본 연구는 PEBAX/PVDF 복합막을 제조하고 에탄올/물 혼합액에 대한 투과증발 성능을 평가하였다. 또한 PVDF 지지체 표면에 ZIF-8 층을 형성하여 복합막의 투과증발 성능을 향상시키고자 하였고, PEBAX 선택층 두께에 따른 성능 비교 를 통해 최적의 막을 선정하였다. 제작된 복합막을 물과 에탄올이 95/5 중량비로 혼합된 공급액에 대하여 투과증발 실험을 수행하였다. 그 결과 ZIF-8 충이 형성된 PVDF 지지체를 사용한 복합막의 경우 플럭스 1.98 kg/m2h, 분리 계수 3.88로 일반 PVDF 지지체를 사용한 복합막보다 투과량과 선택도가 모두 높은 값을 나타내었다.
환경 오염과 천연 자원의 고갈에 대한 증가하는 우려는 환경적으로 지속 가능한 기술의 개발을 촉진했습니다. 퍼 바포레이션은 낮은 에너지 소비, 환경 영향 및 성능 효율로 인해 최근 수십 년 동안 주목을 받아 왔습니다. 이 방법은 막이 원하는 선택도를 충족하도록 미세 조정될 수 있기 때문에 화학 종을 분리하고 유기 용매를 탈수하는 데 사용되었습니다. 역 삼투 및 증류와 같은 여러 분리 공정은 실험 환경 및 산업 응용 분야에서 모두 활용되고 있습니다. 그러나 퍼바포레이션은 작동 압력 및 온도가 낮고 거부율이 높은 등 여러 이점이 있습니다. 그럼에도 불구하고, 현재 막 기술의 상태만으로는 실용적 인 응용에 대한 요구를 충분하게 할 수 없습니다. 반면, 복합막은 유기 물질과 무기 물질의 장점을 모두 활용할 수 있습니다. 많은 연구들이 현재 한계를 해결하기 위해 그래핀 산화물(GO) 및 MXene (MX)과 같은 무기 나노 물질을 고분자 막에 효과 적으로 통합했습니다. 이 검토는 투과증발에서의 2D 복합막의 최근 발전을 조사하고 성능 향상을 평가합니다.
In this study, a pilot-scale (3 m3/day) membrane distillation (MD) process was operated to treat digestate produced from anaerobic digestion of livestock wastewater. In order to evaluate the performance and energy cost of MD process, it was compared with the pilot scale (10 m3/day) reverse osmosis (RO) process, expected competitive process, under same feed condition. As results, MD process shows stable permeate flux (average 10.1 L/m2/hr) until 150 hours, whereas permeate flux of RO process was decreased from 5.3 to 1.5 L/m2/hr within 24 hours. In the case of removal of COD, TN, and TP, MD process shows a high removal rate (98.7, 93.7, and 99% respectively) stably until 150 hours. However, in the case of RO process, removal rate was decreased from 91.6 to 69.5% in COD and from 93.7 to 76.0% in TP during 100 hours of operation. Removal rate of TN in RO process was fluctuated in the range of 34.5-62.9% (average 44.6%) during the operation. As a result of energy cost analysis, MD process using waste heat for heating the feed shows 18% lower cost compare with RO process. Thus, overall efficiency of the MD process is higher then that of the RO process in terms of permeate flux, removal rate of salts, and operating cost (in the case of using waste heat) in treating the anaerobic digestate of livestock wastewater.
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.
In the epoxy resin manufacturing process, carcinogenic ECH (epichlorohydrin), IPA (isopropanol) and Biphenol-A materials has been generally used. After the reaction, byproducts containing ECH/IPA/Water is remained along with final product. But, in the recovery process, ECH and IPA forming an azeotropic mixture with water containing feed solution at any temperature condition, the recovery of high purity ECH is difficult only by distillation. Therefore, pervaporation process could be suitable countermeasure due to its mild operation condition for separation of azeotropic mixtures at the point of energy and cost saving. In this study, Alumina-PVA composite membrane was prepared for pervaporation dehydration of ECH/IPA/Water feed mixtures and pervaporation performance and stability of the prepared composite membrane was identified.
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.
The general separation processes for liquid mixtures need the energy consumed and causes of primary cost. The pervaporation separation process could be regarded as the energy saving process[1]. In this study, it is introduced that the preferential isopropyl alcohol separation from the aqueous feed was carried out using the composite membranes according to the operating conditions, such as, the operating temperature, feed concentration etc. And the commercial scale module was prepared and tested for the long-term period, and finally the stabilized and consistent results of both permeability and selectivity were obtained.
본 연구에서는 물/에탄올 분리 성능이 우수한 모데나이트 제올라이트 분리막을 제조하였다. 모데나이트 분리막은 다공성 알루미나 지지체 표면에 종결정이 분산된 종결정 수용액을 이용하여 침지코팅한 후 1SiO2:0.05Al2O3: 0.76NaOH:40H2O 의 몰비로 제조된 수열용액을 이용하여 170°C에서 24시간 동안 이차성장 시켰다. 이때 종결정 수용액의 농도가 모데나이트 분리막의 미세구조 및 투과증발성능에 미치는 영향에 대하여 분석하였다. 종결정 수용액의 농도를 0.025, 0.05, 0.1, 0.25, 0.5 wt%로 한 후 합성한 경우, b축으로 성장된 바늘 구조의 모데나이트 결정은 농도가 증가할수록 c축으로 성장하는 것을 확인하였다. c축으로 성장 된 분리막의 물/에탄올 분리성능은 > 10000의 선택도와 0.2 kg/m2h의 투과도 를 나타냈다.
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.
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.
투과증발 공정은 공비점 부근의 함수 유기화합물로부터 선택적으로 물은 분리하는 기술로 에너지 절약형 분리 기술이다. 본 연구에서는 이와 같은 투과증 발 플랜트의 개발을 위하여 α-Alumina 지지체에 합성한 NaA제올라이트 분리막 을 사용하였으며, 1 ton/day급과 250 L/batch급의 플랜트를 개발하였다. 개발한 투과증발 플랜트는 함수에탄올을 대상으로 탈수 평가를 수행하였으며, 250 L/batch급의 플랜트는 억새의 발효를 통해 생산한 함수 바이오에탄올을 이용하여 탈수 성능을 평가하였다.