• Title/Summary/Keyword: First-order kinetics

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Degradation Kinetic and Mechanism of Methyl Tert-butyl Ether (MTBE) by the Modified Photo-Fenton Reaction (Modified Photo-Fenton Reaction을 이용한 Methyl Tert-butyl Ether (MTBE)의 분해 Kinetic 및 메커니즘 규명에 관한 연구)

  • Kim, Min-Kyoung;Kong, Sung-Ho
    • Journal of Soil and Groundwater Environment
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    • v.11 no.6
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    • pp.69-75
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    • 2006
  • Improper disposal of petroleum and spills from underground storage tanks have created large areas with highly toxic contamination of the soil and groundwater. Methyl tert-butyl ether (MTBE) is widely used as a fuel additive because of its advantageous properties of increasing the octane value and reducing carbon monoxide and hydrocarbon exhausts. However, MTBE is categorized as a possible human carcinogen. This research investigated the Modified Photo-Fenton system which is based on the Modified Fenton reaction and UV light irradiation. The Modified Fenton reaction is effective for MTBE degradation near a neutral pH, using the ferric ion complex composed of a ferric ion and environmentally friendly organic chelating agents. This research was intended to treat high concentrations of MTBE; thus, 1,000 mg/L MTBE was chosen. The objectives of this research are to find the optimal reaction conditions and to elucidate the kinetic and mechanism of MTBE degradation by the Modified Photo-Fenton reaction. Based on the results of experiments, citrate was chosen among eight chelating agents as the candidate for the Modified Photo-Fenton reaction because it has a relatively higher final pH and MTBE removal efficiency than the others, and it has a relatively low toxicity and is rapidly biodegradable. MTBE degradation was found to follow pseudo-first-order kinetics. Under the optimum conditions, [$Fe^{3+}$] : [Citrate] = 1 mM: 4 mM, 3% $H_2O_2$, 17.4 kWh/L UV dose, and initial pH 6.0, the 1000 ppm MTBE was degraded by 86.75% within 6 hours and 99.99% within 16 hours. The final pH value was 6.02. The degradation mechanism of MTBE by the Modified Photo-Fenton Reaction included two diverse pathways and tert-butyl formate (TBF) was identified to be the major degradation intermediate. Attributed to the high solubility, stability, and reactivity of the ferric-citrate complexes in the near neutral condition, this Modified Photo-Fenton reaction is a promising treatment process for high concentrations of MTBE under or near a neutral pH.

Residual Characteristics of Bistrifluron and Chlorantraniliprole in Strawberry (Fragaria ananassa Duch.) for Establishing Pre-Harvest Residue Limit (생산단계 잔류허용기준 설정을 위한 딸기 중 bistrifluron과 chlorantraniliprole의 잔류 특성 연구)

  • Lee, Jae Won;Kim, Ji Yoon;Kim, Hee gon;Hur, Kyung Jin;Kwon, Chan Hyeok;Hur, Jang Hyun
    • Korean Journal of Environmental Agriculture
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    • v.36 no.1
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    • pp.57-62
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    • 2017
  • BACKGROUND: Pesticide residue analysis is essentially required for safety evaluation of agricultural products. Bistrifluron and chlorantraniliprole have been currently considered as potentials to deeply evaluate their residues in agricultural products because they are frequently found in strawberry. This work was performed to investigate the residual patterns of bistrifluron and chlorantraniliprole in strawberry after harvest. METHODS AND RESULTS: Strawberry was treated with bistrifluron and chlorantraniliprole 0, 1, 2, 3, 5, 7 and 10 days before harvest under greenhouse conditions. The strawberry samples were subjected to solvent and solid phase extractions followed by LC-MS/MS analysis. There covery percentages of bistrifluron and chlorantraniliprole for tified in the control samples ranged from approximately 82 to 103% with the method limit of 0.005 mg/kg. The concentrations of bistrifluron and chlorantraniliprole in strawberry samples decreased significantly in 10 days after treatment, giving the safety levels of 0.04 to 0.06 mg/kg at 10 days after application, as considered maximum residue limit. The half-lives of bistrifluron and chlorantraniliprole based on first order kinetics were determined to 6.3 days and 6.4 days, respectively. CONCLUSION: Bistrifluron and chlorantraniliprole are suggested to use in strawberry 10 days before harvest to reach residual safety levels.

Numerical Analysis of Unstable Combustion Flows in Normal Injection Supersonic Combustor with a Cavity (공동이 있는 수직 분사 초음속 연소기 내의 불안정 연소유동 해석)

  • Jeong-Yeol Choi;Vigor Yang
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 2003.05a
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    • pp.91-93
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    • 2003
  • A comprehensive numerical study is carried out to investigate for the understanding of the flow evolution and flame development in a supersonic combustor with normal injection of ncumally injecting hydrogen in airsupersonic flows. The formulation treats the complete conservation equations of mass, momentum, energy, and species concentration for a multi-component chemically reacting system. For the numerical simulation of supersonic combustion, multi-species Navier-Stokes equations and detailed chemistry of H2-Air is considered. It also accommodates a finite-rate chemical kinetics mechanism of hydrogen-air combustion GRI-Mech. 2.11[1], which consists of nine species and twenty-five reaction steps. Turbulence closure is achieved by means of a k-two-equation model (2). The governing equations are spatially discretized using a finite-volume approach, and temporally integrated by means of a second-order accurate implicit scheme (3-5).The supersonic combustor consists of a flat channel of 10 cm height and a fuel-injection slit of 0.1 cm width located at 10 cm downstream of the inlet. A cavity of 5 cm height and 20 cm width is installed at 15 cm downstream of the injection slit. A total of 936160 grids are used for the main-combustor flow passage, and 159161 grids for the cavity. The grids are clustered in the flow direction near the fuel injector and cavity, as well as in the vertical direction near the bottom wall. The no-slip and adiabatic conditions are assumed throughout the entire wall boundary. As a specific example, the inflow Mach number is assumed to be 3, and the temperature and pressure are 600 K and 0.1 MPa, respectively. Gaseous hydrogen at a temperature of 151.5 K is injected normal to the wall from a choked injector.A series of calculations were carried out by varying the fuel injection pressure from 0.5 to 1.5MPa. This amounts to changing the fuel mass flow rate or the overall equivalence ratio for different operating regimes. Figure 1 shows the instantaneous temperature fields in the supersonic combustor at four different conditions. The dark blue region represents the hot burned gases. At the fuel injection pressure of 0.5 MPa, the flame is stably anchored, but the flow field exhibits a high-amplitude oscillation. At the fuel injection pressure of 1.0 MPa, the Mach reflection occurs ahead of the injector. The interaction between the incoming air and the injection flow becomes much more complex, and the fuel/air mixing is strongly enhanced. The Mach reflection oscillates and results in a strong fluctuation in the combustor wall pressure. At the fuel injection pressure of 1.5MPa, the flow inside the combustor becomes nearly choked and the Mach reflection is displaced forward. The leading shock wave moves slowly toward the inlet, and eventually causes the combustor-upstart due to the thermal choking. The cavity appears to play a secondary role in driving the flow unsteadiness, in spite of its influence on the fuel/air mixing and flame evolution. Further investigation is necessary on this issue. The present study features detailed resolution of the flow and flame dynamics in the combustor, which was not typically available in most of the previous works. In particular, the oscillatory flow characteristics are captured at a scale sufficient to identify the underlying physical mechanisms. Much of the flow unsteadiness is not related to the cavity, but rather to the intrinsic unsteadiness in the flowfield, as also shown experimentally by Ben-Yakar et al. [6], The interactions between the unsteady flow and flame evolution may cause a large excursion of flow oscillation. The work appears to be the first of its kind in the numerical study of combustion oscillations in a supersonic combustor, although a similar phenomenon was previously reported experimentally. A more comprehensive discussion will be given in the final paper presented at the colloquium.

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Catalytic Wet Oxidation of Azo Dye Reactive Black 5 (아조염료 Reactive Black 5 폐수의 촉매습식산화)

  • Suh, Il-Soon;Yoo, Shin-Suk;Ko, Mi-So;Jeong, Samuel;Jung, Cheol-Goo;Hong, Jeong-Ah;Yoon, Wang-Lai
    • Korean Chemical Engineering Research
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    • v.48 no.2
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    • pp.259-267
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    • 2010
  • The catalytic wet oxidations of the wastewater containing azo dye Reactive Black 5(RB5) with heterogeneous catalyst of CuO have been carried out to investigate the effects of temperature($190{\sim}230^{\circ}C$) and catalyst concentration(0.00~0.20 g/l) on the removals of colour and total organic carbon TOC. The wastewater colour was measured with spectrophotometer, and the oxidation rate was estimated with TOC. About 90% of colour was removed during 120 min in thermal degradation of the RB5 wastewater at $230^{\circ}C$, while TOC was not removed at all. As increasing reaction temperature and catalyst concentration, the removal rates of colour and TOC increased in the catalytic wet oxidations of RB5 wastewater. The effects of catalyst were already considerable even at 0.01 g CuO/l, while the removal rates of colour and TOC increased negligibly with increasing the catalyst concentration above 0.05 g CuO/l. The initial destruction rates of the wastewater colour have shown the first-order kinetics with respect to the wastewater colour. TOC changes during catalytic wet oxidations have been well described with the global model, in which the easily degradable TOC was distinguished from non-degradable TOC of the wastewater. The impacts of reaction temperature on the destruction rate of the wastewater colour and TOC could be described with Arrhenius relationship. Activation energies of the colour removal reaction in thermal degradation, wet oxidation, and catalytic wet oxidation(0.20 g CuO/l) of the RB5 wastewater were 108.4, 78.3 and 74.1 kJ/mol, respectively. The selectivity of wastewater TOC into the non-degradable intermediates relative to the end products in the catalytic wet oxidations of RB5 wastewater was higher compared to that in phenol wet oxidations.

Studies on Persistence of Pesticides in Soils and Crops under Polyethylene Film Mulching Culture;III. Persistence of Soil Insecticides Endosulfan, Fonofos and Ethoprophos (폴리에틸렌 멀칭재배시(栽培時) 농약(農藥)의 토양(土壤) 및 작물체중(作物體中) 잔류(殘留)에 관한 연구(硏究);제(第)3보(報) 토양살충제 Endosulfan, Fonofos, Ethoprophos의 잔류성(殘留性))

  • Ryang, Hwan-Seung;Moon, Young-Hee;Kim, Nak-Eung
    • Korean Journal of Environmental Agriculture
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    • v.7 no.1
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    • pp.8-13
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    • 1988
  • This experiment was conducted to evaluate the effect of polyethylene film(P.E.) mulching on degradation of the soil insecticides, endosulfan(6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin-3-oxide), fonofos(O-ethyl S-phenyl ethylphosphonodithioate), and ethorprophos(O-ethyl S, S-dipropyl phosphorodithioate) in red pepper, peanut, and sesame fields. Degradation of endosulfan, fonofos and ethoprophos in the soils under P.E. mulching and non-mulching followed first-order kinetics. The half-lives of fonofos, ethoprophos, ${\alpha}-$ and ${\beta}-endosulfan$ were $19{\sim}21$, $25{\sim}37$, $33{\sim}39$ and $56{\sim}81$ days, respectively. There were few differences in the half-lives of fonofos in either mulching or non-mulching concitions. However, half-lives of α-endosulfan, ethoprophos, and ${\beta}-endosulfan$ were 6, 12 and 25 days longer under P.E. mulching than under non-mulching conditions, respectively. The effect of P.E. mulching on degradation was remarkable for the slower degrading insecticides. Residues of ethoprophos in the harvested sesame under P.E. mulching and non-mulching conditions were 0.024 and 0.074ppm, respectively. Residues of fonofos in the harvested peanuts under P.E. mulching and non-mulching conditions were 0.078 and 0.017ppm, respectively. However, no endosulfan was detected in the harvested red peppers under either condition.

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Effects of silage storage period of grass clippings on methane production by anaerobic digestion (잔디 예지물의 혐기소화에서 사일리지 저장기간이 메탄 생산에 미치는 영향)

  • Jin Yeo;Tae-Hee Kim;Chang-Gyu Kim;Seo-Yeong Lee;Young-Man Yoon
    • Journal of the Korea Organic Resources Recycling Association
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    • v.31 no.4
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    • pp.13-28
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    • 2023
  • This study assessed the biochemical methane potential (Bu-P) of three grass species-Poa pratensis (PP), Zoysia japonica (ZJ), and Agrostis stolonifera (AS). Bu-P values were determined as 0.330 Nm3/kg-VSadded for PP, 0.297 Nm3/kg-VSadded for ZJ, and 0.261 Nm3/kg-VSadded for AS. Notably, PP exhibited superior suitability for methane production. The investigation also examined the impact of silage storage duration on PP grass clippings, revealing a 19% decline in Bu-P from an initial value of 0.269 Nm3/kg-VSadded on day 0 to 0.217 Nm3/kg-VSadded on day 180. Throughout the storage period, there were significant increases in neutral detergent fiber (NDF), acid detergent fiber (ADF), and crude protein (CP) contents, rising from 67.59%, 39.68%, and 3.02% on day 0 to 77.12%, 54.65%, and 6.24% on day 180, respectively. These findings highlight the influence of storage duration on the anaerobic digestibility of PP grass clippings. To effectively utilize grass clippings as a renewable resource for methane production, further studies considering factors such as initial moisture content, pretreatment methods, and potential effects of residual pesticides are necessary to optimize anaerobic digestion efficiency for herbaceous biomass.