An advanced treatment of high-strength opium alkaloid processing industry wastewaters with membrane technology: pretreatment, fouling and retention characteristics of membranes

This paper presents the results of the laboratory and pilot-scale membrane experiments of opium alkaloid processing industry effluents. Different types of ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) membranes were evaluated for membrane fouling, permeate flux and their suitability in separating COD, color and conductivity. Experiments demonstrated that membrane treatment is a very promising advanced treatment option for pollution control for opium alkaloid processing industry effluents. Almost complete color removal was achieved with NF and RO membranes. COD and conductivity removals were also greater than 95% and met the current local standards. Nevertheless, pretreatment was an important factor for the NF and RO membrane applications. Membrane fouling occurred with direct NF membrane applications without UF pretreatment. The total estimated cost of the UF and NF treatment system was calculated as $0.96/m³, excluding the concentrate disposal cost.     

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.     

纳滤/反渗透膜处理重金属废水的性能

The performance of different nanofiltration （NF） and reverse osmosis （RO） membranes was studied in treating the toxic metal effluent from metallurgical industry. The characteristics and filtration behavior of the processes including the wastewater flux, salt rejection and ion rejection versus operating pressure were evaluated. Then the wastewater flux of RO membrane was compared with theoretical calculation using mass transfer models, and good consistency was observed. It was found that a high rejection rate more than 95% of metal ions and a low Chemical Oxygen Demand （COD） value of 10 mg·L^-1 in permeate could be achieved using the RO composite membrane, while the NF rejection of the salt could be up to 78.9% and the COD value in the permeate was 35 mg·L^-1. The results showed that the product water by both NF and RO desalination satisfied the State Reutilization Qualification, but NF would be more suitable for large-scale industrial practice, which offered significantly higher permeate flux at low operating pressure.     

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.     

Benefits of High Shear Rate Dynamic Nanofiltration and Reverse Osmosis: A Review

Dynamic filtration permits to increase permeate flux and membrane selectivity, as compared to crossflow filtration. It consists in creating the shear rate by a disk rotating near the membrane or by rotating or vibrating the membrane, avoiding the need for large feed flow rates. The benefits of high shear rates are important in microfiltration and ultrafiltration, but they are even larger in nanofiltration (NF) and reverse osmosis (RO). The reduction in concentration polarization by high shear rate can increase the permeate flux by a ratio of 3 to 5 as compared to a spiral wound module and augments also solutes rejection as their diffusive transfer through the membrane is reduced by a factor of 4 to 5. This paper describes available dynamic filtration modules suitable for NF and RO and reviews the treatment of dairy effluents, desalination, oil emulsions, and oligosaccharides recovery using a rotating disk module or a VSEP module with vibrating membranes and compares their performances with those of crossflow filtration. These examples confirm the high potential of dynamic NF and RO when operated at high shear rate and high TMP. The availability of large rotating NF ceramic membrane disks could permit the fabrication of highly efficient modules.     

垃圾渗滤液生化出水絮凝-纳滤处理及过程机理

垃圾焚烧发电厂渗滤液是一种含高浓度腐殖酸类物质和高盐含量的复杂有机废水, 传统生化处理后仍难达标排放。本工作围绕垃圾渗滤液生化出水的特性, 开展了Ca(OH)₂絮凝、臭氧氧化预处理与NF处理相结合的处理工艺, 并对处理过程的机理进行了探讨。研究表明, 渗滤液生化出水经过Ca(OH)₂絮凝处理, 可以有效地去除其中的杂环类化合物。生化出水经8 g·L^-1的Ca(OH)₂絮凝处理后, 比MBR出水产水通量提高达8.2%。对Ca(OH)₂絮凝出水进行臭氧氧化处理, 虽然降低了它的COD, 但并未进一步提高其NF膜通量, 其主要原因可能是臭氧氧化生成的硅氧烷类物质造成了膜的污染;与RO处理垃圾渗滤液生化出水相比较, NF膜无法分离废水中的酮类、胺和酰胺类、杂环类化合物, 使得NF产水的COD处在100~160 mg·L^-1。NF平均膜通量的增大可导致产水COD略有上升;垃圾渗滤液生化出水及其预处理水在NF处理过程中, 都没有表现出严重的膜污染。     

The effect of transmembrane pressure and pH on treatment of paper machine process waters by using a two-step nanofiltration process: Flux decline analysis

In this work, the treatment of paper machine whitewater obtained from paper production by using loose and tight Nanofiltration (NF) membranes in a lab-scale plant with a plate and frame module was investigated. The NF membranes were evaluated for fouling, flux decline due to concentration polarization and their suitability for removing of components present in wastewater. The loose NF membrane was used for the first step under different transmembrane pressure (8 to 32 bars) and pH (3, 5.6 and 10) values. The best filtration performances were provided under a pressure of 32 bar and a pH of 5.6. The fouling mechanism at different transmembrane pressures and pH values was investigated by “Hermia's model”. Also, fouling on pores and on the surface of NF membranes was characterized by Scanning electron microscopy (SEM) and contact angle measurements, respectively. For the advanced treatment of permeate obtained from the loose NF membrane that provided the lowest fouling and flux decline, a tight NF membrane was used in the second step. Even better retentions were achieved from experiments with this NF membrane. Results obtained in this study showed that the combination loose and tight NF membranes achieved reuse of paper machine white water for use as shower water of paper machine.     

Nanofiltration and reverse osmosis of model process waters fromthe dairy industry to produce water for reuse

In dairy plants the process waters generated during the starting, equilibrating, interrupting and rinsing steps contribute to the production of effluents. They correspond to milk products (milk, whey, cream) diluted with water without chemicals. The treatment of these dairy process waters by nanofiltration (NF) or reverse osmosis (RO) operations was proposed to concentrate dairy matter and to produce purified water for reuse in the dairy plant. The study reports one-stage and two-stage (NF + RO and RO + RO) spiral-wound membrane treatments with five model process waters representative of the main composition variations observed in dairies. Performances (permeate flux, milk components rejection, purified water characteristics) of the different operations were compared. Discussion was focused on the comparison between quality of produced waters and vapour condensates (from product drying and evaporation processes) reused in dairy plants. Accordingly, both total organic carbon (TOC) and conductivity of water treated by a single RO or NF + RO operations were convenient for reuse as heating, cooling, cleaning and boiler feed water. With the two-stage RO + RO process, a more purified water complying with the TOC drinking water limit was achieved.     

Surface characterization and performance evaluation of commercial fouling resistant low-pressure RO membranes

This paper describes the characterization and evaluation of various RO/NF membranes for the treatment of seasonally brackish surface water with high organic contents (TOC ≈21 mg/L). Twenty commercially available RO and NF membranes were initially evaluated by performing controlled bench-scale flat-sheet tests and surface characterization. Based on the results, four low pressure RO membranes were selected for use in the pilot study. The surface characterization revealed that each of four selected membranes had unique surface characteristics to minimize membrane fouling. Specifically, the LFC1 membrane featured a neutral or low negative surface to minimize electrostatic interactions with charged foulants. The X20 showed a highly negatively charged surface, and thus, was expected to perform well with feed waters containing negatively charged organics and colloids. The BW30FR1 exhibited a relatively neutral and hydrophilic surface, which could be beneficial for lessening organic and/or biofouling. The SG membrane had a smooth surface that made it quite resistant to fouling, particularly for colloidal deposition. In the large-scale pilot study using single element, all of the four membranes experienced a gradual increase in specific flux over time, indicating no fouling occurred during the pilot study. The deterioration of permeate water quality such as TDS was also observed over time, suggesting that the integrity of the membranes might be compromised by the monochloramine used for biofouling control.     

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.     

The influence of degreasing agents used at car washes on the performance of ultrafiltration membranes

The influence of washing chemicals used at car washes on the flux and retention of three ultrafiltration (UF) membranes has been studied. Eleven commercial degreasing agents, two shampoo agents and a wax were included in the investigation. The membrane performance when treating waste water collected at a car wash at different times of the year was also studied. The retention of the different chemicals varied greatly, but there was no significant difference in COD retention among the three UF membranes. The highest flux was observed when treating the alkaline degreasing agents and the shampoo solutions. The flux and COD retention when treating the waste water from the car wash were 30–50 l/m ² h and 60%, respectively. One of the low-retention degreasing agents was treated by nanofiltration (NF). The retention was significantly higher when using NF, but the COD concentration in the permeate was still too high to allow the permeate to be discharged without further treatment.     

Treatments of stainless steel wastewater containing a high concentration of nitrate using reverse osmosis and nanomembranes

A nanomembrane (NTR 729HF) and three different types of reverse osmosis (RO) membranes (CPA2, LFC1, and ESPA1) were tested for the treatment of high concentration of nitrate wastewater from stainless steel industry. All the tested RO membranes showed higher rejection rates (90–99% at 1000–60 mg/L of NO₃⁻ -N) than the NF membrane. The rejection rate and flux of RO membranes were not highly affected by pH variation and Ca²⁺ as co-existing ion. However, the rejection rate of NF, which was 67% at 60 mg/L of feed concentration, was decreased as pH decreased and Ca²⁺ concentration increased indicating that charge repulsion is one of the major rejection mechanisms. As nitrate concentration increased from 20 to 1000 mg/L in feed water, the removal rate decreased from 67 to 20% in NF membrane. The flux of RO was relatively high and ESPA1 (a low-pressure RO type) showed more than two times higher flux compared to the NF. ESPA1 was successfully tested for a longterm experiment with real stainless steel wastewater for 30 days of experimental period. Current study implicates that RO membranes could be an alternative for the treatment of stainless steel wastewater.     

Processing of composite industrial effluent by reverse osmosis

Reverse osmosis (RO) is a well‐established process for water desalination and effluent treatment and it is anticipated that its application could be extended to complex mixtures of industrial effluents. Pilot‐scale experiments using a spiral‐wound thin‐film composite (TFC) polyamide membrane were carried out to investigate the potential of RO for processing a composite effluent, which was a mixture of various wastewaters from bulk drug and pharmaceutical factories. Separation performance was evaluated at various feed pressures (0–70 bar) and feed concentrations (2–30 gdm^?3), and was found to improve with increasing pressure. High rejection of dissolved solids (～98%), COD, BOD and almost complete removal of color were achieved with reasonable flux rates and water recovery. The effect of concentration polarization and fouling on flux and rejection rates as functions of time was evaluated. An approximate cost estimate for an aerobic process vis‐à‐vis a RO membrane process for treatment of the composite effluent is presented. Copyright © 2003 Society of Chemical Industry     

Purification and Concentration of Caustic Mercerization Wastewater by Membrane Processes and Evaporation for Reuse

A membrane-based treatment strategy was developed for purifying the highly alkaline textile mercerization wastewater. 0.2-μm MF and 100 kDa UF membranes were evaluated as pretreatment alternatives before 10 kDa UF and 200 Da NF membranes. Turbidity was almost totally removed by both pretreatment options, while UF (100 kDa) showed higher COD retention than MF. In total recycle mode of filtration, fouling of both UF and MF membranes were 80% reversible by physical and almost totally reversible (≥ 97%) by chemical cleaning. In the second stage filtrations applied to the pretreated wastewater samples, NF could yield high (97-98%) COD retentions and low permeate COD concentrations (≤ 22 mg/L), while 10 kDa UF could only reduce the COD concentration to 150 mg/L. While no NaOH was lost in the MF+UF process, the use of NF as second stage resulted in 12-17% NaOH retention. The permeate flux in all second stage processes were stable, implying that the majority of the feed components that would cause fouling had been removed in the pretreatment stages. Permeate of the MF+NF sequence was concentrated by evaporation with no foaming problems, showing that the hybrid process can be applied to recycle a purified and concentrated caustic stream to the mercerization process.     

Optimization Study for Treatment of Acid Mine Drainage Using Membrane Technology

The use of membrane technology in the treatment of Acid Mine Drainage (AMD) can result in reduction of chemical usage and sludge production making the treatment process more environmentally friendly. This study deals with the optimization of membrane filtration performance in the treatment of AMD using two nanofiltration (NF) membranes (NF99 and DK) and one reverse osmosis (RO). All membranes were used in various tests treating a model solution at two different concentration levels in order to cover the concentration of actual AMD found in the mining industry. The main parameters which were studied to determine the optimal condition for AMD filtration are pressure, pH, temperature, and flow rate. Pressure and temperature were found to have a considerable influence on flux, while rejection was only slightly influenced by pressure. The feed flow rate had no effect on rejection. The highest flux with moderate rejection was determined for NF99 while RO had the lowest flux but highest rejection. Therefore, NF is preferable for AMD treatment due to lowest energy consumption. The treatment has also been tried on a large scale to check its applicability at a commercial scale. Finally, PHREEQC has been used to determine the scaling risk in the prepared AMD.     

Membrane fouling and chemical cleaning in water recycling applications

Fouling and subsequent chemical cleaning are two important issues for sustainable operation of nanofiltration (NF) membranes in water treatment and reuse applications. Fouling strongly depends on the feed water quality, especially the nature of the foulants and ionic composition of the feed water. Consequently, appropriate selection of the chemical cleaning solutions can be seen as a critical factor for effective fouling control. In this study, membrane fouling and chemical cleaning under condition typical to that in water recycling applications were investigated. Fouling conditions were achieved over approximately 18 h with foulant cocktails containing five model foulants namely humic acids, bovine serum albumin, sodium alginate, and two silica colloids in a background electrolyte solution. These model foulants were selected to represent four distinctive modes of fouling: humic acid, protein, polysaccharide, and colloidal fouling. Three chemical cleaning solutions (alkaline solution at pH 11, sodium dodecyl sulphate (SDS), and a combination of both) were evaluated for permeate flux recovery efficiency. The results indicated that with the same mass of foulant, organic fouling was considerably more severe as compared to colloidal fouling. While organic fouling caused a considerable increase in the membrane surface hydrophobicity as indicated by contact angle measurement, hydrophobicity of silica colloidal fouled membrane remained almost the same. Furthermore, a mechanistic correlation amongst cleaning efficiency, characteristics of the model foulants, and the cleaning reagents could be established. Chemical cleaning of all organically fouled membranes by a 10 mM SDS solution particularly at pH 11 resulted in good flux recovery. However, notable flux decline after SDS cleaning of organically fouled membranes was observed indicating that SDS was effective at breaking the organic foulant—Ca²⁺ complex but was not able to effectively dissolve and completely remove these organic foulants. Although a lower permeate flux recovery was obtained with a caustic solution (pH 11) in the absence of SDS, the permeate flux after cleaning was stable. In contrast, the chemical cleaning solutions used in this study showed low effectiveness against colloidal fouling. It is also interesting to note that membrane fouling and chemical cleaning could permanently alter the hydrophobicity of the membrane surface.     

Recovery and recycle of tannins in the leather industry by nanofiltration membranes

The aim of this work was the study of the application of membrane concentration to exhausted tanning baths from vegetable tannage operations in order to increase the tannin/non‐tannin (T/NT) ratio and obtain recyclable material. For this purpose four samples of tanning baths at different T/NT ratios (from 0.7 to 1.4) were processed using six different types of membranes which ranged from reverse osmosis (RO) to nanofiltration (NF). The membrane module Fluid Systems TFC S 2540 gave the best results in terms of permeate flux and also in terms of increased T/NT ratio in the retentate (from 1.4 to 1.7). In order to compare the permeate flux reduction with time (J_t) for the different modules, the osmotic pressure differences (Δπ) between permeate and retentate were estimated by electrical conductivity measures. The fouling phenomena for the different membranes in the processing of each sample were evaluated by comparing the pressures required to obtain the same VRF (volume reduction factor), NPF (normalized permeate flux) and membrane performances with tap water before and after tannin concentration. The retention of tannins, which are polyphenols capable of significant hydrogen bonding, was found to be governed by the chemistry of the interactions between their complexes and the polyamide membrane material. Copyright © 2004 Society of Chemical Industry     

纳米ZrO2修饰Al2O3微滤膜处理废冷却液的实验研究

膜分离技术处理含油废水表现出明显的技术优势,其应用还应解决膜表面易被污染,分离效果逐渐下降的问题,主要原因是由于油滴的易变形性引起的膜堵塞。为解决膜渗透通量与膜选择性的矛盾,本文在市售Al2O3微滤膜孔道表面制备纳米ZrO2涂层,利用纳米涂层改变微滤膜的表面亲水憎油性,阻止油滴的变形。研究了陶瓷膜修饰条件和膜过滤操作参数对膜渗透通量的影响,结果表明:纳米涂层能有效提高微滤膜的渗透通量。膜面流速的增加在一定程度上能提高膜渗透通量,但超过一定程度后,增加不明显。当膜面流速为7m/s,修饰陶瓷膜的最大渗透通量为280 L.m-2.h-1,油截留率为96.4%。纳米涂层修饰微滤膜具有良好的抗油滴污染性能,能有效实现稳定含油废水的油水分离。     

Fabrication of basalt embedded composite fiber membrane using electrospinning method and response surface methodology

In this study, a novel basalt embedded fiber membranes was prepared by the electrospinning method. The effects of the feed rate, voltage, tip to collector distance, and the basalt content on the prepared composite fiber membranes were investigated and optimized using the response surface method. Four models were built to compare the fibers in terms of deionized water flux (DWF), activated sludge flux, chemical oxygen demand (COD) removal, and porosity of fiber membranes. All the developed models were significant and adequately precise. The maximum flux of DWF was obtained when the voltage was 17.25 kV, the tip to collector distance of 19 cm, and a basalt content in polymer of 1.25%. COD removal decreased at higher voltage values as the feed rate increased. The porosity, pore size, and the contact angle values decreased for basalt embedded fiber membrane. The increases in the basalt percentage in polymer increased the hydrophilicity of the fiber. The flux decline for the basalt embedded fiber membrane was compared with the pristine fiber membrane. The permeate fluxes of pristine and basalt embedded fiber membranes were 42.3 and 59.6 L/m²/h, respectively. The biofouling performances of pristine and basalt embedded fiber membranes were also examined. Irreversible fouling decreased from 42.9% to 8.0%, and reversible fouling increased from 56.5% to 91.1% after modification of the membrane with basalt powder. Scanning electron microscopy with energy dispersive X-ray analysis (SEM–EDX) analysis showed that basalt powder was successfully embedded into polyether sulfone polymer.     

Threshold performance of a spiral-wound reverse osmosis membrane in the treatment of olive mill effluents from two-phase and three-phase extraction processes

A reverse osmosis (RO) treatment stage was examined for the complete depuration of the different effluents exiting the olive mill factories (OMW) working with diverse extraction procedures, that is, the two-phase and the three-phase extraction processes, respectively. In the present work, the modelization of batch RO purification of OMW by means of the relevant equations of the threshold flux theory for fouling control and plant dimension is addressed. Results show that higher threshold flux values (20.2–22.1% increase) and major feed recovery rates (80.2–85.0%) as well as very significant reduction of the long-term fouling index (27.3–52.7%) were achieved by using as pretreatment steps the following series of processes: pH-T flocculation, UV/TiO₂ photocatalysis, UF and NF in series. This leads to both lower energy and capital costs, in particular a reduction of the required membrane area in case of batch membrane processes equal to 22.3–44.8%. Accurate prediction of the rejection behavior was attained by the used leaky solution-diffusion model in all cases, with reflection coefficients (σ_COD) ranging from 0.86 to 1.0. The purified effluent streams are finally compatible with irrigation water quality standards (COD values below 1000 mg L⁻¹).