Cost factors and chemical pretreatment effects in the membrane filtration of waters containing natural organic matter

This paper compares the membrane processes available for water treatment. Membranes have the advantage of currently decreasing capital cost, a relatively small footprint compared to conventional treatment, generally a reduction in chemicals usage and comparably low maintenance requirements. Three membrane processes applicable to water treatment, micro- (MF), ultra- (UF), and nanofiltration (NF), are compared in terms of intrinsic rejection, variation of rejection due to membrane fouling and increase in rejection by ferric chloride pretreatment. Twelve different membranes are compared on the basis of their membrane pore size which was calculated from their molecular weight cut-off. A pore size of < 6 nm is required to achieve substantial (> 50%) organics removal. For a fouled membrane this pore size is about 11 nm. UV rejection is higher than DOC rejection. Coagulation pretreatment allows a higher rejection of organics by MF and UF and the cut-off criterion due to initial membrane pore size is no longer valid. A water quality parameter (WQP) is introduced which describes the product water quality achieved as a function of colloid, DOC and cation rejection. The relationship between log (pore size) and WQP is linear. Estimation of membrane costs as a function of WQP suggests that open UF is superior to MF (similar cost at higher WQP) and NF is superior to tight UF. Chemical pretreatment could compensate for the difference between MF and UF. However, when considering chemicals and energy costs, it appears that a process operated at a higher energy is cheaper at a guaranteed product quality (less dependent on organic type). This argument is further supported by environmental issues of chemicals usage, as energy may be provided from renewable sources.     

Effects of magnetic ion exchange pretreatment on low pressure membrane filtration of natural surface water

Magnetic ion exchange (MIEX) pretreatment has been increasingly employed by water treatment plants for removal of dissolved organic carbon (DOC). In this study, the effects of MIEX pretreatment on low pressure membrane filtration of natural surface water were investigated under different feedwater qualities, membrane properties, and MIEX dosing conditions. Regardless of feedwater DOC, moderate decrease in the total and hydraulically irreversible fouling was observed for a polyvinylidene fluoride (PVDF) microfiltration membrane and a polyethersulfone ultrafiltration (UF) membrane after MIEX pretreatment, which was coincident with moderate removals of high molecular weight DOC in the feedwaters. Comparatively, the fouling of a PVDF UF membrane did not decrease after MIEX pretreatment, revealing the impact of membrane properties on membrane fouling in the presence of MIEX pretreatment. Reuse of virgin or regenerated MIEX resulted in similar membrane fouling as observed with single use of the virgin MIEX. The level of DOC removal by MIEX was similar to the removal of MS2 bacteriophage spiked in the feedwater, suggesting a potential similarity in the removal of organic and microbial particles. In conclusion, MIEX pretreatment was effective for DOC removal, but less effective in controlling short-term membrane fouling or removing viruses.     

粉末活性炭/污泥回流工艺强化膜前预处理的研究

采用粉末活性炭(PAC)吸附/混凝沉淀/浸没式超滤膜组合工艺处理苏州市某河水,考察了PAC/污泥回流工艺对膜前预处理的强化效果及对膜污染的影响,并与常规混凝沉淀、污泥回流强化混凝沉淀、PAC吸附/混凝沉淀等3种预处理工艺进行了对比。结果表明,PAC/污泥回流强化预处理工艺对浊度、DOC、UV254和THMFP的去除率分别为80.2%、47.5%、42.3%和52.3%,均比其他预处理工艺的高,对MW30 ku和MW1 ku有机物的去除效果明显。PAC/污泥回流强化预处理和超滤膜组合工艺对浊度、DOC、UV254和THMFP的去除率分别可达到99.2%、54.1%、47.2%和60.2%;经过15 d的运行,超滤膜的跨膜压差基本保持稳定,而其他预处理工艺虽能在一定程度上减轻膜污染,但无法避免不可逆膜污染的发生。     

Degradation of natural organic matter by TiO2 photocatalytic oxidation and its effect on fouling of low-pressure membranes

Natural organic matter (NOM) fouling continues to be the major barrier to efficient application of microfiltration (MF) and ultrafiltration (UF) in drinking water treatment. In this study, the potential of TiO2/UV photocatalytic oxidation to control fouling of membranes by NOM was evaluated. Decomposition kinetics of NOM was investigated using a commercial TiO2 catalyst, and the effect of various experimental parameters including TiO2 dosage and initial total organic carbon (TOC) concentration were also determined. The reaction kinetics was found to increase with increasing TiO2 dosage, but decrease with increasing initial TOC concentration. Even though the rate of TOC removal was relatively low, the TiO2/UV process was very effective in controlling membrane fouling by NOM. At a TiO2 concentration of 0.5 g/L, fouling of both an MF and a UF membrane was completely eliminated after 20 min of treatment. Careful analyses of specific UV absorbance (SUVA) and molecular weight (MW) distribution of NOM revealed that the effectiveness in membrane fouling control is the result of the changes in NOM molecular characteristics, namely MW and SUVA due to the preferential removal and transformation of large, hydrophobic NOM compounds. Results from this study show that TiO2/UV photocatalytic oxidation is a promising pretreatment method for MF and UF systems.     

Application of ceramic membranes with pre-ozonation for treatment of secondary wastewater effluent

Membrane fouling is an inevitable problem when microfiltration (MF) and ultrafiltraion (UF) are used to treat wastewater treatment plant (WWTP) effluent. While historically the use of MF/UF for water and wastewater treatment has been almost exclusively focused on polymeric membranes, new generation ceramic membranes were recently introduced in the market and they possess unique advantages over currently available polymeric membranes. Ceramic membranes are mechanically superior and are more resistant to severe chemical and thermal environments. Due to the robustness of ceramic membranes, strong oxidants such as ozone can be used as pretreatment to reduce the membrane fouling. This paper presents results of a pilot study designed to investigate the application of new generation ceramic membranes for WWTP effluent treatment. Ozonation and coagulation pretreatment were evaluated to optimize the membrane operation. The ceramic membrane demonstrated stable performance at a filtration flux of 100 gfd (170 LMH) at 20 °C with pretreatment using PACl (1 mg/L as Al) and ozone (4 mg/L). To understand the effects of ozone and coagulation pretreatment on organic foulants, natural organic matter (NOM) in four waters - raw, ozone treated, coagulation treated, and ozone followed by coagulation treated wastewaters - were characterized using high performance size exclusion chromatography (HPSEC). The HPSEC analysis demonstrated that ozone treatment is effective at degrading colloidal NOMs which are likely responsible for the majority of membrane fouling.     

Granular iron oxide adsorbents to control natural organic matter and membrane fouling in ultrafiltration water treatment

Fine iron oxide particles (IOPs) are effective in removing natural organic matter (NOM) that causes membrane fouling in water treatment, but the separation of used IOPs is problematic. This study focused on the fabrication and use of granular iron oxide adsorbents, in combination with ultrafiltration (UF) membranes while investigating the NOM removal efficiency and fouling control. Sulfonated styrene-divinylbenzene copolymer beads were coated with two types of iron oxides (ferrihydrite and magnetite) and their performances were compared to that of fine IOPs. A significant amount of iron oxide coating (52–63 mg of Fe per g bead) was achieved by means of electrostatic binding and hydrolysis of iron ions. Iron oxide coated polymer (IOCP) beads were able to remove some amounts (～20%) of dissolved organic carbon (DOC) comparable to that achieved by IOPs within a short period of time (<15 min). Regenerated IOCPs exhibited the same sorption capacity as the fresh ones. The integrated IOCP/UF system operation with a 15-min empty bed contact time and 10-h cyclic regeneration maintained the 20% DOC removal with no sign of significant membrane fouling. In contrast, a sharp transmembrane pressure buildup occurred in the UF system when no iron oxide pretreatment was applied, regardless of the types of membranes tested. Iron oxide adsorbed the NOM fraction with molecular weights of >1000 kDa which is believed to be responsible for severe UF fouling.     

Combination of coagulation and ion exchange for the reduction of UF fouling properties of a high DOC content surface water

The treatment of a high DOC content surface water (about 6mg DOC/L) using anion exchange resins (MIEX resin from Orica or IRA958 resin from Rohm and Haas) can remove up to 80% of DOC in less than 45min. The combination of coagulation prior to or after resin treatment only slightly improves the removal of DOC (0.2-0.3mg/L) but eliminates the high MW organic compounds (MW >20kDa) attributed to biopolymers (proteins and polysaccharides) that were not removed using anion exchange resins alone and that were found to be responsible for reversible fouling of UF membranes (YM 100 UF membrane from Millipore with MW cut-off of 100kDa). The combination of treatments then significantly improves the permeability of the UF membrane. Also, the combination of both treatments allows a reduction of the coagulant doses by a factor of 6 with no impact on the DOC removal and the filterability of produced waters.     

Membrane coagulation bioreactor (MCBR) for drinking water treatment

In this paper, a novel submerged ultrafiltration (UF) membrane coagulation bioreactor (MCBR) process was evaluated for drinking water treatment at a hydraulic retention time (HRT) as short as 0.5h. The MCBR performed well not only in the elimination of particulates and microorganisms, but also in almost complete nitrification and phosphate removal. As compared to membrane bioreactor (MBR), MCBR achieved much higher removal efficiencies of organic matter in terms of total organic carbon (TOC), permanganate index (COD(Mn)), dissolved organic carbon (DOC) and UV absorbance at 254nm (UV(254)), as well as corresponding trihalomethanes formation potential (THMFP) and haloacetic acids formation potential (HAAFP), due to polyaluminium chloride (PACl) coagulation in the bioreactor. However, the reduction of biodegradable dissolved organic carbon (BDOC) and assimilable organic carbon (AOC) by MCBR was only 8.2% and 10.1% higher than that by MBR, indicating that biodegradable organic matter (BOM) was mainly removed through biodegradation. On the other hand, the trans-membrane pressure (TMP) of MCBR developed much lower than that of MBR, which implies that coagulation in the bioreactor could mitigate membrane fouling. It was also identified that the removal of organic matter was accomplished through the combination of three unit effects: rejection by UF, biodegradation by microorganism and coagulation by PACl. During filtration operation, a fouling layer was formed on the membranes surface of both MCBR and MBR, which functioned as a second membrane for further separating organic matter.     

MIEX/超滤一体化工艺净化长江原水的研究

水体中的天然有机物是造成超滤膜污染的重要因素。考察了磁性离子交换树脂(MIEX)/超滤膜一体化净水工艺处理长江原水的效果,并通过与超滤膜直接过滤进行比较,探讨了MIEX预处理对去除有机物的影响及控制膜污染的效果。结果表明,与原水直接进行超滤处理相比,组合工艺对CODMn、DOC、UV254的去除率分别提高了40.70%、38.20%和43.90%。MIEX/超滤工艺控制消毒副产物的优势更为明显,对THMFP和HAAFP的去除率分别达62.54%和55.83%。由于MIEX预处理去除了原水中56.72%的疏水性有机物,降低了超滤膜的负荷,延缓了膜表面致密凝胶层的形成,因而减少了膜孔堵塞,可有效控制运行压力的增长速度,延长过滤时间。     

Purification of oily wastewater by hybrid UF/MD

Investigations on the treatment of oily wastewater by a combination of ultrafiltration (UF) and membrane distillation (MD) as a final purification method have been performed. A tubular UF module equipped with polyvinylidene fluoride (PVDF) membranes and a capillary MD module with polypropylene membranes were tested using a typical bilge water collected from a harbour without pretreatment. The permeate obtained from the UF process generally contains less than 5 ppm of oil. A further purification of the UF permeate by membrane distillation results in a complete removal of oil from wastewater and a very high reduction of the total organic carbon (99.5%) and total dissolved solids (99.9%).     

混凝-超滤去除腐殖酸的试验研究

进行了直接超滤和混凝－超滤组合工艺对腐殖酸的去除效果和膜污染状况的试验。结果表明，超滤前另混凝土预处理对腐殖酸的DOC和UV254的去除率分别从28％、40％提高到53％、78％。同时高效液相色普（HPLC）分析表明，混凝－超滤组合工艺对分子质量＜6000u的有机物的去除率提高幅度更为显著。混凝－超滤组合工艺的最佳pH值条件pH=7,通过卷扫混凝使小分子有机物结合成微絮体，降低了膜孔污染，使超滤保持了较同的渗透通量。     

含炭高密度沉淀池/超滤工艺处理污水厂二级出水

采用含炭高密度沉淀池/超滤组合工艺处理污水厂二级出水,考察了其对常规指标和微量有机污染物的去除效能,并对膜污染特性进行了分析。结果表明,组合工艺对浊度的去除率高达99.9%,出水浊度在0.01 NTU左右;对DOC、UV(254)、TP、氨氮和TN的平均去除率分别为41.02%、49.82%、60.44%、23.34%和10.90%;三维荧光光谱分析表明,组合工艺能有效去除水中的腐殖质和蛋白质类有机物;通过LC-MS/MS检测水中微量有机污染物发现,组合工艺可以使水中的微量有机污染物含量下降66%以上;同时含炭高密度沉淀池预处理能有效减轻膜污染,使跨膜压差增长速度减缓。     

Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM)

An understanding of natural organic matter (NOM) as a membrane foulant and the behavior of NOM components in low-pressure membrane fouling are needed to provide a basis for appropriate selection and operation of membrane technology for drinking water treatment. Fouling by NOM was investigated by employing several innovative chemical and morphological analyses.

Source (feed) waters with a high hydrophilic (HPI) fraction content of NOM resulted in significant flux decline. Macromolecules of a relatively hydrophilic character (e.g. polysaccharides) were effectively rejected by low-pressure membranes, suggesting that macromolecular compounds and/or colloidal organic matter in the hydrophilic NOM fraction may be a problematic foulant of low-pressure membranes. Moreover, the significant organic fouling that is contributed by polysaccharides and/or proteins in macromolecular and/or colloidal forms depends on molecular shape (structure) as well as size (i.e. molecular weight). More significant flux decline was observed in microfiltration (MF) compared to ultrafiltration (UF) membrane filtration. MF membrane fouling may be caused by pore blockage associated with large (macromolecular) hydrophilic molecules and/or organic colloids. In the case of UF membranes, the flux decline may be caused by sequential or simultaneous processes of surface (gel layer) coverage during filtration. Morphological analyses support the notion that membrane roughness may be considered as a more important factor in membrane fouling by controlling interaction between molecules and the membrane surface, compared to the hydrophobic/hydrophilic character of membranes. Membrane fouling mechanisms are not only a function of membrane type (MF versus UF) but also depend on source (feed) water characteristics.     

Adsorption combined with ultrafiltration to remove organic matter from seawater

Organic fouling and biofouling are the major severe types of fouling of reverse osmosis (RO) membranes in seawater (SW) desalination. Low pressure membrane filtration such as ultrafiltration (UF) has been developed as a pre-treatment before reverse osmosis. However, UF alone may not be an effective enough pre-treatment because of the existence of low-molecular weight dissolved organic matter in seawater. Therefore, the objective of the present work is to study a hybrid process, powdered activated carbon (PAC) adsorption/UF, with real seawater and to evaluate its performance in terms of organic matter removal and membrane fouling. The effect of different PAC types and concentrations is evaluated. Stream-activated wood-based PAC addition increased marine organic matter removal by up to 70% in some conditions. Moreover, coupling PAC adsorption with UF decreased UF membrane fouling and the fouling occurring during short-term UF was totally reversible. It can be concluded that the hybrid PAC adsorption/UF process performed in crossflow filtration mode is a relevant pre-treatment process before RO desalination, allowing organic matter removal of 75% and showing no flux decline for short-term experiments.     

Studies on the effect of humic acids and phenol on adsorption-ultrafiltration process performance

Application of pressure-driven membrane processes, such as ultrafiltration (UF) and microfiltration (MF) for surface water treatment have become very popular during last decades. Membrane fouling by humic substances (HS) is one of the major limiting factors in these processes. In order to alleviate the unfavorable effects of the presence of HS in the feed on the process performance UF and MF are often combined with adsorption on powdered activated carbon (PAC). The main goal of the present study was to evaluate the effect of humic acid (HA) on membrane fouling during UF. Moreover, the effect of PAC addition to the feed on UF process, especially on flux decline was determined. The applicability of the adsorption-ultrafiltration (PAC/UF) system to purification of water containing low (phenol) and high molecular (HA) was also investigated. Three different polymer UF membranes, prepared from polysulfone (PSF), cellulose acetate (CA) or polyacrylonitrile (PAN) were applied. It was found that the membranes prepared from PSF and CA are very susceptible to fouling caused by HA. The permeate flux decreased for ca. 50% during UF of HA solution through the PSF membrane and for ca. 45%-through the CA membrane. In the case of the PAN membrane, a negligible effect of HA on the flux was observed. On the basis of the FTIR spectra it was found that the drop in the permeate flux through these membranes may result from interactions between the negatively charged functional groups present on the membrane surface, such as carboxyl groups (CA) and sulfone groups (PSF) with HA, which results in coating of the membrane surface with HA. When PAC was added to the feed containing HA, the permeate flux through the CA and PAN membranes was maintained on a practically unchanged level. However, in case of the PSF membrane, a 50% drop in the permeate flux in comparison with the flux value, when process was conducted without PAC addition was observed. That was supposed to be due to attractive forces among hydrophobic PAC particles, HA molecules and PSF membrane surface. The performed studies showed that the application of PAC/UF system was very effective in the removal of organic substances having both, low and high molecular weights. The role of PAC suspended in a feed in the PAC/UF system is the adsorption of low molecular organic compounds, which cannot be removed by UF alone.     

磁性离子交换树脂与超滤膜联用处理淮河原水

采用磁性离子交换树脂(MIEX)/混凝沉淀/超滤膜(UF)工艺处理淮河原水,考察了对有机物的去除特性以及MIEX预处理控制膜污染的效果.结果表明:UF出水浊度稳定在0.1NTU以下,粒径>2 μm的颗粒数平均为11个/mL,粒径>10μm的颗粒物被完全去除;组合工艺对CODMn和UV254的去除率分别为75.3%和90%,且能有效去除不同分子质量区间的有机物;系统对疏水性有机物(HOM)、弱疏水性有机物(WHOM)、荷电亲水有机物(HIC)的去除效果均较好,去除率分别为94.6%、82.7%和81.3%;组合工艺对三卤甲烷生成势(THMFP)和卤乙酸生成势(HAAFP)的去除率分别为90.7%和87.6%;MIEX预处理可有效减缓膜污染,运行期间超滤膜的跨膜压差上升缓慢,经水力反冲洗后跨膜压差就基本得到恢复.     

Fouling characteristics of NF and RO operated for removal of dissolved matter from groundwater

A pilot study had been performed for about 6 months in order to investigate the removal efficiency of dissolved matter and its fouling potential during nanofiltration (NF) and reverse osmosis (RO) of local groundwater that was pretreated with an ultrafiltration (UF) membrane system. After pilot plant operation, autopsy tests were performed to identify the characteristics of foulants that were attached to the membrane surface. In the autopsy tests, the flux recovery for each specific cleaning scheme (hydraulic washing, acid cleaning, and alkaline cleaning) was also measured using a dead-end filtration cell unit. The washing solution used in each chemical cleaning was analyzed to identify major components of the foulants, and the membrane surface was observed using the scanning electron microscopy (SEM).Among three kinds of membranes tested, one NF and two RO membranes, the NF and RO1 membranes showed a rapid flux decline after 100 days of operation. Especially, the RO1 membrane showed the more serious flux decline than the NF membrane. The RO2 membrane, with the lowest recovery rate, demonstrated a gradual flux decline. The removal efficiency of dissolved inorganic matter (as conductivity) for each NF, RO1 and RO2 membrane was 76.3%, 88.2% and 95.3%, respectively. The removal of dissolved organic matter (as total organic carbon) was found to be about 80% for both NF and RO membranes used in this study. During the membrane autopsy tests, five sections of the fouled membrane were cut along each NF and RO membrane module from the feed inlet side to the concentrate outlet side, the specific flux for each membrane section was measured before and after each cleaning step. As expected, the degree of fouling was intensified along the membrane surface as the feed flow approached the outlet. Based on the analysis results of wash water used in each cleaning step, the major foulants attached to the membrane surface appeared to be Ca bound with inorganic matter and Si bound with organic matter. Fe seemed to be a great contributor to irreversible fouling. The SEM analysis indicated that the organic matter was forming the first fouling layer close to the membrane and that the inorganic matter was layered top of the organic fouling layer in a tetragonal shape. Any evidence of biofouling was not observed in this study because most of microorganisms had been already removed by the UF pretreatment.     

Combined coagulation-disk filtration process as a pretreatment of ultrafiltration and reverse osmosis membrane for wastewater reclamation: an autopsy study of a pilot plant

The effects of the combined coagulation-disk filtration (CC-DF) process on the fouling characteristics and behavior caused by interactions between effluent organic matter (EfOM) and the membrane surfaces of the ultrafiltration (UF) and reverse osmosis (RO) membranes in a pilot plant for municipal wastewater reclamation (MWR) were investigated. The feed water from secondary effluents was treated by the CC-DF process used as a pretreatment for the UF membrane to mitigate fouling formation and the permeate from the CC-DF process was further filtered by two UF membrane units in parallel arrangement and fed into four RO modules in a series connection. The CC-DF process was not sufficient to mitigate biofouling but the UF membrane was effective in mitigating biofouling on the RO membrane surfaces. Fouling of the UF and RO membranes was dominated by hydrophilic fractions of EfOM (e.g., polysaccharide-like and protein-like substances) and inorganic scaling (e.g., aluminum, calcium and silica). The desorbed UF membrane foulants included more aluminum species and hydrophobic fractions than the desorbed RO membrane foulants, which was presumably due to the residual coagulants and aluminum-humic substance complexes. The significant change in the surface chemistry of the RO membrane (a decrease in surface charge and an increase in contact angle of the fouled RO membranes) induced by the accumulation of hydrophilic EfOM onto the negatively charged RO membrane surface intensified the fouling formation of the fouled RO membrane by hydrophobic interaction between the humic substances of EfOM with relatively high hydrophobicity and the fouled RO membranes with decreased surface charge and increased contract angle.     

Is semi-flocculation effective as pretreatment to ultrafiltration in wastewater treatment?

In this study, ferric chloride (FeCl(3)) flocculation was used as a pretreatment to ultrafiltration (UF) in treating synthetic wastewater containing synthetic organic matter (SOM). The effect of flocculant dose was studied in terms of organic removal and membrane flux decline. The UF with optimum dose of FeCl(3) (68 mg L(-1)) did not experience any flux decline during the whole operation of 6 h. The preflocculation with a smaller dose of 20 mg L(-1) of FeCl(3) led to a severe flux decline in the UF (more than 65% in 6 h). To understand the phenomenon of the flux decline of UF, the MW ranges of SOM removed by different doses of FeCl(3) and by the post treatment of UF were studied. Flocculation with at least 50 mg L(-1) of FeCl(3) dose was found to be necessary to avoid any significant flux decline and to obtain superior DOC removal.     

PAC/PS预处理对水中镉的去除及UF膜污染控制

采用粉末活性炭耦合过硫酸盐(PAC/PS)作为超滤的预处理工艺,考察其对原水中镉和天然有机物的去除效果,以及对超滤膜污染控制的影响。结果表明,对于镉超标6倍的原水水样,当PAC和PS投加量分别为30 mg/L和300μmol/L、接触时间为60 min时,UV₂₅₄、DOC和镉的去除率分别可达到91.7%、68.2%和92.7%,镉浓度可降至《生活饮用水卫生标准》(GB 5749—2006)规定的限值(5μg/L)以下;与直接超滤相比,设置PAC/PS预处理工艺后超滤膜比通量提升了50.5%,XDLVO预测模型中胶体污染物-超滤膜相互作用的总界面能降低了75.38%,超滤膜污染减轻。