Comparison of physico-chemical pretreatment methods to seawater reverse osmosis: Detailed analyses of molecular weight distribution of organic matter in initial stage

In desalination, effective pretreatment is the key to reduce membrane fouling that occurs during the seawater reverse osmosis (SWRO) process. However, it is difficult to compare the flux decline after different pretreatments using a small-scale reverse osmosis filtration unit. In this study, we successfully evaluated the effect of pretreatment on SWRO in terms of molecular weight distribution (MWD) of seawater organic matter (SWOM) after 20 h of SWRO operation. Microfiltration (MF), ultrafiltration (UF), ferric chloride (FeCl₃) flocculation and powdered activated carbon (PAC) adsorption, were used as pretreatment. The effluents and the retentates after each pretreatment and 20 h of SWRO operation were characterized in terms of MWD.Although the normalized flux of SWRO showed similar flux decline (J/J₀ = 0.17) with/without pretreatment, SWOM concentration in the retentates after different pretreatments was different in quantity and it increased linearly with time. The slope of the SWOM increase was 0.110, 0.096, 0.077 and 0.059 after MF, FeCl₃ flocculation, UF and PAC adsorption pretreatments, respectively. MW peaks for the seawater used in this study consisted of 1200 Da (biopolymers), 950 Da (fulvic acids), 650 Da (hydrolysates of humic substances), 250 Da (low MW acids) and 90 Da (low MW neutrals and amphiphilics). FeCl₃ flocculation preferentially removed 1200 Da (biopolymers), while PAC adsorption mostly removed 950 Da (fulvic acids). UF and NF removed only a marginal amount of relatively large organics, while RO removed the majority of organics. The intensity of 1200, 950, 650 and 250 Da MW in the RO retentates increased with the RO operation time. The organics of MW around 1200 Da (biopolymers) had a relatively low rate of increase with time compared with those of lower MW. This suggests that the SWOM of 1200 Da MW was preferentially retained on the membrane surface.     

Optimum design of reverse osmosis system under different feed concentration and product specification

The design of various multistage RO systems under different feed concentration and product specification is presented in this work. An optimization method using the process synthesis approach to design an RO system has been developed. First, a simplified superstructure that contains all the feasible design in present desalination process has been presented. It offers extensive flexibility towards optimizing various types of RO system and thus may be used for the selection of the optimal structural and operating schemes. A pressure vessel model that takes into account the pressure drop and concentration changes in the membrane channel has also been given to simulate multi-element performance in the pressure vessel. Then the cost equation relating the capital and operating cost to the design variables, as well as the structural variables of the designed system have been introduced in the objective function. Finally the optimum design problem can be formulated as a mixed-integer nonlinear programming (MINLP) problem, which minimizes the total annualized cost. The solution to the problem includes optimal arrangement of the RO modules, pumps, energy recovery devices, the optimal operating conditions, and the optimal selection of types and number of membrane elements. The effectiveness of this design methodology has been demonstrated by solving several seawater desalination cases. Some of the trends of the optimum RO system design have been presented.     

基于海水淡化的正渗透膜分离技术的发展

近年来,水资源危机日益加重。在海水淡化技术中,与反渗透分离技术相比,正渗透分离技术作为一种低能耗、绿色的解决方案,具有明显优势,在国际上得到了广泛的重视,是膜分离技术的研究热点之一。本文从正渗透膜材料结构与性能关系的角度,对膜材料的最新进展进行了综述,同时分析了汲取液的常见类型,并简述了正渗透分离技术的新应用,展望了其未来的发展前景。     

Membrane adsorption bioreactor (MABR) for treating slightly polluted surface water supplies: As compared to membrane bioreactor (MBR)

In this paper, a submerged membrane adsorption bioreactor (MABR) was evaluated for drinking water treatment at a hydraulic retention time (HRT) as short as 0.5 h. As powdered activated carbon (PAC) was added to the bioreactor at 8 mg/L raw water, the MABR achieved much higher removal efficiency for organic matter in the raw water than the parallel-operated membrane bioreactor (MBR). Moreover, the trans-membrane pressure (TMP) of MABR developed much lower than that of MBR, demonstrating PAC in MABR could mitigate membrane fouling. It was also identified here that the removal of dissolved organic matter (DOM) in MABR was accomplished through the combination of three unit effects: rejection by ultrafiltration (UF) membrane, biodegradation by microorganism, and adsorption by PAC; the last was of great importance. A sludge layer was observed on the membranes surface in both MABR and MBR and PAC particles themselves constituted a part of the cake layer and helped to intercept DOM in the mixed liquor by adsorption in MABR, especially for organic molecules of 5000–500 Da. The UF membrane together with the sludge layer and PAC layer in the MABR was able to reject hydrophobic bases (HoBs), hydrophobic neutrals, hydrophobic acids (HoAs), weakly hydrophobic acids (WHoAs) and hydrophilic matter (HiM) in the mixed liquor by 40.0%, 43.9%, 71.8%, 56.6% and 35.9%, respectively.     

Boron reduction performance of reverse osmosis seawater desalination process

In recent years, seawater desalination systems using reverse osmosis (RO) membranes have been constructed to settle the lack of drinking water. RO desalination membranes have high rejection for most of solutes in seawater. Japanese drinking water standards for the water quality of the permeate can be achieved except for boron. Therefore, the boron rejection needs to be considered in the design of the RO process and during the operation of the plant. Luckily, there is a simple and easy method to estimate boron concentration.In this paper, we report measured boron permeabilities and their relation to salt permeabilities using cross-linked polyamide membranes. Chemical degradation of the membranes affected these permeabilities to different degrees. Boron concentrations in the permeate were then calculated using a computer program that was based on the boron permeabilities calculated from the measured salt permeabilities. Results obtained were compared with actual data taken at a RO plant of Toray Industries, Inc., Ehime. The model data fitted the experimental result, well. It was also found that a relationship existed in the permeate between salt and boron concentrations and that the boron concentration can be obtained from measurement of the salt concentration.     

Removal of 17β-estradiol by powdered activated carbon—Microfiltraion hybrid process: The effect of PAC deposition on membrane surface

The removal of 17β-estradiol (E2) was investigated in a powdered activated carbon-submerged microfiltration (PAC-MF) hybrid system to better understand the effect on the system performance of PAC deposition on the membrane. A series of experiments were carried out under various operating conditions. Although the rejection or adsorption of E2 by MF membrane itself was almost negligible, the concentration of E2 in the permeate was always lower than it was in the reactor. This is because E2 was further removed as it passed through the PAC layer deposited on the membrane. As the E2 removal efficiency by the deposited PAC was lower than that by the PAC in the bulk phase, the overall E2 removal was largely dependent on the fraction of the deposited PAC on the membrane which were influenced by operating parameters such as permeate flux, hydraulic retention time (HRT) and mixing intensity in a PAC-MF system. The effect of these parameters on the overall E2 removal rate were also determined quantitatively using model equations developed in this study.     

聚合氯化铝的制备及在微污染水处理中的应用

用酸溶法制备聚合氯化铝,对合成产品进行红外光谱分析,并应用于微污染原水的处理。处理微污染原水结果表明:当投加量为40.0 mg/L,pH值为6.0～9.0时,剩余浊度达到1.0NTU以下,总有机碳(Total Or-ganic Carbon,TOC)去除率达到41.2%。对比试验结果表明自制的聚合氯化铝的除浊效果优于一些常见工业聚合氯化铝。     

Antibacterial ultrafiltration membrane with silver nanoparticle impregnation by interfacial polymerization for ballast water

Interfacial polymerization technology was employed to immobilize silver (Ag) nanoparticles on the surface of commercial polyethersulfone (PES) membrane to develop antibacterial and antifouling ultrafiltration membrane. Ag nanoparticles were prepared from the reduction of silver nitrate (AgNO₃) by sodium borohydride in the presence of polyethyleneimine (PEI) as the stabilizer. The encapsulated Ag nanoparticles in the PEI solution were embedded into the PEI membrane when trimesoyl chloride solution was used to crosslink the PEI solution with the PES membrane, forming Ag-polyamide (PA) networks through the interfacial polymerization reaction. Experimental results showed that the membrane prepared with 50 mmol/L of AgNO₃ and 20 mmol/L of PEI had the optimized antibacterial effect against Escherichia coli. Bacterial concentration and species were also investigated. Exiguobacterium aestuarii and Staphylococcus aureus which are gram-positive bacteria, needed significantly more time for the Ag-PA/PES membrane to kill the bacteria completely when compared to E.coli and Vibrio coralliilyticus which are gram-negative bacteria. This study showed that Ag nanoparticles impregnated in membrane surfaces were 100% effective in killing various types of marine bacteria and bacteria in the seawater collected off Sentosa Island in Singapore. These membranes exhibit excellent antibacterial and antifouling properties which can be used to kill bacteria in ballast water and seawater.     

Influence of Substitutional Defects in ZIF-8 Membranes on Reverse Osmosis Desalination: A Molecular Dynamics Study

In this study, molecular dynamics simulation is used to investigate the effects of water-based substitutional defects in zeolitic imidazolate frameworks (ZIF)-8 membranes on their reverse osmosis (RO) desalination performance. ZIF-8 unit cells containing up to three defect sites are used to construct the membranes. These substitutional defects can either be Zn defects or linker defects. The RO desalination performance of the membranes is assessed in terms of the water flux and ion rejection rate. The effects of defects on the interactions between the ZIF-8 membranes and NaCl are investigated and explained with respect to the radial distribution function (RDF) and ion density distribution. The results show that ion adsorption on the membranes occurs at either the nitrogen atoms or the defect sites. Complete NaCl rejection can be achieved by introducing defects to change the size of the pores. It has also been discovered that the presence of linker defects increases membrane hydrophilicity. Overall, molecular dynamics simulations have been used in this study to show that water-based substitutional defects in a ZIF-8 structure reduce the water flux and influence its hydrophilicity and ion adsorption performance, which is useful in predicting the type and number of defect sites per unit cell required for RO applications. Of the seven ZIF-8 structures tested, pristine ZIF-8 exhibits the best RO desalination performance.     

Innovative beneficial reuse of reverse osmosis concentrate using bipolar membrane electrodialysis and electrochlorination processes

Reverse osmosis (RO) is a widely used and rapidly growing desalination technology. A major disadvantage of this process is that the concentrate from the RO process, which could be as much as 25% of the feed stream, represents a polluting stream. This waste stream could pose a significant challenge to the implementation of this process, particularly for inland communities which do not have the option of ocean disposal. An excellent environmentally benign approach to disposal could be beneficial reuse of the waste stream. This study presents two innovative beneficial reuse strategies for RO concentrate produced by an integrated membrane system (IMS) from a wastewater reclamation facility. The technologies evaluated in this study included bipolar membrane electrodialysis (BMED) for conversion of RO concentrate into mixed acid and mixed base streams, and electrochlorination (EC) for onsite chlorine generation. Bench-scale studies conducted with BMED demonstrated that RO concentrate could be desalted while producing mixed acids and mixed bases with concentrations as high as 0.2N. Similarly, the EC process was capable of producing a 0.6% hypochlorite solution from RO concentrate. The acids and bases as well as the hypochlorite produced could be directly applied to the RO process as well as upstream pre-treatment processes. A preliminary economic evaluation of the viability of these two approaches was conducted by conducting rough order of magnitude cost estimates based on the bench-scale performance of these processes on RO concentrate. A comparison of the overall costs of an Integrated Membrane System utilizing these innovative reuse strategies with conventional disposal options and thermal zero liquid discharge treatment is presented. This comparison indicates that a reuse approach might be economically viable for inland wastewater reuse facilities that utilize RO membranes and have limited options for concentrate disposal.     

Laser-assisted synthesis of cobalt@N-doped carbon nanotubes decorated channels and pillars of wafer-sized silicon as highly efficient three-dimensional solar evaporator

The Co@NCNTs/Si pillars with channels is assemble to a suitable pure water gathering device, which is applied in seawater desalination and sewage purification to produce pure water by utilizing solar energy. High-efficiency utilization of solar energy to generate water vapor is popular, recyclable, and environmentally friendly for seawater desalination and sewage purification, helping to alleviate the global water shortage crisis. Here, we report an efficient and simple method to prepare a three-dimensional (3D) evaporator for steam generation by harnessing the power of the sun. This evaporation is composed of one-dimensional (1D) cobalt embedded and nitrogen doped carbon nanotubes (Co@NCNTs) and 3D silicon pillars array structure (Si pillars). The Co@NCNTs/Si pillars shows a wide light absorption range provided by carbon nanotubes and a long light absorption path because of the silicon pillars. The surface temperature of the sample rises rapidly in 1.5 min and exceed 80 °C under solar illumination of one sun. The water evaporation can be high as 1.21 kg m⁻² h⁻¹ under one sun irradiation (1 kW/m²) with the energy efficiency up to 82.4%. This scalable Co@NCNTs/Si pillars can prepare pure water from seawater and sewage, where the removal rate of ions in seawater and pollutants in sewage is similar to 100%. Based on our research, this multistage three-dimensional structure is a simple and efficient novel photothermal material for extensive seawater desalination and sewage purification.     

Voltammetric Determination of Boric Acid Using the Ternary Complexation System with Salicylaldehyde and H‐Acid

A square‐wave voltammetric method for the determination of boric acid in water has been described based on the new understanding of the electrochemical behavior of boric acid‐Azomethine H complexation. Salicylaldehyde and H‐acid were used as the starting materials of boric acid‐Azomethine H complex and their concentrations were optimized for boric acid determination in water. A glassy carbon electrode, instead of a conventional mercury electrode, was used in the measurement. The detection limit of the proposed method was 0.10 mg B dm^?3. The proposed method was successfully used for boric acid determination in the water from a seawater desalination RO plant.     

Voltammetric evaluation of the antioxidant capacity of tea on electrodes modified with multi-walled carbon nanotubes

The characteristics of the voltammograms of tea polyphenols on a glassy carbon electrode modified with multi-walled carbon nanotubes (MCNT-GCE) were evaluated. With the use of atomic force microscopy, it was found that MCNTs are oriented as rows 0.8–1.0 μm wide with alternating hills to 586 nm in height. Polyphenols other than of tannin are reversibly oxidized at the first step. Corresponding electrode reaction schemes are proposed. A voltammetric procedure for the estimation of the antioxidant capacity (AOC) of tea based on the oxidation of its polyphenol compounds was developed. The voltammograms of tea exhibited clearly defined peaks and oxidation steps whose potentials depend on the type of tea. The area of oxidation peaks was chosen as the parameter that characterizes antioxidant properties. The AOC of tea was expressed in terms of catechin equivalents per 100 mL of a beverage. 27 tea samples were analyzed. It was found that the AOC of green tea is 79% higher than that of black tea (290 ± 40 and 54 ± 22 mg/100 mL, respectively, P < 0.05). The AOC of oolong tea (70 ± 5 mg/100 mL) is considerably lower than that of green tea and statistically insignificantly higher than that of black tea. The AOC of white tea is comparable with the AOC of green tea (255 ± 11 and 290 ± 40 mg/100 mL, respectively, P > 0.05).     

同时测定海水中K+、Na+、Ca2+、Cl-的流动注射离子选择电极分析

建立了一种用于海水中K+、Na+、Ca2+、Cl-同时快速、自动测定的流动注射离子选择电极自动方法(FI-ISE-M),优化了方法的最佳条件:总离子强度调节液(TISAB)的组成为0.3 mmol/L K+、6.0 mmol/L Na+、1.4 mmol/L Ca2+、21.0 mmol/L Cl-及pH8.0的80 mmol/L的tris-H3BO3缓冲溶液,其流量为1.25mL/min;每次测定的样品用量仅为160μL,载流流量为1.42 mL/min,混合盘管长度为30cm(I.D.0.5 mm)。本方法的分析速度为100样/h,相对标准偏差为2.0%(n=11),标准添加回收率为94.9%～104.3%,测定范围分别为1.0～8.0 mmol/L K+、50～290 mmol/L Na+、3.2～16.0 mmol/L Ca2+、70～430 mmol/LCl-。本方法已应用于反渗透海水淡化系统的水质检测。     

Cranberry derived proanthocyanidins reduce bacterial adhesion to selected biomaterials

Catheter associated urinary tract infections (CAUTI) linked with the uropathogens Escherichia coli (E. coli) and Enterococcus faecalis (E. faecalis) account for the majority of nosocomial infections acquired in the clinical environment. Because these infections develop following initial adhesion of the bacterial pathogens to the catheter surface, there is increased interest in developing effective methods to inhibit attachment of cells to biomaterials used in the manufacture of indwelling devices. High molecular weight proanthocyanidins (PAC) extracted from the North American cranberry (Vaccinium macrocarpon) were examined for their potential to reduce the initial adhesion of uropathogenic bacteria (E. coli CFT073 and E. faecalis 29212) to two model biomaterials, poly(vinyl chloride) (PVC) and polytetrafluoroethylene (PTFE). Well-controlled experiments conducted in a parallel-plate flow chamber (PPFC) demonstrated decreased attachment of both bacteria to PVC and PTFE when either the bacteria, biomaterial or both surfaces were treated with PAC. Most significant inhibition of bacterial adhesion was observed for the condition where both the bacteria and biomaterial surfaces were coated with PAC. Additional experiments conducted with nonbiological model particles demonstrate comparable extents of adhesion inhibition, supporting a nonbiospecific mechanism of PAC action. The results of this study are promising for the implementation of PAC in the clinical milieu for prevention of device associated infection as the proposed functional modification is independent of antibacterial mechanisms that may give rise to resistant strains.     

基于离子浓差极化的立体式海水淡化微流控器件研究

海水淡化是解决人类淡水资源匮乏的一个重要途径。现有的海水淡化技术存在设备体积大、海水淡化成本高等问题。本研究采用聚二甲基硅氧烷( PDMS)制备了基于离子浓差极化原理的海水淡化器件,采用盐溶液模拟海水,进行盐离子和水分子分离的研究。研究了不同的外加电压、盐溶液在通道中的流动速度、盐溶液通道深度和Nafion纳米通道的深度等实验条件和结构参数对微流控器件分离盐离子和水分子的影响。对微流控器件的结构参数进行了优化。实验结果表明,采用外加电压为25 V、盐溶液流速为4μL/min、盐溶液通道深宽比为1：20、Nafion纳米通道深度为450~500μm的微流控器件进行盐溶液分离,除盐率可达到99%。研究结果对于开发新型高效、低能耗的海水淡化器件有重要的指导意义。     

高回收率膜法苦咸水淡化工艺的应用研究进展

膜法苦咸水淡化过程中,符合环境保护要求的浓排水处理方法成本高昂,所以只有当回收率达到较高值时,在实际运行中才具有经济可行性。目前,在不加剧膜污染的条件下进一步提高苦咸水淡化系统回收率的方法已成为该领域研究热点。本文详细综述了高回收率膜法苦咸水淡化工艺的应用研究进展,包括基于反渗透、纳滤、正渗透、膜蒸馏、电渗析和电容去离子化淡化工艺过程,以及这些过程面临的热点问题,并对此提出了建议。     

Behavior of extracellular polymers and bio-fouling during hydrogen fermentation with a membrane bioreactor

The characteristics of membrane fouling were investigated by examining the behaviors of extracellular polymer substances (EPSs) produced by hydrogen-producing bacteria during hydrogen fermentation from a submerged membrane bioreactor (MBR). The MBR consisted of a 1.4-L submerged membrane filtration tank and 3-L hydrogen fermenter. An intermittent suction operation was selected to maintain stable filtration performance. The operation of the suction pump was alternately shifted to ON for 7 min followed by OFF for 3 min, with bio-gas sparging at a flow rate of 5.0 L/m²/h (LMH), and manually regulated. Most of the EPS during the continuous hydrogen fermentation using an MBR had accumulated in the reactor because they were retained by the membrane by adsorption onto the polymeric membrane surface. The amount of proteins in the EPS extracted was increased to 179 mg/L and that of carbohydrates was increased to 58 mg/L. Cu²⁺, Mg²⁺, Zn²⁺ in the EPS were increased in the range of 1.6–3.3 mg/L. The high concentration of EPS that is produced has a higher chelation potential in the formation of ligand complexes with metals or cations than that in a conventional continuous stirred tank reactor (CSTR). The EPS directly affected the decrease in the permeate flux, which resulted in the clogging of the membrane.     

Experimental study of desalination using direct contact membrane distillation: a new approach to flux enhancement

New membrane distillation configurations and a new membrane module were investigated to improve water desalination. The performances of three hydrophobic microporous membranes were evaluated under vacuum enhanced direct contact membrane distillation (DCMD) with a turbulent flow regime and with a feed water temperature of only 40 °C. The new configurations provide reduced temperature polarization effects due to better mixing and increased mass transport of water due to higher permeability through the membrane and due to a total pressure gradient across the membrane. Comparison with previously reported results in the literature reveals that mass transport of water vapors is substantially improved with the new approach. The performance of the new configuration was investigated with both NaCl and synthetic sea salt feed solutions. Salt rejection was greater than 99.9% in almost all cases. Salt concentrations in the feed stream had only a minor effect on water flux. The economic aspects of the enhanced DCMD process are briefly discussed and comparisons are made with the reverse osmosis (RO) process for desalination.