This study was aimed to examine inorganic fouling and fouling reduction method in direct contact membrane distillation(DCMD) process. Synthetic seawater of NaCl solution with CaCO3 and CaSO4 was used for this purpose. It was found in this study that both CaCO3 and CaSO4 precipitates formed at the membrane surface. More fouling was observed with CaSO4(anhydrite) and CaSO4･0.5H2O(bassanite) than CaSO4･2H2O(gypsum). CaCO3 and gypsum were detected at the membrane surface when concentrates of SWRO(seawater reverse osmosis) were treated by the DCMD process, while gypsum was found with MED(multi effect distillation) concentrates. Air backwash(inside to out) was found more effective in fouling reduction than air scouring.

막증발 (Membrane Distillation, MD) 기술은 역삼투 해수담수화 공정에서 발생하는 농축수의 처리 문제를 해결하고 공정 회수율을 증가시킬 수 있는 차세대 담수화 기술로 부각되고 있다. 하지만 MD 공정의 효율적 운영을 위해서는, 막의 오염 (Fouling) 및 젖음 (Wetting) 현상을 해결하여야 한다. 이 현상들은, 해수 속에 존재하는 성분, 막의 종류 등을 포함한 여러 가지 운영 조건 등에 따라 다를 수 있다. 따라서 본 연구에서는 막오염과 막젖음 현상이 어떻게 발생하는지 살펴보기 위해, MD 공정 운영 조건을 변화시키며 막투수도 및 여과저항, 처리수 전도도 등을 측정하고, SEM-EDX, LEP (Liquid Entry Pressure) 등을 이용하여 막을 분석하였다.

본 연구에서는 막증류법에서 문제가 되는 젖음 현상을 방지하기 위해 분리막의 표면을 초소수성으로 개질하고, 젖음 현상의 가속화를 통해 초소수성 표면의 젖음 방지의 평가에 관한 연구를 진행하였다. 분리막의 표면을 물리적 처리를 통해 기공을 키우고, 산화 처리를 통해 하이드록실기를 형성시켜 성장을 준비한다. 성장을 통해 표면에서부터 형성된 나노 입자를 통해 코팅 방법이 가지는 분리막과 나노 입자 사이의 불안정성을 해결하였고, 성장한 나노 입자의 화학적 개질을 통해 초소수성 막을 준비하였다. 준비된 분리막은 막 증류법의 운전 도중 계면활성제를 첨가함으로써 젖음 현상의 가속화를 통해 개질 전후의 방지효과를 비교하였고, sonication 처리를 통해 나노 입자와 분리막 사이의 안정성을 확인하였다.

막증발 기술은 최근 해수담수화 분야에서 많은 주목을 받고 있으며, 기존 증발법과 역삼투를 대체하는 대안기술로서 개발이 활발하게 추진되고 있다. 그러나 막증발 기술의 실용화를 위해서는 극복하여야 할 몇 가지 문제점이 있다. 본 연구에서는 막증발 기술을 효율적으로 적용하기 위하여 해결해야 하는 1) 스케일업 2) 막오염 억제 3) 막젖음 예측 및 방지기술 개발하고자 하였으며, 이를 통하여 저탄소 담수화를 실현시키기 위한 방안을 제시하고자 하였다.

Membrane distillation (MD) is a thermally driven desalination process with a hydrophobic membrane. MD process has been known to have a lower fouling potential compared to other pressure-based membrane desalination process (NF, RO). However, membrane fouling also occurs in MD process. In this study, the membrane fouling was observed in MD process according to the pre-treatment processes. The filtration and precipitation processes were applied as the pre-treatment to prevent the membrane fouling. The pore sizes of roughing filters were 0.4, 5, 10, 30, and 60 ㎛. The concentration of the coagulant was 1.2 mg/L as FeCl3. The membrane fouling on MD membrane was successfully removed with both pre-treatment processes.

Membrane distillation (MD) has shown the potential to further reduce the volume of coal seam gas (CSG) reverse osmosis (RO) brine. However, despite its potential, the lack of appropriate MD membranes limits its industrial use. Therefore, this study was aimed on the fabrication of a robust membrane for the treatment of real CSG RO brine via an air gap MD (AGMD) process. Here, graphene/polyvinylidene fluoride (G/PVDF) membranes were prepared through a phase inversion method. Surface characterization revealed that all G/PVDF membranes exhibited favorable membrane properties having high porosity and liquid entry pressure, and suitable pore size. AGMD test results indicated a high water vapor flux of 20.5 L/m²h. Long-term AGMD operation revealed the robustness of G/PVDF membrane with superior performance compared to commercial PVDF membrane.

열유도상분리법(TIPS) 및 연신의 복합공정으로 막증류(Membrane distillation, MD)용의 소수성 및 다공성 PVDF 중공사 분리막을 제조하였다. 제조된 분리막을 막증류 공정에 적용하여 처리수량을 극대화하기 위한 방안으로 모듈의 형태와 운전조건 및 병렬 연결 시 배관의 크기 영향을 확인하고자 하였다. 진공 막증류 모듈의 최적화 실험에서는 모듈 내 분리막의 충진율과 길이가 증가할수록 플럭스는 감소하며, 진공포트의 위치는 모듈을 수직으로 연결하였을 때 원수의 inlet 방향에 위 치할수록 플럭스 측면에서 가장 유리한 것으로 확인되었다. 모듈의 헤더배관의 크기선정에서는 중공사막의 내경면적과 헤더 배관의 내경면적이 동일할 경우 최대 플럭스를 나타냄을 확인할 수 있었으며, 모듈 내 선속도가 높을수록 높은 플럭스를 나타내지만 모듈에 작용하는 압력 역시 비례하여 증가하기 때문에 최적 선속도를 찾는 것이 필요하다.

In this study, thermal performance test of VMD module was performed, prior to the construction of the demonstration plant using the vacuum membrane distillation　(VMD) module of the capacity of 400 m3/day and to the commercialization of the VMD module. For the thermal performance test, the experimental equipment of capacity of 2 m3/day was constructed. The permeate flux test and thermal performance test according to feed water conditions such as temperature and flow rate were conducted. The VMD module used in the study was manufactured by ECONITY Co., LTD with PVDF hollow fiber membrane. As a result, the Performance Ratio (PR) of the VMD module showed the maximum value of 0.904 under the condition of feed water temperature of 75℃ and flow rate of 8 m3/h. PR value of the VMD module using PVDF hollow fiber membrane showed linearly increasing relationship with feed water temperature and flow rate. Also, The permeate flux of the VMD module was analyzed to have maximum value of 18.25 LMH and the salt rejection was 99.99%.

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.

In this study, a direct contact membrane module was manufactured to be used in a pilot scale membrane distillation process to treat 3 m3/day of the digestate produced from anaerobic digestion of livestock manure. In order to investigate the performance of the membrane module, permeate flux was measured with and without spacer inside the module under various condition of temperature difference and cross flow velocity (CFV) through the membrane surfaces. Flux recovery rate after chemical cleaning was also investigated by applying three different cleaning methods. Additionally, thermal energy consumption was theoretically simulated based on actual pilot plant operation conditions. As results, we observed flux of the module with spacer was almost similar to the theoretically predicted value because the installation of spacer reduced the channeling effect inside the module. Under the same operating condition, the permeate flux also increased with increasing temperature difference and CFV. As a result of chemical in-line cleaning using NaOCl and citric acid for the fouled membranes, the recovery rate was 83.7% compared to the initial flux when NaOCl was used alone, and 87% recovery rate was observed when only citric acid was used. However, in the case of using only citric acid, the permeate flux was decreased at a rapid rate. It seemed that a cleaning by NaOCl was more effective to recover the flux of membrane contaminated by the organic matter as compared to a cleaning by citric acid. The total heat energy consumption increased with increasing CFV and temperature difference across the membrane. Thus, further studies should be intensively conducted to obtain a high permeate flux while keeping the energy consumption to a minimum for a practical application of membrane distillation process to treat wastewater.

본 연구에서는 막증류법에서 문제가 되는 젖음 현상을 방지하기 위한 방법으로서, 멤브레인 표면의 화학적 결합을 통해 멤브레인의 소수성을 향상시키고 그에 따른 영향을 확인하고자 한다. 중공사 표면에 pentafluorostyrene을 라디칼합성 방법을 통해 개질하여 소수성을 증가시켰다. 합성 시간에 따른 영향을 확인하기 위하여 15, 20, 25시간 동안 합성하여 개질 하였고, 막의 접촉각과 liquid entry pressure (LEP)를 통해 소수성 증가를 확인하였다. 이후 vacuum membrane distillation (VMD)을 통해 실제 운전에서 앞선 합성이 막의 성능에 미치는 영향을 확인하였다.

이 연구의 목적은 폴리머의 물리적, 화학적 방법을 통해 막증류 법에 사용되는 막의 소수성 향상시킴으로써 막의 젖음 현상을 개선하는 것을 목표로 한다. 막의 소수성을 향상시키기 위해, 폴리머에 소수성을 향상 시켜줄 수 있는 시약 을 화학적 결합 또는 물리적 섞음 방법을 통해 개질을 한다. 화학적 결합으로는 styrene, pentafluorostyrene 등을 ATRP(atom transfer radical polimerization)를 통해 합성하고, 물리적 섞음으로는 PTFE(poly tetra fluoro ethylene)을 섞어 준비하였다. 두 방법 모두 평막을 제조하여 ft-ir로 결과를 확인하였고, 접촉각을 측정해 소수성을 평가하는 것으로 폴리머의 소수성 향상 여부를 확인하였다.

Membrane distillation (MD) is a hydrid membrane process using the temperature difference as a driving force. In order to enhance the performance (flux) of the MD process, various membrane structures (asymmetric or bi-composite) and materials (PP, PVDF or PTFE) have been suggested. In this study, the support layer of the commercial PTFE/PP bi-composite membrane is modifed by forming the macro punctures in it. The size and location of macro punctures were varied according to the designed support layer porosities (50, 60, 70 and 80 %). The modified membrane test was conducted by using the DCMD configuration. The flux of a modified membranewas enhanced up to 27 % compared with that of pristine membrane when the size of the macro puncture and overall porosity of the support layer were larger than 20 mm2 and 60 %, respectively.

선박에 주로 사용되는 기존 해수담수화 공정의 경우 많은 에너지가 소모 된다는 단점이 있다. 막증발법(MD)은 유입수의 삼투압으로 인한 구동력의 저하가 역삼투공정에 비해서 낮은 장점을 가지며, 비교적 낮은 온도(60 ∼ 80℃)에서 운전 가능하기 때문에 선박의 엔진 폐열, 해수열원 등을 활용하여 운전 비용을 절감할 수 있다. 본 연구에서는 실험실 규모의 진공식 막증발 장치에서 도출된 조건을 바탕으로 3 m3/일 규모의 실제 VMD 파일럿플랜트를 설계 및 제작하여 성능을 평가하였다. 운전결과, 3～5 L/㎡-hr의 플럭스와 99.99%의 염제거율을 나타냈다.

Shale gas has become increasingly important as a viable alternative to conventional gas resources. However, one of the critical issues in the development of shale gas is the generation of produced water, which contains high concentration of ionic compounds (> TDS of 100,000 mg/L). Accordingly, membrane distillation (MD) was considered to treat such produced water. Experiments were carried out using a laboratory-scale direct contact MD (DCMD). Synthetic produced water was prepared to examine its fouling propensity in MD process. Antiscalants and in-line filtration were applied to control fouling by scale formation. Fouling rates (-dJ/dt) were calculated for in-depth analysis of fouling behaviors. Results showed that severe fouling occurred during the treatment of high range produced water (TDS of 308 g/L). Application of antiscalant was not effective to retard scale formation. On the other hand, in-line filtration increased the induction time and reduced fouling.

Development of shale gas has drawn increasing attention since it is one of promising alternative energy resources. However, contamination of groundwater and surface water during the extraction of shale gas is becoming a serious environmental issues, which brings the needs to treat wastewater generated from hydraulic fracking. In this study, the feasibility of membrane distillation (MD) for the treatment of shale gas wastewater was investigated using a laboratory scale experimental setup. Flat-sheet MD membranes were used to treat produced water from a shale gas well in the United States. Different configurations such as direct contact MD (DCMD) and air gap MD (AGMD) were compared in terms of flux and fouling propensity. The foulants on the surface of the membranes were examined. The results suggest that MD can treat the shale gas produced water containing more than 200,000 mg/L of total dissolved solids, which is impossible by other technologies such as reverse osmosis (RO) and forward osmosis (FO). In this study, we investigated the possibility of processing and characterization of shale gas produce wastewater using membrane distillation. Laboratory scale membrane distillation experimental device was developed. It was compared the flat-sheet direct contact membrane distillation and flat-sheet air gap membrane distillation. AGMD flux in lower than the flux of DCMD, it was expected that the contamination caused by organic matters.

Membrane distillation (MD) is a novel separation process that have drawn attention as an affordable alternative to conventional desalination processes. However, membrane fouling and pore wetting are issues to be addressed prior to widespread application of MD. In this study, the influence of ultrasonic irradiation on fouling and wetting of MD membranes was investigated for better understanding of the MD process. Experiments were carried out using a direct contact membrane distillation apparatus Colloidal silica was used as a model foulants in a synthetic seawater (35,000 mg/L NaCl solution). A vibrator was directed attached to membrane module to generate ultrasonic waves from 25 kHz (the highest energy) to 75 kHz (the lowest energy). Flux and TDS for the distillate water were continuously monitored. Results suggested that ultrasonic irradiation is effective to retard flux decline due to fouling only in the early stage of the MD operation. Moreover, wetting occurred by a long-term application of ultrasonic rradiation at 75 kHz. These results suggest that the conditions for ultrasonic irradiation should be carefully optimized to maximize fouling control and minimize pore wetting.