Search results for: catalytic membrane

Authors: Bhavana Gulaty, Arshia Chaudhri

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Great civic projects contribute integrally to a city, and every city undergoes a recurring cycle of urban transformations and regeneration by their insertion. The M.I.C.E. (Meetings, Incentives, Convention and Exhibitions) industry is the forbearer of one category of such catalytic civic projects. Through a specific focus on M.I.C.E. destinations, this paper illustrates the multifarious dimensions that urban catalysts impact the city on S.P.U.R. (Seed. Profile. Urbane. Reflections), the theoretical framework of this paper aims to unearth these dimensions in the realm of the COEX (Convention & Exhibition) biosphere. The ‘COEX Biosphere’ is the filter of such catalysts being ecosystems unto themselves. Like a ripple in water, the impact of these strategic interventions focusing on art, culture, trade, and promotion expands right from the trigger; the immediate context to the region and subsequently impacts the global scale. These ripples are known to bring about significant economic, social, and political and network changes. The COEX inventory in the Asian context has one such prominent addition; the proposed India International Convention and Exhibition Centre (IICC) at New Delhi. It is envisioned to be the largest facility in Asia currently and would position India on the global M.I.C.E map. With the first phase of the project scheduled to open for use in the end of 2019, this flagship project of the Government of India is projected to cater to a peak daily footfall of 3,20,000 visitors and estimated to generate 5,00,000 jobs. While the economic benefits are yet to manifest in real time and ‘Good design is good business’ holds true, for the urban transformation to be meaningful, the benefits have to go beyond just a balance sheet for the city’s exchequer. This aspect has been found relatively unexplored in research on these developments. The methodology for investigation will comprise of two steps. The first will be establishing an inventory of the global success stories and associated benefits of COEX projects over the past decade. The rationale for capping the timeframe is the significant paradigm shift that has been observed in their recent conceptualization; for instance ‘Innovation Districts’ conceptualised in the city of Albuquerque that converges into the global economy. The second step would entail a comparative benchmarking of the projected transformations by IICC through a toolkit of parameters. This is posited to yield a matrix that can form the test bed for mapping the catalytic trajectory for projects in the pipeline globally. As a ready reckoner, it purports to be a catalyst to substantiate decision making in the planning stage itself for future projects in similar contexts.

Keywords: catalysts, COEX, M.I.C.E., urban transformations

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Authors: Keping Zuo, Foad Kabinejadian, Gideon Praveen Kumar Vijayakumar, Fangsen Cui, Pei Ho, Hwa Liang Leo

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Carotid artery stenting (CAS) is the standard procedure for patients with severe carotid stenosis at high risk for carotid endarterectomy (CAE). A major drawback of CAS is the higher incidence of procedure-related stroke compared with traditional open surgical treatment for carotid stenosis - CEA, even with the use of the embolic protection devices (EPD). As the currently available bare metal stents cannot address this problem, our research group developed a novel preferential covered-stent for carotid artery aims to prevent friable fragments of atherosclerotic plaques from flowing into the cerebral circulation, and yet maintaining the flow of the external carotid artery. The preliminary animal studies have demonstrated the potential of this novel covered-stent design for the treatment of carotid atherosclerotic stenosis. The purpose of this study is to evaluate the effect of membrane coating on the stent flexibility in order to improve the clinical performance of our novel covered stents. A total of 21 stents were evaluated in this study: 15 self expanding bare nitinol stents and 6 PTFE-covered stents. 10 of the bare stents were coated with 11%, 16% and 22% Polyurethane(PU), 4%, 6.25% and 11% EE, as well as 22% PU plus 5 μm Parylene. Different laser cutting designs were performed on 4 of the PTFE covert stents. All the stents, with or without the covered membrane, were subjected to a three-point flexural test. The stents were placed on two supports that are 30 mm apart, and the actuator is applying a force in the exact middle of the two supports with a loading pin with radius 2.5 mm. The loading pin displacement change, the force and the variation in stent shape were recorded for analysis. The flexibility of the stents was evaluated by the lumen area preservation at three displacement bending levels: 5mm, 7mm, and 10mm. All the lumen areas in all stents decreased with the increase of the displacement from 0 to 10 mm. The bare stents were able to maintain 0.864 ± 0.015, 0.740 ± 0.025 and 0.597 ± 0.031of original lumen area at 5 mm, 7 mm and 10mm displacement respectively. For covered stents, the stents with EE coating membrane showed the best lumen area preservation (0.839 ± 0.005, 0.7334 ± 0.043 and 0.559 ± 0.014), whereas, the stents with PU and Parylene coating were only 0.662, 0.439 and 0.305. Bending stiffness was also calculated and compared. These results provided optimal material information and it was crucial for enhancing clinical performance of our novel covered stents.

Keywords: carotid artery, covered stent, nonlinear, hyperelastic, stress, strain

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Authors: Andi Setiawan, Annisa Ulfah Pristya

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Indonesian rubber plant area reached 2.9 million hectares with productivity reached 1.38 million. High rubber productivity is directly proportional to the amount of waste produced rubber processing industry. Rubber industry would produce a negative impact on the rubber industry in the form of environmental pollution caused by waste that has not been treated optimally. Rubber industrial wastewater containing high-nitrogen compounds (nitrate and ammonia) and phosphate compounds which cause water pollution and odor problems due to the high ammonia content. On the other hand, demand for NPK fertilizers in Indonesia continues to increase from year to year and in need of ammonia and phosphate as raw material. Based on domestic demand, it takes a year to 400,000 tons of ammonia and Indonesia imports 200,000 tons of ammonia per year valued at IDR 4.2 trillion. As well, the lack of phosphoric acid to be imported from Jordan, Morocco, South Africa, the Philippines, and India as many as 225 thousand tons per year. During this time, the process of wastewater treatment is generally done with a rubber on the tank to contain the waste and then precipitated, filtered and the rest released into the environment. However, this method is inefficient and thus require high energy costs because through many stages before producing clean water that can be discharged into the river. On the other hand, Indonesia has the potential of pineapple fruit can be harvested throughout the year in all of Indonesia. In 2010, production reached 1,406,445 tons of pineapple in Indonesia or about 9.36 percent of the total fruit production in Indonesia. Increased productivity is directly proportional to the amount of pineapple waste pineapple leaves are kept continuous and usually just dumped in the ground or disposed of with other waste at the final disposal. Through Eco-Nanofiltration Membrane-Based Fiber Pineapple leaves Waste so that environmental problems can be solved efficiently. Nanofiltration is a process that uses pressure as a driving force that can be either convection or diffusion of each molecule. Nanofiltration membranes that can split water to nano size so as to separate the waste processed residual economic value that N and P were higher as a raw material for the manufacture of NPK fertilizer to overcome the crisis in Indonesia. The raw materials were used to manufacture Eco-Nanofiltration Membrane is cellulose from pineapple fiber which processed into cellulose acetate which is biodegradable and only requires a change of the membrane every 6 months. Expected output target is Green eco-technology so with nanofiltration membranes not only treat waste rubber industry in an effective, efficient and environmentally friendly but also lowers the cost of waste treatment compared to conventional methods.

Keywords: biodegradable, cellulose diacetate, fertilizers, pineapple, rubber

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Authors: Jasneet Kaur, Swapandeep Singh Chimni

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The unfavorable use of metal-based catalysts that are often extortionate and toxic can be overcome by using small organic molecules known as organocatalysts. A variety of small organic molecules, including Brønsted/Lewis bases and acids, based on sulfonic acids, phosphoric acids, amines, phosphines or carbenes, Cinchona alkaloids, have been used as organocatalysts. One of the key reasons for using organocatalysis is their ability to be effectively removed from the final product in comparison to the metallic counterparts, which are exceedingly difficult to remove. The present investigation seeks to explore the catalytic nature of Cinchona alkaloids as an organocatalyst for enantioselective synthesis of 3-substituted-3-aminooxindole, which is known to exhibit a variety of biological activities and pharmacological activities. In this context, an organocatalytic asymmetric route for the synthesis of 3-aminooxindoles via reaction of isatin imine with α-acetoxy-β-ketoesters has been developed. The bifunctional Cinchona derived thiourea catalyzed the reaction of α-acetoxy-β-ketoesters derivatives with isatin imine to afford 3-substituted-aminooxindole derivatives in up to 93% yield, 95% enantiomeric excess and >20:1 diastereomeric ratio. The reaction was performed at room temperature for two hours using 10 mol% of catalyst, in the presence of 4Å molecular sieves in tetrahydrofuran as a solvent at ambient temperature. After the completion of the reaction, the pure product could be easily separated by using column chromatography using hexane and ethyl acetate as solvents. In conclusion, the catalytic potential of Cinchona derived chiral thiourea-tertiary amine catalyst was explored for an organocatalytic enantioselective Mannich reaction of β-ketoester derivatives with various isatin imine derivatives under mild conditions.

Keywords: asymmetric synthesis, aminooxindoles, enantioselective, isatin imine

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Authors: Renu Gautam, S. M. S. Chauhan

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The magnetic Fe3O4 nanoparticles has been used as an efficient and facile acid catalyst for the synthesis of calix[4]pyrrole in moderate to excellent yields by the one pot condensation of different ketones and pyrrole. The catalyst was easily recovered using external magnet and reused over several cycles without losing its catalytic activity.

Keywords: calix[4]pyrrole, magnetic, Fe3O4 nanoparticles, catalysis

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Authors: Ling Ai, Ziyu Zhao, Zeyu Zhou, Xiaochen Yang, Heng Zhai, Stuart Holmes

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Optimizing the catalyst layer structure is crucial for enhancing the performance of proton exchange membrane fuel cells (PEMFCs) with low Platinum (Pt) loading. Current works focused on the utilization, durability, and site activity of Pt particles on support, and performance enhancement has been achieved by loading Pt onto porous support with different morphology, such as graphene, carbon fiber, and carbon black. Some schemes have also incorporated cost considerations to achieve lower Pt loading. However, the design of the catalyst layer (CL) structure in the membrane electrode assembly (MEA) must consider the interactions between the layers. Addressing the crucial aspects of water management, low contact resistance, and the establishment of effective three-phase boundary for MEA, multi-walled carbon nanotubes (MWCNTs) are promising CL support due to their intrinsically high hydrophobicity, high axial electrical conductivity, and potential for ordered alignment. However, the drawbacks of MWCNTs, such as strong agglomeration, wall surface chemical inertness, and unopened ends, are unfavorable for Pt nanoparticle loading, which is detrimental to MEA processing and leads to inhomogeneous CL surfaces. This further deteriorates the utilization of Pt and increases the contact resistance. Robust chemical oxidation or nitrogen doping can introduce polar functional groups onto the surface of MWCNTs, facilitating the creation of open tube ends and inducing defects in tube walls. This improves dispersibility and load capacity but reduces length and conductivity. Consequently, a trade-off exists between maintaining the intrinsic properties and the degree of functionalization of MWCNTs. In this work, MWCNTs were modified based on the operational requirements of the MEA from the viewpoint of interlayer interactions, including the search for the optimal degree of oxidation, N-doping, and micro-arrangement. MWCNT were functionalized by oxidizing, N-doping, as well as micro-alignment to achieve lower contact resistance between CL and proton exchange membrane (PEM), better hydrophobicity, and enhanced performance. Furthermore, this work expects to construct a more continuously distributed three-phase boundary by aligning MWCNT to form a locally ordered structure, which is essential for the efficient utilization of Pt active sites. Different from other chemical oxidation schemes that used HNO3:H2SO4 (1:3) mixed acid to strongly oxidize MWCNT, this scheme adopted pure HNO3 to partially oxidize MWCNT at a lower reflux temperature (80 ℃) and a shorter treatment time (0 to 10 h) to preserve the morphology and intrinsic conductivity of MWCNT. The maximum power density of 979.81 mw cm-2 was achieved by Pt loading on 6h MWCNT oxidation time (Pt-MWCNT6h). This represented a 59.53% improvement over the commercial Pt/C catalyst of 614.17 (mw cm-2). In addition, due to the stronger electrical conductivity, the charge transfer resistance of Pt-MWCNT6h in the electrochemical impedance spectroscopy (EIS) test was 0.09 Ohm cm-2, which was 48.86% lower than that of Pt/C. This study will discuss the developed catalysts and their efficacy in a working fuel cell system. This research will validate the impact of low-functionalization modification of MWCNTs on the performance of PEMFC, which simplifies the preparation challenges of CL and contributing for the widespread commercial application of PEMFCs on a larger scale.

Keywords: carbon nanotubes, electrocatalyst, membrane electrode assembly, proton exchange membrane fuel cell

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Authors: Rajat Mittal, Jung Hee Seo, Jacob Turner, Harshal Raut

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The perpetual advancement in computational capabilities, coupled with the continuous evolution of software tools and numerical algorithms, is creating novel avenues for research, exploration, and application at the nexus of computational fluid and structural mechanics. Fish leverage their remarkably flexible bodies and fins to harness energy from vortices, propelling themselves with an elegance and efficiency that captivates engineers. Bats fly with unparalleled agility and speed by using their flexible membrane wings. Wave-assisted propulsion (WAP) systems, utilizing elastically mounted hydrofoils, convert wave energy into thrust. Each of these problems involves a complex and elegant interplay between fluid dynamics and structural mechanics. Historically, investigations into such phenomena were constrained by available tools, but modern computational advancements now facilitate exploration of these multi-physics challenges with an unprecedented level of fidelity, precision, and realism. In this work, the author will discuss projects that harness the capabilities of high-fidelity sharp-interface immersed boundary methods to address a spectrum of engineering and biological challenges involving fluid-structure interaction.

Keywords: immersed boundary methods, CFD, bioflight, fluid structure interaction

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Authors: Livinus A. Obasi, Augustine N. Ajah

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Biotechnology in recent times has tried to develop a mechanism whereby sustainable electricity can be generated by the activity of microorganisms on waste and renewable biomass (often regarded as “negative value”) in a device called microbial fuel cell, MFC. In this paper, we established how the biocatalytic activities of bacteria on organic matter (substrates) produced some electrons with the associated removal of some water pollution parameters; Biochemical oxygen demand (BOD), chemical oxygen demand (COD) to the tune of 77.2% and 88.3% respectively from a petrochemical sanitary wastewater. The electricity generation was possible by conditioning the bacteria to operate anaerobically in one chamber referred to as the anode while the electrons are transferred to the fully aerated counter chamber containing the cathode. Power densities ranging from 12.83 mW/m² to 966.66 mW/m² were achieved using a dual-chamber starch membrane MFC experimental set-up. The maximum power density obtained in this research shows an improvement in the use of low cost MFC set up to achieve power production. Also, the level of organic matter removal from the sanitary waste water by the operation of this device clearly demonstrates its potential benefit in achieving an improved benign environment. The beauty of the MFCs is their potential utility in areas lacking electrical infrastructures like in most developing countries.

Keywords: bioelectricity, COD, microbial fuel cell, sanitary wastewater, wheat starch

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Authors: S. A. A. Nabeela Nasreen, S. Sundarrajan, S. A. Syed Nizar, Seeram Ramakrishna

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Metal-organic frameworks (MOFs) have attracted considerable interest due to its diverse pore size tunability, fascinating topologies and extensive uses in fields such as catalysis, membrane separation, chemical sensing, etc. Zeolitic imidazolate frameworks (ZIFs) are a class of MOF with porous crystals containing extended three-dimensional structures of tetrahedral metal ions (e.g., Zn) bridged by Imidazolate (Im). Selected ZIFs are used to separate solvent/solvent mixtures. A layer by layer formation of the nanocomposite of Zinc oxide (ZnO) and ZIF on a ceramic support using a solvothermal method was engaged and tested for target solvent/solvent separation. Metal oxide layer was characterized by XRD, SEM, and TEM to confirm the smooth and continuous coating for the separation process. The chemical composition of ZIF films was studied by using X-Ray absorption near-edge structure (XANES) spectroscopy. The obtained ceramic tube with metal oxide and ZIF layer coating were tested for its packing density, thickness, distribution of seed layers and variation of permeation rate of solvent mixture (isopropyl alcohol (IPA)/methyl isobutyl ketone (MIBK). Pervaporation technique was used for the separation to achieve a high permeation rate with separation ratio of > 99.5% of the solvent mixture.

Keywords: metal oxide, membrane, pervaporation, solvothermal, ZIF

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Authors: Michela Terlizzi, Chiara Colarusso, Aldo Pinto, Rosalinda Sorrentino

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Sphingosine-1-phosphate (S1P) is a membrane-derived bioactive phospholipid exerting a multitude of effects on respiratory cell physiology and pathology through five S1P receptors (S1PR1-5). Higher levels of S1P have been registered in a broad range of respiratory diseases, including inflammatory disorders and cancer, although its exact role is still elusive. Based on our previous study in which we found that S1P/S1PR3 is involved in an inflammatory pattern via the activation of Toll-like Receptor 9 (TLR9), highly expressed on lung cancer cells, the main goal of the current study was to better understand the involvement of S1P/S1PR3 pathway/signaling during lung carcinogenesis, taking advantage of a mouse model of first-hand smoke exposure and of carcinogen-induced lung cancer. We used human samples of Non-Small Cell Lung Cancer (NSCLC), a mouse model of first-hand smoking, and of Benzo(a)pyrene (BaP)-induced tumor-bearing mice and A549 lung adenocarcinoma cells. We found that the intranuclear, but not the membrane, localization of S1PR3 was associated to the proliferation of lung adenocarcinoma cells, the mechanism that was correlated to human and mouse samples of smoke-exposure and carcinogen-induced lung cancer, which were characterized by higher utilization of S1P. Indeed, the inhibition of the membrane S1PR3 did not alter tumor cell proliferation after TLR9 activation. Instead, according to the nuclear localization of sphingosine kinase (SPHK) II, the enzyme responsible for the catalysis of the S1P last step synthesis, the inhibition of the kinase completely blocked the endogenous S1P-induced tumor cell proliferation. These results prove that the endogenous TLR9-induced S1P can on one side favor pro-inflammatory mechanisms in the tumor microenvironment via the activation of cell surface receptors, but on the other tumor progression via the nuclear S1PR3/SPHK II axis, highlighting a novel molecular mechanism that identifies S1P as one of the crucial mediators for lung carcinogenesis-associated inflammatory processes and that could provide differential therapeutic approaches especially in non-responsive lung cancer patients.

Keywords: sphingosine-1-phosphate (S1P), S1P Receptor 3 (S1PR3), smoking-mice, lung inflammation, lung cancer

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Authors: Basanti Ekka, Talis Juhna

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Dairy industrial effluents originated by the typical processing activities are composed of various organic and inorganic constituents, and these include proteins, fats, inorganic salts, antibiotics, detergents, sanitizers, pathogenic viruses, bacteria, etc. These contaminants are harmful to not only human beings but also aquatic flora and fauna. Because consisting of large classes of contaminants, the specific targeted removal methods available in the literature are not viable solutions on the industrial scale. Therefore, in this on-going research, a series of coagulation, electrochemical, and catalytic methods will be employed. The bulk coagulation and electrochemical methods can wash off most of the contaminants, but some of the harmful chemicals may slip in; therefore, specific catalysts designed and synthesized will be employed for the removal of targeted chemicals. In the context of Latvian dairy industries, presently, work is under progress on the characterization of dairy effluents by total organic carbon (TOC), Inductively Coupled Plasma Mass Spectrometry (ICP-MS)/ Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), High-Performance Liquid Chromatography (HPLC), Gas Chromatography-Mass Spectrometry (GC-MS), and Mass Spectrometry. After careful evaluation of the dairy effluents, a cost-effective natural coagulant will be employed prior to advanced electrochemical technology such as electrocoagulation and electro-oxidation as a secondary treatment process. Finally, graphene oxide (GO) based hybrid materials will be used for post-treatment of dairy wastewater as graphene oxide has been widely applied in various fields such as environmental remediation and energy production due to the presence of various oxygen-containing groups. Modified GO will be used as a catalyst for the removal of remaining contaminants after the electrochemical process.

Keywords: catalysis, dairy wastewater, electrochemical method, graphene oxide

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Authors: M. Gowri, E. K. Girija, V. Ganesh

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Background and Significance: Among the dental infections, inflammation and infection of the root canal are common among all age groups. Currently, the management of root canal infections involves cleaning the canal with powerful irrigants followed by intracanal medicament application. Though these treatments have been in vogue for a long time, root canal failures do occur. Treatment for root canal infections is limited due to the anatomical complexity in terms of small micrometer volumes and poor penetration of drugs. Thus, infections of the root canal seem to be a challenge that demands development of new agents that can eradicate E. faecalis. Methodology: In the present study, we synthesized and screened silver-curcumin nanoparticle against E. faecalis. Morphological cell damage and antibiofilm activity of silver-curcumin nanoparticle on E. faecalis was studied using scanning electron microscopy (SEM). Biochemical evidence for membrane damage was studied using flow cytometry. Further, the antifungal activity of silver-curcumin nanoparticle was evaluated in an ex vivo dentinal tubule infection model. Results: Screening data showed that silver-curcumin nanoparticle was active against E. faecalis. silver-curcumin nanoparticle exerted time kill effect. Further, SEM images of E. faecalis showed that silver-curcumin nanoparticle caused membrane damage and inhibited biofilm formation. Biochemical evidence for membrane damage was confirmed by increased propidium iodide (PI) uptake in flow cytometry. Further, the antifungal activity of silver-curcumin nanoparticle was evaluated in an ex vivo dentinal tubule infection model, which mimics human tooth root canal infection. Confocal laser scanning microscopy studies showed eradication of E. faecalis and reduction in colony forming unit (CFU) after 24 h treatment in the infected tooth samples in this model. Further, silver-curcumin nanoparticle was found to be hemocompatible, not cytotoxic to normal mammalian NIH 3T3 cells and non-mutagenic. Conclusion: The results of this study can pave the way for developing new antibacterial agents with well deciphered mechanisms of action and can be a promising antibacterial agent or medicament against root canal infection.

Keywords: ex vivo dentine model, inhibition of biofilm formation, root canal infection, silver-curcumin nanoparticle

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Authors: Rachid El Aidani, Phuong Nguyen-Tri, Toan Vu-Khanh

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The filter media in synthetic fibre is the most geotextile materials used in aerosol and drainage filtration, particularly for buildings soil reinforcement in civil engineering due to its appropriated properties and its low cost. However, the current understanding of the durability and stability of this material in real service conditions, especially under severe long-term conditions are completely limited. This study has examined the effects of the chemical aging of a filter media in polyester non-woven under different temperatures (50, 70 and 80˚C) and pH (2. 7 and 12). The effect of aging conditions on mechanical properties, morphology, permeability, thermal stability and molar weigh changes is investigated. The results showed a significant reduction of mechanical properties in term of tensile strength, puncture force and tearing forces of the filter media after chemical aging due to the chemical degradation. The molar mass and mechanical properties changes in different temperature and pH showed a complex dependence of material properties on environmental conditions. The SEM and AFM characterizations showed a significant impact of the thermal aging on the morphological properties of the fibers. Based on the obtained results, the lifetime of the material in different temperatures was determined by the use of the Arrhenius model. These results provide useful information to better understand phenomena occurring during chemical aging of the filter media and may help to predict the service lifetime of this material in real used conditions.

Keywords: nonwoven membrane, chemical aging, mechanical properties, lifetime, filter media

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Authors: Wei-Shan Wang, Klaus Vogel, Felix Gabler, Maik Wiemer, Thomas Gessner

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Metallic glasses, which are free of grain boundaries, have superior properties including large elastic limits, high strength, and excellent wear and corrosion resistance. Therefore, bulk metallic glasses (BMG) and thin film metallic glasses (TFMG) have been widely developed and investigated. Among various kinds of metallic glasses, Pd-Cu-Si TFMG, which has lower elastic modulus and better resistance of oxidation and corrosions compared to Zr- and Fe-based TFMGs, can be a promising candidate for MEMS applications. However, the study of Pd-TFMG membrane is still limited. This paper presents free-standing Pd-based metallic glass membranes with large area fabricated on wafer level for the first time. Properties of Pd-Cu-Si thin film metallic glass (TFMG) with various deposition parameters are investigated first. When deposited at 25°C, compressive stress occurs in the Pd76Cu6Si18 thin film regardless of Ar pressure. When substrate temperature is increased to 275°C, the stress state changes from compressive to tensile. Thin film stresses are slightly decreased when Ar pressure is higher. To show the influence of temperature on Pd-TFMGs, thin films without and with post annealing below (275°C) and within (370°C) supercooled liquid region are investigated. Results of XRD and TEM analysis indicate that Pd-TFMGs remain amorphous structure with well-controlled parameters. After verification of amorphous structure of the Pd-TFMGs, free-standing Pd-Cu-Si membranes were fabricated by depositing Pd-Cu-Si thin films directly on 200nm-thick silicon nitride membranes, followed by post annealing and dry etching of silicon nitride layer. Post annealing before SiNx removal is used to further release internal stress of Pd-TFMGs. The edge length of the square membrane ranges from 5 to 8mm. The effect of post annealing on Pd-Cu-Si membranes are discussed as well. With annealing at 370°C for 5 min, Pd-MG membranes are fully distortion-free after removal of SiNx layer. Results show that, by introducing annealing process, the stress-relief, distortion-free Pd-TFMG membranes with large area can be a promising candidate for sensing applications such as pressure and gas sensors.

Keywords: amorphous alloy, annealing, metallic glasses, TFMG membrane

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Authors: Taoufik Bettaieb, Sihem Soufi

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As a bioactive metalloid, silicon (Si) is an essential element for plant growth and development. It also plays a crucial role in enhancing plants’ resilience to different abiotic and biotic stresses. The morpho-physiological, biochemical, and molecular background of Si-mediated stress tolerance in plants were unraveled. Cold stress is a severe abiotic stress response to the decrease of plant growth and yield by affecting various physiological activities in plants. Several approaches have been used to alleviate the adverse effects generated from cold stress exposure, but the cost-effective, environmentally friendly, and defensible approach is the supply of silicon. Silicon has the ability to neutralize the harmful impacts of cold stress. Therefore, based on these hypotheses, this study was designed in order to investigate the morphological and physiological background of silicon effects applied at different concentrations on cold stress mitigation during early growth of a turfgrass, namely Paspalum vaginatum Sw. Results show that silicon applied at different concentrations improved the morphological development of Paspalum subjected to cold stress. It is also effective on the photosynthetic apparatus by maintaining stability the photochemical efficiency. As the primary component of cellular membranes, lipids play a critical function in maintaining the structural integrity of plant cells. Silicon application decreased membrane lipid peroxidation and kept on membrane frontline barrier relatively stable under cold stress.

Keywords: crops, cold stress, silicon, abiotic stress

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Authors: Rachid El Aidani, Phuong Nguyen-Tri, Toan Vu-Khanh

Abstract:

The filter media in synthetic fibre is the most geotextile materials used in aerosol and drainage filtration, particularly for buildings soil reinforcement in civil engineering due to its appropriated properties and its low cost. However, the current understanding of the durability and stability of this material in real service conditions, especially under severe long-term conditions are completely limited. This study has examined the effects of the chemical aging of a filter media in polyester nonwoven under different temperatures (50, 70 and 80˚C) and pH (2. 7 and 12). The effect of aging conditions on mechanical properties, morphology, permeability, thermal stability and molar weigh changes is investigated. The results showed a significant reduction of mechanical properties in term of tensile strength, puncture force and tearing forces of the filter media after chemical aging due to the chemical degradation. The molar mass and mechanical properties changes in different temperature and pH showed a complex dependence of material properties on environmental conditions. The SEM and AFM characterizations showed a significant impact of the thermal aging on the morphological properties of the fibres. Based on the obtained results, the lifetime of the material in different temperatures was determined by the use of the Arrhenius model. These results provide useful information to better understand phenomena occurring during chemical aging of the filter media and may help to predict the service lifetime of this material in real used conditions.

Keywords: nonwoven membrane, chemical aging, mechanical properties, lifetime, filter media

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Authors: Vidula Shevade, B. J. Nagare, Sajeev Chacko

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First principles simulation, meaning density functional theory (DFT) calculations with plane waves and pseudopotential, has become a prized technique in condensed matter theory. Nanoparticles (NP) have been known to possess good catalytic activities, especially for molecules such as CO, O₂, etc. Among the metal NPs, Aluminium based NPs are also widely known for their catalytic properties. Aluminium metal is a lightweight, excellent electrical, and thermal abundant chemical element in the earth’s crust. Aluminium NPs, when added to solid rocket fuel, help improve the combustion speed and considerably increase combustion heat and combustion stability. Adding aluminium NPs into normal Al/Al₂O₃ powder improves the sintering processes of the ceramics, with high heat transfer performance, increased density, and enhanced thermal conductivity of the sinter. We used VASP and Gaussian 0₃ package to compute the geometries, electronic structure, and bonding properties of Al₁₂Ni as well as its interaction with O₂ and CO molecules. Several MD simulations were carried out using VASP at various temperatures from which hundreds of structures were optimized, leading to 24 unique structures. These structures were then further optimized through a Gaussian package. The lowest energy structure of Al₁₂Ni has been reported to be a singlet. However, through our extensive search, we found a triplet state to be lower in energy. In our structure, the Ni atom is found to be on the surface, which gives the non-zero magnetic moment. Incidentally, O2 and CO molecules are also triplet in nature, due to which the Al₁₂-Ni cluster is likely to facilitate the oxidation process of the CO molecule. Our results show that the most favourable site for the CO molecule is the Ni atom and that for the O₂ molecule is the Al atom that is nearest to the Ni atom. Al₁₂Ni-O₂ and Al₁₂-Ni-CO structures we extracted using VMD. Al₁₂Ni nanocluster, due to in triplet electronic structure configuration, indicates it to be a potential candidate as a catalyst for oxidation of CO molecules.

Keywords: catalyst, gaussian, nanoparticles, oxidation

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Authors: Hossein Anaraki-Ardakani, Tayebe Heidari-Rakati

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An environmentally benign protocol for the one-pot, three-component synthesis of Triazolo[1,2-a]indazole-1,3,8-trione derivatives by condensation of dimedone, urazole and aromatic aldehydes catalyzed by HClO4/SiO2 NPS as an ecofriendly catalyst with high catalytic activity and reusability at 100 ºC under solvent-free conditions is reported. The reaction proceeds to completion within 20-30 min in 77-86 % yield.

Keywords: one-pot reaction, dimedone, triazoloindazole, urazole

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Authors: Abdelkader Anouzla, Soukaina Bouaouda, Roukaya Bouyakhsass, Salah Souabi, Abdeslam Taleb

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During storage and under the combined action of rainwater and natural fermentation, these wastes produce over 800.000 m3 of landfill leachates. Due to population growth and changing global economic activities, the amount of waste constantly generated increases, making more significant volumes of leachate. Leachate, when leaching into the soil, can negatively impact soil, surface water, groundwater, and the overall environment and human life. The leachate must first be treated because of its high pollutant load before being released into the environment. This article reviews the different leachate treatments in September 2022 techniques. Different techniques can be used for this purpose, such as biological, physical-chemical, and membrane methods. Young leachate is biodegradable; in contrast, these biological processes lose their effectiveness with leachate aging. They are characterized by high ammonia nitrogen concentrations that inhibit their activity. Most physical-chemical treatments serve as pre-treatment or post-treatment to complement conventional treatment processes or remove specific contaminants. After the introduction, the different types of pollutants present in leachates and their impacts have been made, followed by a discussion highlighting the advantages and disadvantages of the various treatments, whether biological, physicochemical, or membrane. From this work, due to their simplicity and reasonable cost compared to other treatment procedures, biological treatments offer the most suitable alternative to limit the effects produced by the pollutants in landfill leachates.

Keywords: landfill leachate, landfill pollution, impact, wastewater

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Authors: Kashan Bashir, Salah Naji Ahmed Sufyan, Mirza Umar Baig

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In this study, n-dodecane, tetralin, decalin, and tetramethybenzene (TMBE) were used as model compounds of alkanes, naphthenic-aromatic, cycloalkanes and alkyl-benzenes presented in hydro-diesel. The catalytic cracking properties of four model compounds over Y zeolite catalyst (Y-Cat.) and ZSM-5 zeolite catalysts (ZSM-5-Cat.) were probed. The experiment results revealed that high conversion of macromolecular paraffin and naphthenic aromatics were achieved over Y-Cat, whereas its low cracking activity of intermediate products micromolecules paraffin and olefin and high activity of hydride transfer reaction goes against the production of value-added products (light olefin and gasoline). In contrast, despite the fact that the hydride transfer reaction was greatly inhabited over ZSM-5-Cat, the low conversion of macromolecules was observed attributed to diffusion limitations. Interestingly, the mixed catalyst compensates for the shortcomings of the two catalysts, and a “relay reaction” between Y-Cat and ZSM-5-Cat was proposed. Specifically, the added Y-Cat acts as a “pre-cracking booster site” and promotes macromolecules conversion. The addition of ZSM-5-Cat not only significantly suppresses the hydride transfer reaction but also contributes to the cracking of immediate products paraffin and olefin into ethylene and propylene, resulting in a high yield of alkyl-benzene (gasoline), ethylene, and propylene with a low yield of naphthalene (LCO) and coke. The catalytic cracking evaluation experiments of mixed hydro-LCO were also performed to further clarify the “relay reaction” above, showing the highest yield of LPG and gasoline over mixed catalyst. The results indicate that the Y-cat and ZSM-5-cat have a synergistic effect on the conversion of hydro-diesel and corresponding value-added product yield and selective coke yield.

Keywords: synergistic effect, hydro-diesel cracking, FCC, zeolite catalyst, ethylene and propylene

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Authors: Hyunuk Kim, Yang No Yun, Muhammad Sohail, Jong-Ho Moon, Young Cheol Park

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Metal-organic frameworks (MOFs), which are emerging absorbents assembled from metal ions and organic ligands, have attracted attention for their permanent porosity and design of tunable pore size. These microporous materials showed interesting properties for CO₂ storage and separation. In particular, MOFs with high surface area and open metal sites showed the remarkable adsorption capacity and selectivity for CO₂. [Mg₂ (DOBDC)] (DOBDC = 2,5-dioxidobenzene-1,4-dicarboxylate) (MOF-74 or CPO-27) is a well-known absorbent showing an exceptionally high CO₂ sorption capacity at low partial pressure and room temperature. In this work, we synthesized [M₂(DOBDC)(DMF)₂] (M = Mg, Co, Ni) and determined their single-crystal structures by X-ray crystallography. The removal of coordinated guest molecules generates Lewis acidic sites and showed high CO₂ adsorption affinity. Both CO₂ adsorption capacity and surface area are much higher than reported values in literature. To fabricate MMMs, microcrystalline [M₂ (DOBDC)(DMF)₂] was synthesized by microwave reaction and dispersed in PDMS solution. The MMMs with a various amount of [M₂ (DOBDC)(DMF) ₂] in PDMS were fabricated by a solution casting method. [M₂ (DOBDC)(DMF)₂]@PDMS membrane showed higher CO2 permeability and CO₂/N₂ selectivity than those of PDMS. Therefore, we believe that MMMs combining polymer and MOFs provide new materials for CO₂ separation technology.

Keywords: metal-organic frameworks, mixed matrix membrane, CO2/N2 separation, polydimethylsiloxane (PDMS)

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Authors: Boukary Lam, Sebastien Deon, Patrick Fievet, Nadia Crini, Gregorio Crini

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Treatment of heavy metal-contaminated industrial wastewater has become a major challenge over the last decades. Conventional processes for the treatment of metal-containing effluents do not always simultaneously satisfy both legislative and economic criteria. In this context, coupling of processes can then be a promising alternative to the conventional approaches used by industry. The polymer-assisted ultrafiltration (PAUF) process is one of these coupling processes. Its principle is based on a sequence of steps with reaction (e.g., complexation) between metal ions and a polymer and a step involving the rejection of the formed species by means of a UF membrane. Unlike free ions, which can cross the UF membrane due to their small size, the polymer/ion species, the size of which is larger than pore size, are rejected. The PAUF process was deeply investigated herein in the case of removal of nickel ions by adding chitosan and carboxymethyl cellulose (CMC). Experiments were conducted with synthetic solutions containing 1 to 100 ppm of nickel ions with or without the presence of NaCl (0.05 to 0.2 M), and an industrial discharge water (containing several metal ions) with and without polymer. Chitosan with a molecular weight of 1.8×105 g mol⁻¹ and a degree of acetylation close to 15% was used. CMC with a degree of substitution of 0.7 and a molecular weight of 9×105 g mol⁻¹ was employed. Filtration experiments were performed under cross-flow conditions with a filtration cell equipped with a polyamide thin film composite flat-sheet membrane (3.5 kDa). Without the step of polymer addition, it was found that nickel rejection decreases from 80 to 0% with increasing metal ion concentration and salt concentration. This behavior agrees qualitatively with the Donnan exclusion principle: the increase in the electrolyte concentration screens the electrostatic interaction between ions and the membrane fixed the charge, which decreases their rejection. It was shown that addition of a sufficient amount of polymer (greater than 10⁻² M of monomer unit) can offset this decrease and allow good metal removal. However, the permeation flux was found to be somewhat reduced due to the increase in osmotic pressure and viscosity. It was also highlighted that the increase in pH (from 3 to 9) has a strong influence on removal performances: the higher pH value, the better removal performance. The two polymers have shown similar performance enhancement at natural pH. However, chitosan has proved more efficient in slightly basic conditions (above its pKa) whereas CMC has demonstrated very weak rejection performances when pH is below its pKa. In terms of metal rejection, chitosan is thus probably the better option for basic or strongly acid (pH < 4) conditions. Nevertheless, CMC should probably be preferred to chitosan in natural conditions (5 < pH < 8) since its impact on the permeation flux is less significant. Finally, ultrafiltration of an industrial discharge water has shown that the increase in metal ion rejection induced by the polymer addition is very low due to the competing phenomenon between the various ions present in the complex mixture.

Keywords: carboxymethyl cellulose, chitosan, heavy metals, nickel ion, polymer-assisted ultrafiltration

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Authors: Azad Khalid, Sifa Dogan

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Because of its persistence in conventional treatment plants and broad prevalence in water bodies, the pharmaceutical chemical carbamazepine (CBZ) has been suggested as an anthropogenic marker to evaluate water quality. This study provides a thorough examination of the origins and occurrences of CBZ in water bodies, as well as the drug's toxicological effects and laws. Given CBZ's well-documented negative consequences on the human body when used medicinally, cautious monitoring in water is advised. CBZ residues in drinking water may enter embryos and newborns via intrauterine exposure or breast-feeding, causing congenital abnormalities and/or neurodevelopmental issues over time. The insufficiency of solo solutions was shown after an in-depth technical study of traditional and sophisticated treatment technologies. Nanofiltration and reverse osmosis membranes are more successful at removing CBZ than traditional activated sludge and membrane bioreactor techniques. Recent research has shown that severe chemical cleaning, which is essential to prevent membrane fouling, may lower long-term removal efficiency. Furthermore, despite the efficacy of activated carbon adsorption and advanced oxidation processes, a few issues such as chemical cost and activated carbon renewal must be carefully examined. Individual technology constraints lead to the benefits of combined and hybrid systems, namely the heterogeneous advanced oxidation process.

Keywords: carbamazepine, occurrence, toxicity, conventical treatment, advanced oxidation process (AOPs)

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Authors: Hugo Daneluzzo, Christelle Rabbat, Alan Jean-Marie

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Water electrolysis is one of the most advanced technologies for producing hydrogen and can be easily combined with electricity from different sources. Under the influence of electric current, water molecules can be split into oxygen and hydrogen. The production of hydrogen by water electrolysis favors the integration of renewable energy sources into the energy mix by compensating for their intermittence through the storage of the energy produced when production exceeds demand and its release during off-peak production periods. Among the various electrolysis technologies, anion exchange membrane (AEM) electrolyser cells are emerging as a reliable technology for water electrolysis. Modeling and simulation are effective tools to save time, money, and effort during the optimization of operating conditions and the investigation of the design. The modeling and simulation become even more important when dealing with multiphysics dynamic systems. One of those systems is the AEM electrolysis cell involving complex physico-chemical reactions. Once developed, models may be utilized to comprehend the mechanisms to control and detect flaws in the systems. Several modeling methods have been initiated by scientists. These methods can be separated into two main approaches, namely equation-based modeling and graph-based modeling. The former approach is less user-friendly and difficult to update as it is based on ordinary or partial differential equations to represent the systems. However, the latter approach is more user-friendly and allows a clear representation of physical phenomena. In this case, the system is depicted by connecting subsystems, so-called blocks, through ports based on their physical interactions, hence being suitable for multiphysics systems. Among the graphical modelling methods, the bond graph is receiving increasing attention as being domain-independent and relying on the energy exchange between the components of the system. At present, few studies have investigated the modelling of AEM systems. A mathematical model and a bond graph model were used in previous studies to model the electrolysis cell performance. In this study, experimental data from literature were simulated using OpenModelica using bond graphs and mathematical approaches. The polarization curves at different operating conditions obtained by both approaches were compared with experimental ones. It was stated that both models predicted satisfactorily the polarization curves with error margins lower than 2% for equation-based models and lower than 5% for the bond graph model. The activation polarization of hydrogen evolution reactions (HER) and oxygen evolution reactions (OER) were behind the voltage loss in the AEM electrolyzer, whereas ion conduction through the membrane resulted in the ohmic loss. Therefore, highly active electro-catalysts are required for both HER and OER while high-conductivity AEMs are needed for effectively lowering the ohmic losses. The bond graph simulation of the polarisation curve for operating conditions at various temperatures has illustrated that voltage increases with temperature owing to the technology of the membrane. Simulation of the polarisation curve can be tested virtually, hence resulting in reduced cost and time involved due to experimental testing and improved design optimization. Further improvements can be made by implementing the bond graph model in a real power-to-gas-to-power scenario.

Keywords: hydrogen production, anion-exchange membrane, electrolyzer, mathematical modeling, multiphysics modeling

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Authors: H. Ishii, S. Araki, H. Yamamoto

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In recent years, the carbon dioxide (CO2) separation technology is required in terms of the reduction of emission of global warming gases and the efficient use of fossil fuels. Since the emission amount of CO2 gas occupies the large part of greenhouse effect gases, it is considered that CO2 have the most influence on global warming. Therefore, we need to establish the CO2 separation technologies with high efficiency at low cost. In this study, we focused on the membrane separation compared with conventional separation technique such as distillation or cryogenic separation. In this study, we prepared carbonate-ceramic dual-phase membranes to separate CO2 at high temperature. As porous ceramic substrate, the (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+σ, La0.6Sr0.4Ti0.3 Fe0.7O3 and Ca0.8Sr0.2Ti0.7Fe0.3O3-α (PLNCG, LSTF and CSTF) were examined. PLNCG, LSTF and CSTF have the perovskite structure. The perovskite structure has high stability and shows ion-conducting doped by another metal ion. PLNCG, LSTF and CSTF have perovskite structure and has high stability and high oxygen ion diffusivity. PLNCG, LSTF and CSTF powders were prepared by a solid-phase process using the appropriate carbonates or oxides. To prepare porous substrates, these powders mixed with carbon black (20 wt%) and a few drops of polyvinyl alcohol (5 wt%) aqueous solution. The powder mixture were packed into stainless steel mold (13 mm) and uniaxially pressed into disk shape under a pressure of 20 MPa for 1 minute. PLNCG, LSTF and CSTF disks were calcined in air for 6 h at 1473, 1573 and 1473 K, respectively. The carbonate mixture (Li2CO3/Na2CO3/K2CO3: 42.5/32.5/25 in mole percent ratio) was placed inside a crucible and heated to 793 K. Porous substrates were infiltrated with the molten carbonate mixture at 793 K. Crystalline structures of the fresh membranes and after the infiltration with the molten carbonate mixtures were determined by X-ray diffraction (XRD) measurement. We confirmed the crystal structure of PLNCG and CSTF slightly changed after infiltration with the molten carbonate mixture. CO2 permeation experiments with PLNCG-carbonate, LSTF-carbonate and CSTF-carbonate membranes were carried out at 773-1173 K. The gas mixture of CO2 (20 mol%) and He was introduced at the flow rate of 50 ml/min to one side of membrane. The permeated CO2 was swept by N2 (50 ml/min). We confirmed the effect of ceramic materials and temperature on the CO2 permeation at high temperature.

Keywords: membrane, perovskite structure, dual-phase, carbonate

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Authors: Reza Vakili, Xiaolei Fan, Alex Walton

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The first near ambient pressure (NAP)-XPS study of CO oxidation over Pt nanoparticles (NPs) incorporated into Zr-based UiO (UiO for Universitetet i Oslo) MOFs was carried out. For this purpose, the MOF-based Catalysts were prepared by wetness impregnation (WI-PtNPs@UiO-67) and linker design (LD-PtNPs@UiO-67) methods along with PtNPs@ZrO₂ as the control catalyst. Firstly, the as-synthesized catalysts were reduced in situ prior to the operando XPS analysis. The existence of Pt(II) species was proved in UiO-67 by observing Pt 4f core level peaks at a high binding energy of 72.6 ± 0.1 eV. However, by heating the WI-PtNPs@UiO-67 catalyst in situ to 200 °C under vacuum, the higher BE components disappear, leaving only the metallic Pt 4f doublet, confirming the formation of Pt NPs. The complete reduction of LD-PtNPs@UiO-67 is achieved at 250 °C and 1 mbar H₂. To understand the chemical state of Pt NPs in UiO-67 during catalytic turnover, we analyzed the Pt 4f region using operando NAP-XPS in the temperature-programmed measurements (100-260 °C) with reference to PtNPs@ZrO₂ catalyst. CO conversion during NAP-XPS experiments with the stoichiometric mixture shows that LD-PtNPs@UiO-67 has a better CO turnover frequency (TOF, 0.066 s⁻¹ at 260 °C) than the other two (ca. 0.055 s⁻¹). Pt 4f peaks only show one chemical species present at all temperatures, but the core level BE shifts change as a function of reaction temperature, i.e., Pt 4f peak from 71.8 eV at T < 200 °C to 71.2 eV at T > 200 °C. As this higher BE state of 71.8 eV was not observed after in situ reductions of the catalysts and only once the CO/O₂ mixture was introduced, we attribute it to the surface saturation of Pt NPs with adsorbed CO. In general, the quantitative analysis of Pt 4f data from the operando NAP-XPS experiments shows that the surface chemistry of the Pt active phase in the two PtNPs@UiO-67 catalysts is the same, comparable to that of PtNPs@ZrO₂. The observed difference in the catalytic activity can be attributed to the particle sizes of Pt NPs, as well as the dispersion of active phase in the support, which are different in the three catalysts.

Keywords: CO oxidation, heterogeneous catalysis, MOFs, Metal Organic Frameworks, NAP-XPS, Near Ambient Pressure X-ray Photoelectron Spectroscopy

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Authors: Sinwook Park, Gilad Yossifon

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The presence of a floating electrode array located within the depletion layer formed due to concentration-polarization (CP) across a microchannel-membrane device, produces not only induced-charge electro-osmosis (ICEO) vortex and but also a bipolar current resulting from faradaic reactions. It has been shown that there exists an optimal SiO2 layer thickness of ~50nm which is sufficient to suppress bipolar currents (at least up to 5V applied voltage) but still enables ICEO vortices that stir the depletion layer, thereby affecting its I-V response. This effect is pronounced beyond the limiting current where the existence of the depletion layer results in increased local electric field due to decreased solution conductivity. This comprehensive study of the interaction of embedded electrodes with the induced CP in microchannel-perm selective medium systems, allows one to choose the thickness of the thin dielectric coating to either enhance the mixing as a means to control the diffuse layer, or suppress it, for example, in the case where electrodes are intended for local measurements of the solution conductivity with minimal invasion. In addition, the use of alternating-current electro-osmosis by activating electrodes results in further enhancement of the fluid stirring and opens new routes for on-demand spatiotemporal control of the CP length. In addition, the use of embedded heaters within the depletion layer generates electro-thermal vortices that in turn also control the CP length.

Keywords: AC electrokinetics, microchannel, concentration-polarization, bipolar current

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Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

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Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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Authors: W. Ketren, J. Wannapeera, Z. Heishun, A. Ryuichi, K. Toshiteru, M. Kouichi, O. Hideaki

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Degradative solvent extraction is the method developed for biomass upgrading by dewatering and fractionation of biomass under the mild condition. However, the conversion mechanism of the degradative solvent extraction method has not been fully understood so far. The rice straw was treated in 1-methylnaphthalene (1-MN) at a different solvent-treatment temperature varied from 250 to 350 ^oC with the residence time for 60 min. The liquid membrane-Fourier Transform Infrared Spectroscopy (FTIR) technique is applied to study the processing mechanism in-depth without separation of the solvent. It has been found that the strength of the oxygen-hydrogen stretching  (3600-3100 cm^-1) decreased slightly with increasing temperature in the range of 300-350 ^oC. The decrease of the hydroxyl group in the solvent soluble suggested dehydration reaction taking place between 300 and 350 ^oC. FTIR spectra in the carbonyl stretching region (1800-1600 cm^-1) revealed the presence of esters groups, carboxylic acid and ketonic groups in the solvent-soluble of biomass. The carboxylic acid increased in the range of 200 to 250 ^oC and then decreased. The prevailing of aromatic groups showed that the aromatization took place during extraction at above 250 ^oC. From 300 to 350 ^oC, the carbonyl functional groups in the solvent-soluble noticeably decreased. The removal of the carboxylic acid and the decrease of esters into the form of carbon dioxide indicated that the decarboxylation reaction occurred during the extraction process.

Keywords: biomass waste, degradative solvent extraction, mechanism, upgrading

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Authors: Ramzi Farra, Detre Teschner, Marc Willinger, Robert Schlögl

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Introduction: The conventional approach of characterizing solid catalysts under static conditions, i.e., before and after reaction, does not provide sufficient knowledge on the physicochemical processes occurring under dynamic conditions at the molecular level. Hence, the necessity of improving new in situ characterizing techniques with the potential of being used under real catalytic reaction conditions is highly desirable. In situ Prompt Gamma Activation Analysis (PGAA) is a rapidly developing chemical analytical technique that enables us experimentally to assess the coverage of surface species under catalytic turnover and correlate these with the reactivity. The catalytic HCl oxidation (Deacon reaction) over bulk ceria will serve as our example. Furthermore, the in situ Transmission Electron Microscopy is a powerful technique that can contribute to the study of atmosphere and temperature induced morphological or compositional changes of a catalyst at atomic resolution. The application of such techniques (PGAA and TEM) will pave the way to a greater and deeper understanding of the dynamic nature of active catalysts. Experimental/Methodology: In situ Prompt Gamma Activation Analysis (PGAA) experiments were carried out to determine the Cl uptake and the degree of surface chlorination under reaction conditions by varying p(O2), p(HCl), p(Cl2), and the reaction temperature. The abundance and dynamic evolution of OH groups on working catalyst under various steady-state conditions were studied by means of in situ FTIR with a specially designed homemade transmission cell. For real in situ TEM we use a commercial in situ holder with a home built gas feeding system and gas analytics. Conclusions: Two complimentary in situ techniques, namely in situ PGAA and in situ FTIR were utilities to investigate the surface coverage of the two most abundant species (Cl and OH). The OH density and Cl uptake were followed under multiple steady-state conditions as a function of p(O2), p(HCl), p(Cl2), and temperature. These experiments have shown that, the OH density positively correlates with the reactivity whereas Cl negatively. The p(HCl) experiments give rise to increased activity accompanied by Cl-coverage increase (opposite trend to p(O2) and T). Cl2 strongly inhibits the reaction, but no measurable increase of the Cl uptake was found. After considering all previous observations we conclude that only a minority of the available adsorption sites contribute to the reactivity. In addition, the mechanism of the catalysed reaction was proposed. The chlorine-oxygen competition for the available active sites renders re-oxidation as the rate-determining step of the catalysed reaction. Further investigations using in situ TEM are planned and will be conducted in the near future. Such experiments allow us to monitor active catalysts at the atomic scale under the most realistic conditions of temperature and pressure. The talk will shed a light on the potential and limitations of in situ PGAA and in situ TEM in the study of catalyst dynamics.

Keywords: CeO2, deacon process, in situ PGAA, in situ TEM, in situ FTIR

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