본 연구에서는 해수를 유도용액으로 사용하고 하수처리수를 공급수로 사용하는 정삼투막 공정의 유기/바이오 오염물에 의한 막오염을 저감하기 위해 폴리도파민/탄소 나노 튜브 복합 분리막을 제작하였다. 분리막은 기존 계면중합반응에 탄소 나노 튜브를 첨가하여 초박형 복합 분리막을 제조한 후, 폴리도파민으로 코팅시켜 제조하였다. 제작 된 분리막은 알긴산나트륨(Sodium alginate)용액과 미생물(Pseudomonas aeruginosa PA01) 부착 실험을 통하여 수투과도와 막오염도를 평가하였다. 그 결과, 폴리도파민/탄소 나노 튜브 복합 분리막은 복합되지 않은 분리막에 비하여 높은 수투과도와 낮은 막오염 성능을 보였다.

In this study, various physical cleaning methods such as physical washing and osmotic backwash, were conducted to understand membrane fouling properties by employing real secondary wastewater effluent (SWWE). In addition, microfiltration (MF) and ultrafiltration (UF) pretreatments were compared to maximize removal of organic matter and to control membrane fouling efficiently. Organic foulants deposited on the active layer of FO membrane were observed by fouling behavior test. The relationship between concentrations of natural organic matter and membrane fouling was also investigated from the bench-scale FO tests.

In this study, the effects of operating conditions on the formation of reversible and irreversible fouling were investigated in the filtration using ceramic membrane for water treatment process. The effect of coagulation pretreatment on fouling formation was also evaluated by comparing the performance of membrane filtration both with and without addition of coagulant. A resistance-in-series-model was applied for the analysis of membrane fouling. Total resistance (RT) and internal fouling resistance (Rf) increased in the membrane filtration process without coagulation as membrane flux and feed water concentrations increased. Internal fouling resistance, which was not recovered by physical cleaning, was more than 70% of the total resistance at the range of the membrane flux more than 5 m3/m2･day. In the combined process with coagulation, the cake layer resistance (Rc) increased to about 30-80% of total resistance. As the cake layer formed by coagulation floc was easily removed by physical cleaning, the recovery rate by physical cleaning was 54~90%. It was confirmed from the results that the combined process was more efficient to recover the filtration performance by physical cleaning due to higher formation ratio of reversible fouling, resulted in the mitigation of the frequency of chemical cleaning.

고분자 재질의 압력 구동 기반 분리막을 이용하여 담수를 얻기 위한 공정은 에너지 효율이 높은 방법으로 알려져 있다. 하지만, 분리막 운전 중에 투과성능을 떨어트리는 막 오염 문제가 발생 하기에, 막 오염을 제어하는 것은 분리막 공정의 에너지 효율을 높이는 데 필수적이다. 막 오염은 일반적으로 분리막 표면과 막 오염 물질과의 상호 작용으로 발생하며, 분 리막 표면을 개질하는 방법은 막 오염을 방지하여 높은 투과 특성을 지속적으로 유지하게 할 수 있는 좋은 방법 중 하나이다. 본 논문에서는 압력 구동 기반 분리막인 미세여과, 한외여과, 나노여과 및 역삼투용 분리막의 표면을 개질할 수 있는 방법을 정리하였다. 구체적인 개질 방법으로는 개질 물질의 흡착 및 코팅 방법인 물리적 방법과 가교제 이용, 자유 라디칼 중합 (FRP), 원자 이동 라디칼 중합(ATRP), 플라즈마 및 자외선 조사 기반 중합인 화학적 방법으로 나누어 정리하였다. 본 총설에서는 최근 논문상에 보고되고 있는 물리화학적 표면 개질 방법을 소개하고, 막 오염 저항성을 높일 수 있는 분리막 제조를 위한 연구방향을 제시하고자 한다.

In water treatment process using microfiltration membranes, manganese is a substance that causes inorganic membrane fouling. As a result of analysis on the operation data taken from I WTP(Water Treatment Plant), it was confirmed that the increase of TMP was very severe during the period of manganese inflow. The membrane fouling fastened the increase of TMP and shortened the service time of filtration or the cleaning cycle. The TMP of the membrane increased to the maximum of 2.13 kgf/cm2, but it was recovered to the initial level (0.17 kgf/cm2) by the 1st acid cleaning step. It was obvious that the main membrane fouling contaminants are due to inorganic substances. As a result of the analysis on the chemical waste, the concentrations of aluminum(146-164 mg/L) and manganese(110-126 mg/L) were very high. It is considered that aluminum was due to the residual unreacted during coagulation step as a pretreatment process. And manganese is thought to be due to the adsorption on the membrane surface as an adsorbate in feed water component during filtration step. For the efficient maintenance of the membrane filtration facilities, optimization of chemical concentration and CIP conditions is very important when finding the abnormal level of influent including foulants such as manganese.

In this work, we studied systematically the effects of NCIF on defouling for a range of solutes that foul (BSA protein) and form cakes (alumina colloids) on the membrane thereby causing severe reduction in the flux. Changing the gravitational orientation of the batch cell induces NCIF in the membrane module and higher inclined angle offers stronger NCIF. This induced NCIF enhances back transport of the deposited solutes away from the membrane surface, therefore gives for the improvement of membrane performance. The flux results according to the inclined angles (from 0° to 180°) of the batch cell were analyzed by the pore blocking filtration model. It was shown that NCIF reduced the fouling of intermediate pore blocking by about 66% at the beginning of UF operation, and thereafter reduced the fouling of cake filtration by about 98%.

본 연구에서는 역전기투석 공정에서 발생 가능한 막오염 현상을 in-situ로 측정하기 위하여 임피던스 스펙트로스 코피 방법을 도입하여 실제 발생한 막오염 현상 측정 방법을 제시하였다. 얻어진 임피던스 데이터를 활용하여 Nyquist 도시 법과 어드미턴스 도시법으로 스펙트럼을 도시하였으며 두 도시법 모두 유의미한 막오염 현상을 감지할 수 있었다. 또한 초기 막오염 현상에서 음이온 교환막 표면에 막오염물의 불안정한 축적 현상 및 역전기투석 공정의 운전 시간에 따른 막오염층의 구조적 변화를 감지할 수 있었다.

In this paper, we investigate the characteristics of membrane fouling caused by water temperature in the Membrane bioreactor(MBR) process and try to derive the membrane fouling control by chemical enhanced backwashing(CEB). The extracellular polymeric substances(EPS) concentration was analyzed according to the water temperature in the MBR, and the membrane fouling characteristics were investigated according to the conditions, with sludge & without sludge, through a lab-scale reactor. As shown in the existing literature the fouling resistance rate was increased within sludge with the water temperature was lowered. However, in the lab-scale test using the synthetic wastewater, the fouling resistance increased with the water temperature. This is because that the protein of the EPS was more easily adsorbed on the membrane surface due to the increase of entropy due to the structural rearrangement of the protein inside the protein as the water temperature increases. In order to control membrane fouling, we tried to derive the cleaning characteristics of CEB by using sodium hypochlorite(NaOCl). We selected the condition with the chemicals and the retention time, and the higher the water temperature and the chemical concentration are the higher the efficiencies. It is considered that the increasing temperature accelerated the chemical reaction such as protein peptide binding and hydrolysis, so that the attached proteinaceous structure was dissolved and the frequency of the reaction collision with the protein with the chemical agent becomes higher. These results suggest that the MBRs operation focus on the fouling control of cake layer on membrane surface in low temperatures. On the other hand, the higher the water temperature is the more the operation strategies of fouling control by soluble EPS adsorption are needed.

해수담수화는 최근 전 세계적으로 대두되고 있는 물부족 현상을 해결하기 위한 최적 기술 중 하나이다. 막분리 및 투과 현상의 근본적인 이해는 차후의 막여과 기술의 발전을 위해서 뿐만 아니라, 현재 막기술 증진을 위한 통합적 디자인, 최적화 제어법, 그리고 중장기적 유지관리를 위해서도 매우 중요하다. 이에, 본 연구는 물질 전달 및 여과 현상에 대한 기존 의 주요 모델들을 상세히 재검토하고, 통계물리학에 근간하여 주요 막분리 현상들을 이론적으로 분석하며, 원천적 모델에 기 초한 물리적 의미와 그들이 실제 막공정에서 미치는 영향들에 대해서 함축적으로 토의하고자 한다. 이론적 재검토의 과정에 서 새로이 유도된 복합적 막오염도(Combined Fouling Index (CFI))의 소개도 포함한다.

Recently EC-MBR (Elctrocoagulation - Membrane Bio Reactor) has been suggested as one of alternative processes to overcome membrane fouling problems. Most important operational parameters in the EC-MBR are known to current density and contact time. Their effect on membrane filtration performances has been reported well, however, quantitative interrelationship between both parameters not been investigated yet. The purpose of this study is to give a kinetic model suggesting the current density and the contact time required to reduce the membrane fouling. The 4 different set of current densities (2.5, 6, 12 and 24 A/m2) and contact times (0, 2, 6 and 12 hr) were selected as operational parameters. After each electro-coagulation under the 16 different conditions, a series of membrane filtration was carried out. The membrane fouling decreased as the current density and contact time increased, Total fouling resistances under different conditions, Rt(=Rc+Rf) were calculated and compared to those of the controls (R0), which were calculated from the data of experiments without electro-coagulation. A kinetic approach for the fouling reduction rate (Rt / R0) was carried out and the equation ρi0.46t=7.0 was obtained, which means that the product of current density and the contact time needed to reduce the fouling in certain amounts (in this study, 10% of fouling reduction) is always constant.

Scale formation is inevitable problem when seawater is treated by vacuum membrane distillation. The reason is the high concentration of calcium ion(Ca2+), sulfate ion(SO4 2-) and bicarbonate ion(HCO3 -). These ions form calcium sulfate(CaSO4) and calcium carbonate(CaCO3) on the membrane. The scale formed on membrane has to be removed, because the flux can be severely reduced and membrane wetting can be incurred. This study was carried out to investigate scale formation and effectiveness of acid cleaning in vacuum membrane distillation for SWRO brine treatment. It was found that permeate flux gradually declined until volume concentration factor(VCF) reached around 1.55 and membrane wetting started over VCF over 1.6 in the formation of precipitates containing CaSO4 during VMD operation. In contrast, when calcium carbonate formed on membrane, permeate flux was gradually reduced until VCF 3.0. The precipitates containing both CaSO4 and CaCO3 were formed on the membrane surface and in the membrane pore.

산업폐수 처리에서 미량오염물질(독성 유기물, 화합물, 연료 등)의 제거가 중요하다. 생물학적 처리에 의해서는 미량오염물질을 제거하기 어렵다. 따라서 본 연구에서는 분리막과 고도전기산화를 접목하여 색도, 미세입자등을 효과적으로 제거하고 막오염을 저감시키는 막결합형 고도전기산화시스템을 개발하였다. 색도는 원수 120 도(Pt-Co 색도 값)에서 처리수 20 도이하로 제거되었고, 탁도의 경우 처리수 0.1 NTU이하의 수준으로 감소하였다. 또한 막오염 저감의 성능으로 전극을 켜지않고 실험하였을때 16 kPa까지 증가하였으며 0.5 A/L전류를 공급하였을 때 5 kPa으로 유지되었다. 본 연구는 한국환경산업기술원의 환경융합 신기술 개발사업(No. 2015001640004) 연구결과의 일부이다.

막여과 수처리 공정에서 막오염은 플럭스 감소나 막간차압 증가를 야기하는 중요한 문제로 남아있다. 막오염을 저감하는 여러 가지 방법 중, 막의 표면에 패턴을 입혀 그 패턴의 형상에 따라 유체의 이동을 변화시킴으로써 막오염을 저감시키는 방법이 연구되어 왔다. 특히 45° 회전된 피라미드 패턴은 피라미드 패턴에 비해 막오염 저감 효과가 크다는 연구결과가 있었다. 본 연구에서는 비용매상분리법과 소프트리소그래피(soft-lithograhy)를 이용하여 막의 표면에 45° 회전된 피라미드 패턴을 입히고, 크기가 다른 입자를 포함한 원수를 여과하면서 막오염 저감 효과를 비교해 보았다.

This study applied microbubbles to reduce membrane fouling in wastewater reuse membrane processes, evaluated and compared the transmembrane pressure with or without the application of microbubbles and the cleaning efficiency with the application of aeration and microbubbles. In addition, this study analyzed foulants removed from the membrane surface. Changes in the transmembrane pressure of membranes with the presence or absence of microbubbles were observed. As a result, transmembrane pressure (TMP) increasing rate decreased twofold when applying microbubbles to realize stable operations. This study compared and evaluated cleaning efficiency applying aeration and microbubbles. As a result, the cleaning efficiency was 5% higher on average when applying microbubbles. In turbidity and total organic carbon (TOC), foulants were discharged when applying microbubbles twice as much as applying aeration. It is thought that particulate foulants precipitated on the membrane surface were more likely to desorb because the adhesion between the membrane surface and particle was weakened by microbubbles. Therefore, it is considered possible to effectively control membrane fouling because of the increase in cleaning efficiency when applying microbubbles to wastewater reuse membrane processes.

Microfiltration (MF) and Ultrafiltration (UF) membrane processes capable of producing highly purified water have been extensively applied as a pretreatment process in the wastewater reuse field with the improvement of membrane properties and resistance, development of operating protocols, and improvement of technologies of backwashing and physicochemical cleaning, and improvement of scale and antifoulants. However, despite of the development of membrane production and process technologies, fouling still remains unresolved. This study confirmed that foulants such as polysaccharides, proteins and humic substances existed in final treated effluent (secondary effluent) by fluorescence excitation emission matrix (FEEM) and fourier transform infrared spectroscopy (FTIR) analysis. In addition, when constructing ozone oxidation and coagulation processes as a hybrid process, the removal efficiency was 5.8%, 6.9%, 5.9%, and 28.2% higher than that of the single process using coagulation in turbidity, color, dissolved organic carbon (DOC), and UV254, respectively. The reversible and irreversible resistances in applying the hybrid process consisting of ozone oxidation and coagulation processes were lower than those in applying ozone oxidation and coagulation processes separately in UF membrane process. Therefore, it is considered possible to apply ozonation/coagulation as a pretreatment process for stable wastewater reuse by and then contributing to the reduction of fouling when calculating the optimal conditions for ozone oxidation and coagulation and then to applying them to membrane processes.

A membrane module including grid was designed and introduced to MBR (membrane bio-reactor) for the purpose of better control of membrane fouling. It could be anticipated that the grid enhances the shear force of fluid-air mixture into the membrane surface by even-distributing the fluid-air to the membrane module. As MLSS concentration, packing density which is expressed in the ratio of the housing and the cross-sectional area of membrane fibers (Am/At) and air-flow rate were changed, membrane foulings were checked by monitoring fouling resistances. The total fouling resistance (Rc+Rf) without grid installation (i.e., control) was 2.13×1012 m-1 , whereas it was reduced to 1.69×1012 m-1 after the grid was installed. Regardless of the grid installation, the Rc+Rf increased as the packing density increased from 0.09 to 0.28, however, the increment of resistance for the grid installation was less than that of the control. Increase in the air flow rate did not always guarantee the reduction of fouling resistance, indicating that the higher air flow rate can partially de-flocculate the activated sludge flocs, which led to severer membrane fouling. Consequently, installation of grids inside the housing have brought a beneficial effect on membrane fouling and optimum air flow rate is important to keep the membrane lowering fouling.

수처리용 분리막 여과 공정에서 막오염의 문제는 여전히 해결해야 할 난제이다. 막오염 현상을 제어하기 위한 방안으로 막표면에 패턴을 도입하는 방법이 연구되어 왔다. 분리막의 패턴은, 막표면에서의 유체 흐름에 변화를 일으켜 오염물이 쌓이지 않게 하거나 쌓인 오염물이 일부 떨어져 나가는 효과를 주는 것 으로 보고된 바 있다. 본 연구에서는 수처리용 패턴 분리막을 제조하고, 패턴의 막오염 방지 효과를 평가하고자 하였다. 이를 위하여 CFD 기법을 이용하여 유 체 흐름을 시뮬레이션으로 분석하고, 시뮬레이션 결과와 실제 실험 결과를 비교 분석하기 위해 구형의 모델 입자로 막여과 실험을 수행하였다. 다양한 크기의 모델 입자를 이용함으로써 오염물의 크기에 따른 패턴의 막오염 방지 효과를 분석해 보고자 하였다.

MBR공정에서 물리적 세정방법인 공기폭기(Aeration)는 장기간 막성능을 유지시키기 위한 주요 핵심 방법으로, 기존의 연구들은 산기관의 성능을 극대화시켜 공기세정을 최적화시키려 하였다. 분리막의 효율적인 슬러지 탈리를 위해 폭기위 치⋅시간⋅균일 배출성 및 데드존(Dead Zone) 감소 등에 대한 다양한 연구들이 진행되어 왔으나, 이를 통한 더 이상의 성능향상은 기대하기 어려운 상황이다. 본 연구에서는 기존의 분리막 모듈을 개량하여 공기폭기의 효과를 극대화 하는 연구를 진행하였다. 선행연구로 진행된 Lab-scale실험을 기반으로, Pilot-scale 장치를 세팅하여 장기평가 및 분석 등을 진행하였다. 동일 site에서 개량모듈한 것과 그렇지 아니한 것에 대하여 비교분석하였다.

Membrane bioreactors (MBRs) employ a process of biological treatment that is based on a membrane that has the advantages of producing high-quality treated water and possessing a compact footprint. However, despite these advantages, the occurrence of “fouling” during the operation of these reactors causes the difficulty of maintenance.Hence, in this study, three physical cleaning methods, namely, backwashing, air scrubbing, and mechanical cleaning ball was performed to identify optimum operating conditions through laboratory scale experiments, and apply them in a pilot plant. Further, the existing MBR process was compared with these methods, and the field applicability of a combination of these physical cleaning methods was investigated.Consequently, MCB, direct control of cake fouling on the membrane surface was found to be the most effective. Moreover, as a result of operating with combination of the physical cleaning process in a pilot plant, the TMP increasing rate was found to be – 0.00007 MPa/day, which was 185% higher than that obtained using the existing MBR process. Therefore, assuming fouling only by cake filtration, about one year of operation without chemical cleaning is considered to be feasible through the optimization of the physical cleaning methods.

This study compares characteristic of membrane fouling in MBR-RO systems. In lab. scale MBRs test, MBRs were operated at different Flux(10, 20, 30 & 40 LMH) and temperature(10, 15, 20, 25 & 30°C). The results show that MBR permeate was measured lower amounts of organic substances in Higher flux and lower temperature and led to lower RO fouling rates. The main cause was that due to cake fouling formed on membrane surfaces in MBRs. Under both cases, Cake layer of membrane surfaces formed in MBRs removed RO fouling factors, polysaccharide and protein, because of cake layer attached on membrane surfaces greater amounts of organic substances. This study implies that optimization of MBR with operating conditions is a crucial strategy to RO membrane fouling control.