• Title/Summary/Keyword: Reactor kinetics

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A Kinetic Study of Allylchloride Epoxidation using Titanium Silicalite-1 Catalyst (Titanium Silicalite-1 촉매를 이용한 Allylchloride 에폭시화 반응: 속도론적 고찰)

  • Yang, Seung-Tae;Choi, Jung-Sik;Kwon, Young-Chul;Lee, Sang-Wook;Ahn, Wha-Seung
    • Korean Chemical Engineering Research
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    • v.46 no.1
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    • pp.142-146
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    • 2008
  • Titanium silicalite-1 catalyst was prepared using a $SiO_2-TiO_2$ xerogel and applied to allylchloride (ALC) epoxidation by $H_2O_2$ as oxidant in a batch reactor. The reaction temperature was varied from 25 to $55^{\circ}C$, and the concentrations of ALC and $H_2O_2$ were changed from 0.2 to 3 M and from 0.2 to 1.5 M, respectively. The kinetic data obtained were applied to the power rate law, Eley-Rideal, and a Langmuir-Hinshelwood model, and power rate law fits the experimental data best. Activation energy was 27.9 kJ/mol, and the reaction orders with respect to $H_2O_2$ and ALC were determined to be 0.41 and 0.52, respectively.

LIMITED OXIDATION OF IRRADIATED GRAPHITE WASTE TO REMOVE SURFACE CARBON-14

  • Smith, Tara E.;Mccrory, Shilo;Dunzik-Gougar, Mary Lou
    • Nuclear Engineering and Technology
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    • v.45 no.2
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    • pp.211-218
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    • 2013
  • Large quantities of irradiated graphite waste from graphite-moderated nuclear reactors exist and are expected to increase in the case of High Temperature Reactor (HTR) deployment [1,2]. This situation indicates the need for a graphite waste management strategy. Of greatest concern for long-term disposal of irradiated graphite is carbon-14 ($^{14}C$), with a half-life of 5730 years. Fachinger et al. [2] have demonstrated that thermal treatment of irradiated graphite removes a significant fraction of the $^{14}C$, which tends to be concentrated on the graphite surface. During thermal treatment, graphite surface carbon atoms interact with naturally adsorbed oxygen complexes to create $CO_x$ gases, i.e. "gasify" graphite. The effectiveness of this process is highly dependent on the availability of adsorbed oxygen compounds. The quantity and form of adsorbed oxygen complexes in pre- and post-irradiated graphite were studied using Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and Xray Photoelectron Spectroscopy (XPS) in an effort to better understand the gasification process and to apply that understanding to process optimization. Adsorbed oxygen fragments were detected on both irradiated and unirradiated graphite; however, carbon-oxygen bonds were identified only on the irradiated material. This difference is likely due to a large number of carbon active sites associated with the higher lattice disorder resulting from irradiation. Results of XPS analysis also indicated the potential bonding structures of the oxygen fragments removed during surface impingement. Ester- and carboxyl-like structures were predominant among the identified oxygen-containing fragments. The indicated structures are consistent with those characterized by Fanning and Vannice [3] and later incorporated into an oxidation kinetics model by El-Genk and Tournier [4]. Based on the predicted desorption mechanisms of carbon oxides from the identified compounds, it is expected that a majority of the graphite should gasify as carbon monoxide (CO) rather than carbon dioxide ($CO_2$). Therefore, to optimize the efficiency of thermal treatment the graphite should be heated to temperatures above the surface decomposition temperature increasing the evolution of CO [4].

Removal of Iron from Ilmenite through Selective Chlorination Using PVC (PVC에 의한 일메나이트 광석 중 선택염화에 의한 Fe의 제거)

  • Son, Yongik;Ring, Rie;Sohn, Ho-Sang
    • Resources Recycling
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    • v.25 no.3
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    • pp.74-81
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    • 2016
  • Study on chlorination of ilmenite ore were carried out by using PVC(polyvinyl chloride) as the chlorinating agent in a static bed reactor for selective removal of iron. The effect of amount of PVC and reaction temperature were investigated. It was found that the removal ratio of iron increased with amount of PVC and temperature. After reaction with HCl gas generated from PVC, porous surface of the specimens were observed. As a result, HCl gas could react with iron in the central portion of ilmenite particle through these pores. Examination of data using kinetic model suggest that the selective chlorination rate is controlled by chemical reaction at the interface of particles. The activation energy for the selective chlorination of ilmenite using PVC was calculated as 20.47 kJ/mol.

The Kinetics of Transesterification between Dimethylterephthalate and 1,3-Propanediol (디메틸 테레프탈레이트와 1,3-프로판디올 사이의 에스테르교환반응에 관한 연구)

  • Na, Sang-Kuwon;Kong, Byeong-Gi;Choi, Chang-Yong;Kim, Jung-Gyu;Hong, Wan-Hae;Nah, Jae-Woon
    • Polymer(Korea)
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    • v.29 no.1
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    • pp.41-47
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    • 2005
  • The transesterification of dimethyl terephthalate (DMT) with 1,3-propanediol (PDO) was investigated in the presence of catalyst, titanium (IV) butoxide (TBO), at 175~190 $^{\circ}C$ . The degree of transesterification reaction was measured by the output of methanol which was distilled from the reactor. The amount of methanol increased as the reaction temperature, molar ratio and catalyst concentration increased. The observed overall rate of the transesterification was third order; first order with respect to DMT, PDO, and the concentration of catalyst, respectively. Using calculated rate constants, the activation energy for transesterification was 26.93 kcal/mole. The melting temperature of bis(2-hydroxytrimethyl) terephthalate (BHTMT) was 85.2$^{\circ}C$ and heat of fusion 141.3 J/g.

Comparison of TiO2 and ZnO catalysts for heterogenous photocatalytic removal of vancomycin B

  • Lofrano, Giusy;Ozkal, Can Burak;Carotenuto, Maurizio;Meric, Sureyya
    • Advances in environmental research
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    • v.7 no.3
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    • pp.213-223
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    • 2018
  • Continuous input into the aquatic ecosystem and persistent structures have created concern of antibiotics, primarily due to the potential for the development of antimicrobial resistance. Degradation kinetics and mineralization of vancomycin B (VAN-B) by photocatalysis using $TiO_2$ and ZnO nanoparticles was monitored at natural pH conditions. Photocatalysis (PC) efficiency was followed by means of UV absorbance, total organic carbon (TOC), and HPLC results to better monitor degradation of VAN-B itself. Experiments were run for two initial VAN-B concentrations ($20-50mgL^{-1}$) and using two catalysts $TiO_2$ and ZnO at different concentrations (0.1 and $0.5gL^{-1}$) in a multi-lamp batch reactor system (200 mL water volume). Furthermore, a set of toxicity tests with Daphnia magna was performed to evaluate the potential toxicity of oxidation by-products of VAN-B. Formation of intermediates such as chlorides and nitrates were monitored. A rapid VAN-B degradation was observed in ZnO-PC system (85% to 70% at 10 min), while total mineralization was observed to be relatively slower than $TiO_2-PC$ system (59% to 73% at 90 min). Treatment efficiency and mechanism of degradation directly affected the rate of transformation and by-products formation that gave rise to toxicity in the treated samples.

Modeling of the effect of current density and contact time on membrane fouling reduction in EC-MBR at different MLSS concentration (EC-MBR 공정의 MLSS, 전류밀도 및 접촉시간이 막 오염 감소에 미치는 영향 모델링)

  • Kim, Wan-Kyu;Chang, In-Soung
    • Journal of Korean Society of Water and Wastewater
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    • v.33 no.2
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    • pp.111-119
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    • 2019
  • Electro-coagulation process has been gained an attention recently because it could overcome the membrane fouling problems in MBR(Membrane bio-reactor). Effect of the key operational parameters in electro-coagulation, current density(${\rho}_i$) and contact time(t) on membrane fouling reduction was investigated in this study. A kinetic model for ${\rho}_i$ and t required to reduce the membrane fouling was suggested under different MLSS(mixed liquor suspended solids) concentration. Total 48 batch type experiments of electro-coagulations under different sets of current densities(2.5, 6, 12 and $24A/m^2$), contact times(0, 2, 6 and 12 hr) and MLSS concentration(4500, 6500 and 8500mg/L) were carried out. After each electro-coagulation under different conditions, a series of membrane filtration was performed to get information on how much of membrane fouling was reduced. The membrane fouling decreased as the ${\rho}_i$ and t increased but as MLSS decreased. Total fouling resistances, Rt (=Rc+Rf) were calculated and compared to those of the controls (Ro), which were obtained from the experiments without electro-coagulation. A kinetic approach for the fouling reduction rate (Rt/Ro) was carried out and three equations under different MLSS concentration were suggested: i) ${\rho}_i^{0.39}t=3.5$ (MLSS=4500 mg/L), ii) ${\rho}_i^{0.46}t=7.0$ (MLSS=6500 mg/L), iii) ${\rho}_i^{0.74}t=10.5$ (MLSS=8500 mg/L). These equations state that the product of ${\rho}_i$ and t needed to reduce the fouling in certain amounts (in this study, 10% of fouling reduction) is always constant.

Sonochemical Oxidation Reactions in 300 kHz Sonoreactor for Various Liquid Height/Volume Conditions (다양한 액상 수위/부피 조건에서의 300kHz 초음파 캐비테이션 산화반응 분석 연구)

  • Lee, Seongeun;Son, Younggyu
    • Journal of Korean Society on Water Environment
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    • v.38 no.5
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    • pp.211-219
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    • 2022
  • In this study, the effect of liquid height/volume on sonochemical oxidation reactions was investigated in 300 kHz sonoreactors. The gas mixture of Ar/O2 (50:50) was applied in two modes including saturation and sparging, and zero-order reaction (KI dosimetry) and first-order reaction (Bisphenol A (BPA) degradation) were used to quantitatively analyze sonochemical oxidation reactions. For the zero-order reaction, the highest sonochemical oxidation activity was obtained for the liquid height of 5𝛌, and the lowest height for both the gas saturation and sparging conditions. In addition, the sparging did not enhance the sonochemical oxidation activity for all height conditions except for 50𝛌, where very low activity was obtained. It was found that in sonochemiluminescence (SCL) images the sonochemical active zone was formed adjacent to the liquid surface for the gas sparging condition due to the formation of the standing wave field while the active zone was formed adjacent to the transducer at the bottom due to the blockage of ultrasound. For the first-order reaction, the highest activity was also obtained at 5𝛌 and the comparison based on the reactant mass was not appropriate because the concentration of the reactant (BPA) decreased significantly as the reaction time elapsed. Consequently, it was revealed that the determination of optimal liquid height (ultrasound irradiation distance) based on the wavelength of the applied ultrasound frequency was very important for the optimal design of sonoreactors in terms of reaction efficiency and reactor size.

The optimization study of core power control based on meta-heuristic algorithm for China initiative accelerator driven subcritical system

  • Jin-Yang Li;Jun-Liang Du;Long Gu;You-Peng Zhang;Cong Lin;Yong-Quan Wang;Xing-Chen Zhou;Huan Lin
    • Nuclear Engineering and Technology
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    • v.55 no.2
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    • pp.452-459
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    • 2023
  • The core power control is an important issue for the study of dynamic characteristics in China initiative accelerator driven subcritical system (CiADS), which has direct impact on the control strategy and safety analysis process. The CiADS is an experimental facility that is only controlled by the proton beam intensity without considering the control rods in the current engineering design stage. In order to get the optimized operation scheme with the stable and reliable features, the variation of beam intensity using the continuous and periodic control approaches has been adopted, and the change of collimator and the adjusting of duty ratio have been proposed in the power control process. Considering the neutronics and the thermal-hydraulics characteristics in CiADS, the physical model for the core power control has been established by means of the point reactor kinetics method and the lumped parameter method. Moreover, the multi-inputs single-output (MISO) logical structure for the power control process has been constructed using proportional integral derivative (PID) controller, and the meta-heuristic algorithm has been employed to obtain the global optimized parameters for the stable running mode without producing large perturbations. Finally, the verification and validation of the control method have been tested based on the reference scenarios in considering the disturbances of spallation neutron source and inlet temperature respectively, where all the numerical results reveal that the optimization method has satisfactory performance in the CiADS core power control scenarios.

Nitrification Performance of a Moving Bed Bioreactor (MBBR) at Different Ammonia and Hydraulic Air-Loading Rates under Seawater Conditions (해수 조건에서 총암모니아성 질소 부하량과 수리학적 공기 부하량에 따른 유동상 여과조의 질산화 성능 평가)

  • Jaegeon Lee;Younghun Lee;Jeonghwan Park
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.56 no.6
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    • pp.870-877
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    • 2023
  • The purpose of this study was to assess the efficiency of nitrification based on ammonia loading rates and hydraulic air-loading rates in a moving bed bioreactor (MBBR) under seawater conditions. The goal was to provide foundational data for the design of these bio reactors. At an ammonia loading rate of 0.2 g TAN·m-2 surface area·day-1, the influent TAN concentration was determined to be 1.76±0.33 mg·L-1, which is below the safe concentration for fish survival (2 mg·L-1). Considering operational aspects, the optimal ammonia-loading rate was derived. Subsequently, experimental results for nitrification efficiency at the optimal ammonia-loading rate revealed that the optimum hydraulic air-loading rate was 1.8 L·air·m-2 surface area·min-1. This condition resulted in the lowest concentrations of TAN and NO2-N in the influent water, thus establishing the optimal hydraulic air-loading rate. A regression equation was derived for the ammonia-removal rate (Y) based on the ammonia-loading rate (x) and expressed as a 0.5-order equation (Y=ax0.5+b). Specifically, for TAN concentrations of 0-6 mg·L-1, the regression equation Y=0.1683x0.5-0.13628, was established.

Analysis of the thermal-mechanical behavior of SFR fuel pins during fast unprotected transient overpower accidents using the GERMINAL fuel performance code

  • Vincent Dupont;Victor Blanc;Thierry Beck;Marc Lainet;Pierre Sciora
    • Nuclear Engineering and Technology
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    • v.56 no.3
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    • pp.973-979
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    • 2024
  • In the framework of the Generation IV research and development project, in which the French Commission of Alternative and Atomic Energies (CEA) is involved, a main objective for the design of Sodium-cooled Fast Reactor (SFR) is to meet the safety goals for severe accidents. Among the severe ones, the Unprotected Transient OverPower (UTOP) accidents can lead very quickly to a global melting of the core. UTOP accidents can be considered either as slow during a Control Rod Withdrawal (CRW) or as fast. The paper focuses on fast UTOP accidents, which occur in a few milliseconds, and three different scenarios are considered: rupture of the core support plate, uncontrolled passage of a gas bubble inside the core and core mechanical distortion such as a core flowering/compaction during an earthquake. Several levels and rates of reactivity insertions are also considered and the thermal-mechanical behavior of an ASTRID fuel pin from the ASTRID CFV core is simulated with the GERMINAL code. Two types of fuel pins are simulated, inner and outer core pins, and three different burn-up are considered. Moreover, the feedback from the CABRI programs on these type of transients is used in order to evaluate the failure mechanism in terms of kinetics of energy injection and fuel melting. The CABRI experiments complete the analysis made with GERMINAL calculations and have shown that three dominant mechanisms can be considered as responsible for pin failure or onset of pin degradation during ULOF/UTOP accident: molten cavity pressure loading, fuel-cladding mechanical interaction (FCMI) and fuel break-up. The study is one of the first step in fast UTOP accidents modelling with GERMINAL and it has shown that the code can already succeed in modelling these type of scenarios up to the sodium boiling point. The modeling of the radial propagation of the melting front, validated by comparison with CABRI tests, is already very efficient.