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.     

New chlorine‐resistant polyamide reverse osmosis membrane with hollow fiber configuration

New asymmetric hollow fiber reverse osmosis (RO) membrane was developed from a new chlorine‐resistant copolyamide [4T‐PIP(30)] with a piperazine moiety by a conventional phase‐separation method. The new 4T‐PIP(30) hollow fiber membrane has the same low‐pressure RO performance as cellulose triacetate hollow fiber membrane (FR = 205 L/m² day, Rj = 99.6%) and superior chlorine resistance as well as pH resistance to conventional aramid RO membranes. Structural analysis and viscoelastic study revealed that the new hollow fiber consisted of a top skin, dense layer, and microporous layer, and that it began to decrease its elasticity at 80°C in water, which is possibly related to its good and stable RO performance around room temperature. Several kinds of RO modules were made from the new hollow fiber membranes, for which RO performances were stable for 2 years in chlorinated feed water desalination (the free residual chlorine ranged from 0.l to 1.1 mg/L). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 517–527, 2001     

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。     

Modification of preparation method for polymer inclusion membrane (PIM) to produce hollow fiber PIM

A new preparation method for polymer inclusion membrane (PIM) was developed. The preparation method—called post‐treatment method—is very convenient to prepare a hollow fiber PIM. Using this method, a commercial cellulose triacetate (CTA) hollow fiber membrane can be easily converted into a hollow fiber PIM. Thus, a CTA hollow fiber membrane was allowed to swell in 2‐nitrophenyl‐n‐octyl ether (NPOE) in the presence of chloroform as a solvent for CTA and N,N,N′,N′‐tetraoctyl‐3‐oxapentane diamide (TODGA) as a carrier. After evaporating chloroform, a hollow fiber PIM containing NPOE and TODGA was obtained. The result of the transport experiment of cerium(III) ions using the hollow fiber PIM showed that cerium ions were effectively transported from the feed solution to the strip solution through the hollow fiber PIM, indicating that the hollow fiber PIM was successfully prepared using the post‐treatment method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4372–4377, 2006     

PDMS/ZIF-8 coating polymeric hollow fiber substrate for alcohol permselective pervaporation membranes

In order to develop high performance composite membranes for alcohol permselective pervaporation (PV), poly (dimethylsiloxane)/ZIF-8 (PDMS/ZIF-8) coated polymeric hollow fiber membranes were studied in this research. First, PDMS was used for the active layer, and Torlon®, PVDF, Ultem®, and Matrimid® with different porosity were used as support layer for fabrication of hollow fiber composite membranes. The performance of the membranes varied with different hollow fiber substrates was investigated. Pure gas permeance of the hollow fiber was tested to investigate the pore size of all fibers. The effect of support layer on the mass transfer in hydrophobic PV composite membrane was investigated. The results show that proper porosity and pore diameter of the support are demanded to minimize the Knudsen effect. Based on the result, ZIF-8 was introduced to prepare more selective separation layer, in order to improve the PV performance. The PDMS/ZIF-8/Torlon® membrane had a separation factor of 8.9 and a total flux of 847 g·m^-2·h^-1. This hollow fiber PDMS/ZIF-8/Torlon® composite membrane has a great potential in the industrial application.     

Analysis of hollow fiber reverse osmosis membrane module of axial flow type

Several analyses of hollow fiber reverse osmosis (RO) modules in which permeate water flows from the outer to the inner side of the membrane have been attempted over the past 20 years. In our previous work, an FCP (Friction Concentration Polarization) model showed good agreement with a wide range of actual performance data of a hollow fiber RO membrane module of radial flow type. In this work, this analytical model was applied to axial flow type hollow fiber modules. The performance of the axial flow type module with high packing density of hollow fibers was analyzed, taking into consideration the axial concentration profile in the module. It was confirmed that this model showed good agreement with experimental data for an axial flow type RO membrane module. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

CTA高盐度苦咸水脱盐中空纤维反渗透膜

本文介绍高盐度苦咸水反渗透中空纤维膜的研制，主要涉及某些重要参数对纤维成型和膜性能的影响。     

Polymer membranes for separating organic mixtures

Polyvinyl alcohol (PVA), polyacrylonitrile (PAN), and cellulose ester were respectively chosen as the separation layer and the support in the composite membranes based on the concept of the solubility parameter and the permselectivities for separating ethanol/water mixture, isopropanol/water mixture, and caprolactam/water mixture. The effects of the membrane materials and the construction of the composite membrane on the separation performance were preliminary discussed. The separation performance of the membranes prepared by several making‐membrane techniques, i.e., the polymer solution making‐membrane technique, and the membrane treatment technique (heat treatment, organic solvent modification) were presented. The composite membranes of PVA/PAN and PVA/cellulose acetate, and cellulose triacetate hollow fiber membrane modified, which possess good performance in separating the organic systems, were developed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1160–1164, 2006     

影响渗透汽化中空纤维复合膜分离性能的制备工艺研究

采用聚乙烯醇（ＰＶＡ）为分离层的模材料,以浸涂工艺把ＰＶＡ复合到聚砜（ＰＳ）或聚丙烯腈（ＰＡＮ）的中空纤维支撑层上,在长度为０．４ｍ的不锈钢管中组装若干根中空纤维复合膜测定对乙醇水溶液的渗透汽化（ＰＶ）分离性能。结果表明,ＰＶＡ／ＰＡＮ中空纤维复合膜的性能优于ＰＶＡ／ＰＳ,内径较大（１．３ｍｍ）的优于内径上（０．４ｍｍ）者,ＰＶＡ水溶液在中空纤维支撑层上的涂复次数对复合膜ＰＶ分离性能、以及ＰＶＡ／     

Effect of cellulose acetate/cellulose triacetate ratio on reverse osmosis blend membrane performance

Surface functionalization and modification including the grafting process are effective approaches to improve and enhance the reverse osmosis (RO) membrane performance. This work is aimed to synthesize grafted/crosslinked cellulose acetate (CA)/cellulose triacetate (CTA) blend RO membranes using N-isopropylacrylamide (N-IPAAm) as a monomer and N,N-methylene bisacrylamide (MBAAm) as a crosslinker. The morphology of these membranes was analyzed by scanning electron microscopy and their surface roughness was characterized by atomic force microscopy. The performance of these membranes was evaluated through measuring two major parameters of salt rejection and water flux using RO unit at variable operating pressures. It was noted that the surface average roughness obviously decreased from 148 nm for the pure CA/CTA blend membrane with 2.5% CTA to 110 nm and 87 nm for the grafted N-IPAAm and grafted/crosslinked N-IPAAM/MBAAm/CA/CTA-RO membranes, respectively. Moreover, the contact angle decreased from 51.98° to 47.6° and 43.8° after the grafting and crosslinking process. The salt rejection of the grafted CA/CTA-RO membrane by 0.1% N-IPAAm produced the highest value of 98.12% and the water flux was 3.29 L/m²h at 10 bar.     

Control of organic fouling at two seawater reverse osmosis plants

Organic fouling of seawater Reverse Osmosis (RC) membranes is a phenomenon not well understood; it can result in a loss of membrane productivity and salt rejection properties. Two seawater RO plants using DuPont B-10 hollow fiber permeators had experienced organic fouling and were studied.The two plants used different sources of feedwater; one RO plant at Culebra, Puerto Rico, used open seawater; while the other RO plant at Grand Cayman Island, British West Indies, used a sea well. Both feed water sources possessed high concentrations of soluble organics (40–80mg/1) which were mainly humic acids. In an attempt to remove these organics with in-line cationic polyelectrolyte coagulation, the plants experienced organic fouling which caused excessive loss of productivity and salt rejection; both plants initially failed their acceptance tests.It was discovered that the fouling was actually caused by interactions between the humic acids and in-line cationic, polyelectrolyte coagulants which were not removed by in-dedth and cartridge filtration. Rather than remove the humic acid material, acid addition was initiated and in-line cationic coagulants use discontinued to keep the humic acids soluble. It should be noted that with the open seawater intake ferrous sulfate was still used to remove colloidal material and reduce the SDI. Both plants subsequently have passed their 720-hour acceptance test.Culebra and Grand Cayman plants have now exceeded design specification for both productivity and salt rejection. The aramid hollow fiber permeators on acidified feed have shown 100% rejection of these organics at both 25% and 50% conversion and organic fouling has not been evident.     

Permselectivity of polyamide composite membrane modified by solvent

Asymmetric reverse osmosis (RO) polyamide (PA) composite membrane may be modified by means of a solvent‐processing technique into pervaporation (PV) membrane for separating organic aqueous solution. Formic acid, acetic acid, phosphoric acid, hydrochloric acid, phenol, and so forth, better solvents for PA, were selected as the modifying agents in this study. The effect of the modifying conditions (type and concentration of the modifying agent, processing time of membrane in liquid medium) on the sorption of modified membranes was investigated. After the PA composite membrane was treated with 8 wt % acetic acid for 1 h, the swelling rate for water (S_w) increased, whereas that for isopropanol (S_IPA) decreased, compared with that of the nonmodified membrane. The difference between S_w and S_IPA of the membrane treated with acetic acid was greater than that with other modifying agents. The separation factor and flux of the modified membrane were correspondingly maximal when it was used in a PV separating isopropanol aqueous solution. The contact of solvent molecules in liquid medium with polymer chains in the PA membrane and the intranodular chains in the PA membrane tending to diffuse by reptation toward the solvent molecules were the principal causes leading to a change of structure of asymmetric PA composite membrane. The mechanism of changing membrane structure by means of the solvent‐processing technique may better interpret the modification of PA composite RO membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1005–1010, 2004     

PAN／PS共混中空纤维超滤膜研究

本文将聚丙烯腈（ＰＡＮ）和聚砜（ＰＳ）材料共混，采用二甲基甲酰胺（ＤＭＦ）作溶剂，以干－湿纺丝工艺制备中空纤维超滤膜，研究了二种膜材料和溶剂的热力学性质，确定合适的共混体系，并相同共混比下共混物浓度对中空纤维超滤膜性能影响。以磷酸三乙酯（ＴＥＰ）和冰醋酸作为添加剂，分别观测其不同含量膜性能变化规律。认为磷酸三乙酯作用添加剂有一定的优越性。提高铸膜液温度，有助于增强ＰＡＮ－ＰＳ－ＤＭＦ所组成部分互溶     

Effect of coating and surface modification on water and organic solvent nanofiltration using ceramic hollow fiber membrane

Nanofiltration ceramic hollow fiber membranes were developed to simplify the manufacturing process and improve water and organic solvent permeation performance. The alumina hollow fiber support was prepared by a phase-inversion/sintering method, and a γ-Al₂O₃ sol was coated thereon as a selective layer. Polyvinyl alcohol and ethanol were used as the drying control chemical additive in the coating solution, so that a coating layer could be formed without defects in only one coating step. The coating layer thickness could be adjusted to 0.6–2 μm depending on the coating drawing speed. A sintering temperature of 350 °C was selected to provide both reasonable water permeability (6.91 LMH/bar) and rejection (a molecular weight cutoff of 1000 Da or less) and to form a stable γ-Al₂O₃ phase. In the case of a membrane that was surface-modified with (3-chloropropyl)-trimethoxysilane, the permeability of toluene and hexane was 2.3 and 4.3 LMH/bar, respectively. The newly developed ceramic membrane showed excellent permeability and separation properties, as well as potential effectiveness for organic solvent nanofiltration applications.     

Extraction of a dissolved organic contaminant from water into an aqueous surfactant solution across a microporous membrane

A novel extraction process, aqueous micellar solvent extraction (AMSE), was demonstrated. In ASME an solute is extracted from a wastewater across a microporous membrane into an aqueous surfactant solution containing micelles that solubilize the solute. The membrane retains the surfactant micelles in the aqueous micellar solvent. ASME was carried out in hollow fiber ultrafiltration modules with benzoic acid as the solute and a fatty amine ethoxylate surfactant. Flowing the micellar solvent through the fibers and the wastewater outside gave good extraction and low contamination of the treated water by surfactant. The major resistance to extraction of solute was diffusion across the wall of the hollow fiber.     

Preparation of a heterogeneous hollow‐fiber affinity membrane modified with a mercapto chelating resin

A high‐quality, heterogeneous hollow‐fiber affinity membranes modified with mercapto was prepared through phase separation with blends of a chelating resin and polysulfone as membrane materials, poly(ethylene glycol) as an additive, N,N‐dimethylacetamide as a solvent, and water as an extraction solvent. The effects of the blending ratio and chelating resin grain size on the structure of the hollow‐fiber affinity membrane were studied. The effects of the composition of the spin‐cast solution and process parameters of dry–wet spinning on the structure of the heterogeneous hollow‐fiber affinity membrane were investigated. The pore size, porosity, and water flux of the hollow‐fiber affinity membrane all decreased with an increase in the additive content, bore liquid, and dry‐spinning distance. With an increase in the extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow‐fiber affinity membrane all increased, but the pore size and water flux of the hollow‐fiber affinity membrane decreased. It was also found that the effects of the internal coagulant composition and external coagulant composition on the structure of the heterogeneous hollow‐fiber affinity membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of the heterogeneous hollow‐fiber affinity membrane and decrease the pore size, porosity, and water flux of the heterogeneous hollow‐fiber affinity membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the heterogeneous hollow‐fiber affinity membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Recognition properties of poly(vinylidene fluoride) hollow‐fiber membranes modified by levofloxacin‐imprinted polymers

Through the use of thermal polymerization, poly(vinylidene fluoride) (PVDF) hollow‐fiber membranes modified by a thin layer of molecularly imprinted polymers (MIPs) were developed for the selective separation of levofloxacin. To demonstrate the changes induced by thermal polymerization, PVDF hollow‐fiber membranes with different modification degrees by repeated polymerization were weighed. The total weight of the imprinted membranes increased by 14 μg/cm² after a five‐cycle polymerization. An increase in the membrane weight indicated the deposition of an MIP layer on the external surface of PVDF hollow‐fiber membranes during each polymerization cycle, which was also characterized by scanning electron microscopy. MIP membranes with different degrees of surface modification provided highly selective binding of levofloxacin. Both hollow‐fiber MIP membranes and nonimprinted membranes showed enhanced adsorption of levofloxacin and ofloxacin gradually with an increase in the modification degrees of PVDF hollow‐fiber membranes to a maximum value followed by a decrease. These results indicate that thermal polymerization indeed produces an MIP layer on the external surface of PVDF hollow‐fiber membranes and that it is feasible to control the permeability by repeated polymerization cycles. Different solvent systems in the permeation experiments were used to understand the hydrophobic interaction as one of the results of the binding specificity of MIP membranes. Selective separation was obtained by multisite binding to the template via ionic, hydrogen‐bond, and hydrophobic interactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

热致相分离法iPP中空纤维微空膜结构与性能--稀释剂的作用

Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.     

溶胀对中空纤维膜萃取器中的流动和传质性能的影响

溶胀是中空纤维膜萃取工业化必须要解决的关键问题之一。本文通过拍摄电镜照片，观察了溶胀前后中空纤维膜表面形态，孔隙率，膜孔径，膜孔道弯曲状况等微观结构的变化。结果表明，溶胀会使中空纤维膜孔隙率减小，膜孔径变小，弯曲因子增大，通过测量发现，溶胀后膜长度增加，而膜的内外径，膜厚基本不变。本文还研究了溶胀时间对中空纤维膜器中的流动及传质效果的影响，通过测量聚丙烯和聚砜中空纤维膜器管程和壳程的停留时间分布曲线表明，对于装填密度较高的膜器，溶胀时间对壳程和管程中的流动状况的影响可以忽略。此外，本文以正辛醇－苯胺－水为实验体系，在中空纤维膜器中进行了循环逆流传质实验。实验证明，由于溶胀使纤维膜阻增加，膜器的传质性能随时间的增加而下降。