2단의 슬러지-고정상 반응기에서 페놀 함유 폐수의 혐시성 처리에 관한 연구

정종식,안재동,박동일,신승훈,장인용 한국환경보건학회 1995 한국환경보건학회지 Vol.21 No.4

This study was carried to investigate the biodegradability of phenol in the wastewater with the two sludge blanket-packed bed reactor in series. Each reactor had a dimension of 0.09 m i.d. and 1.5 m height and consisted of two regions. The lower region was a sludge blanket of 0.5 m height and the upper region was a packed-bed of 1 m height. The packed bed region was charged with ceramic raschig rings of 10 mm i.d., 15 mm o.d. and 20 mm length. The reactors were operated at 35$\circ$C and the hydraulic retention time(HRT) was maintained 24 hours. The synthetic wastewater composed of glucose and phenol as major components was fed into the reactor in a continuous mode with incereasing phenol concentration. In addition, the nutrient trace metals($Na^+, Mg^{2+}, Ca^{2+}, PO_4^{3-}, NH_4^+, Co^{2+}, Fe^{2+}$ etc.) were added for growing anaerobes. The phenol concentration of the effluent, the overall gas production, the composition of product gas, the efficiency of COD reduction and the duration of acclimation period were measured to determine the performance of the anaerobic wastewater treatment system as the phenol concentration of the influent was increased from 600 to 2400 mg//l. Successfully stable biodegradation of phenol could be achieved with the anaerobic treatment system from 600 to 1, 800 mg/l of the influent phenol concentration. The upper level of influent phenol loading was high enough to meet most of the practical requirement. The duration of acclimation increased with the phenol loading. At steady state of the influent phenol concentration of 1800 mg/l, the treatment performance indicated the phenol reduction efficiency of 99%, the COD reduction efficiency of 99% and the gas production rate of 37 l/day. At the influent phenol concentration of 2400 mg/l, however, the operation of the treatment system was noted unstable. While the concentration of methane in biogas decreased with increasing the influent phenol loading, the carbon dioxide was increased. However, the concentration of hydrogen was varied negligibly. The concentration of methane was high enough to be used as a fuel. As a result, it is suggested that anaerobic phenol wastewater treament was economical in the sense of energy recovery and wastewater treatment.

유근피(Ulmus pumila)로부터 분리한 phenol성 물질의 건강기능식품 활성

김경범 ( Kyung Bum Kim ),조분성 ( Bun Sung Jo ),박혜진 ( Hye Jin Park ),박기태 ( Ki Tae Park ),안봉전 ( Bong Jeun An ),안동현 ( Dong Hyun Ahn ),김명욱 ( Myung Uk Kim ),채정우 ( Jung Woo Chae ),조영제 ( Young Je Cho ) 한국식품저장유통학회(구 한국농산물저장유통학회) 2012 한국식품저장유통학회지 Vol.19 No.6

유근피에 함유된 페놀성 물질은 70% ethanol을 용매로 하여 12시간 추출하였을 때 17.9±1.0 mg/g으로 가장 많이 용출되었다. 유근피 추출물의 항산화력을 측정한 결과 전자공여능은 50 μg/mL 이상의 phenolic 농도에서 물추출물과 70% ethanol 추출물 모두에서 80% 이상의 높은 전자공여 능이 확인되었다. ABTS radical cation decolorization을 측정한 결과 유근피는 물과 70% ethanol 추출물에서 96.8±2.9%의 높은 항산화활성이 측정되었으며, antioxidant protection factor 측정에서는 물추출물과 에탄올 추출물 모두 200 μg/mL의 phenolic 농도에서 BHA 보다 높은 2.5 PF의 높은 항산화력이 확인되었다. 유근피 추출물의 thiobarbituric acid reactive substance를 측정한 결과 물 추출물과 에탄올 추출물 전 농도에서 약 80%의 높은 항산화 효과를 나타내었다. 유근피 추출물의 항고혈압 효과를 살펴보기 위하여 angiotensin converting enzyme 저해활성을 측정한 결과 물 추출물에서 약 50%, 70% ethanol 추출물에서 58.5%의 저해 활성을 나타내었으며, 200 μg/mL phenolics의 처리농도에서 물 추출물이 77.4%, 70% ethanol 추출물에서 90.6%의 저해활성을 나타내었다. 유근피 추출물의 항관절염 효과를 살펴보기 위하여 xanthin oxidase 저해 활성을 측정한 결과 물 추출물에서는 억제 효과를 관찰할 수 없었고, 70% ethanol 추출물에서 30%의 억제효과를 나타내었으며, 200 μg/mL phenolics의 처리 농도에서 48.1%의 억제력을 나타내었다. 유근피 추출물의 염증 억제효과를 측정하기 위하여 hyaluronidase 저해활성을 확인한 결과 물 추출물과 ethanol 추출물에서 70% 이상의 높은 저해 양상을 나타내었으며, 50 μg/mL phenolics의 낮은 농도로 처리하였을 경우에도 80%의 항염증효과를 나타내었고, 처리한 phenolic compound의 농도가 높아질수록 억제효과가 높아져 농도 의존적인 양상을 나타내었다. 기능성 식품으로의 활용을 위한 방안으로 유근피 추출물을 함유한 tablet(정제)를 개발하고, 개발된 제품의 관능평가를 실시한 결과 색깔의 관능평점이 8.3으로 평가되었고, 맛과 향은 8.8과 8.6의 높은 관능평가 점수를 획득하였으며, 전체적인 기호도 역시 8.7점으로 높은 평가를 받았다. The phenolic compounds which were extracted with 70% ethanol from Ulmus pumila for 12 hr were the highest as 17.9±1.0 mg/g. DPPH scavenging activity of 70% ethanol extracts was also the highest as 89.5±1.9% and it was confirmed to be high as 80% over in both of water and 70% ethanol extracts containing 50 μg/mL over phenolic concentration. ABTS radical cation decolorization activities of water and 70% ethanol extracts were higher as 96.8±2.9%, antioxidant protection factor (PF) was 2.0 PF in 70% ethanol and showed higher activities in both of water and 70% ethanol extracts containing 200 μg/mL phenolic concentration as 2.5 PF than BHA. TBARs of 70% ethanol extracts was 86.5±4.6%, it showed high anti-oxidative activity in 50∼200 μg/mL phenolic concentrations of water and 70% ethanol extracts as 80% over. The angiotensin converting enzyme (ACE) inhibitory activity of Ulmus pumila extracts against hypertension was 77.4% and 90.6% in water and 70% ethanol extracts of 200 μg/mL phenolic concentration. Xanthine oxidase inhibitory activity of Ulmus pumila extracts for anti-gout effect was not observed in water extracts, but it showed 30% inhibitory activity in 70% ethanol extracts, and 48.1% at 200 μg/mL phenolics concentration.

페놀 노출 근로자의 요중 페놀농도에 영향을 미치는 요인

심규진(Gyu Jin Shim),노재훈(Jaehoon Roh),김치년(Chinyon Kim),이신영(Shinyoung Lee),원종욱(Jong Uk Won) 한국실내환경학회 2011 한국실내환경학회지 Vol.8 No.2

Objectives : The purpose of this study is to identify the characteristics that affect the urinary phenol of workers exposed to phenol. Subjects and Methods : Total 41 workers were selected at bisphenol A manufacturing plant and their urinary phenol concentration were measured before and after work along with the phenol concentration in the workplace air, and carried out a survey on work characteristics and lifestyle factors that could affect urinary phenol. Results : The phenol concentration in air during work hours was 0.91 (non-detection~2.88) ㎎/㎥, and the worker’s urinary phenol concentrations before and after work were 100.27±75.76 and 138.13±109. 58 ㎎/g creatinine, respectively, which showed a statistically significant increase. Comparing smoking and urinary phenol concentration, smokers had 194.54±137.52 ㎎/g creatinine while non-smokers had 108.88±80.10 ㎎/g creatinine, thus showing the urinary phenol concentration of smokers to be statistically significantly higher (p=0.046). The urinary phenol concentration increased as work hours, the frequency of skin exposure to phenol, and the amount of drinking increased, and there were differences in its concentration depending on the work type and whether or not workers wore protective gear. The results of carrying out a multiple regression analysis showed that phenol concentration in air, work hours, frequency of skin exposure, and smoking were statistically significant. In other words, the urinal phenol concentration increased more for smokers than for non-smokers, when work hours became longer, and when the frequency of skin exposure was over five times. Conclusions : The factors that influenced urinary phenol in workers exposed to phenol were phenol concentration in air, work hour, frequency of skin exposure, smoking, work and lifestyle habits. Accordingly, biological monitoring for phenol exposure assessment must reflect these factors, and effort must be made to reduce skin exposure at workplace.

Phenol 분해균주의 분리 및 페놀함유 폐수의 생물학적 처리

이현돈(Hyun Don Lee),이명은(Myoung Eun Lee),김형갑(Hyung Gab Kim),서현효(Hyun-Hyo Suh) 한국생명과학회 2013 생명과학회지 Vol.23 No.10

방향족화합물들로 오염되어있는 토양 및 산업폐수를 포함한 각종 시료로부터 phenol에 분해활성이 높은 56균주를 순수분리 하였으며, 이들 분리 균주 중 균체생육과 phenol 분해활성이 가장 높은 균주인 GN13을 선별하였다. 분리균주 GN13은 형태학적, 생리학적 및 생화학적 특성을 조사한 결과 Neisseria 속 세균과 유사한 것으로 판명되어 최종적으로 Neisseria sp. GN13으로 명명하였다. 분리균주 Neisseria sp. GN13의 균체생육 및 phenol 분해를 위한 최적온도와 최적 pH는 각각 32℃와 7.0였다. 유일 탄소원으로 phenol 1,000 mg/l를 포함하여 최적화된 배지를 사용한 jar-fermentor 배지에서 배양 30시간에 균체생육이 최대에 이르렀으며 배양 27시간째 거의 모든 phenol이 분해되었으며, catechol deoxygenase 활성측정에 의하여 Neisseria sp. GN13은 meta-와 ortho-pathway를 통하여 catechol 분해가 일어났다. Neisseria sp. GN13은 phenol 함유 인공폐수에서의 phenol 분해율은 배양 30시간 만에 97%의 phenol이 분해되는 것으로 나타났으며, 인공폐수에 대한 Neisseria sp. GN13과 활성슬러지 처리구에서의 TOC 제거효율은 각각 83%와 78%였다. 석유화학폐수에 대한 Neisseria sp. GN13의 COD 제거율은 활성슬러지만을 포함한 대조구보다 약 1.3배 높은 효율을 나타내었다. 이러한 결과로 미루어 분리균주 Neisseria sp. GN13은 phenol을 함유하고 있는 여러 폐수에 효과적으로 적용될 수 있을 것으로 생각된다. Aromatic hydrocarbons, such as phenol, have been detected frequently in wastewater, soil, and groundwater because of the extensive use of oil products. Bacterial strains (56 isolates) that degraded phenol were isolated from soil and industrial wastewater contaminated with hydrocarbons. GN13, which showed the best cell growth and phenol degradation, was selected for further analysis. The GN13 isolate was identified as Neisseria sp. based on the results of morphological, physiological, and biochemical taxonomic analyses and designated as Neisseria sp. GN13. The optimum temperature and pH for phenol removal of Neisseria sp. GN13 was 32°C and 7.0, respectively. The highest cell growth occurred after cultivation for 30 hours in a jar fermentor using optimized medium containing 1,000 mg/l of phenol as the sole carbon source. Phenol was not detected after 27 hours of cultivation. Based on the analysis of catechol dioxygenase, it seemed that catechol was degraded through the meta- and ortho-cleavage pathway. Analysis of the biodegradation of phenol by Neisseria sp. GN13 in artificial wastewater containing phenol showed that the removal rate of phenol was 97% during incubation of 30 hours. The removal rate of total organic carbon (TOC) by Neisseria sp. GN13 and activated sludge was 83% and 78%, respectively. The COD removal rate by Neisseria sp. GN13 from petrochemical wastewater was about 1.3 times higher than that of a control containing only activated sludge.

문신용 염료에 들어 있는 유해화학물질(페놀)의 인체 위해성 평가

조삼래,김경희,최재욱 한국환경보건학회 2019 한국환경보건학회지 Vol.45 No.1

Objectives: This study examined the safety of tattoo ink by analyzing the phenol contents in tattoo inks and its risk assessment of selected phenol. Methods: A sample of 30 tattoo inks was purchased, the phenol contents were analyzed, and a risk assessment on dermal exposure from tattooing was carried out. Hazard identification was collected from toxicity data on systemic effects caused by dermal exposure to phenol, and the most sensitive toxicity value was adopted. Exposure assessment (Exposure phenol ) was calculated by applying phenol contents and standard exposure factors, while dose-response assessment was based on the collected toxicity data and skin absorption rate of phenol, assessment factors (AFs) for derived no-effect level (DNEL demal ). In addition, the risk characterization was calculated by comparing the risk characterization ratio (RCR) with Exposure phenol and DNEL dermal Results: The phenol concentration in the 30 products was from 1.4 to 649.1 µg/g. The toxicity value for systemic effects of phenol was adopted at 107 mg/kg. Exposure phenol in tattooing was from 0.000087 to 0.040442 mg/kg. DNEL dermal was calculated at 0.0072 mg/kg (=toxicity value 107 mg/kg ÷ AFs 650 × skin absorption rate 4.4%). Thirteen out of 30 products showed an RCR between 1.02 and 5.62. The RCR of all red inks was above 1. Conclusions: Phenol was detected in all of the 30 tattoo inks, and the RCR of 13 products above 1 indicates a high level of risk concern, making it necessary to prepare safety management standards for phenol in tattoo inks.

Zr(OH)4를 사용하여 제조한 SO42-/ZrO2 촉매상에서 Phenol과 Styrene으로부터 Styrenated Phenols의 합성

윤현준,조장호,권용철,곽원봉,정성훈,정민철,안호근 한국환경기술학회 2017 한국환경기술학회지 Vol.18 No.1

Styrenated phenols(SPs) are an important raw material of a surfactant for preparing a developing solution of LCD panel. Homogeneous catalyst is mainly used in the SPs synthesis, but the unreacted phenol that can adversely affect the human body is contained in the SPs. In this study, SPs involving very small amount of unreacted phenol and high content of di-styreated phenol(DSP) were synthesized, which can be used to prepare styrenated phenol alkoxylate. The solid SO42-/ZrO2 catalyst was prepared by impregnation method with using Zr(OH)4. SO42- on the catalyst was introduced from an aqueous 1M-H2SO4 solution. The catalysts were characterized by XRD patterns and FT-IR spectra. The catalytic activity was examined by measuring conversion of phenol and styrene in a batch liquid-phase reactor. From XRD patterns, it was confirmed that the crystalline of ZrO2 with a mixture of monoclinic and tetragonal phases was formed by the sulfation of Zr(OH)4 with sulfuric acid solution. FT-IR spectra showed the presence of 1,075 cm-1 and 1,202 cm-1 peaks due to the asymmetric vibration of O-S-O bonds. In synthesis reaction of SPs, selectivity of mono- styrenated phenol(MSP) was decreased while selectivity of tri-styrenated phenol(TSP) was increased with increasing concentration of sulfuric acid solution. Selectivity of DSP was decreased when amount of catalyst was increased. With increasing reaction temperature, selectivity of MSP was decreased, and the selectivity of DSP and TSP was kept to be constant from at reaction temperature of 80℃ and 100℃, respectively. As the results, the optimum synthesis conditions for concentration of sulfuric acid solution, catalyst amount of reactants, reaction temperature over SO42-/ZrO2 catalyst, and reaction time were 5 wt%, 3 wt%, 80℃, and 6 hr, respectively. At these conditions conversion of both phenol and styrene were almost 100%, and the selectivity of MSP, DSP, and TSP was 18.3%, 63.5%, and 18.1%, respectively. LCD 패널 현상액의 주요한 원료로 사용되어지는 계면활성제의 출발물질인 styrenated phenol(SP)을 합성하고자 하였다. 현재 SP합성에는 균일촉매가 사용되고 있으나, 생성물에 잔류 phenol이 함유되어 있어 인체에 악영향을 줄 수 있다. 본 연구에서는 고체촉매를 사용하여 잔류 phenol의 함량이 매우 적으며, SP 혼합물 내 di-styrenated phenol(DSP)의 함량이 높은 SP 혼합물을 합성하고자 하였다. 사용한 고체촉매는 SO42-/ZrO2이었는데, SO42-이온은 1M-H2SO4 수용액에 담체인 Zr(OH)4를 넣고 교반함으로써 담지하였다. 제조한 촉매의 특성은 XRD 패턴과 FT-IR 스펙트럼을 통하여 조사하였다. SPs 합성에 대한 촉매의 활성은 회분식 액상반응장치를 이용하여 조사하였다. XRD 패턴 분석결과, Zr(OH)4를 황산 수용액으로 처리한 후 소성하면 단사정계와 정방정계 결정구조가 혼합된 ZrO2로 변함을 알 수 있었다. FT-IR 스펙트럼에서 O-S-O결합에 의한 비대칭 진동 흡수피크가 1,075 cm-1와 1,202 cm-1에서 나타났으며, 황산 수용액의 처리농도가 증가할수록 1,075 cm-1의 흡수피크가 강하게 나타났다. SPs 합성반응에서 처리한 황산 수용액의 농도가 증가할수록 mono- styrenated phenol(MSP)는 감소하고 tri-styrenated phenol(TSP)은 증가하는 경향을 나타냈다. 촉매량이 증가할수록 DSP는 감소하는 경향을 보였다. 또한, 반응온도가 증가할수록 MSP는 감소하며, DSP와 TSP는 각각 80℃와 100℃부터 일정한 값을 유지하였다. 최적 합성조건은 담체 대비 황산 수용액의 처리농도 5 wt%, 반응물 대비 촉매량 3 wt%, 반응온도 80℃, 반응시간 6시간이었다. 이 때 phenol과 styrene의 전화율은 모두 거의 100%이었으며, MSP, DSP 그리고 TSP의 선택율은 각각 18.3%, 63.5% 그리고 18.1%이었다.

제비고깔(Delphinium grandiflorum)꽃 추출물의 항산화, 항염증, 피부 주름 생성 억제 및 모공축소 효과

김다현,김유경,김희연,김희인,김종석,박혜진,조영제 한국식품영양과학회 2023 한국식품영양과학회지 Vol.52 No.8

Several phenolic compounds obtained from plants exert good biological activities. Delphinium grandiflorum flowers have been used for the prevention or treatment of cancer and osteoporosis. This study examines the antioxidantive and biological enzyme activities of phenolic compounds present in Delphinium grandiflorum flower extracts. Total phenol contents were evaluated using the Folin-Ciocalteu method. Antioxidant activities were determined by measuring DPPH, antioxidant protection factor, ABTS+, and TBARS. We further evaluated inhibitory activity against hyaluronidase, elastase, collagenase and astringent effect. DPPH scavenging activity was determined to be 90.07% and 100% and the ABTS radical scavenging activity was 99.54% and 100% in water and ethanol extract containing 100 μg/mL phenols, respectively. The PF activity confirmed high antioxidant effects at 1.26 PF and 1.27 PF, whereas the TBARs inhibitory activity was 24.05% and 69.55%, in water and ethanol extract, respectively. Examining the inhibitory effects of elastase and collagenase for wrinkle improvement revealed an inhibition rate of 41.21% and 82.58%, respectively, at a phenolics concentration of 400 μg/mL in 70% ethanol extract. Hyaluronidase is known to induce an inflammatory effect. Hyaluronidase inhibitory rates of 24.52% and 16.81% were obtained at 400 μg/mL phenolics concentrations of water and ethanol extract, respectively. The astringent effect showed an activity of 44.82% at a concentration of 400 μg/mL phenolics in the 70% ethanol extract. These results indicate the potential of the DGF extract to be applied as a functional cosmetic and beauty food resource imparting antioxidant, anti-inflammatory, anti-wrinkle and pore-reducing effects. 제비고깔꽃 추출물의 페놀 화합물 함량을 정량한 결과, 70% 에탄올 추출물에서 13.38±0.38 mg/g, 물 추출물에서 13.37 ±0.64 mg/g으로 가장 높게 나타났다. 제비고깔꽃 유래의 고형분(solid)과 추출물(phenolics)의 생리활성을 비교하기 위하여 동일한 농도인 100 μg/mL로 제조하여 생리활성을 비교한 결과, phenolics의 경우 물 추출물과 70% 에탄올 추출물 모두 DPPH와 ABTS 라디칼 소거능이 동일 농도의 고형분에 비해 각각 4배, 10배 정도 높은 것으로 확인되었다. 따라서 제비고깔꽃 추출물의 생리활성은 추출물에 함유된 phenolics에서 기인하는 것으로 판단하였다. 제비고깔꽃 추출물 100 μg/mL phenolics 농도에서 나타내는 항산화 효과 중 DPPH 라디칼 소거 활성은 물 추출물과 에탄올 추출물에서 각각 90.07%와 100.00%, ABTS 라디칼 소거능은 각각 99.54%와 100.00%, antioxidant protection factor는 각각 1.26 PF와 1.27 PF를 나타내었으며, TBARS 활성 저해능은 각각 24.05%와 69.55%를 나타내어 높은 항산화 효과를 나타내는 것으로 판단되었고 항산화 효과들은 phenolics 함량 증가에 따라 농도 의존적으로 효과가 높아지는 것으로 확인되었다. 또한, 주름개선 효과를 나타내는 elastase와 collagenase 억제 효과를 살펴본 결과, elastase 억제 효과는 70% 에탄올 추출물 400 μg/mL phenolics 농도에서 41.21%의 저해율을 나타내었으며, 동일 농도에서 collagenase 저해 효과는 82.58%의 저해율을 나타내어 매우 우수한 주름생성 억제 효능을 나타내는 것으로 확인되었다. 모공축소 효과를 나타내는 수렴 효과는 70% 에탄올 추출물 400 μg/mL phenolics 농도에서 44.82%의 활성을 나타내었으며, 염증 억제 효과를 나타내는 hyaluronidase 억제 효과는 물 추출물과 70% 에탄올 추출물 400 μg/mL phenolics 농도에서 각각 24.52%와 16.81%의 저해율을 나타내었다. 이상의 결과로 제비고깔꽃 추출물은 항산화, 항염증, 주름개선 및 모공축소 효과를 얻을 수 있는 기능성 화장품 원료 및 미용식품 소재로의 활용이 가능할 것이라 판단되었다.

세라믹담체를 이용한 페놀계 산업폐수의 생물학적 처리

오희목,구영환,안극현,장감용,고영희,권기석,윤병대 한국산업미생물학회 1995 한국미생물·생명공학회지 Vol.23 No.6

고농도의 phenol과 formaldehyde를 주성분으로 하는 phenol계 산업폐수를 단계적으로 희석하면서, 혼합균주인 GE2와 세라믹담체를 적용하여 80일간에 걸쳐 생물학적으로 처리하였다. 실험구는 제지폐수 슬러지로 30일간 회분식 운전에 의해 적응시킨 대조구, 이것에 GE2를 첨가한 GE2 처리구 그리고 세라믹담체를 적용한 세라믹처리구로 구분하였다. 원폐수의 80배 희석으로 유입수의 COD_Mn이 1,140mg/l 인 경우 각 실험구의 유출수 COD_Mn은 22∼35mg/l로 큰 차이가 없었으나, 20배 희석의 경우 유입수의 COD_Mn이 4,800mg/l일 때, 대조구, GE2 처리구 그리고 세라믹처리구의 유출수 COD_Mn은 179, 128 그리고 94mg/l로서 세라믹처리구의 처리효율이 98.0%로 가장 높았다. 이때 유출수의 phenol 농도는 각기 10.71, 7.93 그리고 5.60mg/l으로 GE2 및 세라믹담체의 적용에 의하여 처리효율이 향상되었다. 한편, 희석배율이 낮아짐에 따라 COD_Mn과 phenol 처리효율에는 큰 변화가 없으나, 유출수의 COD_Mn과 phenol농도가 높아졌다. 따라서, 원폐수를 40배 희석하여 GE2와 세라믹담체를 첨가하여 처리할 경우 유출수의 COD_Mn과 phenol 농도가 32와 1.02mg/l로 수계의 방류수 수질기준에 충분히 적합한 생물학적 처리로 사료된다. A phenolic resin industrial wastewater containing about 41,000 mg/l of phenol and 2,800 mg/l of formaldehyde was biologically treated by a mixed culture GE2 immobilized on ceramic beads. This study was carried out with three experimental groups : Control-only added the sludge of papermill wastewater ; GE2 treatment-added GE2 to Control ; Ceramic treatment-applied ceramic carrier to GE2 treatment. When the original wastewater was diluted 80 times with aerated tap-water, influent COD_Mn was 1,140 mg/l and that of the effluent was in the range of 22∼35 mg/l, which was not much different among the experimental groups. However, at 20-times dilution, influent COD_Mn was 4,800 mg/l and the effluent COD_Mn of control, GE2 treatment and Ceramic treatment was 179, 128 and 94 mg/l, respectively. COD_Mn removal efficiency by Ceramic treatment was the highest, at 98.0%. At this time, the effluent phenol concentration of Control, GE2 treatment and Ceramic treatment was 10.71, 7.93 and 5.60, respectively. As the dilution times decreased, the removal efficiency of COD_Mn and phenol did not change much, but COD_Mn and phenol concentration of the effluent increased. Consequently, it is likely that the phenolic industrial wastewater containing phenol and formaldehyde can be biologically treated using a GE2 and ceramic carrier and that at 40-times dilution, the effluent completely meets the effluent standards for industrial wastewater treatment plant.

Derivatezation 방법과 GC/MS를 이용한 농업용수 중 phenol에 대한 분석 방법 확립

박선영 ( Sun-young Park ),김윤정 ( Yun-jeong Kim ),정성진 ( Sung-jin Jung ),김희갑 ( He-kap Kim ) 한국환경농학회 2016 한국환경농학회 학술대회집 Vol.2016 No.-

국내 수질환경기준에서는 물 중 phenol을 유해영향 유기물질로 분류하고 있으며, 농업용수에 대한 규제를 5 μg/L 이하의 수준으로 정하고 있다. 하지만 환경부에서 고시한 수질오염공정시험법에서는 페놀류 (phenols)에 대한 분석 방법만을 언급하고 있다. 이 phenols 시험법은 물 중의 phenol뿐만 아니라 기타 phenols의 총량을 측정하는 흡광광도법이므로 농업용수 중 phenol의 정확한 농도를 알 수가 없으며, 실제로 이 분석 방법으로 측정한 대부분의 자연수에는 아직까지도 불검출로 표기되고 있다. 해외의 사례에서는 자연수 중 phenol은 대부분 수 μg/L 수준으로 존재하며, 기존의 분석 방법으로 phenol 분석의 방법검출한계는 solid-phase extraction(SPE, 고상 추출) 방법을 이용 시 10-40 ng/L, liquid-liquid extraction(LLE, 액-액 추출) 방법을 이용할 경우 수 μg/L 수준으로 추정되었다. 따라서 이 연구에서는 농업용수 중 phenol을 유도체화한 후 액-액 추출하여 GC/MS로 정량분석하는 방법을 확립함으로써 기존의 방법들보다 정확하고 신뢰성있는 분석 방법을 개발하고자 하였다. pH 2까지 조절된 50 mL 물 시료를 50 mL ethyl acetate와 separatory funnel에 옮겨 담아 액-액 추출한 후, ethyl acetate 층을 모두 회수하여 약 1 g sodium sulfate anhydrous으로 잔류 수분을 제거하였다. 그 후 원심분리관에 옮겨 ethyl acetate를 모두 농축한 후 다시 1 mL deionized water를 첨가하여 유도체화 과정을 진행하였다. 유도체화 과정은 해당 농축액에 5% K2CO3을 0.5 mL 및 100 μL acetic anhydride를 첨가하여 10분동안 정치하였다. 그 후 1mL butyl acetate로 다시 액-액 추출한 후 GC/MS로 분석하였다. 농축액은 Agilent DB-WAX(30 m × 0.25 mm × 0.25 μm) column을 사용하여 GC/MS(EI mode)로 분석하였다. 분석 방법의 검증을 위해 quality assurance/quality control(QA/QC, 정도보증/정도관리)를 실시하였다. 물 시료 중 phenol의 농도 범위를 고려하여 1-10 μg/L 범위에서(n = 5) 검량선을 작성한 결과 양호한 직선성(linearity)을 보였고, 그 결정계수는(R2)는 0.9968이었다. 분석의 반복성은 상대표준편차(relative standard deviation, RSD)로 평가한 결과 4.3-9.1%의 반복성을 나타내 매우 양호한 결과를 나타내었으며 회수율은 90.6-110.5%으로 산정되어 매우 양호한 정확성을 나타내었다. 방법검출한계(method detection limit, MDL) 및 정량한계(limit of quantification, LOQ)는 각각 0.21 및 0.66 μg/L로 추정되어 현재 방법으로도 목표 수준보다 더 낮은 수준의 phenol까지 검출할 수 있음을 보여주었다. 강원도 강릉 및 동해 일대의 농업용수를 분석한 결과, phenol의 농도는 1.92-7.51 μg/L(n = 10) 범위였으며 최대 7.51 μg/L으로 검출되어 규제 농도보다 다소 높은 것을 확인하였다. 이는 기존의 phenols 분석법보다 더 낮은 검출한계로 분석이 가능하며, phenols의 총량이 아닌 phenol 만을 정확하게 정량을 할 수 있었다.

SO42-/ZrO2 촉매상에서 스티렌에 의한 페놀의 알킬화에 관한 연구

윤현준,이영호,손석환,정민철,장미경,곽원봉,정성훈,안호근 한국환경기술학회 2015 한국환경기술학회지 Vol.16 No.6

Surfactants are an important raw material of the developing solution for liquid crystal display panel. Styrenated phenol in styrenated phenol alkolxylate is a hydrophobic group. Homogeneous catalyst is used in the current SPs synthesis. But this SP contained unreacted phenol. The phenol can adversely affect the human body. In this study, we were synthesized styrenated phenols (SPs) involving high content of di-styrenated phenol (DSP) which can be used to prepare styrenated phenol alkoxylate. And this styrenated phenol contained very small contents of unreacted phenol. The solid catalyst was prepared by impregnation method. SO42- on SO42-/ZrO2 catalyst was introduced from an aqueous 1M-H2SO4 solution. The contents of sulfate groups of the prepared catalyst were 5-15wt% to ZrO2. The prepared catalyst was dried at 110℃ for 12hr, and was calcined for 2hr at 600℃ under air atmosphere. The catalysts were characterized by BET surface area, X-ray diffraction patterns, and FT-IR spectra. The catalytic activity was examined by measuring the conversion of phenol and styrene in a batch liquid-phase reactor. The concentration of phenol, styrene and styrenated phenols was measured by GC with capillary column. Almost 100% conversion of both phenol and styrene over SO42-/ZrO2 catalyst with sulfate contents of 15wt% were obtained at 15wt% of amount of catalyst to the reactants at reaction temperature of 100℃. Reaction time was 6hr. At same reaction conditions, selectivity of MSP, DSP, and TSP were 23.6%, 52.1%, and 5.4%, respectively. It was known that selectivity to DSP was increased as FT-IR absorption peak of 1236 ㎝-1 which corresponds to O-S-O bonds was increased. LCD 패널의 컬러 필터와 박막 트랜지스터용 현상액의 주요한 원료로 사용되어지는 계면활성제를 개발하기 위해, 계면활성제의 출발물질인 styrenated phenol(SP)을 합성하고자 하였다. 현재 SP합성에는 균일촉매가 사용되고 있으나, 생성물에 미반응된 페놀이 함유되어 있어 인체에 악영향을 줄 수 있다. 본 연구에서는 미반응된 페놀의 함량이 매우 적으며, SP혼합물들 중에서 di-styrenated phenol의 함량이 높은 SP혼합물을 합성하고자 하였다. 사용한 촉매는 SO42-/ZrO2촉매로, SO42-이온은 1M-H2SO4 수용액에 담제를 넣고 교반함으로써 담지하였다. 담지 후 110℃에서 12시간 건조 시킨 다음, 600℃에서 2시간 소성하여 SO42-/ZrO2촉매를 제조하였다. 제조한 촉매에 대한 물성을 파악하기 위하여 BET 및 XRD 분석을 수행하였으며, 촉매표면의 SO42- 존재 여부를 알아보기 위해 FT-IR 분석을 수행하였다. 제조한 촉매의 활성을 알아보기 위하여 회분식 액상반응장치를 이용하였다. 반응물의 전화율과 생성물의 선택율은 GC를 이용하여 분석하였다. 반응물 대비 촉매량 15wt%, 반응온도 100℃, 황산 담지량은 담체 대비 15wt%, 반응시간 6시간 일 때, 페놀과 스티렌의 전화율은 모두 거의 100%이었으며, 동일조건에서 MSP, DSP 그리고 TSP의 선택율은 각각 23.6%, 52.1% 그리고 5.4%이었다. DSP의 선택율은 O-S-O 결합에 해당하는 1236 cm-1 에서의 흡수 peak가 강할수록 증가함을 알 수 있었다.