A Comparative study of organic fouling in hollow fiber and spiral wound membranes

The occurrence of flux decline in brackish water reverse osmosis (RO) plants due to dissolved organics is a topic of ongoing research. This type of organic fouling has also been found in seawater RO plants. A study was undertaken to compare organic fouling in hollow fiber and spiral wound membranes using a seawater feed that possessed a high concentration of huraic acid. This study was undertaken at an RO plant on Grand Cayman Island, British West Indies. The feed water came from a sea well and possessed a concentration of humic acid that varied between 35 and 60 mg/l.The hollow fiber membrane was operated at a recovery of 25% while the recovery with the spiral wound membrane varied between 5 and 25%. The performance data which included permeate flow, salt rejection, pressure drops across the membrane and analysis of the membranes for organic fouling were undertaken. This study compared the performance data and organic fouling between the hollow fiber and spiral wound meembranes.     

Two seawater reverse osmosis plants operating at high pressure and 50% conversion

At the Second World Congress on Desalination and Water Re-Use (Bermuda) an evaluation was made on a Reverse Osmosis (RO) plant operating at high pressures (1100-1500 psig) using Middle East conditions; it was concluded that such an RO plant could obtain 50 percent conversion of the feedwater and incur lower capital and operating costs.Two RO seawater plants using DuPont B-10T hollow fiber permeators were studied; these plants, one a 400m³/day facility and the other a 115m³/day facility, were designed for 50% conversion at a maximum 1200 psig operating, pressure. The plants used direct one to one brine staging and have operated at 1140 psig since their start-up.These plants have continually exceeded design specifications for both productivity and salt rejection. Both the first and second stage permeators combined have maintained 50% conversion with a TDS of the product water less than 350 ppm. These hollow fiber aramid permeators have maintained excellent performance at high pressure despite the fact that the feedwater possessed a very high concentration of organics (humic acid).The capital and operating costs of this plant have been significantly less than that of a comparable RO plant using lower pressure (900 psig). The performance data and cost analysis of this high pressure RO plant support the hypothesis that high pressure RO can provide excellent performance at a lower cost.     

RO membrane solute rejection behavior at the initial stage ofcolloidal fouling

This study investigated the rejection of salt and inert organic compounds by reverse osmosis membranes during the initial stage of colloidal fouling. Results of laboratory-scale experiments showed that colloidal fouling caused a marked decrease in flux, salt rejection and rejection of organics with molecular weight (MW) smaller than about 100 g/mol. Removal of neutrally charged organics was mainly by size or steric exclusion. Rejection of xylose, which has MW >100 g/mol, was not affected much by colloidal fouling. The decrease in salt and low MW organic rejections during the initial stage of colloidal fouling was attributed to cake-enhanced concentration polarization, whereby the colloidal cake layer hindered back diffusion of solutes from the membrane surface to the bulk solution, resulting in higher solute concentration gradient across the membrane. At higher channel wall shear rate, the rates of colloidal deposition, flux decline, decrease in salt rejection, and decrease in low MW organic rejection were lower.     

Reverse osmosis in the desalination of brackish water and sea water

To make RO an economical process, plant and operating costs have been reduced by developing compact modules, led by polyamide hollow fibre modules which recover energy from the reject when desalinating highly saline brackish water and seawater. Such plants only start to pay their way at product rates of around 400m³ /d +. Energy costs for desalination systems with lower capacities can also be reduced considerably by operating the RO plants at conversion rates of more than 30%. To what extent the required higher conversion rates can be obtained for a particular application depends on concentration of scales-forming content matter (calcium sulphate, strontium sulphate, barium sulphate and calcium carbonate), salt content of the raw water, concentration of fouling substances such as iron, manganese, anorganic and organic matter, risk of biological growth due to algae, shells and bacteria. The scope and type of conditioning and pre-treatment are based on these factors.     

Chemical control of colloidal fouling of reverse osmosis systems

Fouling of membranes by colloidal organic and inorganic particles continues to be documented as the most common and challenging obstacle in attaining stable continuous operation of reverse osmosis (RO) and ultrafiltration (UF) systems. Much current research is being conducted on physical parameters to mitigate such fouling. The focus has been on membrane synthesis and element design; microfiltration and ultrafiltration pretreatment; electromagnetic devices; correlation with physical factors such as Silt Density Index, zeta potential and critical flux; technique of direct observation of fouling process through a membrane; and classification of macromolecular organics for correlation with fouling characteristics. We report initial successes with chemical control of colloidal fouling. Through screening with a large number of observable coagulations of natural colloids, we have developed a group of proprietary anticoagulants and dispersants that would, at less than 10 ppm dosage to the RO feedwater, control various classes of colloidal foulants. Case studies of the control of humic matter, elemental sulfur and colloidal silicate in problematic RO systems that became stabilized are briefly presented. We conclude that a great need and potential exists in economically controlling the myriads of fouling interactions of colloidal particles during concentration within the brine channels of RO membrane elements. Low dosages of antifoulants can in many cases obviate the need for installation and maintenance of pretreatment unit or operations designed to remove such colloidal foulants from the process stream.     

Organic fouling of RO membranes: Investigating the correlation of RO and UF fouling resistances for predictive purposes

This study examines the characteristics of deposits from dead-end UF and cross-flow RO filtration of dilute mixtures of sodium alginate (SA) and humic acids (HA), which are representative of common foulants in RO and NF feed waters. The data are interpreted in terms of specific cake resistance, α. The presence of alginates in the mixed fouling layers, even in relatively small percentage, imparts characteristic properties to these deposits; i.e. a gel-like structure which is associated with reduced compressibility and permeability. With SA/HA mixtures, high rejection of organic species and high deposition factors are obtained in UF and RO tests, respectively. The specific resistance of mixed SA and HA deposits tends to increase with increasing SA concentration in solution. The resistances α exhibit fairly strong (power law) dependence on the pressure difference across the cake, ΔΡ_c, for both RO and UF tests. The fairly satisfactory correlation of resistance α versus ΔΡ_c data, obtained from both types of tests (for the mixtures of organic species tested at small salinity) is a significant result of this work. Based on this correlation, an approach is suggested for estimating fouling index I and initial membrane fouling rate of a specific RO process, relying on limited UF tests.     

Influence of colloidal fouling and feed water recovery on salt rejection of RO and NF membranes

The influence of colloidal fouling and feed water recovery (or concentration factor, CF) on salt rejection of thin-film composite reverse osmosis (RO) and nanofiltration (NF) membranes was investigated. Fouling experiments were carried out using a laboratory-scale crossflow test unit with continuous permeate disposal to simulate the CF and recovery as commonly observed in full-scale RO/NF systems. For feed waters containing only salt (NaCl), permeate flux declined linearly as CF was increased and salt rejection was nearly constant for both RO and NF membranes. On the other hand, a sharp decrease in permeate flux and significant decline in salt rejection with increasing CF were observed under conditions where colloidal fouling takes place. For both RO and NF membranes, the marked permeate flux decline was attributed to the so-called “cake-enhanced osmotic pressure”. The decline in salt rejection when colloidal fouling predominated was much more substantial for NF than for RO membranes. In all cases, the decline in salt rejection was higher under conditions of more severe colloidal fouling, namely at higher ionic strength and initial permeate flux.     

An experimental study of UF membrane fouling by humic acid and sodium alginate solutions: the effect of backwashing on flux recovery

One of the critical issues for the successful application of ultrafitration in water treatment is membrane fouling due to dissolved organic matter, which negatively affects productivity, product quality and process cost. The aim of the present study is to contribute to the understanding of fouling phenomena by organic matter and the efficiency of the backwashing technique, which is applied in practice to restore membrane flux. In this experimental study commercial humic acid and sodium alginate have been used as model substances representative of natural organic matter and extracellular organic matter, respectively. All fouling experiments were carried out in a special single fiber apparatus. An important parameter considered in the study of both model substances is the concentration of calcium ions, which promote their aggregation and influence the rate of flux decline, the reversibility of fouling and rejection. Membrane fouling by humic acid appears to be the outcome of simultaneous action of several fouling mechanisms. Initially, a relatively rapid irreversible fouling takes place due to internal pore adsorption; however, progressively pore blocking becomes important and a fouling layer develops on the membrane. Sodium alginate fouling on the other hand is apparently due to two consecutive mechanisms; i.e. a rapid irreversible fouling due to internal pore constriction, followed by cake development on the membrane surface which becomes the dominant mechanism. Comparing fouling in both cases it can be inferred that even though sodium alginate fouling is more severe than the one caused by humic acids, it is to a large extent reversible by backwashing. On the contrary, fouling caused by humic acid is characterized by greater and increasing with calcium addition irreversibility, which is not remedied by the periodic backwashing. The different fouling propensity of the two types of macromolecules is apparently due to differences of their physical–chemical characteristics.     

The malta seawater RO facility

The Polymetrics seawater reverse osmosis (RO) facility at Ghar Lapsi, Malta, is one of the largest seawater RO plants in the world, with an installed capacity of 20,000 m³ /d (5.3 U.S. mgd). A second plant, provided under the same contract, has a capacity of 4,500 m³ /d (1.2 U.S. mgd), utilizing highly brakish feedwater. The plants supply potable water for the island's 350,000 residents and its growing tourist trade.The seawater plant is a single pass design, utilizing DuPont permeators and is the first major installations incorporating energy recovery turbo-pumps.This paper summarizes the plant design, manufacture, assembly, and installation, and also reports up-to-date operation and maintenance data. The operating costs are presented.     

Analysis of reverse osmosis membrane behaviors in a long-term verification test

Almost all of reverse osmosis (RO) desalination data have been reported in terms of flux and salt rejection. Fouling phenomena have also been reported in raw data. Such a way of presenting data is misleading to know the real causes of membrane fouling, and thus the reliable design of RO unit becomes impossible. The correct presentation of RO data should be in the form of transport coefficients of a membrane based on the correct transport equations. In this paper a couple of solution-diffusion type equations is compared carefully with those proposed by Spiegler and Kedem. The former uses two parameters, A and B, while the latter uses three, namely, L_p, σ, and P. In long run experiments, however, the only data available are flux and rejection, and it is impossible to determine three coefficients from two parameters. Since RO membranes used for seawater desalination show their σ is very close to 1, it can be shown that value B is very close to P, and it is concluded the former type of equation can be effectively used for a long-run data analysis. An example of such analysis is presented based on the data taken by WRPC, Japan, at Chigasaki, with 12″ Hollosep hollow fiber modules made by Toyobo. Results showed an interesting trend of variation of A and B values and their relation with time. Although real causes of membrane fouling phenomena are not clear at this stage, the method proposed here is valid and should be extended further to compile such data, which will be related to the physical and chemical changes of membranes and their materials.     

正渗透策略和化学清洗海水淡化反渗透膜

为解决海水淡化过程中反渗透膜的污染问题,研究了基于正渗透策略的反渗透产水、模拟反渗透浓水、模拟海水不同的组合清洗和清洗时间对膜通量和截留率的影响。针对不可逆污染,研究了不同化学清洗药剂、浸泡时间、浓度对膜通量和截留率的影响。结果表明,正渗透策略清洗方式中,淡水/模拟反渗透浓水的组合清洗方式效果最佳,其归一化通量从9.48 L/(m²·h·MPa)提升至13.6 L/(m²·h·MPa),截留率从80.59%提升至92.80%。此外,经质量分数为2%的柠檬酸溶液浸泡2 h后,再使用质量分数为1%的乙二胺四乙酸四钠盐和0.3%的三聚磷酸钠溶液浸泡1.5 h,其归一化通量从9.48 L/(m²·h·MPa)提升至14.3 L/(m²·h·MPa),截留率从80.59%提升至96.27%。从SEM和AFM图可以看出,正渗透清洗策略并未对膜表面选择层造成损坏,且可以清洗膜表面的有机污染物和无机污染物,因此,应用这种方法对污染的反渗透膜进行清洗,可延长化学清洗周期,减少化学清洗剂用量,具有一定的工业应用前景。     

Forward-osmosis strategy and chemical cleaning of seawater desalination reverse osmosis membranes

In order to settle the membrane fouling of reverse osmosis membranes in seawater desalination process, this study reported a novel strategy based on forward-osmosis process and discussed the effects of different factors like different cleaning combination among reverse osmosis product, simulated reverse osmosis concentrate and simulated seawater, as well as cleaning time on the membrane permeate flux and salt rejection. For irreversible fouling, the effects of different chemical cleaning agents, immersion time and concentration were also investigated in this study. The results exhibited that the cleaning combination between diluted water and simulated reverse osmosis concentrate possessed the best cleaning performance in the process of forward-osmosis cleaning. Such approach also enhanced normalized flux from 9.48 L/(m²·h·MPa) to 13.6 L/(m²·h·MPa) and enhanced NaCl rejection from 80.59% to 92.80%. Furthermore, the normalized flux was enhanced from 9.48 L/(m²·h·MPa) to 14.3 L/(m²·h·MPa) and NaCl rejection was also enhanced from 80.59% to 96.27% after soaking in 2%(mass) citric acid solution for 2h, soaking with 1%(mass) ethylenediamine tetra-acetic acid tetrasodium salt and 0.3%(mass) sodium tripolyphosphate solution for 1.5 h. According to the result of SEM images and AFM images, the forward-osmosis cleaning strategy could not cause the damage of selective layer of membrane surface and caused the drop of inorganic and organic fouling on the membrane surface. Hence, cleaning fouled RO membranes by such approach could prolong the chemical cleaning cycle and reduce the amount of chemical cleaning agent, which has certain industrial application perspectives.     

Effect of coagulant types on textile wastewater reclamation in a combined coagulation/ultrafiltration system

A combination of coagulation and ultrafiltration (UF) processes for textile wastewater reclamation was investigated using various types of coagulating chemicals such as polyamine, alum, polyaluminum chloride (PACl), and ferric salts. The potential of the combined system was evaluated to replace the existing treatment processes which are composed of a flotation tank (primary step) and a series of filtration beds including sands, granular carbons, and diatomaceous powders. Regardless of the type and dosage of the coagulants, the UF system achieved substantial colloidal particle removal (>97% of turbidity was removed), but membrane fouling was mitigated in a different manner. The degree of fouling reduction was highly dependent upon the type of coagulants used, even though the turbidity and organics removal efficiencies were nearly the same. The polymeric coagulant aggravated membrane fouling, whereas the inorganic coagulants always helped reduce fouling. A residue of the coagulating polymer, which was added in the primary step and its concentration in the effluent was at an immeasurable level, was found to cause serious membrane fouling. The use of polymeric coagulants should be prevented or minimized if UF is considered for textile wastewater reclamation. Polymerized aluminum was found to be the most effective among the coagulants tested, although ferric salt was better than alum in controlling fouling. In particular, it seemed that the characteristics of coagulation chemistry and the coagulated particles had a great impact upon membrane fouling.     

Effects of aluminum sulfate and ferric chloride coagulant residuals on polyamide membrane performance

Pretreatment may constitute up to one-fourth of the total costs of a membrane desalting facility. By using preexisting conventional filtration plants for pretreatment, significant cost savings may be realized. However, coagulant residuals from the pretreatment process may negatively affect reverse osmosis (RO) membrane performance. Various RO membranes were tested at three different treatment plants in southern California, using either aluminum sulfate (alum) or ferric chloride coagulants and chloramines. Repeated testing using alum with multiple RO elements revealed rapid deterioration in specific flux (up to 60% over 100 h of operation), as well as progressive reductions in salt rejection (typically 3-4% over 500 h of operation). Microscopic analysis of the fouled membranes revealed that the foulants were primarily aluminum hydroxide and aluminum silicate materials. In contrast to the RO data for alum coagulation, which showed declining membrane flux, the specific flux data using ferric chloride and chloramines increased over time for all membranes. Salt rejection decreased significantly during testing of each membrane. These data suggest that the RO membranes were physically degrading over time. The RO membranes may have been degraded by residual iron catalyzing a chlorine-amide reaction on the membrane surface, despite the fact that chlorine was present as chloramines.     

Lab and pilot scale investigations on membrane fouling during the ultrafiltration of surface water

In the combined laboratory and pilot plant investigation powder activated carbon dosing and inline coagulation were investigated for surface water from river Spree. The aim was to understand the fouling behaviour of this raw water and to understand and to identify strategies to minimize the irreversible fouling in this application. Trials with activated carbon showed significant differences in the adsorption of biopolymers on different types of carbon. Whereas the TOC removal was in the same range for both types the coarse carbon type showed very small removal of biopolymers. The effect of different types of coagulants, dosage and pH was investigated in a laboratory filtration set up. Samples were investigated by LC-OCD measurements for fractionation of DOC for raw water, flocculated water and permeate. The removal of biopolymers was possible with iron and alumina salts, however the alumina salts tend to remove humic acids as well and this results in a higher overall DOC removal. In the pilot plant the inline coagulation was investigated under actual site conditions. Whereas the results for the effect of coagulation and DOC removal were confirmed it turned out that aluminium coagulants give a significantly higher increase in differential pressure. The use of ferric coagulants at slightly acidic pH was thus identified as a robust method to achieve a stable performance of the ultrafiltration system at this site.     

铝系混凝剂减缓膜污染的红外光谱-多变量曲线分辨分析

超滤是一种高效的水处理技术,近年来被广泛应用于工业废水处理、生活污水回用、海水淡化预处理等领域。然而,超滤长期运行会造成膜污染。本文采用了在线混凝结合超滤工艺,使用不同形态的铝系混凝剂（硫酸铝、氯化铝或聚合氯化铝）,处理含有不同溶解性有机质组分（腐殖酸、牛血清白蛋白和高岭土）的模拟原水,研究不同铝形态、不同组分及其相互作用对超滤膜污染过程的影响。本研究建立了流量衰减模型模拟膜污染过程,结合衰减全反射红外光谱（IR-ATR）和多变量曲线分辨-交替最小二乘法（MCR-ALS）的数据处理方法对膜上的多种污染物进行定性和定量分析。结果表明硫酸铝和氯化铝混凝剂均可明显提高膜比通量,减缓膜污染。该工艺混凝剂投加量低于常规处理工艺即可明显减缓膜污染。混凝剂投加量为0.4mg/L时,氯化铝混凝效果较好,混凝剂投加量为2.4mg/L时,硫酸铝混凝效果较好。低投加量（0.2mg/L、0.4mg/L）下,PAC对缓解膜污染程度不明显,反而加重膜污染。牛血清白蛋白对超滤膜的污染比腐殖酸严重。因为牛血清白蛋白的存在大大降低了混凝的效果,阻碍疏松滤饼层的形成。向原水中投加硫酸铝混凝剂,膜污染主要发生在过滤前期,即...     

High-performance desalination of high-salinity reverse osmosis brine by direct contact membrane distillation using superhydrophobic membranes

In this study, the direct contact membrane distillation (DCMD) with a superhydrophobic membrane (SM-DCMD) herein was designed and applied to desalinate RO brine, showing excellent performance in desalinating high salinity. The superhydrophobic membrane with good resistance to pore wetting and fouling was prepared by coating silica nanospheres onto a porous glass fiber substrate and subsequent fluorination. It maintained a stable flux (31.27 LMH at feed temperate of 80°C) and outstanding salt rejection (~100%) even in the presence of natural organic matter (NOM, a typical organic foulant) and sodium dodecyl sulfate (SDS, a typical wetting agent with low surface tension). During handling practical reverse osmosis brine, such SM-DCMD system presented excellent performances in terms of a stable flux of 23.70 LMH and salt rejection efficiency of >99% over 24 h continuous operations. The relevant COD and color removal efficiency kept a constant value of 100%. These overall findings indicate that the SM-DCMD is a hopeful candidate for desalinating practical RO brine with high performance.     

Foulant interaction and RO productivity in textile wastewater reclamation plant

Foulant interaction and productivity of reverse osmosis (RO) membrane during textile wastewater reclamation were studied. Synthetic textile wastewater composed of salt, surfactant and reactive dye was used in the experiment. RO productivity was assessed using cross-flow membrane filtration unit. The result revealed that surfactant was the major cause of membrane fouling. When the surfactant concentration maintains lower than the critical micelle concentration (CMC), RO productivity was influenced by the concentration of surfactant. Therefore, lowest productivity was observed when the surfactant concentration approached CMC. When the concentration level rose above CMC, the surfactant micelle was formed within the bulk solution and this subsequently yielded an increase in RO productivity. The formed micelle decreased the adsorption capacity of surfactant monomer. Moreover, the appearance of aggregation between surfactant and reactive dye lowered the fouling potential of the mixtures especially when compared to the wastewater containing only surfactant at a higher concentration than CMC.     

CTA中空纤维反渗透膜的远红外辐射干燥

本文介绍了三醋酸纤维素（ＣＴＡ）中空纤维反渗透的远红外辐射干燥试验结果及其设备的结构特点，试验结果表明，ＣＴＡ中空纤维反渗透膜远红外辐射干燥可提高其脱盐率，探索最佳干燥条件有可能简化中空纤维反渗透组的生产过程或进一步提高中空纤维反渗透组件的性能。     

Nanofiltration and reverse osmosis thin film composite membrane module for the removal of dye and salts from the simulated mixtures

Nanofiltration (NF) and reverse osmosis (RO) thin film composite polyamide membrane modules were used to remove the color from the contaminated solution mixture. The feasibility of membrane processes for treating simulated mixture by varying the feed pressures (100-400 psi) and feed concentrations was studied to assess the separation performance of both NF and RO membranes. It was found that the efficiency of NF and RO membranes used in the treatment of colored water effluents was greatly affected by the presence of salts and dyes in the mixture. Color removal by NF with a high rejection of 99.80% and total dissolved solids (TDS) of 99.99% was achieved from RO by retaining significant flux rate compared to pure water flux, which suggested that membranes were not affected by fouling during the simulated wastewater process operation. The effect of varying concentrations of Na₂SO₄ salt and methyl orange (MO) dye on the performance of spiral wound membranes was determined. Increasing the dye concentration from 500 to 1000 mg/L resulted in a decrease of salt rejection at all operating pressures and for both concentrations of 5000 and 10,000 mg/L as the feed TDS. Increasing the salt concentration from 5000 to 10,000 mg/L resulted in a slight decrease in dye removal.