• 대한환경공학회지
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• 제36권5호
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• pp.311-316
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• 2014

오존-활성탄 복합공정에 의한 페놀제거 특성과 그에 미치는 운전변수의 영향에 관해 회분식 실험을 통하여 동력학적 연구를 수행하였다. 활성탄은 오존의 자가분해를 촉진시켜 $OH{\cdot}$ 발생시키므로 페놀분해 속도를 증가시키는 것으로 나타났다. 활성탄의 투입량이 증가함에 따라 페놀분해 반응의 유사 일차반응 속도상수가 증가하고 페놀제거의 반감기가 감소하는 것으로 나타났다. 수용액의 pH 증가는 수산화이온이 개시하는 오존분해의 연쇄반응에 의해 $OH{\cdot}$를 생성시키므로 페놀분해 속도를 증가시키는 것으로 나타났다. 페놀의 완전산화 지표인 총유기탄소(TOC) 제거효율은 활성탄을 투입할 때 투입하지 않은 조건보다 약 3.2배 높은 결과를 얻을 수 있었다.

• 대한화학회지
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• 제38권10호
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• pp.705-709
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• 1994

1M 황산용액에서 세륨(Ⅳ) 이온에 의한 말론산의 산화반응에 관한 반응속도를 분광광도법으로 연구하였다. 말론산이 과량으로 존재하는 조건하에서 측정된 유사일차 속도상수, $k_{obs}$는 말론산의 농도, [MA]에 따라 크게 의존함을 보였으며 $k_{obs}$ = (0.592[MA])/(1+14.5[MA]$^2$)의 관계를 만족하였다. 이에 근거하여 반응메카니즘을 제안하였다. 말론산의 산해리에 의해 생성된 enolate형 음이온과 Ce(Ⅳ)간의 전자이동반응이 반응속도 결정단계이며, MA의 고농도하에서 Ce(Ⅳ)과 enolate형 음이온간의 1:2 chelate생성반응에 의하여 Ce(Ⅳ)의 농도가 감소하여 산화반응이 억제됨을 알 수 있었다. 본 연구에서 제안된 메카니즘에 근거하여 Sengupta 등에 의해 연구된 pH 의존성을 설명할 수 있었다.

• Journal of Microbiology and Biotechnology
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• 제20권3호
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• pp.574-578
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• 2010

Archaebacteria Sulfolobus acidocaldarius contains the highly thermophilic cytochrome P450 enzyme (CYP119). CYP119 possesses stable enzymatic activity at up to $85^{\circ}C$. However, this enzyme is still considered as an orphan P450 without known physiological function with endogenous or xenobiotic substrates. We characterized the regioselectivity of lauric acid by CYP119 using the auxiliary redox partner proteins putidaredoxin (Pd) and putidaredoxin reductase (PdR). Purified CYP119 protein showed a tight binding affinity to lauric acid ($K_d=1.1{\pm}0.1{\mu}M$) and dominantly hydroxylated (${\omega}-1$) position of lauric acid. We determined the steady-state kinetic parameters; $k_{cat}$ was 10.8 $min^{-1}$ and $K_m$, was 12 ${\mu}M$. The increased ratio to $\omega$-hydroxylated production of lauric acid catalyzed by CYP119 was observed with increase in the reaction temperature. These studies suggested that the regioselectivity of CYP119 provide the critical clue for the physiological enzyme function in this thermophilic archaebacteria. In addition, regioselectivity control of CYP119 without altering its thermostability can lead to the development of novel CYP119-based catalysts through protein engineering.

• 상하수도학회지
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• 제23권4호
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• pp.471-479
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• 2009

A Nanoscale Zero-Valent Iron(NZVI) was modified to build a reactor system to treat nitrate. Shell layer of the NZVI was modified by slow exposure of the iron surface to air flow, which produced NZVI particles that are resistant to aerial oxidation. A XANES (X-ray Absorption Near-Edge Structure) analysis revealed that the shell consists of magnetite ($Fe_3O_4$) dominantly. The shell-modified NZVI(0.5 g NZVI/ 120 mL) was able to degrade more than 95% of 30 mg/L of nitrate within $30 hr^{-1}$ ( pseudo first-order rate constant($k_{SA}$) normalzed to NZVI surface area ($17.96m^2/g$) : $0.0050L{\cdot}m^{-2}{\cdot}hr^{-1}$). Ammonia occupied about 90% of degradation products of nitrate. Nitrate degradation efficiencies increased with the increase of NZVI dose generally. Initial pH values of the reactor systems at 4, 7, and 10 did not affect nitrate removal rate and final pH values of all experiments were near 12. Nitrate removal experiments by using the shell-modified NZVI immobilized on a cellulose acetate (CA) membrane were also conducted. The nitrate removal efficiency of the CA membrane supported NZVI ($k_{SA}=0.0036L{\cdot}m^{-2}{\cdot}hr^{-1}$) was less than that of the NZVI slurries($k_{SA}=0.0050L{\cdot}m^{-2}{\cdot}hr^{-1}$), which is probably due to less surface area available for reduction and to kinetic retardation by nitrate transport through the CA membrane. The detachment of the NZVI from the CA membrane was minimal and impregnation of up to 1 g of NZVI onto 1 g of the CA membrane was found feasible.

• 전기화학회지
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• 제10권1호
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• pp.1-6
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• 2007

금 나노 입자를 회합시킨 흑연전극 표면에 mercaptopropionic acid(mpa)를 사용하여 자기조립 단층막(self-assembled monolayer: SAMs)을 생성시키고 이어서 도파민(dopa)과의 짝지움 반응을 통하여 Gr(Au)/mpa-dopa형의 수식된 전극을 제작하여 NADH의 전기촉매 산화반응에 적용하였다. 이 수식 전극이 전자전달반응속도와 반응과정에 대하여 연구하였다. 전극 표면에 고정된 도파민이 NADH와 이차반응 속도상수는 회전 전극법으로 0.1 M 인산염 완충용액(pH=7.0)에서 결정하였으며 그 값이 $5.06{\times}10^5M^{-1}s^{-1}$였고, $EC_{cat}$ 및 전자전달이 지배적인 과정이었다. 그러나 반응초기 즉, $10^{-3}s$ 이내에서는 이 전극에서 확산에 영향을 받으며 그 때 확산계수는 $4.64{\times}10^{-4}cm^2s^{-1}$이다.

• 공업화학
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• 제23권2호
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• pp.241-246
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• 2012

크롬(VI)-헤테로고리 착물(2,2'-bipyridinium dichromate)를 합성하여, 적외선분광광도법(IR), 유도결합 플라즈마(ICP) 등으로 구조를 확인하였다. 여러 가지 용매 하에서 2,2'-bipyridinium dichromate를 이용하여 벤질 알코올의 산화반응을 측정한 결과 유전상수(${\epsilon}$) 값이 큰 용매 순서인 시클로헥센 < 클로로포름 < 아세톤 < N,N-디메틸포름아미드 용매 하에서 높은 산화반응성을 보였다. 산 촉매($H_2SO_4$)를 이용한 DMF 용매 하에서 2,2'-bipyridinium dichromate는 벤질 알코올과 그의 유도체들($p-OCH_3$, $m-CH_3$, H, $m-OCH_3$, m-Cl, $m-NO_2$)을 효과적으로 산화시켰다. 그리고 전자받개 그룹들은 반응 속도가 감소한 반면에 전자주개 치환체들은 반응속도를 증가시켰다. 또한 Hammett 반응상수$({\rho})$ 값은 -0.66 (303 K)이였다. 그러므로 본 실험에서 알코올의 산화반응 과정은 속도결정단계에서 수소화 전이가 일어나는 메카니즘임을 알 수 있었다.

• 대한금속재료학회지
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• 제46권5호
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• pp.289-295
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• 2008

The effect of the alloy elements(Si/Mn) ratio on the coating quality including wettabilty with molten zinc, galvannealing kinetics and crater has been investigated in interstitial-free high strength steel(IFHSS) containing Si and Mn. When the Si/Mn ratio was below 0.75, IF-HSS exhibited a good wettability leading to a good galvannealed coating quality after annealing at $800^{\circ}C$ for 40s in $15%H_2-N_2$ mixed gas with dew point $-60^{\circ}C$. In contrast, the wettability and galvannealed coating quality were deteriorated in the Si/ Mn ratio above 0.75. It is shown that they have relevance to oxides forms by selective oxidation on the steel surface. The oxide particles dispersed on the steel surface with a surface coverage of below 40% resulted in good wettability and galvannealed coating quality. The oxide particle is mainly consisted of $Mn_2SiO_4$ with low contact angle in molten zinc. On the other hand, the continuous oxide layer on the steel surface, such as network- and film-type,caused to poor wettability and galvannealed coating quality. The coverage of oxide layer was above 80%, and its chemical species was $SiO_2$ with high contact angle in molten zinc. Consequently, the Si/Mn alloy ratio played an importance role in galvannealed coating quality of IF-HSS.

• Korean Chemical Engineering Research
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• 제61권2호
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• pp.226-233
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• 2023

To create an environmentally sustainable fuel with a low sulfur concentration, requires alternative sulfur removal methods. During the course of this study, a high surface gamma alumina-supported ZnO nanocatalyst with a ZnO/-Al₂O₃ ratio of 12% was developed and tested for its ability to improve the activity of the oxidative desulfurization (ODS) process for the desulfurization of kerosene fuel. Scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) were used to characterize the produced nanocatalyst. In a digital batch baffled reactor (20~80 min), the effectiveness of the synthesized nanocatalyst was tested at different initial concentrations of dibenzothiophene (DBT) of 300~600 ppm, oxidation temperatures (25~70 ℃), and oxidation periods (0.5, 1, and 2 hours). The baffles included in the digital baffled batch reactor resist the swirling of the reaction mixture, thus facilitating mixing. The ODS procedure yielded the maximum DBT conversion (95.5%) at 70 ℃ with an 80-minute reaction time and an initial DBT level of 600 ppm. The most precise values of kinetic variables were subsequently determined using a mathematical modelling procedure for the ODS procedure. The average absolute error of the simulation findings was less than 5%, demonstrating a good degree of agreement with the experimental results acquired from all runs. The optimization of the operating conditions revealed that 99.1% of the DBT can be removed in 140 minutes.

• 대한토목학회논문집
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• 제26권4B호
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• pp.421-426
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• 2006

본 연구는 생물학적 질산화 공정에서 암모늄 이온과 활성을 가진 질산화균의 초기 농도가 질산화에 미치는 영향을 확인하고, 이에 따른 동역학식을 제시하고자 하였다. 먼저 실험에 이용된 슬러지의 질산화균 농도는 미생물 호흡률 실험으로 측정하였는데, 배양된 슬러지 중 42.8%가 활성을 가진 질산화균으로 나타났다. 암모늄 이온과 질산화균의 초기 농도를 달리하여 $N_0/X_0$비가 0.025~0.493의 조건에서 잘산화 실험을 실시하였으며, 이를 통해 암모늄 이온과 질산화균의 농도가 상이하더라도 $N_0/X_0$ 비가 동일할 경우 암모늄 산화율이 동일함을 확인하였다. 또한 $N_0/X_0$ 비와 비기질이용율의 관계는 Contois 형태의 관계식으로 표현되었으며, 최대 비암모늄산화율($q_{Nmax}$)은 4.32 gN/gVSS/day, 반 포화속도 상수($K_N{^{\prime}}$)는 0,013 gN/gVSS인 것으로 확인되었다.

• 폴리머
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• 제32권2호
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• pp.150-156
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• 2008

Two different polyacrylonitrile samples (PANs, triad tacticity fraction is 0.25 and 0.64) were synthesized and used to study the kinetics of cyclization. Polymers were treated at different temperatures between 250 to $300^{\circ}C$ under air atmosphere, and analyzed by X-ray diffractometer. The sharp and strong peak at $2{\theta}=16.5^{\circ}$ corresponds to a lateral repeat distance that is the (100) diffraction in hexagonal lattice, while the peak at $2{\theta}=25.5^{\circ}$ reflects the (101) diffraction. In comparing their areas of different heat treated samples, the cyclization of both PANs was identified as a first-order reaction. The rate constants of cyclization reaction at different temperatures and the active energy parameter were obtained. This results might provide an important effect on pre-oxidation of polyacrylonitrile fiber.