활성탄에 의한 Acid Red 66의 흡착에 대한 등온선, 동력학 및 열역학적 특성

이종집(Jong-Jib Lee) 한국청정기술학회 2020 청정기술 Vol.26 No.1

입상 활성탄에 대한 Acid Red 66의 흡착 등온선과 동력학적, 열역학적 파라미터에 대해 염료의 초기농도, 접촉시간, 온도를 흡착변수로 하여 조사하였다. 흡착평형자료는 Langmuir, Freundlich, Temkin, Redlich-Peterson 및 Temkin 등온흡착식에 적용하였다. Freundlich 등온흡착식이 가장 잘 맞았으며, 계산된 Freundlich 분리계수 값(1/n = 0.125 ~ 0.232)으로부터 입상 활성탄이 Acid Red 66을 효과적으로 처리할 수 있다는 것을 알 수 있었다. Temkin의 흡착열관련상수(BT = 2.147 ~ 2.562 J mol<SUP>-1</SUP>)는 이 공정이 물리흡착임을 나타냈다. 동력학적 실험으로부터 흡착공정은 유사 이차 반응속도식에 잘 맞았다. 입자 내 확산식에 대한 결과는 경계층 확산을 나타내는 첫 번째 직선의 기울기보다 입자내 확산을 나타내는 두 번째 직선의 기울기가 작게 나타나서 입자 내 확산이 율속단계인 것을 확인하였다. 열역학 실험으로부터 활성화 에너지는 35.23 kJ mol-1로 흡착공정이 물리흡착공임을 확인하였다. Gibbs 자유에너지 변화(ΔG = -0.548 ~ -7.802 kJ mol<SUP>-1</SUP>)와 엔탈피 변화(ΔH = +109.112 kJ mol<SUP>-1</SUP>)은 각각 흡착공정이 자발적 공정 및 흡열과정임을 나타내었다. 등량흡착열은 흡착된 염료분자들의 측면상호작용을 나타내는 표면부하량이 증가함에 따라 증가하였다. The kinetic and thermodynamic parameters of Acid Red 66, adsorbed by granular activated carbon, were investigated on areas of initial concentration, contact time, and temperature. The adsorption equilibrium data were applied to Langmuir, Freundlich, Temkin, Redlich-Peterson, and Temkin isotherms. The agreement was found to be the highest in the Freundlich model. From the determined Freundlich separation factor (1/n = 0.125 ~ 0.232), the adsorption of Acid Red 66 by granular activated carbon could be employed as an effective treatment method. Temkin’s constant related to adsorption heat (BT = 2.147 ~ 2.562 J mol<SUP>-1</SUP>) showed that this process was physical adsorption. From kinetic experiments, the adsorption process followed the pseudo-second order model with good agreement. The results of the intraparticle diffusion equation showed that the inclination of the second straight line representing the intraparticle diffusion was smaller than that of the first straight line representing the boundary layer diffusion. Therefore, it was confirmed that intraparticle diffusion was the rate-controlling step. From thermodynamic experiments, the activation energy was determined as 35.23 kJ mol-1, indicating that the adsorption of Acid Red 66 was physical adsorption. The negative Gibbs free energy change (ΔG= -0.548 ~ -7.802 kJ mol<SUP>-1</SUP>) and the positive enthalpy change (ΔH = +109.112 kJ mol<SUP>-1</SUP>) indicated the spontaneous and endothermic nature of the adsorption process, respectively. The isosteric heat of adsorption increased with the increase of surface loading, indicating lateral interactions between the adsorbed dye molecules.

입상 활성탄을 이용한 말라카이트 그린의 흡착평형, 동력학 및 열역학 연구

이종집 ( Jong Jib Lee ) 한국공업화학회 2013 공업화학 Vol.24 No.2

In the present study, batch experiments were carried out for the utilizatioin of activated carbon as a potential adsorbent to remove a hazardous malachite green from an aqueous solution. The effects of various parameters such as temperature, contact time, initial concentration on the adsorption system were investigated. On the basis of adsorption data Langmuir and Freundlich adsorption isotherm model were also confirmed. The equilibrium process was described well by Langmuir isotherm model. From determined separation factor, the activated carbon could be employed as an effective treatment for removal of malachite green. From kinetic experiments, the adsorption process followed the pseudo second order model, and the adsorption rate constant (k2) decreased with increasing both the initial concentration of malachite green and the adsoprtion temperature. Thermodynamic parameters like that activation energy, change of free energy, enthalpy, and entropy were also calculated to predict the adsorption nature. The activation energy calculated from Arrhenius equation indicated that the adsortpion of malachite green on the zeolite was physical process. The negative Gibbs free energy change (ΔG=-3.68∼-7.76kJ/mol) and the positive enthalpy change (ΔH=+26.34kJ/mol) indicated the spontaneous and endothermic nature of the adsorption in the temperature range of 298∼318 K.

입상활성탄에 의한 수용액으로부터 오로라 레드의 흡착에 대한 평형, 동력학 및열역학 파라미터에 관한 연구

이종집 ( Jong Jib Lee ) 한국공업화학회 2014 공업화학 Vol.25 No.4

Allura Red (AR) is a water-soluble harmful tar-based food colorant (FD & C Red 40). Batch adsorption studies were performedfor the removal of AR using bituminous coal based granular activated carbon as adsorbent by varying the operationparameters such as adsorbent dosage, initial concentration, contact time and temperature. Experimental equilibrium adsorptiondata were analyzed by Langmuir, Freundlich and Temkin isotherms. The equilibrium process was described well by Freundlichisotherm. From determined separation factor (RL), adsorption of AR by granular activated carbon could be employed as effectivetreatment method. Temkin parameter, B was determined to 1.62∼3.288 J/mol indicating a physical adsorption process. By estimationof adsorption rate experimental data, the value of intraparticle diffusion rate constant (km) increased with the increasingadsorption temperature. The adsorption process were found to confirm to the pseudo second order model with good correlation. Thermodynamic parameters like change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorptionin the temperature range of 298∼318 K. The negative Gibbs free energy change (ΔG = -2.16∼-6.55 kJ/mol) and thepositive enthalpy change (ΔH = + 23.29 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption process,respectively.

열분해액화반응에 의한 헤미셀룰로오스의 분해특성 및 연료물질 생성

이종집 ( Jong Jib Lee ) 한국공업화학회 2008 공업화학 Vol.19 No.2

석탄계 활성탄에 의한 Carbol Fuchsin의 흡착 특성과 파라미터: 동력학 및 열역학

이종집 ( Jong Jib Lee ) 한국공업화학회 2021 공업화학 Vol.32 No.3

석탄계 활성탄(CAC)에 의한 carbol fuchsin (CF) 염료의 흡착 특성을 pH, 초기농도, 온도 및 접촉시간을 흡착변수로 사용하여 조사하였다. CF는 수중에서 해리하여 양이온인 NH₂⁺를 가지게 되는데, 염기성 영역에서 음전하를 가진 활성탄의 표면과 정전기적 인력으로 결합하였으며 최적조건인 pH 11에서 96.6%를 흡착하였다. 등온흡착은 Langmuir, Freundlich, Temkin 및 Dubinin-Radushkevich 모델을 사용하여 해석하였다. 실험결과는 Langmuir 식이 더 잘 맞았다. 따라서 흡착 메카니즘은 균일한 에너지 분포를 가진 활성탄 표면에서 단분자층으로 흡착된다고 예상되었다. 평가된 Langmuir의 무차원 분리계수 값들(R_L = 0.503~0.672)로부터 활성탄에 의해 CF를 효과적으로 처리할 수 있다는 것을 알았다. Temkin식과 Dubinin-Radushkevich 식에 의해 구한 흡착에너지는 각각 B_T = 4.397~6.281 kJ/mol과 E = 1.456~2.319 J/mol이었다. 따라서 흡착공정은 물리흡착(B_T < 20 J/mol, E < 8 kJ/mol)으로 나타났다. 흡착속도실험결과는 유사 2차 속도식에 더 잘 맞았다. CAC에 대한 CF 염료의 흡착반응은 온도가 올라갈수록 자유에너지 변화의 음수값이 증가하였기 때문에 온도 증가와 함께 자발성도 높아지는 것으로 나타났다. 양수 값의 엔탈피 변화(12.747 kJ/mol)는 흡열반응임을 알려주었다. Adsorption characteristics of carbol fuchsin (CF) dye by coal-based activated carbon (CAC) were investigated using pH, initial concentration, temperature and contact time as adsorption variables. CF dissociates in water to have a cation, NH₂ ⁺, which is bonded to the negatively charged surface of the activated carbon in the basic region by electrostatic attraction. Under the optimum condition of pH 11, 96.6% of the initial concentration was adsorbed. Isothermal adsorption behavior was analyzed using Langmuir, Freundlich, Temkin and Dubinin-Radushkevich models. Langmuir's equation was the best fit for the experimental results. Therefore, the adsorption mechanism was expected to be adsorbed as a monolayer on the surface of activated carbon with a uniform energy distribution. From the evaluated Langmuir’s dimensionless separation coefficients (R_L = 0.503∼0.672), it was found that CF can be effectively treated by activated carbon. The adsorption energies determined by Temkin and Dubinin-Radushkevich models were E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. Therefore, the adsorption process was physical (E < 20 J/mol, B < 8 kJ/mol). The experimental result of adsorption kinetics fit better the pseudo second order model. In the adsorption reaction of CF dye to CAC, the negative free energy change increased as the temperature increased. It was found that the spontaneity also increased with increasing temperature. The positive enthalpy change (40.09 kJ/mol) indicated an endothermic reaction.

석탄계 활성탄에 의한 Acid Black 1 염료의 흡착에 있어서 평형, 동력학, 및 열역학적 특성

이종집(Jong-Jib Lee) 한국청정기술학회 2021 청정기술 Vol.27 No.3

석탄계 입상 활성탄(CGAC)에 의한 acid black 1 (AB1) 염료의 평형, 동력학 및 열역학적 특성을 초기농도, 접촉 시간, 온도 및 pH 를 흡착변수로 하여 조사하였다. 활성탄에 의한 AB1의 흡착반응은 산성에서는 활성탄의 표면(H<SUP>+</SUP>)과 AB1이 가지고 있는 sulfite ion (SO₃<SUP>-</SUP>), nitrite ion (NO₂<SUP>-</SUP>) 사이의 정전기적 인력에 의해 일어났고, 최고 흡착률은 pH 3에서 97.7%였다. AB1의 등온데이터는 Freundlich 등온식에 가장 잘 맞았으며, 계산된 분리계수(1/n) 값으로부터 활성탄에 의한 AB1의 흡착이 효과적인 처리과정이 될 수 있음을 알았다. Temkin 식의 흡착열 관련상수의 값은 물리 흡착 공정(< 20 J mol<SUP>-1</SUP>)임을 나타냈다. 동역학 실험에서는 유사 2차 모델이 유사 1차 모델보다 더 일관성이 있었으며 추정된 평형 흡착량은 오차 백분율의 9.73% 이내에서 잘 일치하였다. 입자내 확산이 흡착 과정에서 속도 조절 단계였다. 활성화 에너지와 엔탈피 변화값으로부터 흡착반응이 물리흡착으로 진행되는 흡열반응임을 확인하였다. 엔트로피 변화는 활성탄 표면에서 AB1의 흡착이 일어나는 동안 고-액 계면에서 활발한 반응에 의해 엔트로피가 증가하는 것으로 나타났다. 자유에너지 변화는 온도증가와 함께 흡착반응의 자발성이 더 커지는 것을 나타냈다. Equilibrium, kinetics, and thermodynamics of adsorption of acid black 1 (AB1) by coal-based granular activated carbon (CGAC) were investigated with the adsorption variables of initial concentration of dye, contact time, temperature, and pH. The adsorption reaction of AB1 by activated carbon was caused by electrostatic attraction between the surface (H<SUP>+</SUP>) of activated carbon and the sulfite ions (SO₃<SUP>-</SUP>) and nitrite ions (NO₂<SUP>-</SUP>) possessed by AB1, and the degree of reaction was highest at pH 3(97.7%). The isothermal data of AB1 were best fitted with Freundlich isotherm model. From the calculated separation factor (1/n) of Freundlich, it was confirmed that adsorption of AB1 by activated carbon could be very effective. The heat of adsorption in the Temkin model suggested a physical adsorption process (< 20 J mol<SUP>-1</SUP>). The kinetic experiment favored the pseudo second order model, and the equilibrium adsorption amount estimated from the model agreed to that given by the experiments (error < 9.73% ). Intraparticle diffusion was a rate controlling step in this adsorption process. From the activation energy and enthalpy change, it was confirmed that the adsorption reaction is an endothermic reaction proceeding with physical adsorption. The entropy change was positive because of an active reaction at the solid-liquid interface during adsorption of AB1 on the activated carbon surface. The free energy change indicated that the spontaneity of the adsorption reaction increased as the temperature increased.

활성탄에 의한 Acid Blue 40 흡착에 있어서 평형, 동력학 및 열역학적 특성

이종집(Jong Jib Lee) 한국산학기술학회 2018 한국산학기술학회논문지 Vol.19 No.12

활성탄에 의해 수용액으로부터 acid blue 40을 흡착하는 과정을 통해 흡착평형, 동력학 및 열역학적 특성을 활성탄양, pH, 온도, 접촉시간, 초기농도를 함수로 해서 알아내고자 하였다. 활성탄에 대한 acid blue 40의 흡착에 대한 pH별 흡착특성은 Sulfonate ion(SO₃<SUP>-</SUP>)과 amine ion(NH₂<SUP>+</SUP>)의 존재 때문에 pH 3과 pH 11에서 흡착률이 높아지는 욕조현상을 나타내었다. 활성탄에 대한 Acid Blue 40의 흡착평형관계를 흡착등온식에 적용해본 결과 Langmuir 식이 Freundlich 식과 Temkin 식보다 더 잘 맞는 것으로 나타났다. Langmuir 식과 Freundlich 식의 분리계수로 부터 활성탄에 의한 Acid Blue 40 의 흡착처리가 유효한 흡착공정이 될 수 있음을 알았다. Temkin 식에 의해 구한 흡착에너지 값으로부터 흡착공정이 물리흡착공정이라는 것을 알았다. 활성탄에 대한 acid blue 40의 흡착공정에 대한 동력학적 해석을 통해 반응속도식의 적용결과는 유사이차반응속도식이 유사일차반응속도식에 비해 일치도가 높은 것으로 나타났다. 평가된 활성화 에너지 값은 42.308 kJ/mol이었으며, 엔탈피변화는 80.088 J/mol로 흡열반응의 특성을 가지는 것으로 판단되었다. 또한 자유에너지변화가 .0.0553.-5.5855 kJ/mol로 온도가 올라갈수록 흡착공정의 자발성이 더 높아진다는 것을 알았다. The kinetics and thermodynamics of the adsorption of acid blue 40 from an aqueous solution by activated carbon were examined as a function of the activated carbon dose, pH, temperature, contact time, and initial concentration. The adsorption efficiency in a bathtub was increased at pH 3 and pH 11 due to the presence of sufonate ions (SO3-) and amine ions (NH2-). The equilibrium adsorption data were fitted to the Langmuir, Freundlich and Temkin isotherms. The results indicated that the Langmuir model provides the best correlation of the experimental data. The separation factor of the Langmuir and Freundlich model showed that the adsorption treatment of acid blue 40 by activated carbon could be an effective adsorption process. The adsorption energy determined by the Temkin equation showed that the adsorption step is a physical adsorption process. Kinetics analysis of the adsorption process of acid blue 40 on activated carbon showed that a pseudo second order kinetic model is more consistent than a pseudo second order kinetic model. The estimated activation energy was 42.308 kJ/mol. The enthalpy change (80.088 J/mol) indicated an endothermic process. The free energy change (-0.0553 ~ -5.5855 kJ/mol) showed that the spontaneity of the process increased with increasing adsorption temperature.

활성탄을 이용한 Acid Yellow 14 흡착에 대한 평형, 동역학 및 열역학 파라미터의 연구

이종집 ( Jong Jib Lee ) 한국화학공학회 2016 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.54 No.2

활성탄을 사용한 Acid Yellow 14 염료의 흡착 실험은 흡착제의 양, pH, 초기농도, 접촉시간과 온도를 흡착변수로 사용하여 수행하였다. 흡착평형자료는 Langmuir, Freundlich 및 Temkin 등온식을 사용하여 해석하였는데, Freundlich 식이 가장 좋은 일치도를 나타냈다. 평가된 Freundlich 상수(1/n=0.129~0.212)와 Langmuir 분리계수(R_{L}=0.202~0.243)로부터 활성탄에 의한 Acid Yellow 14의 흡착조작은 적절한 처리방법이 될 수 있음을 알았다. Temkin의 흡착열관련상수(B)는 5.101~9.164 J/mol로 평가되어, 흡착공정이 물리흡착임을 알았다. 흡착속도실험자료를 유사일차반응속도식과 유사이차반응속도식에 적용해 본 결과, 흡착동력학은 유사이차반응속도식에 잘 맞는 것으로 나타났다. Gibbs 자유에너지(-4.81~-10.33 kJ/mol)와 엔탈피(+78.59 kJ/mol)는 흡착이 자발적이고 흡열공정으로 진행된다는 것을 나타낸다. Adsorption experiments of Acid Yellow 14 dye using activated carbon were carried out as function of adsorbent dose, pH, initial concentration, contact time and temperature. The equilibrium adsorption data were analyzed by Langmuir, Freundlich and Temkin isotherm model. The experimental data were best represented by Freundlich isotherm model. Base on the estimated Freundlich constant (1/n=0.129~0.212) and Langmuir separation factor (R_{L}=0.202~0.243), this process could be employed as effective treatment method. The heat of adsorption of Temkin isotherm model was 5.101~9.164 J/mol indicated that the adsorption process followed a physical adsorption. Adsorption kinetics experimental data were modeled using the pseudo-first-order and pseudo-second-order kinetic equation. It was shown that pseudosecond-order kinetic equation could best describe the adsorption kinetics. Base on the negative Gibbs free energy (-4.81~-10.33 kJ/mol) and positive enthalpy (+78.59 kJ/mol) indicate that the adsorption is spontaneous and endothermic process.

입상 활성탄에 의한 Coomassi Brilliant Blue G의 흡착에 대한 평형, 동력학 및 열역학에 관한 연구

이종집(Jong-Jib Lee) 한국청정기술학회 2014 청정기술 Vol.20 No.3

본 연구에서는 활성탄을 사용하여 coomassi brilliant blue G (CBBG)염료를 흡착하는데 필요한 흡착평형과 흡착동역학 및 열역학 파라미터들에 대하여 조사하였다. 등온흡착평형관계로 부터 Langmuir 식과 Freundlich 식의 분리계수를 평가하여 활성탄에 의한 CBBG의 흡착조작이 유효한 처리방법이 될 수 있음을 알았고, Dubinin-Radushkevich 식으로부터 흡착공정이 물리흡착공정임을 알았다. 흡착공정에 대한 동력학적 해석을 통해 흡착반응은 유사이차반응속도식이 유사일차반응속도식에 비해 일치도가 높은 것으로 나타났으며, 입자내확산이 흡착공정의 지배단계임을 알았다. 유사이차반응속도식을 적용한 열역학적 해석을 통해 평가된 엔탈피 변화값(406.12 kJ/mol)으로부터 흡착공정이 흡열반응으로 진행됨을 알았다. 또한 엔트로피 변화값(1.66 kJ/mol K)은 흡착공정의 무질서도가 증가한다는 것을 나타내었다. 온도가 올라갈수록 자유에너지 값이 감소하는 경향을 보인 것은 활성탄에 대한 CBBG의 흡착반응은 온도가 올라갈수록 자발성이 높아지는 것으로 판단되었다. Batch adsorption studies were carried out for equilibrium, kinetics and thermodynamic parameters for adsorption of coomassi brilliant blue G (CBBG) using activated carbon with varying the operating variables like initial concentration, contact time and temperature. Equilibrium adsorption data were fitted into Langmuir, Freundlich and Dubinin-Radushkevich isotherms. From estimated separation factor of Langmuir and Freundlich, this process could be employed as effective treatment for removal of CBBG. Also from Dubinin-Radushkevich isotherm model, adsorption energy (E) indicated adsorption process is physical adsorption. From kinetic experiments, the adsorption reaction was found to confirm to the pseudo second order model with good correlation. Intraparticle diffusion was rate controlling step. Thermodynamic parameters like change of free energy, enthalpy, and entropy were also calculated to predict the nature of adsorption. The change of enthalpy (406.12 kJ/mol) indicated endothermic nature of the adsorption process. The change of entropy (1.66 kJ/mol K) showed increasing disorder in process. The change of free energy found that the spontaneity of process increased with increasing adsorption temperature.

석탄계 입상활성탄에 의한 Reactive Red 120의 흡착 특성 : 등온선, 동력학 및 열역학 파라미터

이종집 ( Jong Jib Lee ) 한국공업화학회 2020 공업화학 Vol.31 No.2

석탄계 활성탄을 사용한 Reactive Red 120 (RR 120) 염료의 흡착특성을 활성탄의 양, pH, 초기농도, 접촉시간 및 온도를 흡착변수로 사용하여 조사하였다. 등온흡착평형관계는 Langmuir 식이 Freundlich 식보다 더 잘 맞았다. 흡착 메카니즘은 균일한 에너지 분포를 가진 단분자층 흡착이 우세하다고 판단되었다. 평가된 Langmuir 분리계수(RL = 0.181~0.644)로부터 이 흡착공정이 효과적인 처리영역(RL = 0~1)에 속하는 것을 알았다. Temkin 식과 Dubinin-Radushkevich 식에 의해 구한 흡착에너지는 각각 E = 15.31~7.12 J/mol과 B = 0.223~0.365 kJ/mol로 흡착공정은 모두 물리흡착(E < 20 J/mol, B < 8 kJ/mol)으로 나타났다. 흡착속도실험결과는 유사 1차 반응속도식에 잘 맞았다. CGAC에 대한 RR 120 염료의 흡착반응은 온도가 올라갈수록 자유에너지 변화값이 감소하였기 때문에 온도 증가와 함께 자발성이 높아지는 것으로 나타났다. 엔탈피 변화(12.747 kJ/mol)는 흡열반응임을 알려주었다. CGAC에 의한 RR 120의 흡착반응의 등량흡착열은 9.78~24.21 kJ/mol로 물리흡착(< 80 kJ/mol)임을 밝혔다. Adsorption characteristics of reactive red 120 (RR 120) dye by a coal-based granular activated carbon (CGAC) from an aqueous solution were investigated using the amount of activated carbon, pH, initial concentration, contact time and temperature as adsorption variables. Isotherm equilibrium relationship showed that Langmuir's equation fits better than that of Freundlich’s equation. The adsorption mechanism was considered to be superior to the adsorption of monolayer with uniform energy distribution. From the evaluated Langmuir separation coefficients (R_L = 0.181~0.644), it was found that this adsorption process belongs to an effective treatment area (R_L = 0~1). The adsorption energy determined by Temkin's equation and Dubinin-Radushkevich’s equation was E = 15.31~7.12 J/mol and B = 0.223~0.365 kJ/mol, respectively. The adsorption process showed the physical adsorption (E < 20 J/mol and B < 8 kJ/mol). The adsorption kinetics followed the pseudo first order model. The adsorption reaction of RR 120 dye on CGAC was found to increase spontaneously with increasing the temperature because the free energy change decreased with increasing the temperature. The enthalpy change (12.747 kJ/mol) indicated an endothermic reaction. The isosteric heat of adsorption (△H_x = 9.78~24.21 kJ/mol) for the adsorption reaction of RR 120 by CGAC was revealed to be the physical adsorption (△H_x < 80 kJ/mol).