Fouling and natural organic matter removal in adsorbent/membrane systems for drinking water treatment

Adsorbent particles added to ultrafiltration (UF) systems treating drinking water can remove natural organic matter (NOM) and some other contaminants from the water, but their effect on membrane fouling is inconsistent-in some cases, fouling is reduced, and in others, it is exacerbated. This research investigated the behavior of UF systems to which powdered activated carbon (PAC), heated iron oxide particles (HIOPs), or (nonadsorbent) SiO2 particles were added. On a mass basis, the PAC removed the most NOM from solution, the HIOPs removed less, and the SiO2 removed essentially none. However, in the case of both PAC and SiO2, increasing the dose of solids led to a steady increase in fouling, whereas the opposite trend applied when HIOPs were added. In the absence of NOM, none of the solids fouled the membrane significantly. Thus, even though NOM is a causative agent for fouling, removing it from solution does not necessarily reduce fouling; the mechanism of removal can be just as important as the absolute amount removed, if the removal occurs in a cake layer near the membrane surface. Scanning electron microscopy images of the cake layers formed in the three systems suggest that the NOM binds PAC or SiO2 particles to one another and to the membrane surface, so that the particles become part of the foulant in the system. By contrast, the NOM appears to bind HIOPs to one another but not to the membrane. This process leaves enough pore space in the cake layer for water to reach the membrane with minimal resistance, and it reduces the tendency for either the NOM or the HIOPs to foul the membrane surface.     

膜集成工艺浓缩灵芝水提液的研究

高效节能的膜集成技术已开始应用于食品和药用植物中有效成分的分离提取。文中针对灵芝提取液的特性,依据微孔过滤(MF)、超滤(UF)、纳滤(NF)各种膜对特定物质的选择分离性能,设计了新型膜集成工艺,即筛网和滤纸粗过滤除杂和MF净化处理,进而用不同切割分子质量(MWCO)膜进行两级UF、最后用NF净化浓缩灵芝水提液的创新技术。在操作压力≤0.20 MPa和15 m/s的高膜面流速,1.0 mL/(cm~2·h)恒通量模式下,灵芝水提液先后经MWCO分别为5万的聚丙烯腈(PAN)膜和1万的醋酸纤维素(CA)膜进行UF批次处理。UF渗透液再经截留分子质量为1 50～300的DK(标准)型聚酰胺(PA)膜进行纳滤浓缩,浓缩倍数达6倍时,渗透通量在0.92～0.33 mL/(cm~2·h),纳滤渗透液的色度在浓缩过程稳定在70～80,有效成分截留率高。     

Effects of palm oil-based fatty acids on fouling of ultrafiltration membranes during the clarification of glycerin-rich solution

Ultrafiltration (UF) is an alternative option that can be used to clarify glycerin-rich solutions in the oleochemical industry. However, the UF membranes used in the process were observed to have been seriously fouled in our preliminary study. Thus, the ultrafiltration of a glycerol-water-fatty acid mixture was carried out to investigate the membrane binding properties of the components and their contributions to membrane fouling. Palmitic, stearic, and oleic acid were used as fouling substances in the glycerol-water mixture. The flux decline experiments were carried out using polyvinylidenefluoride (PVDF) as well as polyethersulphone (PES) membranes with a MWCO of 30 and 25 kDa, respectively at specific conditions (T = 40 °C; ΔP = 2 bar). It was found that the PES membrane exhibited severe fouling for all types of fatty acids in solution with glycerol-water. As the pH decreased to acidic conditions, the PES membrane tended to exhibit more severe fouling than the PVDF membrane.     

Three-component competitive adsorption model for flow-through PAC systems. 2. Model application to a PAC/membrane system

A three-component competitive adsorption kinetic model, developed and validated in part 1 of this study, was applied to a continuous-flow PAC/membrane system to study the effects of various system and operating parameters on organic removal. The model quantitatively describes the two competitive adsorption mechanisms that occur during adsorption of trace organic compounds by powdered activated carbon (PAC) in flow-through systems where the PAC is retained in the system: pore blockage and direct competition for adsorption sites. Model simulations were conducted to investigate the effects of influent water composition, membrane cleaning water quality, PAC pore size distribution, and system operation conditions such as hydraulic retention time, membrane cleaning interval, and PAC dosing method on treatment efficiency. Effects of these factors on adsorption capacity as well as surface diffusion rate and consequent removal of the trace organic compound were discussed. It was found that optimal operating conditions for maximum trace organic compound removal must be determined on the basis of the adsorption properties and concentrations of the competing compounds in the influent. For the conditions investigated in this study, the small strongly competing compound, p-DCB, had greater impact on atrazine removal than the large pore-blocking compound, PSS-1.8k. Various process design and operating parameters had complex and interrelated effects on the impact of competitive adsorption and corresponding trace contaminant removal efficiency in hybrid PAC/membrane systems.     

PES亲水改性超滤膜澄清葡萄原酒研究

以抗菌、亲水性的TiO2为改性材料,采用相转化法制备PES/TiO2亲水改性超滤膜,用于葡萄原酒澄清研究。通过扫描电镜、傅立叶红外光谱仪和接触角测定仪对超滤前后的膜进行表征,结果显示,TiO2的加入增加了膜面粗糙度及亲水性,降低了原酒中蛋白质、多糖等大分子物质在膜面的吸附污染,使得改性膜超滤葡萄原酒渗透通量衰减率低于纯PES膜,提高了膜的抗污染性。当TiO2添加量为0.75%时,超滤2h,其渗透通量为18.09L/(m2·h)(纯膜为16.88L/(m2·h)),超滤后的葡萄酒液澄清度好。      

Modes of natural organic matter fouling during ultrafiltration

The fouling of ultrafiltration membranes by natural organic matter (NOM), isolated from a potable surface water source, was studied with an emphasis on elucidating fouling modes and the role of aggregates. NOM size was related to membrane pore sizes using parallel membrane fractionation and size exclusion chromatography, such analyses confirmed the predominance of low MW species and identified the presence of aggregates in concentrated NOM solutions. Cake formation was the dominant mode of fouling by the unfiltered feed, which contained aggregates. This was identified by a constant rate of increase in membrane resistance with permeate throughput and was independent of pore size over a 10-1000 kDa molecular weight cutoff (MWCO) range. Prefiltration (to remove aggregates) and dilution (to reduce aggregate concentration) reduced the rate of increase in membrane resistance for the low MWCO membranes but did not change the fouling mode. In contrast, such pretreatment prevented cake formation on the larger MWCO membranes and shifted the mode of fouling to pore blockage. The date lend support for the idea that an initial fouling layer of large aggregates can catalyze the fouling by lower MW species. The fouling layer could be removed from the large MWCO membranes by backwashing, but the lower MWCO membranes exhibited some irreversible fouling, suggesting that low MW species penetrated into the pore structure. A combined pore blockage-cake formation model described the data well and provided insight into how fouling modes evolve during filtration.     

Effect of Membrane Material on the Separation of Proteins and Polyphenol Oxidase in Ultrafiltration of Potato Fruit Juice

Ultrafiltration was applied to diluted potato fruit juice, a side-stream from potato starch production. The aim of the study was to selectively concentrate the potato proteins in the permeate, while isolating polyphenol oxidase (PPO) in the retentate. A profound difference was found in protein retention between two 300-kDa molecular weight cutoff (MWCO) ultrafiltration membranes, of either regenerated cellulose (RC) or polyethersulfone (PES). The use of the 300-kDa MWCO RC membrane resulted in a twofold higher retentate protein content as well as total retention of all PPO activity, as compared with the PES membrane. Comparison tests with 100- and 300-kDa MWCO PES membranes indicated that concentration polarization and gel layer formation, and not MWCO definitions, were governing factors for protein retention, since proteins with a MW of 10 kDa were retained in all the experiments. PPO activity in potato fruit juice was measured in permeate and retentate to assess its selective retention by the applied ultrafiltration processes. Of the specific PPO activity, 94–100 % was retained by either 300 MWCO RC or 100 MWCO PES, while only 49 % specific activity was retained by the 300 MWCO PES. By in situ blotting experiments, the molecular weight of active PPO was found to be present at three different molecular weights, at positions of 40, 47, and 100 kDa, respectively, with the major activity present at 47 kDa.     

Influence of flocculation and adsorption as pretreatment on the fouling of ultrafiltration and nanofiltration membranes: application with biologically treated sewage effluent

Membrane fouling is a critical limitation on the application of membranes to wastewater reuse. This work aims to understand the fouling phenomenon which occurs in ultrafiltration (UF; 17500 molecular weight cutoff (MWCO)) and nanofiltration (NF; 250 MWCO) membranes, with and without pretreatment. For this purpose, the molecular weight (MW) distribution of the organics has been used as a parameter to characterize the influent, the permeate, and the foulant on the membrane surface. The variation of foulant concentration on the membrane due to pretreatment of the influent by flocculation and/or adsorption was investigated in detail. With the UF membrane, the peak of the MW distribution of organics in the permeate depended on the pretreatment; for example, the weight-averaged MW (Mw) of 675 without pretreatment shifted down to 314 with pretreatment. In the case of the NF membrane, the Mw of organics in the permeate was 478 (without pretreatment) and 310 (with flocculation followed by adsorption). The Mw of the organics in the foulant on the membrane surface was 513 (UF) and 192 (NF) without pretreatment and 351 (UF) and 183 (NF) after pretreatment with flocculation followed by adsorption, respectively. Without the pretreatment, the foulant concentration was higher on both membranes. The difference was more significant on the UF membrane than on the NF membrane. For both membranes, the flocculation-and-then-adsorption pretreatment proved very effective.     

Stoichiometry of removal of natural organic matter by ion exchange

Five anion exchange resins, including a magnetic ion exchange (MIEX) resin, were evaluated for removal of Suwannee River Fulvic Acid (SRFA) in the presence of bicarbonate and chloride. The charge density of SRFA, obtained by potentiometric titration, was used to perform charge balances for ion exchange reactions involving SRFA, bicarbonate, and chloride under different solution conditions. The results clearly show the equivalence of SRFA uptake and chloride release by ion exchange. Although the structure of the anion exchange resins did not affect the stoichiometry of the reaction, the polyacrylic resins did exhibit greater removal of SRFA than the polystyrene resins. The hindered removal of SRFA by the polystyrene resins was hypothesized to be a result of size exclusion. The MIEX resin, which has a polyacrylic structure, performed similarly to the other polyacrylic resins. For the MIEX resin, the separation factor for SRFA over chloride was approximately 8 times greater than for bicarbonate over chloride. This work provides an improved understanding of the interactions between natural organic matter (NOM), inorganic anions, and anion exchange resins, and should result in more effective applications of ion exchange for the removal of NOM in the treatment of drinking water.     

Low molecular weight components in an aquatic humic substance as characterized by membrane dialysis and orbitrap mass spectrometry

Suwannee River fulvic acid (SRFA) was dialyzed through a 100-500 molecular weight cutoff dialysis membrane, and the dialysate and retentate were analyzed by UV-visible absorption and high-resolution Orbitrap mass spectrometry (MS). A significant fraction (36% based on dissolved organic carbon) of SRFA passed through the dialysis membrane. The fraction of SRFA in the dialysate had a different UV-visible absorption spectrum and was enriched in low molecular weight molecules with a more aliphatic composition relative to the initial SRFA solution. Comparison of the SRFA spectra collected by Orbitrap MS and Fourier transform ion cyclotron resonance MS (FT-ICR MS) demonstrated that the mass accuracy of the Orbitrap MS is sufficient for determination of unique molecular formulas of compounds with masses <600 Da in a complex mixture, such as SRFA. The most intense masses detected by Orbitrap MS were found in the 100-200 Da mass range. Many of these low molecular masses corresponded to molecular formulas of previously identified compounds in organic matter, lignin, and plants, and the use of the standard addition method provided an upper concentration estimate of selected target compounds in SRFA. Collectively, these results provide evidence that SRFA contains low molecular weight components that are present individually or in loosely bound assemblies.     

Fractionation of Soy Protein Hydrolysates using Ultrafiltration Membranes

The effect of membrane pore size on the molecular weight distribution and selected functional properties of a protein hydrolysate produced from soy isolate and Pronase was examined. Molecular weight distributions were similar for permeates from 5000, 10,000 and 50,000 molecular weight cut-off (MWCO) membranes: two large fractions at 2300 and 1000 daltons. The 100,000 MWCO membrane resulted in three fractions of 25,000, 13,000 and 2300 daltons. Solubility of the hydrolysate increased with decrease in MWCO, while foam stability decreased.     

超滤对石榴汁抗氧化活性的影响

主要探讨不同截留分子量(100、30、10ku)的超滤膜对石榴汁的澄清效果及抗氧化活性的影响,以确定生产高抗氧化活性澄清石榴汁的最适超滤膜。结果表明,30ku超滤膜对石榴汁的澄清效果较好,可保存其酚类化合物、花色苷、VC等抗氧化活性成分80%左右,使DPPH自由基清除活性和FRAP损失在16%以下。因此,建议采用30ku超滤膜澄清石榴汁,以得到具有高抗氧化活性的石榴汁。      

An economic assessment of proteins recovery from fish meal effluents by ultrafiltration

The main objective of this work was to assess the technical and economical feasibility of proteins recovery from fish meal effluents using crossflow membrane technology, namely, ultrafiltration (UF) and nanofiltration (NF).Mackerel processing effluents were pre-treated by microfiltration (MF cartridges battery of 80, 20 and 5 μm pore size) followed by UF (membrane Carbosep M2, 15 kDa MWCO) or NF (membrane Kerasep NanoN01A, 1 kDa MWCO). A suitable treatment for the fish meal effluents consisted of a MF pre-treatment followed by UF operating at 4 bar, 4 m/s, natural pH and ambient temperature. UF yielded an average permeation flux of 28 l/(m² h),¹ and 62% proteins rejection for a volume reduction factor of 2.3. Both membranes fully recovered their original permeabilities through an acidic/basic washing cycle. The economic assessment of proteins recovery from fish meal effluents by UF was accomplished for a production of 544 ton/yr of fish meal (66% protein content), yielding a net present worth of 160×10³ US$, interest rate of return of 17% and payback time of 8 years.     

Preparation of milk protein concentrates by ultrafiltration and continuous diafiltration: Effect of process design on overall efficiency

High-milk-protein concentrates (>80% on a dry weight basis) are typically produced by ultrafiltration (UF) with constant-volume diafiltration (DF). To maximize protein retention at a commercial scale, polymeric spiral-wound UF membranes with a molecular weight cut-off (MWCO) of 10 kDa are commonly used. Flux decline and membrane fouling during UF have been studied extensively and the selection of an optimal UF-DF sequence is expected to have a considerable effect on both the process efficiency and the volumes of by-products generated. The objective of this study was to characterize the performance of the UF-DF process by evaluating permeate flux decline, fouling resistance, energy and water consumption, and retentate composition as a function of MWCO (10 and 50 kDa) and UF-DF sequence [3.5×–2 diavolumes (DV) and 5×–0.8DV]. The UF-DF experiments were performed on pasteurized skim milk using a pilot-scale filtration system operated at 50°C under a constant transmembrane pressure of 465 kPa. The results showed that MWCO had no effect on permeate flux for the same UF-DF sequence. Irreversible resistance was also similar for both sequences, whatever the MWCO, suggesting that soluble protein deposition within the pores is similar for all conditions. Despite lower permeate fluxes and greater reversible resistance for the 5×–0.8DV sequence, the overall energy consumption of the 2 UF-DF sequences was similar. However, the 3.5×–2DV sequence required more water for DF and generated larger volumes of permeate to be processed, which will require more membrane area and lead to greater environmental impact. A comparative life cycle assessment should however be performed to confirm which sequence has the lowest environmental impact.     

Charge effects in the fractionation of natural organics using ultrafiltration

Comparison of two commonly used techniques for molecular weight determination of natural organics, ultrafiltration (UF) fractionation and high-performance size exclusion chromatography (SEC), shows that neither technique gives absolute measures of molecular weight. Investigations of International Humic Substances Society standard humic and fulvic acids as well as natural organic matter concentrated from surface freshwaters show that charge effects and solution conditions are important in both SEC and UF fractionation with various components of the natural organics being affected differently. Membranes with a smaller molecular weight cutoff (MWCO) produce permeates with a lower UV/DOC ratio, suggesting that the more aromatic components of natural organics are removed by the lower molecular weight cutoff membranes. Variation in ionic strength has little effect on the rejection of humic acid fractions but does significantly influence the rejection of low molecular weight acids. pH and organic concentration do not affect DOC rejection significantly over the pH range of 4.5-10 and the DOC concentration range of 15-60 mgL(-1). These results indicate that UF should not be applied for quantitative "size" analysis unless performed under well-defined conditions. If performed under conditions appropriate to water treatment, UF fractionation can give information of direct applicability to treatment such as the MWCO required to achieve significant organics removal.     

Soymilk concentration by ultrafiltration: effects of pore size and transmembrane pressure on filtration performance

The effects of membrane pore size and operating pressure on filtration flux, membrane fouling and solute rejections of soymilk during ultrafiltration were studied. Soymilk was concentrated from an initial level of 6.5% solid content to 20% solid content using ultrafiltration membranes. Hollow fibre cross‐flow type cartridges having molecular weight cut‐off (MWCO) as 1, 10 and 30 kDa were used in the experiments. Filtration data were satisfactorily fitted to De La Garza and Boulton's exponential model to find the exponential fouling coefficient (k) and the membrane resistance (R_m). The permeate fluxes obtained in 10 and 30‐kDa MWCO membranes were found to be approximately four times higher than that of 1‐kDa MWCO membrane, at transmembrane pressure between 100 and 240 kPa. The average flux obtained was 0.7, 3.15 and 2.7 L m^?2‐h for 1, 10 and 30‐kDa MWCO membranes, respectively. The R_m value of membranes was found to decrease as the MWCO of membranes increased and transmembrane pressure decreased. The total solid content of permeates obtained by these membranes was between 0.45% and 1.4%. Membrane‐concentrated soymilk was found to have lighter colour and almost half the value of viscosity compared with evaporated milk.     

Competitive effects of natural organic matter: parametrization and verification of the three-component adsorption model COMPSORB

Natural organic matter (NOM) hinders adsorption of trace organic compounds on powdered activated carbon (PAC) via two dominant mechanisms: direct site competition and pore blockage. COMPSORB, a three-component model that incorporates these two competitive mechanisms, was developed in a previous study to describe the removal of trace contaminants in continuous-flow hybrid PAC adsorption/membrane filtration systems. Synthetic solutions containing two model compounds as surrogates for NOM were used in the original study to elucidate competitive effects and to verify the model. In the present study, a quantitative method to characterize the components of NOM that are responsible for competitive adsorption effects in natural water was developed to extend the application of COMPSORB to natural water systems. Using batch adsorption data, NOM was differentiated into two fictive fractions, representing the strongly competing and pore blocking components, and each was treated as a single compound. The equilibrium and kinetic parameters for these fictive compounds were calculated using simplified adsorption models. This parametrization procedure was carried out on two different natural waters, and the model was verified with experimental data obtained for atrazine removal from natural water in a PAC/membrane system. The model predicted the system performance reasonably well and highlighted the importance of considering both direct site competition and pore blockage effects of NOM in modeling these systems.     

结冷胶发酵液微滤除菌工艺

采用有机微滤膜对结冷胶发酵液进行过滤除菌实验。考察了不同膜材料的过滤性能,以及结冷胶浓度、温度、压力等操作参数对除菌效果的影响。将结冷胶发酵液脱酰基处理后稀释成浓度为3 g/L的料液,再将酸碱度调至pH10,在0.1 MPa、65℃下用孔径为0.45μm的聚醚砜膜过滤,菌体去除率和结冷胶回收率分别为97%和84%。滤膜污染后采用0.75%HCl和1%NaOH交替清洗,可使膜通量得到较好地恢复。     

超滤技术在芹菜汁澄清工艺中的应用研究

选用芹菜(犹他改良5270品种)为原料,研究了国产超滤膜聚砜(PS)、磺化聚砜(CMPS)、聚丙烯腈(PAN)对芹菜澄清汁的质量影响,获得了超滤芹菜汁的工艺参数。结果表明,国产PAN-1万平板超滤膜对芹菜汁的澄清效果明显,在0.15MPa压力下,透光率由18.7%.上升至98.8%,除果胶和蛋白质被截留外,超滤前后芹菜汁中可溶性固形物、总糖、还原糖、pH、矿质元素的含量变化不大,表明超滤可较大程度地保存芹菜汁中的营养物质。     

Three-component adsorption modeling to evaluate and improve integrated sorption-membrane processes

Integrated sorption-membrane (ISM) processes combining low-pressure membranes with adsorbents are increasingly popular because they cost-effectively expand low-pressure membrane treatment to include dissolved contaminant removal. However, contemporary ISM processes often exhibit antagonistic tradeoffs between adsorption and membrane performance that were investigated using state-of-the-art adsorption models that include both of the predominant competitive effects of natural organic matter: direct site competition and pore blockage. Two currently used ISM process configurations, powdered activated carbon-ultrafiltration (PAC-UF) and adsorptive floc blanket reactor-ultrafiltration (FBR-UF), were compared with a novel configuration, upflow adsorption-ultrafiltration (UA-UF), which consists of a moving-bed of granular activated carbon upstream of a membrane. Model simulations quantitatively compared performance and evaluated potential improvements for each configuration. For instance, using contemporary PAC-UF practices and 90% atrazine removal as a baseline, alternative membrane backwashing procedures can lower carbon usage rates (CURs) by 75% but may also reduce membrane hydraulic performance. Using the same baseline, FBR-UF can reduce CURs by 92% while simultaneously improving membrane performance via pretreatment; however, process size increases 10-fold. The novel UA-UF configuration only increases process size modestly, but can still yield CURs 96% lower than the PAC-UF baseline while simultaneously providing beneficial membrane pretreatment and improving sustainability features by reducing residuals.