicity, air/liquid interface cell exposure, Vitrocell®, catalytic oxidation

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Authors: Igor B. Sivaev

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Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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Authors: Wenjun Zhang, Thao Thi Le, Dongyup Shin, Jong Min Kim

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Electrochemical hydrogen peroxide (H₂O₂) synthesis holds significant promise for decentralized environmental remediation through the electro-Fenton process. However, challenges persist, such as the absence of robust electrocatalysts for the selective two-electron oxygen reduction reaction (2e⁻ ORR) and the high cost and sluggish kinetics of conventional electro-Fenton systems in treating highly concentrated wastewater. This study introduces an efficient water treatment system for removing substantial quantities of organic pollutants using an advanced electro-Fenton system coupled with a high-valent NiO catalyst. By employing a precipitation method involving crystal facet and cation vacancy engineering, a trivalent Ni (Ni³⁺)-rich NiO catalyst with a (111)-domain-exposed crystal facet, named {111}-NivO, was synthesized. This catalyst exhibited a remarkable 96% selectivity and a high mass activity of 59 A g⁻¹ for H₂O₂ production, outperforming all previously reported Ni-based catalysts. Furthermore, an advanced electro-Fenton system, integrated with a flow cell for electrochemical H₂O₂ production, was utilized to achieve 100% removal of 50 ppm bisphenol A (BPA) in 200 mL of wastewater under heavy-duty conditions, reaching a superior rapid degradation rate (4 min, k = 1.125 min⁻¹), approximately 102 times faster than the conventional electro-Fenton system. The hyper-efficiency is attributed to the continuous and appropriate supply of H₂O₂, the provision of O₂, and the timely recycling of the electrolyte under high current density operation. This catalyst also demonstrated a 93% removal of total organic carbon after 2 hours of operation and can be applied for efficient removal of highly concentrated phenol pollutants from aqueous systems, which opens new avenues for wastewater treatment.

Keywords: hydrogen peroxide production, nickel oxides, crystal facet and cation vacancy engineering, wastewater treatment, flow cell, electro-Fenton

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Authors: Chiau Yuan Lim, Hayyiratul Fatimah Mohd Zaid, Fai Kait Chong

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Deep Eutectic Solvent (DES) is used in various applications due to its simplicity in synthesis procedure, biodegradable, inexpensive and easily available chemical ingredients. Graphene Oxide is a popular catalyst that being used in various processes due to its stacking carbon sheets in layer which theoretically rapid up the catalytic processes. In this study, choline chloride based DESs were synthesized and ChCl-PEG(1:4) was found to be the most effective DES in performing desulfurization, which it is able to remove up to 47.4% of the sulfur content in the model oil in just 10 minutes, and up to 95% of sulfur content after repeat the process for six times. ChCl-PEG(1:4) able to perform up to 32.7% desulfurization on real diesel after 6 multiple stages. Thus, future research works should focus on removing the impurities on real diesel before utilising DESs in petroleum field.

Keywords: choline chloride, deep eutectic solvent, fuel desulfurization, graphene oxide

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Authors: Hui-Hsin Huang, Yi-Feng Lin, Che-Chia Hu

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To date, photocatalytic wastewater treatment using solar energy has attracted considerable attention. In this study, strontium titanates with various morphologies, i.e., nanofibers and cubic-like particles, were prepared as photocatalysts using the electrospinning (ES), solid-state (SS), and sol-gel (SG) methods. X-ray diffraction (XRD) analysis showed that ES and SS can be assigned to pure phase SrTiO3, while SG was referred to Sr2TiO4. These samples displayed optical absorption edges at 385-395 nm, indicating they can be activated in UV light irradiation. Scanning electron microscope (SEM) analyses revealed that ES SrTiO3 has a uniform fibrous structure with length and diameter of several microns and 100-200 nm, respectively. After loading of nanoparticulate Ag as a co-catalyst onto the surface of strontium titanates, ES sample exhibited highest photocatalytic activity to degrade methylene orange dye solution in comparison to that of SS and SG ones. These results indicate that Ag-loaded ES SrTiO3, which has a desirable SrTiO3 phase and a facile electron transfer along the preferential direction in fibrous structure, can be a promising photocatalyst.

Keywords: photocatalytic degradation, strontium titanate, electrospinning, co-catalyst

Procedia PDF Downloads 267