Analysis of the fouling mechanisms during cross-flow ultrafiltration of apple juice

The purpose of this work was to study the fouling mechanisms of a Carbosep^® M8 membrane during the cross-flow ultrafiltration of apple juice. A new fouling model has been developed that simultaneously considers membrane blocking within the pores, at the pore mouths and by cake formation at the membrane surface. Membrane fouling by apple juice was due to internal pore blocking as well as cake formation. When operating ultrafiltration at a transmembrane pressure of 150 kPa and a cross-flow velocity of 7 m/s, fouling was minimal with a gradual decrease of the relative contribution of cake formation; however, transmembrane pressure still exceeds critical pressure. The fouling model predicts no cake formation at a cross-flow velocity of 7.4 m/s and a transmembrane pressure of 150 kPa or at a cross-flow velocity of 7.0 m/s and a transmembrane pressure of 120 kPa. Under these conditions, internal membrane blocking would be the only mechanism responsible for the decrease of permeate flux.     

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.     

柚皮果胶超滤的凝胶-衰减模型

采用陶瓷膜时柚皮果胶提取液进行超滤浓缩,考察并分析了膜通量与跨膜压力的关系,建立了描述柚皮果胶提取液超滤过程膜污染的凝胶_衰减模型:当跨膜压力△P＜最佳跨膜压力△Popt时,超滤行为遵循凝胶极化模型,通量随跨膜压力的增加而上升,当达到稳定态时有J=Kln(cG/cB),此时凝胶层中溶质果胶的浓度cG为20.53mg·mL-1;当△P≥△Popt时,超滤行为遵循衰减模型,其衰减方程为:J=5.464×1010(△P)-3.026,膜通量按指数形式衰减.该模型较合理地解释了膜通量与跨膜压力之间呈现钟形关系的原因,有助于指导柚皮果胶提取液的超滤工艺.     

Secondary wastewater polishing with ultrafiltration membranes for unrestricted reuse: fouling and flushing modeling

The effects of operating parameters such astransmembrane pressure, retentate, and recirculation volumetric flow rates on the productivity of an ultrafiltration membrane were studied using field data and development of a management model. Correlation equations for predicting the volumetric permeate flow rates were derived from general membrane blocking laws and experimental data. The experimental data were obtained from a pilot study carried out in the Arad wastewater treatment system (a pilot plant operating in feed and bleed operation mode) located several kilometers west of the City of Arad, Israel. Correlation predictions were confirmed with the independent experimental results. The results enabled us to develop a mathematical expression accurately describing the decline in flux due to fouling.     

Flux pattern and fouling of membranes during ultrafiltration of some dairy products

The flux pattern of milk (whole milk, skimmed milk and buttermilk) showed a distinct contrast to whey (sweet whey and acid casein whey) systems during ultrafiltration (UF) at constant composition. For milk systems, the initial flux was lower than for whey systems, but the flux stabilised within a few minutes of operation. However, for both acid and sweet whey, the flux continued to fall with time for nearly 1 h. The fouling coefficient (FC) for buttermilk was 0.6 after 5 min, rising to 0.68 after 60 min. During this time flux did not decline, suggesting that concentration polarisation (CP), rather than fouling, was controlling the flux rate. In contrast, the FC for whey was 0.5 after 5 min with a progressive rise over the next 55 min, but the flux also fell throughout this period suggesting that flux was controlled by fouling rather than CP. The higher concentration of protein in milk systems appeared to be responsible for CP, rather than fouling, being the controlling mechanism.     

Optimising operating conditions in ultrafiltration fouling of pomegranate juice by response surface methodology

The resistance‐in‐series model was used to analyse flux behaviour, which involved the resistances of membrane itself, the fouling and solute concentration polarisation. Response surface methodology was used to establish the relationships between operating parameters and ultrafiltration (UF) efficiency and thus to determine optimal conditions. Experiments were performed according to Box–Behnken design by changing the levels of three parameters, namely transmembrane pressure, feed flow rate and temperature. The fitted mathematical models allowed us to plot isoresponse curves. It was shown that the resistance due to solute concentration polarisation (R_cp) dominated the flux decline (40–74%). The fouling resistance (R_f) varied from 12 to 46%. To optimise simultaneously the three responses studied (R_f, R_cp and permeate limit flux), we applied the desirability function approach which allowed us to determine the best acceptable compromise. The selected UF conditions of the compromise were as follows: three bars, 0.95 L min^?1 and 30 °C. Optimal values of R_f, R_cp and permeate limit flux were equal to 18%, 72% and 19 L h^?1 m^?2, respectively.     

Mechanism involved in the evolution of physically irreversible fouling in microfiltration and ultrafiltration membranes used for drinking water treatment

Control of membrane fouling is important for more efficient use of membranes in water treatment. Control of physically irreversible fouling, which is defined as fouling that requires chemical cleaning to be cancelled, is particularly important for reduction of operation cost in a membrane process. In this study, a long-term filtration experiment using three different types of MF and UF membranes was carried out at an existing water purification plant, and the evolution of physically irreversible fouling was investigated. The experimental results demonstrated that the extent of physically irreversible fouling differed significantly depending on the membrane type. Cleaning of the fouled membranes with various chemical reagents demonstrated that organic matter was mainly responsible for physically irreversible fouling. Organic matter that had caused physically irreversible fouling in the long-term operation was desorbed from the fouled membranes and was subjected to Fourier transform infrared and 13C nuclear magnetic resonance analyses. These analyses revealed that carbohydrates were dominant in the membrane foulant regardless of the type of membrane. Based on measurements of molecular weight distribution of organic matter in the feedwater and the permeates from the membranes, a two-step fouling mechanism is proposed to explain the dominance of carbohydrates in the foulant: hydrophobic (humic-like) components with small molecular weight are first adsorbed on the membrane and, consequently, narrow the size of micro-pores of membranes, and then hydrophilic (carbohydrate-like) compounds with larger molecular weight plug the narrowed pores or the hydrophilic compounds are adsorbed onto the membrane surface conditioned by the hydrophobic components.     

Effect of skim milk treated with high hydrostatic pressure on permeate flux and fouling during ultrafiltration

Ultrafiltration (UF) is largely used in the dairy industry to generate milk and whey protein concentrate for standardization of milk or production of dairy ingredients. Recently, it was demonstrated that high hydrostatic pressure (HHP) extended the shelf life of milk and improved rennet coagulation and cheese yield. Pressurization also modified casein micelle size distribution and promoted aggregation of whey proteins. These changes are likely to affect UF performance. Consequently, this study determined the effect of skim milk pressurization (300 and 600 MPa, 5 min) on UF performance in terms of permeate flux decline and fouling. The effect of HHP on milk proteins was first studied and UF was performed in total recycle mode at different transmembrane pressures to determine optimal UF operational parameters and to evaluate the effect of pressurization on critical and limiting fluxes. Ultrafiltration was also performed in concentration mode at a transmembrane pressure of 345 kPa for 130 or 140 min to evaluate the decline of permeate flux and to determine fouling resistances. It was observed that average casein micelle size decreased by 32 and 38%, whereas β-lactoglobulin denaturation reached 30 and 70% at 300 and 600 MPa, respectively. These results were directly related to UF performance because initial permeate fluxes in total recycle mode decreased by 25% at 300 and 600 MPa compared with nonpressurized milk, critical flux, and limiting flux, which were lower during UF of milk treated with HHP. During UF in concentration mode, initial permeate fluxes were 30% lower at 300 and 600 MPa compared with the control, but the total flux decline was higher for nonpressurized milk (62%) compared with pressure-treated milk (30%). Fouling resistances were similar, whatever the treatment, except at 600 MPa where irreversible fouling was higher. Characterization of the fouling layer showed that caseins and β-lactoglobulin were mainly involved in membrane fouling after UF of pressure-treated milk. Our results demonstrate that HHP treatment of skim milk drastically decreased UF performance.     

Organic fouling and chemical cleaning of nanofiltration membranes: measurements and mechanisms

Fouling and subsequent chemical cleaning of nanofiltration (NF) membranes used in water quality control applications are often inevitable. To unravel the mechanisms of organic fouling and chemical cleaning, it is critical to understand the foulant-membrane, foulant-foulant, and foulant-cleaning agent interactions at the molecular level. In this study, the adhesion forces between the foulant and the membrane surface and between the bulk foulant and the fouling layer were determined by atomic force microscopy (AFM). A carboxylate modified AFM colloid probe was used as a surrogate for humic acid, the major organic foulant in natural waters. The interfacial force data were combined with the NF membrane water flux measurements to elucidate the mechanisms of organic fouling and chemical cleaning. A remarkable correlation was obtained between the measured adhesion forces and the fouling and cleaning behavior of the membrane under various solution chemistries. The AFM measurements further confirmed that divalent calcium ions greatly enhance natural organic matter fouling by complexation and subsequent formation of intermolecular bridges among organic foulant molecules. Efficient chemical cleaning was achieved only when the calcium ion bridging was eliminated as a result of the interaction between the chemical cleaning agent and the fouling layer. The cleaning efficiency was highly dependent on solution pH and the concentration of the chemical cleaning agent.     

超滤法分离棉籽粕水提液中的棉籽低聚糖

采用超滤工艺脱除棉籽粕水提取液中的蛋白质、胶质、色素等大分子杂质。通过比较不同截留分子质量、操作压力、温度下超滤膜的超滤效果,优化确定膜的最佳截留分子质量、操作压力和温度分别为5 kDa、1.379×105Pa和35℃。在此工艺条件下,棉籽粕水提液中总糖、棉籽糖、水苏糖、蔗糖的透过率分别达到88.7%、86.3%、87.2%和98.1%,蛋白质脱除率达到75%。超滤工艺是分离纯化棉籽粕水提液的有效手段。     

Modeling of permeate flux of synthetic fruit juice and mosambi juice (Citrus sinensis (L.) Osbeck) in stirred continuous ultrafiltration

Ultrafiltration studies of synthetic sucrose and pectin mixture and enzymatically treated mosambi juice have been performed in a stirred continuous cell. A model based on gel layer theory is developed to predict the flux decline during filtration for both synthetic and actual juice. From the steady state flux data, the mass transfer coefficient is observed to vary with operating pressure only and a modified Sherwood number relationship is proposed for such a system. The permeate of the filtered juice contains almost all the nutritional values of the original juice with significant improvement in clarity.     

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.     

Study of different fouling mechanisms during membrane clarification of red plum juice

In this study, the flux decline mechanisms were identified during membrane clarification of red plum juice at several processing parameters, including pore size, membrane type, transmembrane pressure, temperature and velocity. The results were used to investigate the effect of changes in operating conditions on the intensity of membrane fouling. Also, scanning electron microscopy (SEM) was used for analysing fouling‐layer morphology. These results showed that the main mechanism responsible for membrane fouling was cake formation (over 95% fitness) occurring in the first stage of the process. Intermediate, standard and complete blockings were formed during most of the runs as filtration proceeded. The results also indicated that increasing the temperature from 30 to 40 °C was the most effective factor in decreasing cake‐layer fouling, reducing it by about 66.7%. Furthermore, an increase in processing velocity of up to 0.5 m s^?1 had the greatest effect on intermediate blocking, reducing it by about 86.1%. Also, increasing pressure up to 2.9 bar completely eliminated standard blocking and complete blocking. Finally, microstructure analysis of membrane using SEM confirmed that cake formation had the greatest impact on membrane fouling.     

Development of genetic marker specific for Korean hwanggi medicine (Radix Astragali)

Sequence characterized amplified region (SCAR) markers were developed to selectively detect Korean hwanggi medicine (Radix Astragali) from imported ones from China. The SCAR markers were designed based on the nucleotide sequence of the psbA/trnH intergenic region (cpDNA) and significant bands obtained by inter-simple sequence repeat (ISSR) analysis. The psF/trnH marker was developed was based on the inserted sequence (TAAAA) within all of the Chinese samples (imports and local). Based on UBC 850 primer-amplified specific bands from all Chinese hwanggi medicine, the 15F/15R marker was designed. This primer showed high stability through 6 repeated amplifications, whereas psF/trnH marker showed 50% stability. Therefore, the designed SCAR marker (15F/ 15R) could be able to identify Korean hwanggi medicine as well as that imported from China.     

Examination of cottage cheese whey proteins by scanning electron microscopy: relationship to membrane fouling during ultrafiltration.

Deposits formed on the membrane during ultrafiltration of aqueous solutions of individual whey proteins were examined under a scanning electron microscope. Gamma-globulin formed granules which agglomerated and stacked into layers to form a porous matrix on the membrane. Beta-lactoglobulin and bovine serum albumin both formed sheets on the membrane and formed multimers which were identified by sodium dodecyl sulfate gel electrophoresis. Beta-lactoglobulin also formed strands where deposits were not thick. Alpha-lactalbumin formed smooth spherical particles which did not hinder water permeation greatly. Studies of ultrafiltration rate indicated that beta-lactoglobulin and gamma-globulin were most significant in causing permeation flux decline by surface fouling.     

Role of soluble microbial products (SMP) in membrane fouling and flux decline

Soluble microbial products (SMP), a significant component of effluent organic matter (EfOM), play an important role in membrane fouling and flux decline in wastewater reclamation/reuse applications. The SMP compounds of a microbial origin are derived during biological processes of wastewater treatment. They exhibit the characteristics of hydrophilic organic colloids and macromolecules. These high molecular weight compounds play an important role in creating high resistance of the membrane, leading to a reduction of permeate flux. The SMP fouling of RO, NF, and tight UF membranes is associated with formation of a cake/gel layer due to size (steric) exclusion. FTIR spectra of SMP- and EfOM-fouled membranes exhibited foulants' composition, consisting of polysaccharides, proteins, and/or aminosugar-like compounds. This finding reveals the important role of the SMP components as factors in membrane fouling and flux decline associated with EfOM source waters. Solids retention time (SRT) affects the characteristics and amounts of SMP, however, SRT did not affect flux decline trends of RO and NF membranes.     

Kinetics and mechanisms for reactions of Fe(II) with iron(III) oxides

Uptake of Fe(II) onto hematite (alpha-Fe2O3), corundum (alpha-Al2O3), amorphous ferric oxide (AFO), and a mixture of hematite and AFO was measured. Uptake was operationally divided into adsorption (extractable by 0.5 N HCl within 20 h) and fixation (extractable by 3.0 N HCl within 7 d). For 0.25 mM Fe(II) onto 25 mM iron(III) hematite at pH 6.8: (i) 10% of Fe(II) was adsorbed within 1 min; (ii) 20% of Fe(II) was adsorbed within 1 d; (iii) uptake slowly increased to 24% of Fe(II) during the next 24 d, almost all adsorbed; (iv) at 30 d, the uptake increased to 28% of Fe(II) with 6% of total Fe(II) fixed; and (v) uptake slowly increased to 30% of Fe(II) by 45 d with 10% of total Fe(II) fixed. Similar results were observed for 0.125 mM Fe(II) onto 25 mM iron(III) hematite, except that percent of adsorption and fixation were increased. There was adsorption but no fixation for 0.25 mM Fe(II) onto corundum [196.2 mM Al(III)] at pH 6.8, for 0.125 mM Fe(II) onto 25 mM iron(III) hematite at pH 4.5, and for 0.25 mM Zn(II) onto 25 mM iron(III) hematite at pH 6.8. A small addition of AFO to the hematite suspension increased Fe(II) fixation when 0.25 mM Fe(II) was reacted with 25 mM iron(III) hematite and 0.025 mM Fe(III) AFO at pH 6.8. Reaction of 0.125 mM Fe(II) with 2.5 mM Fe(III) AFO resulted in rapid adsorption of 30% of added Fe(II), followed by conversion of AFO to goethite and a decrease in adsorption without Fe(II) fixation. The fixation of Fe(II) by hematite at pH 6.8 is consistent with interfacial electron transfer and the formation of new mineral phases. We propose that electron transfer from adsorbed Fe(II) to structural Fe(III) in hematite results in oxidation of Fe(II) to AFO on the surface of hematite and that solid-phase contact among hematite, AFO, and structural Fe(II) produces magnetite (Fe3O4). The unique interactions of Fe(II) with iron(III) oxides would be environmentally important to understand the fate of redox-sensitive chemicals.     

Modeling of cross flow ultrafiltration of stevia extract in a rectangular cell

Prediction of ultrafiltration performance during clarification of pre-treated stevia extract by cross flow ultrafiltration in a rectangular cell is presented in this work. The steady state performance is modeled by using classical film theory. The transient state behaviour is quantified by using a model available in literature. In the model, higher molecular weight solutes are clubbed in one gel-forming component and Stevioside is assumed to be other component. In the process of modeling, the gel characteristics are estimated. Both total recycle and batch concentration mode of operations are modeled. The model results are in good agreement with the experimental data.     

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.