||The effect of coagulation on each fraction of DOM removal and UF membrane fouling
||Department of Environmental Engineering
Natural organic matter
本研究目的在於探討混凝前處理對各類溶解性有機物之去除與後續UF薄膜通量下降減緩之關係。首先，分別採集阿公店水庫水與金門太湖淨水廠慢砂濾出流水作為研究之對象。所採集之水樣先經匣式過濾器以去除水中懸浮性顆粒與微生物，接著以明礬於不同劑量下進行混凝前處理，並收集其沉澱後之上澄液，作為後續薄膜過濾之進流水。利用PVC (Polyvinyl chloride)與CA (Cellulose acetate)兩種不同材質之中空纖維膜，於定壓條件下行端點式過濾，並將過濾前後之水樣進行水質分析。主要利用高效能粒徑排除層析儀(HPSEC)連接線上型OC及UV/vis偵測器，分析水中有機物之分子量分佈及特性，並搭配Peak-fit軟體量化之。然後再就溶解性有機物之去除與UF通量下降緩解間之關係進行探討。
The effect of coagulation on each fraction of DOM removal and UF membrane fouling
Department of Environmental Engineering, Cheng Kung Univeristy, Tainan, Taiwan
The effect of coagulation pretreatment on NOM removal from two sources water, namely Lu-Jhu and Kinmen, and on the following UF membrane fouling control was investigated. Two kinds of membrane, made from PVC and CA, were used. The dissolved organics were characterized by HPSEC with UV/Vis and DOC detectors. The results confirmed the hydrophilic biopolymer, which existed in water with high concentration, as the major foulant which caused severe flux decline in the initial stage of UF membrane filtration. Besides biopolymers, PVC and CA membrane also removed small amounts of humic substances and LMW acids, respectively. However, if the concentration of biopolymers was too high, the removal of other organic fractions could be inhibited. Coagulation pretreatment preferably removed biopolymers and humic substances over LMW acids, and the latter was more easily absorbed by CA membrane than PVC membrane. Therefore, the effect of increasing alum dosage on membrane fouling control could be more significant for PVC membrane than for CA membrane. Generally speaking, flux decline was dominated by biopolymers, if it existed in high concentration. The effect of other dissolved organic fractions could become significant, only after the concentration of biopolymers had been reduced to certain level.
Key words: Natural organic matter (NOM), membrane material, coagulation pretreatment, membrane fouling.
As the demand for water sources and its quality increased, the applications of ultrafiltration membrane in drinking water treatment has been more popular. UF membrane can be used to remove particulate matter, microorganic, especially pathogenic protozoa, such as Giardia and Crytosporidia, from source water. However, the phenomenon of rapid flux decline induced by membrane fouling is still a main problem. In literature, NOM has been found to be the major material which caused severe membrane fouling. NOM is a very complex heterogeneous matrix of organic compounds with wide ranges in molecular weight (MW), and with diversified characteristic, which can be originated from the catchment, such as humic substances, and from the water body itself, such as the extracellular polymeric substance (EPS). However, the results from various researchers, concerning the fraction of the organic matter which causes major fouling is still not conclusive or sometimes even contradictory. The objective of this research is to investigate the relationship between the removal of each fraction of dissolved organic matter (DOM) by coagulation pretreatment and the reduction of flux decline in the following UF membrane filtration. The HPSEC with UV/Vis and DOC detectors were used to characterize the NOM of both feed water and permeate, and to clarify the major foulant in UF membrane filtration.
MATERIALS AND METHODS
1.UF feed water preparation
There were two sources of water used in this study, namely that from Lu-Jhu reservoir and slow sand filter effluent of Tai-hu water treatment plant located in Kinmen. As this study was focused on the effect of dissolved organic matter on membrane filtration, the source waters were first filtered by cartridge filters (1.2/0.5 μm & 0.45μm disposable capsule filter, Millipore Corporation, USA) to remove algae and other suspended solids. Then, the filtrate was coagulated by alum with the conventional jar test apparatus and procedure. After that the supernatant was collected, and used as the feed water for the UF membrane filtration.
2.UF membrane filtration
Constant-pressure filtrations (0.68 bar), with PVC (polyvinyl chloride) or CA (cellulose acetate) UF membranes, were conducted with bench-scale dead-end membrane testing system. Single hollow fiber with inside-out flow pattern was used. Membrane flux was determined by weighting the permeate in a top-loading balance at timed intervals with computerized data acquisition.
3.Water quality analysis
The water samples, including source water, feed water and permeate from UF membrane filtration, were analyzed for general physicochemical characteristics, such as pH, turbidity, alkalinity, NPDOC, and UV254. High performance liquid chromatography (HPLC)- size exclusion chromatography (SEC) with sequential on-line ultraviolet (UV) and organic carbon (OC) detectors was used to characterize the composition of dissolved organic matter as a function of apparent molecular weight (AMW). Peak-fitting technique (with software PeakFit) was used to analyze the chromatograms.
RESULTS AND DISCUSSION
1.The source water from Kinmen contained higher concentration of dissolved organic than Lu-Jhu, but the opposite is true for SUVA values, which meant the organic matter from Kinmen was more hydrophilic than that of Lu-Jhu. HPSEC-OCD results also showed that the dominant organic fractions for Kinmen and Lu-Jhu were biopolymers (29.1 %) and humic substances (32.9 %), respectively.
2.For both PVC and CA membranes, the flux decline was more significant for the source water from Kinmen than that from Lu-Jhu. Biopolymer was the major organic fraction removed by UF membrane, therefore it also was considered as the major foulant. Further, the higher the biopolymer concentration was, the more significant the initial flux decline would be.
3.For Lu-Jhu water, in addition to biopolymer, PVC membrane removed small amount of humic substances, while CA membrane removed part of LMW acids. However, for Kinmen water, besides biopolymers, no significant removal for other organic fractions was detected.
4.Humic substances were easily removed by alum coagulation, while biopolymers could be removed only under higher alum dosage, probably through the mechanism of enhanced coagulation. The removal of lower molecular weight organic fractions were minor.
5.Concerning the effect of increasing alum dosage on the flux decline control for the following UF membrane filtration, the results show that, for Lu-Jhu water, increasing alum dosage effectively reduced the flux decline rate of PVC membrane. However, the effect on CA membrane was minor. For Kinmen water, the effect on increasing alum dosage on flux decline control was insignificant for both PVC and CA membranes.
1.The hydrophilic biopolymer was significantly removed by UF membrane, and confirmed as the major foulant. If existed in high concentration, it could cause sharp flux decline at the initial stage of filtration.
2.UF membranes also removed small amount of humic substances or LMW acids. However, the existence of high concentration of biopolymers could inhibit this phenomenon.
3.Coagulation pretreatment preferably removed biopolymers and humic substances over LMW acids, and the latter was more easily absorbed by CA membrane than PVC membrane. Therefore, the effect of increasing alum dosage on membrane fouling control could be more significant for PVC membrane than for CA membrane.
4.Generally speaking, flux decline was dominated by biopolymers, if it existed in high concentration. The effect of other dissolved organic fractions could become significant, only after the concentration of biopolymers had been reduced to certain level.
第一章 前言 1
第二章 文獻回顧 3
2-1-1 NOM之生成來源 3
2-1-2 NOM對淨水處理的影響 4
2-1-3 NOM特性分析 4
2-1-4螢光光譜儀(Fluorescence Spectrometry)偵測有機物原理與特性 9
2-2-4 UF薄膜介紹 27
2-2-5 UF薄膜材質 30
2-3-4 NOM產生之薄膜堵塞 35
第三章 實驗流程與方法 51
3-4-1 pH值 57
3-4-2 濁度 57
3-4-3 鹼度 57
3-4-4非揮發溶解性有機物(Non-Purgable Dissolved Organic Carbon, NPDOC)分析 58
3-4-5 UV254吸光值 59
3-4-6螢光激發/發散陣列光譜(Fluorscence Excitation/Emission Matrix, F-EEM)分析 60
3-4-7高效能粒徑排除層析儀(High Performance Size Exclusion Chromatography, HPSEC) 61
第四章 結果與討論 65
第五章 結論與建議 95
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