하수 MBR공정에 있어서 막표면 유속과 여과저항

현길수 ( Kil-soo Hyun ) 한국수처리학회 2017 한국수처리학회지 Vol.25 No.4

Membrane fouling patterns in membrane bioreactor (MBR) include blockage of membrane pore, gel layer formation and sludge cake deposition on the membrane surface. Stirred dead-cell filtration has been widely used for fundamental studies on membrane fouling caused by soluble and colloidal matter during membrane filtration. In this study, the performance of MBR using a dead-end stirrer cell was carried out to investigate the characteristics of pollutants removal and membrane filtration resistance with hydraulic shear force on the surface of membrane module. Influent water qualities were on average <65 mgCOD/L, <21 mgT-N/L, and <6 mgT-P/L, <4500 mgMLSS/L, respectively. As a result, the membrane biofiltration achieved higher efficiencies of COD and T-P except T-N having lower efficiency <50% regardless of the hydraulic shear force. An increase in the hydraulic shear force resulted in a decrease in both transmembrane pressure (TMP) and total membrane filtration resistance. This suggests that higher hydraulic shear force is needed to improve membrane filtration resistance in operating a long-term filtration of MBR having a suitable permeate flux to enhance nitrogen removal efficiency.

나노여과에 의한 중금속 함유 산성 폐에칭액의 재생(I): 상용 나노여과 막의 산 안정성 평가

염경호,신화섭,진천덕,Youm, Kyung-Ho,Shin, Hwa-Sup,Jin, Cheon-Deok 한국막학회 2009 멤브레인 Vol.19 No.4

본 연구는 전자 및 반도체 산업의 각종 에칭공정에서 발생되는 중금속 함유 산성 폐에칭액을 NF 막분리법을 이용하여 에칭액 회수와 중금속 처리를 효율적으로 수행하기 위한 NF 막공정의 운전조건을 설정하기 위한 기본 자료를 확보하는데 있다. 이를 위해 3가지 종류의 상용 NF 막(General Electric Co. Duraslick NF-4040 막, Dow Co. Filmtec LP-4040 막 및 Koch Co. SelRO MPS-34 4040 막)을 대상으로 $Pb^{+2}$ 중금속을 함유한 모의 질산 폐에칭액의 회분식(dead-end) 막여과 실험을 수행하여 폐에칭액의 투과 플럭스와 $Pb^{+2}$ 중금속 이온의 총괄 배제도를 측정하여 폐에칭액 처리에 우수한 NF 막을 선정하였다. 실험결과 질산용액에의 막 보관기간이 길수록, 질산용액의 pH가 낮을수록 산에 의한 막의 손상이 심해졌으며, 질산에 의한 막의 손상은 SelRO MPS-34 4040 < Duraslick NF-4040 < Filmtec LP-4040 막의 순서로 심하게 일어났다. 또한 질산용액에의 막 보관기간이 길수록, 질산용액의 pH가 낮을수록 $Pb^{+2}$ 이온의 배제도가 낮아졌으며, 배제도 값은 Duraslick NF-4040 막의 경우에는 95% 수준의 초기 배제도 값에서 질산용액에의 4달 보관 후에는 20% 수준으로, SelRO MPS-34 4040 막의 경우에는 초기 85% 수준에서 4달 후 65% 수준으로, Filmtec LP-4040 막의 경우에는 초기 90% 수준에서 4달 후 10% 이하 수준으로까지 감소하였다. 3종류의 상용 NF 막 중 내산성 용도로 개발된 SelRO MPS-34 4040 막이 중금속 함유 산성 폐에칭액의 재생에 가장 적합하였다. In this study the nanofiltration (NF) membrane treatment of a nitric acid waste solutions containing $Pb^{+2}$ heavy metal ion discharging from the etching processes of an electronics and semiconductors industry has been studied for the purpose of recycling of nitric acid etching solutions. Three kinds of NF membranes (General Electric Co. Duraslick NF-4040 membrane, Dow Co. Filmtec LP-4040 membrane and Koch Co. SelRO MPS-34 4040 membrane) were tested for their separation efficiency (total rejection) of $Pb^{+2}$ ion and membrane stability in nitric acid solution. NF experiments were carried out with a dead-end membrane filtration laboratory system. The membrane permeate flux was increased with the increasing storage time in nitric acid solution and lowering pH of acid solution because of the enhancing of NF membrane damage by nitric acid. The membrane stability in nitric acid solution was more superior in the order of Filmtec LP-4040 < Duraslick NF-4040 < SelRO MPS-34 4040 membrane. The total rejection of Pb+2 ion was decreased with the increasing storage time in nitric acid solution and lowering the pH of acid solution. The total rejection of $Pb^{+2}$ ion after 4 months NF treatment was decreased from 95% initial value to 20% in the case of Duraslick NF-4040 membrane, from 85% initial value to 65% in the case of SelRO MPS-34 4040 membrane and from 90% initial value to 10% in the case of Filmtec LP-4040 membrane. These results showed that SelRO MPS-34 4040 NF membrane was more suitable for the treatment of an acidic etching waste solutions containing heavy metal ions.

나노여과에 의한 중금속 함유 산성 폐에칭액의 재생 1 : 상용 나노여과 막의 산 안정성 평가

염경호,신화섭,진천덕 한국막학회 2009 멤브레인 Vol.19 No.4

본 연구는 전자 및 반도체 산업의 각종 에칭공정에서 발생되는 중금속 함유 산성 폐에칭액을 NF 막분리법을 이용하여 에칭액 회수와 중금속 처리를 효율적으로 수행하기 위한 NF 막공정의 운전조건을 설정하기 위한 기본 자료를 확보하는데 있다. 이를 위해 3가지 종류의 상용 NF 막(General Electric Co. Duraslick NF-4040 막, Dow Co. Filmtec LP-4040 막 및 Koch Co. SelRO MPS-34 4040 막)을 대상으로 Pb+2 중금속을 함유한 모의 질산 폐에칭액의 회분식(dead-end) 막여과 실험을 수행하여 폐에칭액의 투과 플럭스와 Pb+2 중금속 이온의 총괄 배제도를 측정하여 폐에칭액 처리에 우수한 NF 막을 선정하였다. 실험결과 질산용액에의 막 보관기간이 길수록, 질산용액의 pH가 낮을수록 산에 의한 막의 손상이 심해졌으며, 질산에 의한 막의 손상은 SelRO MPS-34 4040 < Duraslick NF-4040 < Filmtec LP-4040 막의 순서로 심하게 일어났다. 또한 질산용액에의 막 보관기간이 길수록, 질산용액의 pH가 낮을수록 Pb+2 이온의 배제도가 낮아졌으며, 배제도 값은 Duraslick NF-4040 막의 경우에는 95% 수준의 초기 배제도 값에서 질산용액에의 4달 보관 후에는 20% 수준으로, SelRO MPS-34 4040 막의 경우에는 초기 85% 수준에서 4달 후 65% 수준으로, Filmtec LP-4040 막의 경우에는 초기 90% 수준에서 4달 후 10% 이하 수준으로까지 감소하였다. 3종류의 상용 NF 막 중 내산성 용도로 개발된 SelRO MPS-34 4040 막이 중금속 함유 산성 폐에칭액의 재생에 가장 적합하였다. In this study the nanofiltration (NF) membrane treatment of a nitric acid waste solutions containing Pb+2 heavy metal ion discharging from the etching processes of an electronics and semiconductors industry has been studied for the purpose of recycling of nitric acid etching solutions. Three kinds of NF membranes (General Electric Co. Duraslick NF-4040 membrane, Dow Co. Filmtec LP-4040 membrane and Koch Co. SelRO MPS-34 4040 membrane) were tested for their separation efficiency (total rejection) of Pb+2 ion and membrane stability in nitric acid solution. NF experiments were carried out with a dead-end membrane filtration laboratory system. The membrane permeate flux was increased with the increasing storage time in nitric acid solution and lowering pH of acid solution because of the enhancing of NF membrane damage by nitric acid. The membrane stability in nitric acid solution was more superior in the order of Filmtec LP-4040 < Duraslick NF-4040 < SelRO MPS-34 4040 membrane. The total rejection of Pb+2 ion was decreased with the increasing storage time in nitric acid solution and lowering the pH of acid solution. The total rejection of Pb+2 ion after 4 months NF treatment was decreased from 95% initial value to 20% in the case of Duraslick NF-4040 membrane, from 85% initial value to 65% in the case of SelRO MPS-34 4040 membrane and from 90% initial value to 10% in the case of Filmtec LP-4040 membrane. These results showed that SelRO MPS-34 4040 NF membrane was more suitable for the treatment of an acidic etching waste solutions containing heavy metal ions.

Articles : Approach From Physicochemical Aspects in Membrane Filtration

( Eiji Iritani ),( Yasuhito Mukai ) 한국화학공학회 1997 Korean Journal of Chemical Engineering Vol.14 No.5

In membrane filtration, solution environment factors such as pH and solvent density are important in controlling the filtration rate and the rejection of the particles and/or the macromolecules. The filtration rate and the rejection in membrane filtration have been investigated from physicochemical aspects. It was shown that the properties of the filter cake formed on the membrane surface play a vital role in determining the filtration rate in membrane filtration. It was clearly demonstrated that such filtration behaviors as the filtration rate and the rejection are highly dependent on the electrical nature of the particles and/or the macromolecules. Furthermore, it was shown that the solvent density ρ has a large effect on the steady filtration rate in upward ultrafiltration.

음이온성 Poly(bis[4-(3-aminophenoxy)phenyl]sulfone pyromellite)Imide Derivatives 한외여과막의 투과특성

Jong Young Jeon 한국막학회 2004 멤브레인 Vol.14 No.1

상전환 방법으로 제조된 음이온 성 Poly(his[4-(3-aminophenoxy)phenyl]sulfone pyromellite)imide(ACPI) 한외여과막의 순수 투과유속과 용질 배재도 측정치로 투과성능을 연구하였다. ACPI 한외여과막의 투과성능은 캐스팅 용액의 조성과 막 제조 및 측정조건에 영향을 받았다. Bovine serum albumin (BSA) 용액을 pH 2.5-9.0 상태에서 ACPI 한외여과 막의 상대투과유속과 membrane filtration index (MFI) 측정한 결과 BSA의 등전점에서 멀어 질수록 상대투과유속은 증가하고 막 오염정도를 나타내는 MFI는 감소하였다. 또한, 친수성인 ACPI 한외여과막의 이온교환용량(IEC)이 증가할수록 상대투과유속은 증가하고, MFI는 감소하였다. Ultrafiltration membranes based on anion charged poly(bis[4-(3-aminophenoxy)phenyl]sulfone pyromellite) imide derivatives (ACPI) were prepared by the phase inversion method. The polymers have good solubility in aprotic polar solvents. The composition of casting solution and the casting conditions played an important role in determining the permeation characteristics of membrane because the membrane structure could be controlled by the preparation conditions. The extent of fouling-repression was observed by the relative ratio of permeate flux (Jt)/pure water flux (J0) and the membrane filtration index (MFI). The characteristics were measured by aqueous solution of bovine serum albumin (BSA) over a pH range of 2.5-9.0. The ACPI membrane having a hydrophilic property was less fouled than the membrane prepared from the original polyimide. With increasing the ion exchange capacity of ACPI membrane, the relative ratio of flux was higher while the membrane filtration index was lower as compared with the original polyimide membrane. From the further away from isoelectric point of bovin serum albumin, the permeation was higher as well as the formation of fouling was more diminish. ACPI membranes having various their properties could be obtained. Further, it was proved that their permeation properties could be determined from the preparation conditions, various operating conditions, and dimerent ion exchange capacity of anion charged polyimide derivatives.

A novel method for the fabrication of silver nanowires-based highly electro-conductive membrane with antifouling property for efficient microalgae harvesting

Mushtaq, Azeem,Cho, Hoon,Ahmed, Muhammad Ajaz,Rehman, Muhammad Saif Ur,Han, Jong-In Elsevier 2019 Journal of membrane science Vol.590 No.-

<P><B>Abstract</B></P> <P>In this study, a new method of fabricating highly electro-conductive membranes, namely electroplating, was developed and its product performance was examined via microalgae harvesting. In this method, a layer of silver nanowires (AgNWs) was first vacuum-deposited on a poly(ether sulfone) support, followed by electroplating of silver layer. The electroplated membrane (C-AgNWs) found to exhibit surpassingly enhanced electrical conductivity (3.9 × 10<SUP>4</SUP> S/cm) and a satisfactory level of mechanical stability under prolonged filtration. When microalgae, <I>Chlorella</I> sp. HS-2, was harvested via electro-filtration, the membrane exhibited the intended effect of fouling mitigation, both in continuous and intermittent electric fields. This was attributed to the enhanced electrostatic repulsive forces between foulants and membrane along with in-situ electro-bubble generation from the membrane, reducing the overall blockage of the membrane surface. The intermittent mode was able to effectively mitigate fouling and recover flux to its initial level, with the effect compromised in successive steps. The continuous mode, however, did not display such performance degradation over time, but an increase of 480% in permeate flux at 20 V/mm. All this supported that the electroplating can serve as a promising route for the sake of fabricating the workable electro-membranes, conductive membranes that have boundless application potentials.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Electroplating can be a useful method for workable electro-membrane fabrication. </LI> <LI> Highly electro-conductive (3.9 × 10<SUP>4</SUP> S/cm) yet stable electro-membrane can be synthesized by this method. </LI> <LI> The AgNWs-based electroplated membrane can be used for efficient microalgae harvesting. </LI> <LI> The fabricated membrane can exhibit good antifouling property in continuous and intermittent modes of electro-filtration. </LI> </UL> </P>

대기공 정밀여과막의 수처리 응용 및 문제점

윤창한,김정학,이강원,박성호 한국막학회 2014 멤브레인 Vol.24 No.3

본 연구의 목적은 대기공 정밀여과(Large Pore Micro-Filtration, LPMF)막의 수처리 응용을 위한 실험실 규모에서의 성능을 평가한 것으로 이를 통해 문제점 및 해결방안을 제시하는 것이다. 본 연구에 사용된 평균 기공이 5 µm LPMF막은PET Braid가 보강되어 있는 PVDF 재질의 외압형 중공사막으로 여과실험은 30 cm의 수두차 혹은 1.5 bar 이하의 압력차로수행하였으며, 역세는 여과수에 압축공기로 약 4 bar의 압력을 가한 후 수초 내에 순간 역세하는 가압역세였다. 0.2 bar의 TMP (Trans Membrane Pressure)에서 0.05 µm UF로 전처리한 시수로 0.4 µm의 MF와 flux를 비교한 결과 UF에 비해 LPMF의 flux가 약 2배 정도 높았으며, 동일한 시수에 대해 15~30 cm의 수두차에 따른 flux를 측정한 결과 30 cm 수두차에서 800 LMH 이상의 높은 flux를 확인하였다. 또한 여과수의 탁도 향상과 여과 flux의 안정적 유지를 위해 여러 가지 무기응집제에 대한 5 µm 기공의 여지를 이용한 Time-To-Filter (TTF)를 통해 적정 응집제 및 그 주입량을 결정하였다. 고농도 무기응집제 주입 및 30 cm 이상의 수두차로 LPMF를 중력식으로 운전하였을 때 flux는 80 LMH 이상이었고, 탁도 제거율은 93.5~99.5%이었다. 특히 약 4 bar의 압력의 순간 가압역세를 한 결과 막의 충진율이 19%인 경우 여과수의 회수율을 약 97%로 유지하면서도 여과 flux가 안정적으로 유지되었으나, 막충진율을 약 43%인 경우 순간 가압역세만으로는 역세가 불안정하였던 관계로 여과압력이 지속적으로 상승하는 등의 여과공정이 불안정한 문제점을 보였다. The purpose of this study was to evaluate the performance of newly developed Large Pore Micro-Filtration (LPMF) membrane in Lab size for the application of water treatment, and to find its problems with solutions. The out-to-in-side filtration hollow fiber LPMF membrane of which average pore size was 5 µm was used at this study and its material was the PET braid reinforced PVDF. Filtration tests were done through gravity with 30 cm water head difference or pressure below 1.5 bar, and the backwash was done instantaneously with the filtrate after pressurizing it to about 4 bar. The water flux of the LPMF membrane with 0.2 bar TMP (Trans Membrane Pressure) was 2 times higher than 0.4 µm MF membrane with 0.05 µm UF filtrate of the tap water and it was measured also with 20~30 cm water head difference which showed over 800 LMH at 30 cm water head difference. And Time-To-Filter (TTF) was performed by using 5 µm filter paper to opti-mize coagulants and dosage which enhanced filtrate’s turbidity and stabilized filtration flux. When the LPMF was operated with 30 cm gravity with very high dose of inorganic coagulants, the flux was maintained over 80 LMH with 93.5~99.5% turbidity removal. Especially, the filtration was maintained stably in the flux and about 97% of the recovery rate by instanta-neous pressurized backwash with about 4 bar of the filtrate when the packing density was about 19%. But there was in-stability in filtration, since the TMP was continuously going up by inefficient backwash when the packing density was 43%.

완속모래여과 공정에서 세라믹 MF 막의 적용

최광훈(Kwang Hun Choi),박종율(Jong Yul Park),김수한(Su Han Kim),김정숙(Jeong Sook Kim),강임석(Lim Seok Kang) 大韓環境工學會 2013 대한환경공학회지 Vol.35 No.12

최근 음용수를 위한 UF, MF 막의 적용이 증가하고 있다. UF/MF 막은 재래식 수처리 공정에 비하여 원수 수질 변화에 도 안정적인 운전이 가능하고 부지 면적이 작으며 자동화 운전이 가능하다는 장점을 가지고 있다. 현재 대부분의 UF/MF 막 시설은 고분자 막을 사용하고 있다. 최근 세라믹 막은 고분자막에 비하여 경쟁력이 있다고 알려지고 있다. 세라믹 막은 높은 투 과유량과 약품세정 빈도가 작으며 막의 수명 또한 길어 최근 적용 사례가 증가하고 있다. 따라서 본 연구는 MF 세라믹 막 pilot plant를 완속모래여과 정수장에 적용하였다. 본 연구에 사용된 세라믹 Pilot plant는 3개의 계열이 있으며, 각 계열별로 원 수와 모래 여과수를 막의 유입수로 각각 사용하였다. 또한 세라믹 막 공정의 최적화를 위하여 전처리 응집공정으로서 PACl 응 집제를 사용하였다. 그리고 화학세정(Chemical Enhanced Backwashing, CEB)은 황산 (500 mg/L)과 차아염소산 (200 mg/L)을 1.5일에 1번씩 모든 계열에 주입하여 이루어졌다. 본 연구 결과 세라믹 막 공정의 전처리 응집공정에서 최적의 응집제 사용 은 막의 유입수로 원수와 모래 여과수에 대한 막의 flux를 크게 증가시켰다. 또한 본 연구에서 사용된 최적 응집제 주입량에 서 차압상승률은 원수(25 mg/L)의 경우 2.173 kPa/cycle이며, 모래 여과수(5 mg/L)의 경우 0.301 kPa/cycle으로 나타났다. The application of ultrafiltration (UF) and microfiltration (MF) membranes has been increased for drinking water purification. The advantages of UF/MF membrane process compared to conventional treatment processes are stable operation under varying feed water quality, smaller construction area, and automatic operation. Most membrane treatment plants are designed with polymeric membranes. Recently, some studies suggested that the process of treating surface water with ceramic membranes is competitive to the application of polymeric membranes. Higher water flux, less frequent cleaning, and much longer lifetime are the advantages of ceramic membrane comparing to polymeric membrane. Therefore, this research focused on the application of ceramic MF membrane pilot plant at the slow sand filtration plant. The ceramic membrane pilot plant has three trains that used raw water and sand filtered water as a feed water, respectively. For optimizing the pilot plant process, the coagulation with PACl coagulant was used as a pretreatment of ceramic membrane process. In addition, CEB (Chemical Enhanced Backwash) process using H₂SO₄ and NaOCl was used for 1.5 days, respectively. The experimental results showed that applying the optimum coagulant dose before membrane filtration showed enhancing membrane fluxes for both raw water and sand filtered water. Also, when using raw water as a feed of membrane, minimum fouling rate was 2.173 kPa/cycle with 25 mg/L of PACl and when using sand filtered water, the minimum fouling rate was 0.301 kPa/cycle with 5 mg/L of PACl.

벤토나이트 현탁액에 의한 정밀여과 막의 오염특성

남석태,한명진 한국막학회 2008 멤브레인 Vol.18 No.1

벤토나이트 현탁액에 의한 폴리에틸렌 정밀여과 모세관 막의 오염특성에 대하여 검토하였다. 막오염의 윈인은 막표면 위에서 생성되는 케익층의 성장과 입자들이 세공을 막는 표준 및 완전세공막힘 때문이었으며, 막오염은 이들 세 가지 오염형태가 동시에 발생하지만 케익여과오염에 의해 크게 지배를 받는다. 운전압력 1.0kg/cm2에서 총 막오염에 대한 성분오염의 비율은 표준세공막힘 3.36%, 완전세공막힘 3.18% 그리고 케익여과오염 93.46%이었다. 현탁액의 농도가 1000 ppm인 경우에는 완전세공막힘 1.71%, 표준세공막힘 1.90% 그리고 케익여과오염이 96.39%이었으며, 운전초기에 총 오염의 96.14%가 발생했다. 총 오염에 대한 케익여과의 영향은 세공이 0.34 μm막에서 컸다. 순환흐름속도의 증가로 인해 성분오염은 약 10.20% 감소하였고, 총 오염에 대한 세공막힘의 비율은 높았다. Fouling behavior of polyethylene capillary membranes was examined by measuring the flux of bentonite colloidal suspensions through the cross flow micro filtration. The membrane fouling was due to the three mechanisms: the cake formation on the membrane surface, the standard pore blocking and the complete pore blocking by particles. These mechanisms were simultaneously responsible for the membrane fouling, being significantly governed by the cake filtration. In the total fouling at 1.0kg/cm2 TMP condition, the complete blocking was 3.36%, the standard blocking 3.18% and the cake filtration 96.05%. For 1000 ppm feed solution, the complete blocking was 1.71% compared with the standard blocking of 1.90% and the cake filtration of 96.39%. And 96.14% of the total fouling was generated at the initial period of filtration. The cake filtration effect was larger on 0.34 μm pore membrane than on 0.24 μm pore membrane. With the increase in cross flow velocity, the component fouling decreased by 10.20%, and the ratio of pore blocking to total fouling increased.

MBR공정의 운전조건의 변화에 따른 여과성능 개선연구

정훈섭 ( Hoon-sup Jung ),송인수 ( In-soo Song ),현길수 ( Kil-soo Hyun ) 한국수처리학회 2021 한국수처리학회지 Vol.29 No.3

Membrane bioreactor (MBR) combining an activated sludge process and membrane filtration could achieve high nutrient removal efficiency and complete biomass retention without a secondary clarifier. Membrane fouling remains the most challenging issue in MBR operation and attracts considerable attention in MBR studies. The objective of this study is to investigate the influence of permeate flux, aeration mode and strength, and mixed liquor suspended solid (MLSS) on membrane filtration of small-scale MBR (the capacity 100㎥/d), which consisted of anaerobic, anoxic, and aeration tank coupled with membrane. Experiments were conducted with real MBR using real wastewater (BOD <250 mg/L, COD <220 mg/L, T-N <65 mg/L, T-P <8 mg/L, E-coli <100,000 no/mL). As a result, the increase of both permeate flux and MLSS increased TMP of MBR while the increase of aeration strength decreased the TMP. Compared to the existing operation conditions of MBR, the operation conditions of shorter filtration time (8 min on/ 2 min off) for a cycle and lower MLSS (<3000 mg/L) in MBR resulted in longer filtration duration time (about two times) as well as the reduction of cleaning chemical.