Search results for: well-stirred reactor (WSR)

Authors: Ahmed I. Osman, Jehad K. Abu-Dahrieh, David W. Rooney, Jillian Thompson

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The effect of loading of copper on the catalytic performance of different alumina support during the dehydration of methanol to dimethyl ether (DME) was performed in a fixed bed reactor. There are two levels of loading; low loading (1, 2, 4 and 6% Cu wt/wt) and high loading (10 and 15% Cu wt/wt) on both AC350 (alumina catalyst calcined at 350) and AC550 (alumina catalyst calcined at 550), to study the effect of loading and the effect of the support during methanol dehydration to DME (MTD). The catalysts were characterized by TGA, XRD, BET, TPD-NH3, TEM and DRIFT-Pyridine. Under reaction conditions where the temperature ranged from 180-300˚C with a WHSV= 12.1 h-1 it was found that all the catalysts calcined at 550˚C showed higher activity than those calcined at 350˚C. In this study, the optimum catalyst was 6% Cu/AC550. This catalyst showed a high degree of stability, had one half activity of the pure catalyst (AC550) and double the activity of the optimum catalyst calcined at 350˚C (6% Cu/AC350). So, we recommended 6% Cu/AC550 for the production of DME from methanol.

Keywords: bio-fuel, nano composite catalyst, DME, Cu-Al2O3

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Authors: Ebrahim Ghanbari, Mohammad Reza Nematollahi

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Integrating deterministic and probabilistic safety assessment (IDPSA) is one of the most commonly used issues in the field of safety analysis of power plant accident. It has also been recognized today that the role of human error in creating these accidents is not less than systemic errors, so the human interference and system errors in fault and event sequences are necessary. The integration of these analytical topics will be reflected in the frequency of core damage and also the study of the use of water resources in an accident such as the loss of all electrical power of the plant. In this regard, the SBO accident was simulated for the pressurized water reactor in the deterministic analysis issue, and by analyzing the operator's behavior in controlling the accident, the results of the combination of deterministic and probabilistic assessment were identified. The results showed that the best performance of the plant operator would reduce the risk of an accident by 10%, as well as a decrease of 6.82 liters/second of the water sources of the plant.

Keywords: IDPSA, human error, SBO, risk

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Authors: Hamid Reza Mahdipoor, Mehdi Bahrami, Mohammad Bodaghi, Seyed Ali Akbar Mansoori

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Nowadays, with stricter limitations to reduce emissions, considerable penalties are imposed if pollution limits are exceeded. Therefore, refineries, along with focusing on improving the quality of their products, are also focused on producing products with the least environmental impact. The duty of the sulfur recovery unit (SRU) is to convert H₂S gas coming from the upstream units to elemental sulfur and minimize the burning of sulfur compounds to SO₂. The Claus process is a common process for converting H₂S to sulfur, including a reaction furnace followed by catalytic reactors and sulfur condensers. In addition to a Claus section, SRUs usually consist of a tail gas treatment (TGT) section to decrease the concentration of SO₂ in the flue gas below the emission limits. To operate an SRU properly, the flow rate of combustion air to the reaction furnace must be adjusted so that the Claus reaction is performed according to stoichiometry. Accurate control of the air demand leads to an optimum recovery of sulfur during the flow and composition fluctuations in the acid gas feed. Therefore, the major control system in the SRU is the air demand control loop, which includes a feed-forward control system based on predetermined feed flow rates and a feed-back control system based on the signal from the tail gas online analyzer. The use of online analyzers requires compliance with the installation and operation instructions. Unfortunately, most of these analyzers in Iran are out of service for different reasons, like the low importance of environmental issues and a lack of access to after-sales services due to sanctions. In this paper, an SRU in Iran was simulated and calibrated using industrial experimental data. Afterward, the effect of the malfunction of the online analyzer on the performance of SRU was investigated using the calibrated simulation. The results showed that an increase in the SO₂ concentration in the tail gas led to an increase in the temperature of the reduction reactor in the TGT section. This increase in temperature caused the failure of TGT and increased the concentration of SO₂ from 750 ppm to 35,000 ppm. In addition, the lack of a control system for the adjustment of the combustion air caused further increases in SO₂ emissions. In some processes, the major variable cannot be controlled directly due to difficulty in measurement or a long delay in the sampling system. In these cases, a secondary variable, which can be measured more easily, is considered to be controlled. With the correct selection of this variable, the main variable is also controlled along with the secondary variable. This strategy for controlling a process system is referred to as inferential control" and is considered in this paper. Therefore, a sensitivity analysis was performed to investigate the sensitivity of other measurable parameters to input disturbances. The results revealed that the output temperature of the first Claus reactor could be used for inferential control of the combustion air. Applying this method to the operation led to maximizing the sulfur recovery in the Claus section.

Keywords: sulfur recovery, online analyzer, inferential control, SO₂ emission

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

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

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

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Authors: Young S. Bang, Dong H. Yoon, Seung H. Yoo

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Emergency Core Coolant Bypass (ECC Bypass) has been regarded as an important phenomenon to peak cladding temperature of large-break loss-of-coolant-accidents (LBLOCA) in nuclear power plants (NPP). A modeling scheme to address the ECC Bypass phenomena and the calculation of LBLOCA using that scheme are discussed in the present paper. A hydraulic form loss coefficient (HFLC) from the reactor vessel downcomer to the broken cold leg is predicted by the computational fluid dynamics (CFD) code with a variation of the void fraction incoming from the downcomer. The maximum, mean, and minimum values of FLC are derived from the CFD results and are incorporated into the LBLOCA calculation using a system thermal-hydraulic code, MARS-KS. As a relevant parameter addressing the ECC Bypass phenomena, the FLC to the break and its range are proposed.

Keywords: CFD analysis, ECC bypass, hydraulic form loss coefficient, system thermal-hydraulic code

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Authors: Weerachit Pulsawas, Thirasak Rirksomboon

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

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

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Authors: Joao Teotonio Manzi

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Reversibility, irreversibility, equilibrium and steady-state that play a central role in the thermodynamic analysis of processes arising in the context of reactive systems are discussed in this article. Such concepts have generated substantial doubts, even among the most experienced researchers, and engineers, because from the literature, conclusive or definitive statements cannot be extracted. Concepts such as the time-reversibility of irreversible processes seem paradoxical, requiring further analysis. Equilibrium and reversibility, which appear to be of the same nature, have also been re-examined in the light of maximum entropy. The goal of this paper is to revisit and explore these concepts based on classical thermodynamics in order to have a better understanding them due to their impacts on technological advances, as a result, to generate an optimal procedure for designing, monitoring, and engineering optimization. Furthermore, an effective graphic procedure for dimensioning a Plug Flow Reactor has been provided. Thus, to meet the needs of chemical engineering from a simple conceptual analysis but with significant practical effects, a macroscopic approach is taken so as to integrate the different parts of this paper.

Keywords: reversibility, equilibrium, steady-state, thermodynamics, reactive system

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Authors: Junior B. N. Adohinzin, Ling Xu

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Nitrogen is among the main nutrients encouraging the growth of organic matter and algae which cause eutrophication in water bodies. Therefore, its removal from wastewater has become a worldwide emerging concern. In this research, an innovative Membrane Bioreactor (MBR) system named “moving bed membrane bioreactor (MBMBR)” was developed and investigated under intermittently-aerated mode for simultaneous removal of organic carbon and nitrogen. Results indicated that the variation of the intermittently aerated duration did not have an apparent impact on COD and NH4+–N removal rate, yielding the effluent with average COD and NH4+–N removal efficiency of more than 92 and 91% respectively. However, in the intermittently aerated cycle of (continuously aeration/0s mix), (aeration 90s/mix 90s) and (aeration 90s/mix 180s); the average TN removal efficiency was 67.6%, 69.5% and 87.8% respectively. At the same time, their nitrite accumulation rate was 4.5%, 49.1% and 79.4% respectively. These results indicate that the intermittently aerated mode is an efficient way to controlling the nitrification to stop at nitrition; and also the length of anoxic duration is a key factor in improving TN removal.

Keywords: membrane bioreactor (MBR), moving bed biofilm reactor (MBBR), nutrients removal, simultaneous nitrification and denitrification

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Authors: Mirosław Krzemieniewski, Marcin Zieliński, Marcin Dębowski

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This publication presents a device for depolymerisation of plant substrates applicable to agricultural biogas plants and closed-chamber sewage treatment plants where sludge fermentation is bolstered with plant mass. The device consists of a tank with a cover equipped with a heating system, an inlet for the substrate, and an outlet for the depolymerised substrate. Within the tank, a magnet shaft encased in a spiral casing is attached, equipped on its upper end with an internal magnetic disc. A motoreducer is mounted on an external magnetic disc located on the centre of the cover. Depolymerisation of the plant substrate allows for substrate destruction at much lower power levels than by conventional means. The temperature within the reactor can be lowered by 40% in comparison to existing designs. During the depolymerisation process, free radicals are generated within the magnetic field, oxidizing the conditioned substrate and promoting biodegradation. Thus, the fermentation time in the fermenters is reduced by approximately 20%.

Keywords: depolymerisation, pre-treatment, biomass, fermentation

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Authors: Sanghoon Bae, Hanju Cha

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Failed fuel detector (FFD) in research reactor is a very crucial instrument to detect the anomaly from failed fuels in the early stage around primary cooling system (PCS) outlet prior to the decay tank. FFD is considered as a mandatory sensor to ensure the integrity of fuel assemblies and mitigate the consequence from a failed fuel accident. For the effective function of FFD, the location of them should be determined by contemplating the effect from coolant flow around two outlets. For this, the analysis on computational flow dynamics (CFD) should be first performed how the coolant outlet flow including radioactive materials from failed fuels are mixed and discharged through the outlet plenum within certain seconds. The analysis result shows that the outlet flow is well mixed regardless of the position of failed fuel and ultimately illustrates the effect of detector location.

Keywords: computational flow dynamics (CFD), failed fuel detector (FFD), fresh fuel assembly (FFA), spent fuel assembly (SFA)

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Authors: Anaam H. Al-ShaikhAli, Mansour A. Al-Herz

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The research leverages the proven HS-FCC technology to directly crack crude oils into petrochemical building blocks. Crude oils were subjected to an optimized hydro-processing process where metal contaminants and sulfur were reduced to an acceptable level for feeding the crudes into the HS-FCC technology. The hydro-processing is achieved through a fixed-bed reactor which is composed of 3 layers of catalysts. The crude oil is passed through a dementalization catalyst followed by a desulfurization catalyst and finally a de-aromatization catalyst. The hydroprocessing was conducted at an optimized liquid hourly space velocity (LHSV), temperature, and pressure for an optimal reduction of metals and sulfur from the crudes. The hydro-processed crudes were then fed into a micro activity testing (MAT) unit to simulate the HS-FCC technology. The catalytic cracking of crude oils was conducted over tailored catalyst formulations under an optimized catalyst/oil ratio and cracking temperature for optimal production of total light olefins.

Keywords: petrochemical, catalytic cracking, catalyst synthesis, HS-FCC technology

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Authors: T. Wejrzanowski, M. Grybczuk, E. Tymicki, K. J. Kurzydlowski

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In the present study, numerical simulations of heat and mass transfer in Physical Vapor Transport reactor during silicon carbide single crystal growth are addressed. Silicon carbide is a wide bandgap material with unique properties making it highly applicable for high power electronics applications. Because of high manufacturing costs improvements of SiC production process are required. In this study, numerical simulations were used as a tool of process optimization. Computer modeling allows for cost and time effective analysis of processes occurring during SiC single crystal growth and provides essential information needed for improvement of the process. Quantitative relationship between process conditions, such as temperature or pressure, and crystal growth rate and shape of crystallization front have been studied and verified using experimental data. Basing on modeling results, several process improvements were proposed and implemented.

Keywords: Finite Volume Method, semiconductors, Physica Vapor Transport, silicon carbide

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Authors: Gyeong-Sung Kim, In-soo Ahn, Yong Cho

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SBR (Sequencing Batch Reactor) process is usually applied to membrane water treatment plants to treat its concentrated wastewater. The role of SBR process is to remove COD (Chemical Oxygen Demand) and NH3 from wastewater before discharging it outside of the water treatment plant using microorganism. Microorganism’s nitrification capability is influenced by water temperature because the nitrification rate of the concentrated wastewater becomes ‘zero’ as water temperature approach 0℃. Heating system is necessary to operate SBR in winter season even though the operating cost increase sharply. The operating cost of SBR at ‘D’ RO water treatment plant in Korea was 51.8 times higher in winter (October to March) compare to summer (April to September) season in 2014. Otherwise the effluent water temperature maintained around 8℃ constantly in winter. This study focuses on application heat pump system to recover the thermal energy from the effluent water of ‘D’ RO plant so that the operating cost will be reduced.

Keywords: water treatment, water thermal energy, energy saving, RO, SBR

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Authors: A. Odoom, A. Salama, H. Ibrahim

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Hydrogen is a clean source of energy for power production and transportation. The main source of hydrogen in this research is biodiesel. Glycerol also called glycerine is a by-product of biodiesel production by transesterification of vegetable oils and methanol. This is a reliable and environmentally-friendly source of hydrogen production than fossil fuels. A typical composition of crude glycerol comprises of glycerol, water, organic and inorganic salts, soap, methanol and small amounts of glycerides. Crude glycerol has limited industrial application due to its low purity thus, the usage of crude glycerol can significantly enhance the sustainability and production of biodiesel. Reforming techniques is an approach for hydrogen production mainly Steam Reforming (SR), Autothermal Reforming (ATR) and Partial Oxidation Reforming (POR). SR produces high hydrogen conversions and yield but is highly endothermic whereas POR is exothermic. On the downside, PO yields lower hydrogen as well as large amount of side reactions. ATR which is a fusion of partial oxidation reforming and steam reforming is thermally neutral because net reactor heat duty is zero. It has relatively high hydrogen yield, selectivity as well as limits coke formation. The complex chemical processes that take place during the production phases makes it relatively difficult to construct a reliable and robust numerical model. Numerical model is a tool to mimic reality and provide insight into the influence of the parameters. In this work, we introduce a finite volume numerical study for an 'in-house' lab-scale experiment of ATR. Previous numerical studies on this process have considered either using Comsol or nodal finite difference analysis. Since Comsol is a commercial package which is not readily available everywhere and lab-scale experiment can be considered well mixed in the radial direction. One spatial dimension suffices to capture the essential feature of ATR, in this work, we consider developing our own numerical approach using MATLAB. A continuum fixed bed reactor is modelled using MATLAB with both pseudo homogeneous and heterogeneous models. The drawback of nodal finite difference formulation is that it is not locally conservative which means that materials and momenta can be generated inside the domain as an artifact of the discretization. Control volume, on the other hand, is locally conservative and suites very well problems where materials are generated and consumed inside the domain. In this work, species mass balance, Darcy’s equation and energy equations are solved using operator splitting technique. Therefore, diffusion-like terms are discretized implicitly while advection-like terms are discretized explicitly. An upwind scheme is adapted for the advection term to ensure accuracy and positivity. Comparisons with the experimental data show very good agreements which build confidence in our modeling approach. The models obtained were validated and optimized for better results.

Keywords: autothermal reforming, crude glycerol, hydrogen, numerical model

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Authors: Ying Zhang

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In ASME Boiler and Pressure Vessel Code, the plastic load is defined by applying the twice elastic slope (TES) criterion of plastic collapse to a characteristic load-deformation curve for the vessel. Several other plastic criterion such as tangent intersection (TI) criterion, plastic work (PW) criterion have been proposed in the literature, but all exhibit a practical limitation: difficult to define the load parameter for vessels subject to several combined loads. An alternative criterion: plastic work-tangent (PWT) criterion for evaluating plastic load in pressure vessel design by analysis is presented in this paper. According to the plastic work-load curve, when the tangent variation is less than a given value in the plastic phase, the corresponding load is the plastic load. Application of the proposed criterion is illustrated by considering the elastic-plastic response of the lower head of reactor pressure vessel (RPV) and nozzle intersection of (RPV). It is proposed that this is because the PWT criterion more fully represents the constraining effect of material strain hardening on the spread of plastic deformation and more efficiently ton evaluating the plastic load.

Keywords: plastic load, plastic work, strain hardening, plastic work-tangent criterion

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Authors: Alberto Veses, Olga Sanhauja, María Soledad Callén, Tomás García

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The appropriate use of renewable sources emerges as a decisive point to minimize the environmental impact caused by fossil fuels use. Particularly, the use of lignocellulosic biomass becomes one of the best promising alternatives since it is the only carbon-containing renewable source that can produce bioproducts similar to fossil fuels and it does not compete with food market. Among all the processes that can valorize lignocellulosic biomass, pyrolysis is an attractive alternative because it is the only thermochemical process that can produce a liquid biofuel (bio-oil) in a simple way and solid and gas fractions that can be used as energy sources to support the process. However, in order to incorporate bio-oils in current infrastructures and further process in future biorefineries, their quality needs to be improved. Introducing different low-cost catalysts and/or incorporating different polymer residues to the process are some of the new, simple and low-cost strategies that allow the user to directly obtain advanced bio-oils to be used in future biorefineries in an economic way. In this manner, from previous thermogravimetric analyses, local agricultural wastes such as grape seeds (GS) were selected as lignocellulosic biomass while, waste tires (WT) were selected as polymer residue. On the other hand, CaO was selected as low-cost catalyst based on previous experiences by the group. To reach this aim, a specially-designed fixed bed reactor using N₂ as a carrier gas was used. This reactor has the peculiarity to incorporate a vertical mobile liner that allows the user to introduce the feedstock in the oven once the selected temperature (550 ºC) is reached, ensuring higher heating rates needed for the process. Obtaining a well-defined phase distribution in the resulting bio-oil is crucial to ensure the viability to the process. Thus, once experiments were carried out, not only a well-defined two layers was observed introducing several mixtures (reaching values up to 40 wt.% of WT) but also, an upgraded organic phase, which is the one considered to be processed in further biorefineries. Radical interactions between GS and WT released during the pyrolysis process and dehydration reactions enhanced by CaO can promote the formation of better-quality bio-oils. The latter was reflected in a reduction of water and oxygen content of bio-oil and hence, a substantial increase of its heating value and its stability. Moreover, not only sulphur content was reduced from solely WT pyrolysis but also potential and negative issues related to a strong acidic environment of conventional bio-oils were minimized due to its basic pH and lower total acid numbers. Therefore, acidic compounds obtained in the pyrolysis such as CO₂-like substances can react with the CaO and minimize acidic problems related to lignocellulosic bio-oils. Moreover, this CO₂ capture promotes H₂ production from water gas shift reaction favoring hydrogen-transfer reactions, improving the final quality of the bio-oil. These results show the great potential of grapes seeds to carry out the catalytic co-pyrolysis process with different plastic residues in order to produce a liquid bio-oil that can be considered as a high-quality renewable vector.

Keywords: advanced bio-oils, biorefinery, catalytic co-pyrolysis of biomass and waste tires, lignocellulosic biomass

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Authors: Huirui Han, Chao Zhang

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The rod bundle is used in the fuel assembly of the supercritical water-cooled nuclear reactor. In the rod bundle, the coolant absorbs the heat contributed by the fission process. Because of the dramatic variations in the thermophysical properties of water at supercritical conditions, it is essential to investigate the heat transfer characteristics of supercritical water in the rod bundle to ensure the safety of the nuclear power plant. In this study, the effects of the flow direction, including horizontal, upward, and downward, on the fluid flow and heat transfer of the supercritical water in the rod bundle were studied numerically. The results show the possibility of gap vortices in the flow subchannels of the rod bundle. In addition, the distributions of the circumferential wall temperature show differences in different flow direction conditions. It was also found that the circumferential cladding surface temperature distribution in the upward flow condition is extremely non-uniform, and there is a large difference between the maximum wall temperatures for different fuel rods.

Keywords: heat transfer, rod bundle, supercritical water, wall temperature

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Authors: Raymond Limen Njinga

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The comparator factors (Fc) for miniature research reactors are of great importance in the field of nuclear physics as it provide accurate bases for the evaluation of elements in all form of samples via ko-NAA techniques. The Fc was initially simulated theoretically thereafter, series of experiments were performed to validate the results. In this situation, the experimental values were obtained using the alloy of Au(0.1%) - Al monitor foil and a neutron flux setting of 5.00E+11 cm-2.s-1. As was observed in the inner irradiation position, the average experimental value of 7.120E+05 was reported against the theoretical value of 7.330E+05. In comparison, a percentage deviation of 2.86 (from theoretical value) was observed. In the large case of the outer irradiation position, the experimental value of 1.170E+06 was recorded against the theoretical value of 1.210E+06 with a percentage deviation of 3.310 (from the theoretical value). The estimation of equivalent dose rate at 5m from neutron flux of 5.00E+11 cm-2.s-1 within the neutron energies of 1KeV, 10KeV, 100KeV, 500KeV, 1MeV, 5MeV and 10MeV were calculated to be 0.01 Sv/h, 0.01 Sv/h, 0.03 Sv/h, 0.15 Sv/h, 0.21Sv/h and 0.25 Sv/h respectively with a total dose within a period of an hour was obtained to be 0.66 Sv.

Keywords: neutron flux, comparator factor, NAA techniques, neutron energy, equivalent dose

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Authors: Khalid Almarri

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The UAE is currently developing a peaceful nuclear energy program as part of its low Carbon energy strategy to meet future energy demands. Research of nuclear energy technologies is required to support nuclear energy generation projects and maximize their performance. Research of this type will require building an operating a research reactor (RR), a costly undertaking in most circumstances. Collaboration between government and private parties through public, private partnerships (PPP) can maximize the benefits expected from the adoption of an RR project. The aim of this research is to establish the critical success factors (CSF) for developing an RR project for newcomer countries, with the UAE taken as a case study, through the utilization of public, private partnerships (PPP). The results of this study were arrived at through the use of semi-structured interviews conducted with ten experts in the field of research reactors, using grounded theory method. Underutilization was identified as the main stumbling block that impairs the success of research reactors.

Keywords: public private partnerships, research reactors, grounded theory, critical success factors

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Authors: Djalal Hamed

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The aim of this paper is to perform an analytic solution of steady state natural convection in a narrow rectangular channel between two vertical parallel MTR-type fuel plates, imposed under a cosine shape heat flux to determine the margin of the nuclear core power at which the natural convection cooling mode can ensure a safe core cooling, where the cladding temperature should not be reach the specific safety limits (90 °C). For this purpose, a simple computer program is developed to determine the principal parameter related to the nuclear core safety such as the temperature distribution in the fuel plate and in the coolant (light water) as a function of the reactor power. Our results are validated throughout a comparison against the results of another published work, which is considered like a reference of this study.

Keywords: buoyancy force, friction force, natural convection, thermal hydraulic analysis, vertical heated rectangular channel

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Authors: Sudhakar Saroj, Satya Vir Singh

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Undoped and Fe doped TiO₂, Ti₁₋ₓFeₓO₂ (x=0.00, 0.01, 0.03, 0.05, 0.07 and 0.09) have been synthesized by solution combustion method using Titanium (IV) oxide as a precursor, and also were characterized by XRD, DRS, FTIR, XPS, SEM, and EDX. The formation of anatase phase of undoped and Fe TiO₂ nanoparticles were confirmed by XRD, and the average crystallite size was determined by Debye-Scherer's equation. The DRS analysis indicates the shifting of light absorbance in visible region from UV region with increasing the doping concentration in TiO₂. The vibrational band of the Ti-O lattice was confirmed by the FT-IR spectrum. The XPS results confirm the presence of elements of titanium, oxygen and iron in the synthesized samples and determine the binding energy of elements. SEM image of the above-synthesized nanoparticles showed the spherical shape of nanoparticles. The purities of the synthesized nanoparticles were confirmed by EDX analysis. The photocatalytic activities of the synthesized nanoparticles were tested by studying the degradation of dye (Direct Blue 199) in the photocatalytic reactor. The Ti₀.₉₇Fe₀.₀₃O₂ photocatalyst shows highest photodegradation activity among all the synthesized undoped and Fe doped TiO₂ photocatalyst.

Keywords: direct blue 199, nanoparticles, TiO₂, photodegradation

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Authors: D. Nareshyadav, K. Anand Kishore, D. Bhagawan

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Water scarcity is the much-identified issue all over the world. The available sources of water need to be reused to sustainable future. The present work explores the treatment of dye wastewater using combinative photocatalysis and ceramic nanofiltration membrane. Commercial ceramic membrane and TiO₂ catalyst were used in this study to investigate the removal of crystal violet dye from the aqueous solution. The effect of operating parameters such as inlet pressure, initial concentration of crystal violet dye, catalyst (TiO₂) loading, initial pH was investigated in the individual system as well as the combined system. In this study, 95 % of dye water was decolorized and 89 % of total organic carbon (TOC) was removed by the hybrid system for 500 ppm of dye and 0.75 g/l of TiO₂ concentrations at pH 9. The operation of the integrated photocatalytic reactor and ceramic membrane filtration has shown the maximum removal of crystal violet dye compared to individual systems. Hence this proposed method may be effective for the removal of Crystal violet dye from effluents.

Keywords: advanced oxidation process, ceramic nanoporous membrane, dye degradation/removal, hybrid system, photocatalysis

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Authors: Ahmed Arkoazi, Hussein Znad, Ranjeet Utikar

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The synergistic impact and optimization of gas flow rate, concentration of CO₂, and light intensity on CO₂ biofixation rate were investigated using wastewater as a medium to cultivate Chlorella vulgaris under different conditions (gas flow rate 1-8 L/min), CO₂ concentration (0.03-7%), and light intensity (150-400 µmol/m².s)). Response Surface Methodology and Box-Behnken experimental Design were applied to find optimum values for gas flow rate, CO₂ concentration, and light intensity. The optimum values of the three independent variables (gas flow rate, concentration of CO₂, and light intensity) and desirability were 7.5 L/min, 3.5%, and 400 µmol/m².s, and 0.904, respectively. The highest amount of biomass produced and CO₂ biofixation rate at optimum conditions were 5.7 g/L, 1.23 gL^-1d^-1, respectively. The synergistic effect between gas flow rate and concentration of CO₂, and between gas flow rate and light intensity was significant on the three responses, while the effect between CO₂ concentration and light intensity was less significant on CO₂ biofixation rate. The results of this study could be highly helpful when using microalgae for CO₂ biofixation in wastewater treatment.

Keywords: bubble column reactor, gas holdup, hydrodynamics, sparger

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Authors: Ayu Minamizawa, Jae-Ho Kim, Susumu Yonezawa

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Aqueous peroxotitanium acid solution was prepared by the reaction between H₂O₂ solution and TiO₂ fluorinated using F₂ gas. The coating of TiO₂/SiO₂ multilayer on the surface of polycarbonate (PC) resin was carried out step by step using the TEOS solution and aqueous peroxotitanium acid solution. We confirmed each formation of SiO₂ and TiO₂ layer by scanning electron microscopy and energy-dispersive X-ray spectroscopy, and x-ray photoelectron spectroscopy results. The formation of a TiO₂ thin layer on SiO₂ coated on polycarbonate (PC) was carried out at 120 ℃ and for 15 min ~ 3 h with aqueous peroxotitanium acid solution using a hydrothermal synthesis autoclave reactor. The morphology TiO₂ coating layer largely depended on the reaction time, as shown in the results of SEM-EDS analysis. Increasing the reaction times, the TiO₂ layer expanded uniformly. Moreover, the surface fluorination of the SiO₂ layer can promote the formation of the TiO₂ layer on the surface.

Keywords: aqueous peroxotitanium acid solution, photocatalytic activity, polycarbonate, surface fluorination

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Authors: Francisco Espinosa, Juan Chavarría

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

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

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Authors: Jianli Chang, Yusheng Zhang, Yali Yao, Diane Hildebrandt, Xinying Liu

Abstract:

The influence of feed-gas ratio on the ethene hydroformylation over an Rh-Co bimetallic catalyst supported by reduced graphene oxide (RGO) has been investigated in a tubular fixed bed reactor. Argon was used as balance gas when the feed-gas ratio was changed, which can keep the partial pressure of the other two kinds of gas constant while the ratio of one component in feed-gas was changed. First, the effect of single-component gas ratio on the performance of ethene hydroformylation was studied one by one (H₂, C₂H₄ and CO). Then an optimized ratio was found to obtain a high selectivity to C₃ oxygenates. The results showed that: (1) 0.5%Rh-20%Co/RGO is a promising heterogeneous catalyst for ethene hydroformylation. (2) H₂ and CO have a more significant influence than C₂H₄ on selectivity to oxygenates. (3) A lower H₂ ratio and a higher CO ratio in feed-gas can lead to a higher selectivity to oxygenates. (4) The highest selectivity to oxygenates, 61.70%, was obtained at the feed-gas ratio CO: C₂H₄: H₂ = 4: 2: 1.

Keywords: ethene hydroformylation, reduced graphene oxide, rhodium cobalt bimetallic catalyst, the effect of feed-gas ratio

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Authors: Hamid Rezaei, Xiaotao Bi, C. Jim Lim, Anthony Lau, Shahab Sokhansanj

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A one-dimensional heat transfer model coupled with the kinetic information has been used to predict the overall pyrolysis mass loss of a single wood particle. The kinetic parameters were determined experimentally and the regime and characteristics of the conversion were evaluated in terms of the particle size and reactor temperature. The order of overall mass loss changed from n=1 at temperatures lower than 350 °C to n=0.5 at temperatures higher that 350 °C. Conversion time analysis showed that particles larger than 0.5 mm were controlled by internal thermal resistances. The valid range of particle size to use the simplified lumped model depends on the fluid temperature around the particles. The critical particle size was 0.6-0.7 mm for the fluid temperature of 500 °C and 0.9-1.0 mm for the fluid temperature of 100 °C. Experimental pyrolysis of moist particles did not show distinct drying and pyrolysis stages. The process was divided into two hypothetical drying and pyrolysis dominated zones and empirical correlations are developed to predict the rate of mass loss in each zone.

Keywords: pyrolysis, kinetics, model, single particle

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Authors: Amritanshu Shriwastav, Purnendu Bose

Abstract:

Algal photo bioreactors were operated at incident light intensities of 0.24, 2.52 and 5.96 W L-1 to determine the impact of light on algal growth. Low specific Chlorophyll-a content of algae was a strong indicator of light induced stress on algal cells. It was concluded that long term operation of photo bioreactors in the continuous illumination mode was infeasible under the range of incident light intensities examined and provision of a dark period after each light period was necessary for algal cells to recover from light-induced stress. Long term operation of photo bioreactors in the intermittent illumination mode was however possible at light intensities of 0.24 and 2.52 W L-1. Further, the incident light intensity in the photo bioreactors was found to decline exponentially with increase in algal concentration in the reactor due to algal ‘self-shading’. This may be an important determinant for photo bioreactor performance at higher algal concentrations.

Keywords: Algae, algal growth, photo bioreactor, photo-inhibition, ‘self-shading’

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Authors: Grzegorz Raniszewski, Zbigniew Kolacinski, Lukasz Szymanski, Slawomir Wiak, Lukasz Pietrzak, Dariusz Koza

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One of the most promising area for carbon nanotubes (CNTs) application is medicine. One of the most devastating diseases is cancer. Carbon nanotubes may be used as carriers of a slowly released drug. It is possible to use of electromagnetic waves to destroy cancer cells by the carbon nanotubes (CNTs). In our research we focused on thermal ablation by ferromagnetic carbon nanotubes (Fe-CNTs). In the cancer cell hyperthermia functionalized carbon nanotubes are exposed to radio frequency electromagnetic field. Properly functionalized Fe-CNTs join the cancer cells. Heat generated in nanoparticles connected to nanotubes warm up nanotubes and then the target tissue. When the temperature in tumor tissue exceeds 316 K the necrosis of cancer cells may be observed. Several techniques can be used for Fe-CNTs synthesis. In our work, we use high-temperature methods where arc-discharge is applied. Low-temperature systems are microwave plasma with assisted chemical vapor deposition (MPCVD) and hybrid physical-chemical vapor deposition (HPCVD). In the arc discharge system, the plasma reactor works with a pressure of He up to 0,5 atm. The electric arc burns between two graphite rods. Vapors of carbon move from the anode, through a short arc column and forms CNTs which can be collected either from the reactor walls or cathode deposit. This method is suitable for the production of multi-wall and single-wall CNTs. A disadvantage of high-temperature methods is a low purification, short length, random size and multi-directional distribution. In MPCVD system plasma is generated in waveguide connected to the microwave generator. Then containing carbon and ferromagnetic elements plasma flux go to the quartz tube. The additional resistance heating can be applied to increase the reaction effectiveness and efficiency. CNTs nucleation occurs on the quartz tube walls. It is also possible to use substrates to improve carbon nanotubes growth. HPCVD system involves both chemical decomposition of carbon containing gases and vaporization of a solid or liquid source of catalyst. In this system, a tube furnace is applied. A mixture of working and carbon-containing gases go through the quartz tube placed inside the furnace. As a catalyst ferrocene vapors can be used. Fe-CNTs may be collected then either from the quartz tube walls or on the substrates. Low-temperature methods are characterized by higher purity product. Moreover, carbon nanotubes from tested CVD systems were partially filled with the iron. Regardless of the method of Fe-CNTs synthesis the final product always needs to be purified for applications in medicine. The simplest method of purification is an oxidation of the amorphous carbon. Carbon nanotubes dedicated for cancer cell thermal ablation need to be additionally treated by acids for defects amplification on the CNTs surface what facilitates biofunctionalization. Application of ferromagnetic nanotubes for cancer treatment is a promising method of fighting with cancer for the next decade. Acknowledgment: The research work has been financed from the budget of science as a research project No. PBS2/A5/31/2013

Keywords: arc discharge, cancer, carbon nanotubes, CVD, thermal ablation

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Authors: Tomasz Borowski, Dawid Sołoducha, Rafał Rakoczy, Marian Kordas

Abstract:

The growing interest in magnetic fields applications is visible due to the increased number of articles on this topic published in the last few years. In this study, the influence of various magnetic fields (MF) on the mass transfer process was examined. To carry out the prototype set-up equipped with an MF generator that is able to generate a pulsed magnetic field (PMF), oscillating magnetic field (OMF), rotating magnetic field (RMF) and static magnetic field (SMF) was used. To demonstrate the effect of MF’s on mass transfer, the calcium carbonate precipitation process was selected. To the vessel with attached conductometric probes and placed inside the generator, specific doses of calcium chloride and sodium carbonate were added. Electrical conductivity changes of the mixture inside the vessel were measured over time until equilibrium was established. Measurements were conducted for various MF strengths and concentrations of added chemical compounds. Obtained results were analyzed, which allowed to creation of mathematical correlation models showing the influence of MF’s on the studied process.

Keywords: mass transfer, oscillating magnetic field, rotating magnetic field, static magnetic field

Procedia PDF Downloads 180