Search results for: catalytic

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

Abstract:

Light olefins are important building blocks for chemical industry. Direct conversion of syngas to light olefins has been investigated for decades. Meanwhile, the limit for light olefins selectivity described by Anderson-Schulz-Flory (ASF) distribution model is still a great challenge to conventional Fischer-Tropsch synthesis. The emerging strategy called oxide-zeolite concept (OX-ZEO) is a promising way to get rid of this limit. ZnCrO_x was prepared by co-precipitation method and (NH₄)₂CO₃ was used as precipitant. SAPO-34 was prepared by hydrothermal synthesis, and Tetraethylammonium hydroxide (TEAOH) was used as template, while silica sol, pseudo-boehmite, and phosphoric acid were Al, Si and P source, respectively. The bifunctional catalyst was prepared by mechanical mixing of ZnCrO_x and SAPO-34. Catalytic reactions were carried out under H₂/CO=2, 380 ℃, 1 MPa and 6000 mL·g_cat^-1·h^-1 in a fixed-bed reactor with a quartz lining. Catalysts were characterized by XRD, N₂ adsorption-desorption, NH₃-TPD, H₂-TPR, and CO-TPD. The addition of Al as structure promoter enhances CO conversion and selectivity to light olefins. Zn/Cr ratio, which decides the active component content and chemisorption property of the catalyst, influences CO conversion and selectivity to light olefins at the same time. C_2-4⁼ distribution of 86% among hydrocarbons at CO conversion of 14% was reached when Zn/Cr=1.5.

Keywords: Light olefins, OX-ZEO, syngas, ZnCrOx.

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Authors: Michele R. Spier, Denise N. X. Salmon, Renato L. Binati, Luíza C. Piva, Adriane B.P. Medeiros, Carlos R. Soccol

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Phytases are enzymes used as an important component in monogastric animals feeds in order to improve phosphorous availability, since it is not readily assimilated by these animals in the form of the phytate presented in plants and grains. As these enzymes are used in industrial activities, they must retain its catalytic activities during a certain storage period. This study presents information about the stability of 4 different phytases, produced by four macromycetes fungi through solid-state fermentation (SSF). There is a lack of data in literature concerning phytase from macromycetes shelf-life in storage conditions at room, cooling and freezing temperatures. The 4 phytases from macromycetes still had enzymatic activities around 100 days of storage at room temperature. At cooling temperature in 146 days of studies, the phytase from G. stipitatum was the most stable with 44% of the initial activity, in U.gds (units per gram of dried fermented substrate). The freezing temperature was the best condition storage for phytases from G. stipitatum and T. versicolor. Each condition provided a study for each mushroom phytase, totalizing 12 studies. The phytases showed to be stable for a long period without the addition of additives.

Keywords: macromycetes, phytase, solid-state fermentation, wheat bran, stability

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Authors: Shyam Kumar, Nannuri Srinivasulu, Ashok Khanna

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Bubble columns have a variety of applications in absorption, bio-reactions, catalytic slurry reactions, and coal liquefaction; because they are simple to operate, provide good heat and mass transfer, having less operational cost. The use of Computational Fluid Dynamics (CFD) for bubble column becomes important, since it can describe the fluid hydrodynamics on both local and global scale. Euler- Euler two-phase fluid model has been used to simulate two-phase (air and water) transient up-flow in bubble column (15cm diameter) using FLUENT6.3. These simulations and experiments were operated over a range of superficial gas velocities in the bubbly flow and churn turbulent regime (1 to16 cm/s) at ambient conditions. Liquid velocity was varied from 0 to 16cm/s. The turbulence in the liquid phase is described using the standard k-ε model. The interactions between the two phases are described through drag coefficient formulations (Schiller Neumann). The objectives are to validate CFD simulations with experimental data, and to obtain grid-independent numerical solutions. Quantitatively good agreements are obtained between experimental data for hold-up and simulation values. Axial liquid velocity profiles and gas holdup profiles were also obtained for the simulation.

Keywords: Bubble column, Computational fluid dynamics, Gas holdup profile, k-ε model.

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Authors: Dyah Iswantini, Trivadila, Novik Nurhidayat, Waras Nurcholis

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The antioxidant compounds are needed for the food, beverages, and pharmaceuticals industry. For this purpose, an appropriate method is required to measure the antioxidant properties in various types of samples. Spectrophotometric method usually used has some weaknesses, including the high price, long sample preparation time, and less sensitivity. Among the alternative methods developed to overcome these weaknesses is antioxidant biosensor based on superoxide dismutase (SOD) enzyme. Therefore, this study was carried out to measure the SOD activity originating from Deinococcus radiodurans and to determine its kinetics properties. Carbon paste electrode modified with ferrocene and immobilized SOD exhibited anode and cathode current peak at potential of +400 and +300mv respectively, in both pure SOD and SOD of D. radiodurans. This indicated that the current generated was from superoxide catalytic dismutation reaction by SOD. Optimum conditions for SOD activity was at pH 9 and temperature of 27.50C for D. radiodurans SOD, and pH 11 and temperature of 200C for pure SOD. Dismutation reaction kinetics of superoxide catalyzed by SOD followed the Lineweaver-Burk kinetics with D. radiodurans SOD KMapp value was smaller than pure SOD. The result showed that D. radiodurans SOD had higher enzyme-substrate affinity and specificity than pure SOD. It concluded that D. radiodurans SOD had a great potential as biological recognition component for antioxidant biosensor.

Keywords: Antioxidant biosensor, Deinococcus radiodurans, enzyme kinetic, superoxide dismutase (SOD).

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Authors: Osama M. Darwesh, Sahar H. Hassan, Abd El-Raheem R. El-Shanshoury, Shawky Z. Sabae

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Nanotechnology as multidisciplinary technology is growing rapidly with important applications in several sectors. Also, nanobiotechnology is known for the use of microorganisms for the synthesis of targeted nanoparticles. The present study deals with the green synthesis of silver nanoparticles using aquatic bacteria and the development of a biogenic nanocomposite for environmental applications. 20 morphologically different colonies were isolated from the collected water samples from eight different locations at the Rosetta branch of the Nile Delta, Egypt. The obtained results illustrated that the most effective bacterial isolate (produced the higher amount of AgNPs after 24 h of incubation time) is isolate R3. Bacillus tequilensis was the strongest extracellular bio-manufactory of AgNPs. Biosynthesized nanoparticles had a spherical shape with a mean diameter of 2.74 to 28.4 nm. The antimicrobial activity of silver nanoparticles against many pathogenic microbes indicated that the produced AgNPs had high activity against all tested multi-antibiotic resistant pathogens. Also, the stabilized prepared AgNPs-SA nanocomposite has greater catalytic activity for the decolourization of some dyes like Methylene blue (MB) and Crystal violet. Such results represent a promising stage for producing eco-friendly, cost-effective, and easy-to-handle devices for the bioremediation of contaminated industrial wastewater.

Keywords: Bioremediation, AgNPs, AgNPs-SA nanocomposite, Bacillus tequilensis, nanobiotechnology.

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Authors: Alaa Y. Ali, Natalie P. Holmes, John Holdsworth, Warwick Belcher, Paul Dastoor, Xiaojing Zhou

Abstract:

Multi-layered graphene has been produced under low temperature chemical vapour deposition (CVD) growth conditions by utilizing an organic solvent and polymer film source. Poly(methylmethacrylate) (PMMA) was dissolved in chlorobenzene solvent and used as a drop-cast film carbon source on a quartz slide. A source temperature (T_source) of 180 °C provided sufficient carbon to grow graphene, as identified by Raman spectroscopy, on clean copper foil catalytic surfaces.  Systematic variation of hydrogen gas (H₂) flow rate from 25 standard cubic centimeters per minute (sccm) to 100 sccm and CVD temperature (T_growth) from 400 to 800 °C, yielded graphene films of varying quality as characterized by Raman spectroscopy. The optimal graphene growth parameters were found to occur with a hydrogen flow rate of 75 sccm sweeping the 180 °C source carbon past the Cu foil at 600 °C for 1 min. The deposition at 600 °C with a H₂ flow rate of 75 sccm yielded a 2D band peak with ~53.4 cm^-1 FWHM and a relative intensity ratio of the G to 2D bands (I_G/I_2D) of 0.21. This recipe fabricated a few layers of good quality graphene.

Keywords: Graphene, chemical vapour deposition, carbon source, low temperature growth.

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Authors: T. Maruyama, T. Saida, S. Naritsuka, S. Iijima

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Single-walled carbon nanotubes (SWCNTs) are generally synthesized by chemical vapor deposition (CVD) using Fe, Co, and Ni as catalysts. However, due to the Ostwald ripening of metal catalysts, the diameter distribution of the grown SWCNTs is considerably wide (>2 nm), which is not suitable for electronics applications. In addition, reduction in the growth temperature is desirable for fabricating SWCNT devices compatible with the LSI process. Herein, we performed SWCNT growth by alcohol catalytic CVD using platinum-group metal catalysts (Pt, Rh, and Pd) because these metals have high melting points, and the reduction in the Ostwald ripening of catalyst particles is expected. Our results revealed that web-like SWCNTs were obtained from Pt and Rh catalysts at growth temperature between 500 °C and 600 °C by optimizing the ethanol pressure. The SWCNT yield from Pd catalysts was considerably low. By decreasing the growth temperature, the diameter and chirality distribution of SWCNTs from Pt and Rh catalysts became small and narrow. In particular, the diameters of most SWCNTs grown using Pt catalysts were below 1 nm and their diameter distribution was considerably narrow. On the contrary, SWCNTs can grow from Rh catalysts even at 300 °C by optimizing the growth condition, which is the lowest temperature recorded for SWCNT growth. Our results demonstrated that platinum-group metals are useful for the growth of small-diameter SWCNTs and facilitate low-temperature growth.

Keywords: Carbon nanotube, chemical vapor deposition, catalyst, Pt, Rh, Pd.

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Authors: Panatcha Bovornseripatai, Siriporn Jongpatiwut, Somchai Osuwan, Suchada Butnark

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Hydrogenated biodiesel is one of the most promising renewable fuels. It has many advantages over conventional biodiesel, including higher cetane number, higher heating value, lower viscosity, and lower corrosiveness due to its absence of oxygen. From previous work, Pd/TiO2 gave high conversion and selectivity in hydrogenated biodiesel. In this work, the effect of biomass feedstocks (i.e. beef fat, chicken fat, pork fat, and jatropha oil) on the production of hydrogenated biodiesel over Pd/TiO2 has been studied. Biomass feedstocks were analyzed by ICP-OES (inductively coupled plasma optical emission spectrometry) to identify the content of impurities (i.e. P, K, Ca, Na, and Mg). The deoxygenation catalyst, Pd/TiO2, was prepared by incipient wetness impregnation (IWI) and tested in a continuous flow packed-bed reactor at 500 psig, 325°C, H2/feed molar ratio of 30, and LHSV of 4 h-1 for its catalytic activity and selectivity in hydrodeoxygenation. All feedstocks gave high selectivity in diesel specification range hydrocarbons and the main hydrocarbons were n-pentadecane (n-C15) and n-heptadecane (n- C17), resulting from the decarbonylation/decarboxylation reaction. Intermediates such as oleic acid, stearic acid, palmitic acid, and esters were also detected in minor amount. The conversion of triglycerides in jatropha oil is higher than those of chicken fat, pork fat, and beef fat, respectively. The higher concentration of metal impurities in feedstock, the lower conversion of feedstock.

Keywords: Hydrogenated biodiesel, hydrodeoxygenation, Pd/TiO2, biomass feedstock

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Authors: Andreas L. Savvides

Abstract:

These This paper looks into frameworks which aim at furthering the discussion of the role of regenerative design practices in a city-s historic core and the tool of urban design to achieve urban revitalization on the island of Cyprus. It also examines the region-s demographic mix, the effectiveness of its governmental coordination and the strategies of adaptive reuse and strategic investments in older areas with existing infrastructure. The two main prongs of investigation will consider the effect of the existing and proposed changes in the physical infrastructure and fabric of the city, as well as the catalytic effect of sustainable urban design practices. Through this process, the work hopes to integrate the contained potential within the existing historic core and the contributions and participation of the migrant and immigrant populations to the local economy. It also examines ways in which this coupling of factors can bring to the front the positive effects of this combined effort on an otherwise sluggish local redevelopment effort. The data for this study is being collected and organized as part of ongoing urban design and development student workshop efforts in urban planning and design education. The work is presented in graphic form and includes data collected from interviews with study area organizations and the community at large. Planning work is also based on best practices initiated by the staff of the Nicosia Master Plan task force, which coordinates holistic planning efforts for the historic center of the city of Nicosia.

Keywords: Urban Design, Urban Development, Urban Regeneration, Historic Core, Cultural Planning.

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

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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 varying grades of glycerol, i.e. 70%, 86% and 99% purity, that is 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. Amidst 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 demonstrated itself as an energy efficient route by achieving 94.2% 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: Biodiesel, glycerol, glycerol carbonate, microwave irradiation.

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Authors: T. Sungkaworn, W. Triampo, P. Nalakarn, D. Triampo, I. M. Tang, Y. Lenbury, P. Picha

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Semiconductor nanomaterials like TiO2 nanoparticles (TiO2-NPs) approximately less than 100 nm in diameter have become a new generation of advanced materials due to their novel and interesting optical, dielectric, and photo-catalytic properties. With the increasing use of NPs in commerce, to date few studies have investigated the toxicological and environmental effects of NPs. Motivated by the importance of TiO2-NPs that may contribute to the cancer research field especially from the treatment prospective together with the fractal analysis technique, we have investigated the effect of TiO2-NPs on colony morphology in the dark condition using fractal dimension as a key morphological characterization parameter. The aim of this work is mainly to investigate the cytotoxic effects of TiO2-NPs in the dark on the growth of human cervical carcinoma (HeLa) cell colonies from morphological aspect. The in vitro studies were carried out together with the image processing technique and fractal analysis. It was found that, these colonies were abnormal in shape and size. Moreover, the size of the control colonies appeared to be larger than those of the treated group. The mean Df +/- SEM of the colonies in untreated cultures was 1.085±0.019, N= 25, while that of the cultures treated with TiO2-NPs was 1.287±0.045. It was found that the circularity of the control group (0.401±0.071) is higher than that of the treated group (0.103±0.042). The same tendency was found in the diameter parameters which are 1161.30±219.56 μm and 852.28±206.50 μm for the control and treated group respectively. Possible explanation of the results was discussed, though more works need to be done in terms of the for mechanism aspects. Finally, our results indicate that fractal dimension can serve as a useful feature, by itself or in conjunction with other shape features, in the classification of cancer colonies.

Keywords: Tumor growth, Cell colonies, TiO2, Nanoparticles, Fractal, Morphology, Aggregation.

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Authors: Lalita Saeaeh, Sirirat Jitkarnka

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Pyrolysis of waste tire is one of alternative technique to produce petrochemicals, such as light olefins, mixed C4, and monoaromatics. Noble metals supported on acid zeolite catalysts were reported as potential catalysts to produce the high valuable products from waste tire pyrolysis. Especially, Pd supported on HBeta gave a high yield of olefins, mixed C4, and mono-aromatics. Due to the high prices of noble metals, the objective of this work was to investigate whether or not a non-noble Ni metal can be used as a substitute of a noble metal, Pd, supported on HBeta as a catalyst for waste tire pyrolysis. Ni metal was selected in this work because Ni has high activity in cracking, isomerization, hydrogenation and the ring opening of hydrocarbons Moreover, Ni is an element in the same group as Pd noble metal, which is VIIIB group, aiming to produce high valuable products similarly obtained from Pd. The amount of Ni was varied as 5, 10, and 20% by weight, for comparison with a fixed 1 wt% Pd, using incipient wetness impregnation. The results showed that as a petrochemical-producing catalyst, 10%Ni/HBeta performed better than 1%Pd/HBeta because it did not only produce the highest yield of olefins and cooking gases, but the yields were also higher than 1%Pd/HBeta. 5%Ni/HBeta can be used as a substitute of 1%Pd/HBeta for similar crude production because its crude contains the similar amounts of naphtha and saturated HCs, although it gave no concentration of light mono-aromatics (C6-C11) in the oil. Additionally, 10%Ni/HBeta that gave high olefins and cooking gases was found to give a fairly high concentration of the light mono-aromatics in the oil.

Keywords: Catalytic pyrolysis; Waste tire; Pd; Ni; HBeta

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Authors: Mohammad Asif

Abstract:

A large number of chemical, bio-chemical and pollution-control processes use heterogeneous fixed-bed reactors. The use of finite hollow cylindrical catalyst pellets can enhance conversion levels in such reactors. The absence of the pellet core can significantly lower the diffusional resistance associated with the solid phase. This leads to a better utilization of the catalytic material, which is reflected in the higher values for the effectiveness factor, leading ultimately to an enhanced conversion level in the reactor. It is however important to develop a rigorous heterogeneous model for the reactor incorporating the two-dimensional feature of the solid phase owing to the presence of the finite hollow cylindrical catalyst pellet. Presently, heterogeneous models reported in the literature invariably employ one-dimension solid phase models meant for spherical catalyst pellets. The objective of the paper is to present a rigorous model of the fixed-bed reactors containing finite hollow cylindrical catalyst pellets. The reaction kinetics considered here is the widely used Michaelis–Menten kinetics for the liquid-phase bio-chemical reactions. The reaction parameters used here are for the enzymatic degradation of urea. Results indicate that increasing the height to diameter ratio helps to improve the conversion level. On the other hand, decreasing the thickness is apparently not as effective. This could however be explained in terms of the higher void fraction of the bed that causes a smaller amount of the solid phase to be packed in the fixed-bed bio-chemical reactor.

Keywords: Fixed-bed reactor, Finite hollow cylinder, Catalyst pellet, Conversion, Michaelis-Menten kinetics.

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Authors: Krasimir I. Ivanov, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Georgi V. Avdeev, Tatyana T. Tabakova

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In recent research copper and manganese systems were found to be the most active in CO and organic compounds oxidation among the base catalysts. The mixed copper manganese oxide has been widely studied in oxidation reactions because of their higher activity at low temperatures in comparison with single oxide catalysts. The results showed that the formation of spinel CuxMn3−xO4 in the oxidized catalyst is responsible for the activity even at room temperature. That is why the most of the investigations are focused on the hopcalite catalyst (CuMn2O4) as the best coppermanganese catalyst. Now it’s known that this is true only for CO oxidation, but not for mixture of CO and VOCs. The purpose of this study is to investigate the alumina supported copper-manganese catalysts with different Cu/Mn molar ratio in terms of oxidation of CO, methanol and dimethyl ether. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and the catalytic activity measurements were carried out in two stage continuous flow equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions closest possible to the industrial. Gas mixtures on the input and output of the reactor were analyzed with a gas chromatograph, equipped with FID and TCD detectors. The texture characteristics were determined by low-temperature (- 196oС) nitrogen adsorption in a Quantachrome Instruments NOVA 1200e (USA) specific surface area & pore analyzer. Thermal, XRD and TPR analyses were performed. It was established that the active component of the mixed Cu- Mn/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio. Highly active alumina supported Cu-Mn catalysts for CO, methanol and DME oxidation were synthesized. While the hopcalite is the best catalyst for CO oxidation, the best compromise for simultaneous oxidation of all components is the catalyst with Cu/Mn molar ratio 1:5.

Keywords: Supported copper-manganese catalysts, CO and VOCs oxidation.

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Authors: F. Gholami, M. Torabi Angaji, Z. Gholami

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Fischer-Tropsch synthesis is one of the most important catalytic reactions that convert the synthetic gas to light and heavy hydrocarbons. One of the main issues is selecting the type of reactor. The slurry bubble reactor is suitable choice for Fischer- Tropsch synthesis because of its good qualification to transfer heat and mass, high durability of catalyst, low cost maintenance and repair. The more common catalysts for Fischer-Tropsch synthesis are Iron-based and Cobalt-based catalysts, the advantage of these catalysts on each other depends on which type of hydrocarbons we desire to produce. In this study, Fischer-Tropsch synthesis is modeled with Iron and Cobalt catalysts in a slurry bubble reactor considering mass and momentum balance and the hydrodynamic relations effect on the reactor behavior. Profiles of reactant conversion and reactant concentration in gas and liquid phases were determined as the functions of residence time in the reactor. The effects of temperature, pressure, liquid velocity, reactor diameter, catalyst diameter, gasliquid and liquid-solid mass transfer coefficients and kinetic coefficients on the reactant conversion have been studied. With 5% increase of liquid velocity (with Iron catalyst), H2 conversions increase about 6% and CO conversion increase about 4%, With 8% increase of liquid velocity (with Cobalt catalyst), H2 conversions increase about 26% and CO conversion increase about 4%. With 20% increase of gas-liquid mass transfer coefficient (with Iron catalyst), H2 conversions increase about 12% and CO conversion increase about 10% and with Cobalt catalyst H2 conversions increase about 10% and CO conversion increase about 6%. Results show that the process is sensitive to gas-liquid mass transfer coefficient and optimum condition operation occurs in maximum possible liquid velocity. This velocity must be more than minimum fluidization velocity and less than terminal velocity in such a way that avoid catalysts particles from leaving the fluidized bed.

Keywords: Modeling, Fischer-Tropsch Synthesis, Slurry Bubble Column Reactor.

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Authors: Gaurav Bhanjana, Ganga Ram Chaudhary, Sandeep Kumar, Neeraj Dilbaghi

Abstract:

Main sources of endocrine disrupting compounds in the ecosystem are hormones, pesticides, phthalates, flame retardants, dioxins, personal-care products, coplanar polychlorinated biphenyls (PCBs), bisphenol A, and parabens. These endocrine disrupting compounds are responsible for learning disabilities, brain development problems, deformations of the body, cancer, reproductive abnormalities in females and decreased sperm count in human males. Although discharge of these chemical compounds into the environment cannot be stopped, yet their amount can be retarded through proper evaluation and detection techniques. The available techniques for determination of these endocrine disrupting compounds mainly include high performance liquid chromatography (HPLC), mass spectroscopy (MS) and gas chromatography-mass spectrometry (GC–MS). These techniques are accurate and reliable but have certain limitations like need of skilled personnel, time consuming, interference and requirement of pretreatment steps. Moreover, these techniques are laboratory bound and sample is required in large amount for analysis. In view of above facts, new methods for detection of endocrine disrupting compounds should be devised that promise high specificity, ultra sensitivity, cost effective, efficient and easy-to-operate procedure. Nowadays, electrochemical sensors/biosensors modified with nanomaterials are gaining high attention among researchers. Bioelement present in this system makes the developed sensors selective towards analyte of interest. Nanomaterials provide large surface area, high electron communication feature, enhanced catalytic activity and possibilities of chemical modifications. In most of the cases, nanomaterials also serve as an electron mediator or electrocatalyst for some analytes.

Keywords: Sensors, endocrine disruptors, nanoparticles, electrochemical, microscopy.

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Authors: R. D. Kulkarni, Mayur Chaudhari, S. Mishra

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Curing of paints by exposure to UV radiations is emerging as one of the best film forming technique as an alternative to traditional solvent borne oxidative and thermal curing coatings. The composition and chemistry of UV curable coatings and role of multifunctional and monofunctional monomers, oligomers, and photoinitiators have been discussed. The limitations imposed by thermodynamic equilibrium and tendency for acrylic double bond polymerizations during synthesis of multifunctional acrylates have been presented. Aim of present investigation was thus to explore the reaction variables associated with synthesis of multifunctional acrylates. Zirconium oxychloride was evaluated as catalyst against regular acid functional catalyst. The catalyzed synthesis of glyceryl acrylate and neopentyl glycol acrylate was conducted by variation of following reaction parameters: two different reactant molar ratios- 1:4 and 1:6; catalyst usage in % by moles on polyol- 2.5, 5.0 and 7.5 and two different reaction temperatures- 45 and 75 0C. The reaction was monitored by determination of acid value and hydroxy value at regular intervals, besides TLC, HPLC, and FTIR analysis of intermediates and products. On the basis of determination of reaction progress over 1-60 hrs, the esterification reaction was observed to follow 2nd order kinetics with rate constant varying from 1*10-4 to 7*10-4. The thermal and catalytic components of second order rate constant and energy of activation were also determined. Uses of these kinetic and thermodynamic parameters in design of reactor for manufacture of multifunctional acrylate ester have been presented. The synthesized multifunctional acrylates were used to formulate and apply UV curable clear coat followed by determination of curing characteristics and mechanical properties of cured film. The overall curing rates less than 05 min. were easily attained indicating economical viability of radiation curable system due to faster production schedules

Keywords: glyceryl acrylate, neopentyl glycol acrylate, kinetic modeling, zirconium oxychloride.

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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 asprepared 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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