Simultaneous removal of humic acid and heavy metal from aqueous solutions using charged ultrafiltration membranes

Lab-made negatively charged ultrafiltration (UF) membranes were used for simultaneous removal of humic acid (HA) and heavy metals from water. Effects of the HA/metal ratio, solution pH and ionic strength on rejection coefficients of HA and metals were investigated. The results showed that the rejection coefficients of both HA and metals increase with the increase of pH and the HA/metal ratio, and the decrease of ionic strength. This study indicated that charged UF could be an effective method for the simultaneous removal of HA and heavy metal harnessing the principle of complexation UF and electrostatic repulsion between the membrane and the HA–M complex of the same charges.     

Direct drinking water treatment by spiral-wound ultrafiltration membranes

This paper presents the results of a research on direct drinking water treatment through an ultrafiltration pilot plant unit using spiral-wound membranes (3500 MWCO). The source of water is the Guarapiranga Reservoir, an eutrophicated water body located in the metropolitan region of São Paulo, Brazil. The data were collected during a period of almost 3400 h, from August 2005 to January 2006. The main objective of the study was to evaluate the membrane production capacity and contaminant removal efficiency. It was verified that the system was able to produce a high quality permeate with a flow close to the specified by the membrane manufacturer. The average permeate flow was 19.7 L.h⁻¹.m⁻², at 467 kPa and 25°C, with a global water recovery of almost 85%. The removal efficiencies for TOC, UV light absorption, and turbidity were 85%, 56%, and 95%, respectively. The results provide substantial evidence of the technical feasibility of spiral-wound UF membranes for direct drinking water treatment from euthrophicated sources, as an alternative for conventional drinking water treatment systems.     

Characteristics of unburned carbons and their application for humic acid removal from water

Two unburned carbons (UCs) were separated from coal fly ash and their physicochemical properties were characterised using N₂ adsorption, XRD, SEM, XPS, FT-IR and potentiometric mass titration. Chemical treatments using HNO₃ and KOH were also conducted on one of the unburned carbons. The adsorption of humic acid from aqueous solution was performed on these untreated and chemically treated UCs. It was found that the UCs showed different porous structure and surface chemical properties, which influenced their adsorption behaviour. UCs exhibited high adsorption capacity for humic acid. After chemical treatment, the textural structure and surface functional groups of the unburned carbon were changed and the adsorption behaviour showed significant difference. Acid treatment did not change the surface area but reduced the functional groups while basic treatment significantly enhanced the surface area in microporous section but still reduced the surface functional groups. Particle size and pH solution will also influence the adsorption capacity. The adsorption will increase with decreasing particle size for humic acid. Higher pH solution will reduce humic acid adsorption on unburned carbon. Ionic strength will also affect humic acid adsorption showing positive effect on adsorption capacity.     

两种材质超滤膜在饮用水处理中的比较研究

采用PVC合金和PVDF 2种材质的浸没式超滤膜对南方某水厂受污染的水源进行中试试验,对比2种膜材质在净水处理中的应用性能。结果表明,浸没式超滤膜工艺对浊度、细菌总数和有机物具有较好的去除效果:出水浊度稳定在0.1 NTU以下,高锰酸盐指数低于3 mg/L,细菌总数和大肠菌群数均达到GB 5749—2006《生活饮用水卫生标准》的要求。在净水效能对比分析中,2种材质的超滤膜性能表现基本相当。试验同时对比了2种超滤膜的膜污染及能耗情况,PVDF超滤膜在抗污染性能及吨水能耗上要优于PVC合金超滤膜。     

Synthesis,characterization, and anti-fouling properties of cellulose acetate/polyethylene glycol-grafted nanodiamond nanocomposite membranes for humic acid removal from contaminated water

Polyethylene glycol-grafted nanodiamond (ND-PEG) was synthesized from pristine detonation NDs and utilized to prepare novel cellulose acetate/polyethylene glycol-grafted nanodiamond(CA/ND-PEG)nanocomposite membranes. Due to unique thermal, mechanical, and antibacterial properties and very easy cleaning of fouled ND-embedded CA nanocomposite membranes, we tried to investigate the performance of CA/ND-PEG membrane for humic acid (HA) removal from contaminated water. Surface functionalization was confirmed by Fourier transform infrared spectroscopy and thermogravimetry analysis. Pristine and functionalized ND with different concentration was added in the casting solution containing CA. The prepared membranes were characterized using contact angle, mechanical strength, scanning electron microscopy (SEM), transmission electron microscopy, and permeation tests. SEM micrographs of the surface of the membranes depicted the increase in the number of pores by the addition of ND and especially ND-PEG into polymer matrix. The results indicated that the nanocomposite membrane with 0.5 wt% ND-PEG exhibited excellent hydrophilicity, mechanical properties, permeability, high rejection, high abrasion resistance, and good anti-fouling performance. The HA adsorption on the membrane surface decreased from 2.85 to 2.15 mg cm^?2 when the ND-PEG content increased from 0 to 0.5 wt%. Most importantly, the HA filtration experiments revealed that the incorporation of ND and especially ND-PEG particles reduced membrane irreversible fouling, dramatically. Meanwhile, the analysis of the fouling mechanism based on Hermia’s model revealed that cake formation is a prevailing mechanism for all membranes.     

Morphological and separation performance study of polysulfone/titanium dioxide (PSF/TiO2) ultrafiltration membranes for humic acid removal

In this study, polysulfone (PSF) hollow fiber membranes with enhanced performance for humic acid removal were prepared from a dope solution containing PSF/DMAc/PVP/TiO₂. The main reason for adding titanium oxide during dope solution preparation was to enhance the antifouling properties of membranes prepared. In the spinning process, air gap distance was varied in order to produce different properties of the hollow fiber membranes. Characterizations were conducted to determine membrane properties such as pure water flux, molecular weight cut off (MWCO), humic acid (HA) rejection and resistance to fouling tendency. The results indicated that the pure water flux and MWCO of membranes increased with an increase in air gap distance while HA retention decreased significantly with increasing air gap. Due to this, it is found that the PSF/TiO₂ membrane spun at zero air gap was the best amongst the membranes produced and demonstrated > 90% HA rejection. Analytical results from FESEM and AFM also provided supporting evidence to the experimental results obtained. Based on the anti-fouling performance investigation, it was found that membranes with the addition of TiO₂ were excellent in mitigating fouling particularly in reducing the fouling resistances due to concentration polarization, cake layer formation and absorption.     

Adsorptive removal of tetracycline from water using Fe (III)-functionalized carbonized humic acid

Humic acid (HA) was carbonized at 300, 400 and 500 ℃ and then functionalized with 1 wt%-12 wt% Fe(III) respectively [CHA300/400/500-Fe(III)]. Adsorption of such Fe(III)-functionalized carbonized HA as adsorbents to aqueous tetracycline (TC: 25 mg·L^-1) was studied. The adsorption equilibrium time for CHA400-Fe(III) to TC was 6 h faster and the adsorption removal efficiency (R_e) was two times higher than that of HA/CHA. The adsorption R e of CHA400-Fe(III) loaded 10% iron [CHA400-(10%)Fe(III)] to TC could reach 99.8% at 8 h and still kept 80.6% after 8 cycles. The adsorption kinetics were well fitted to the pseudo-second-order equation and the adsorption isotherms could be well delineated via Langmuir equations(R² > 0.99), indicating that the homogeneous chemical adsorption of TC occurred on the adsorbents. The main adsorption mechanisms of TC were complexation Fe(III) and hydrophobic distribution. Electropositive and electronegative repulsion between TC and CHA400-(10%)Fe(III) at lowly pH(2) and highly pH(8-10) respectively, leaded to the relatively low adsorption capacity and more notable influence of ion concentration. When the pH was between 4 and 8, TC mainly existed in neutral molecules (TCH₂), so the influence of ion concentration was not obvious. The dynamic adsorption results showed that the CHA400-(10%)Fe(III) could continuously treat about 2.4 L TC(27 mg·L^-1) wastewater with the effluent concentration as low as 0.068 mg·L^-1. Our study suggested a broad application prospect of a new, effective, lowcost and environment-friendly adsorbent CHA400-(10%)Fe(III) for treatment of low-concentration TC polluted wastewater.     

Adsorptive removal of tetracycline from water using Fe(III)-functionalized carbonized humic acid

Humic acid (HA) was carbonized at 300, 400 and 500 °C and then functionalized with 1 wt%–12 wt% Fe(III) respectively [CHA300/400/500-Fe(III)]. Adsorption of such Fe(III)-functionalized carbonized HA as adsorbents to aqueous tetracycline (TC: 25 mg·L⁻¹) was studied. The adsorption equilibrium time for CHA400-Fe(III) to TC was 6 h faster and the adsorption removal efficiency (R_e) was two times higher than that of HA/CHA. The adsorption R_e of CHA400-Fe(III) loaded 10% iron [CHA400-(10%)Fe(III)] to TC could reach 99.8% at 8 h and still kept 80.6% after 8 cycles. The adsorption kinetics were well fitted to the pseudo-second-order equation and the adsorption isotherms could be well delineated via Langmuir equations(R² > 0.99), indicating that the homogeneous chemical adsorption of TC occurred on the adsorbents. The main adsorption mechanisms of TC were complexation Fe(III) and hydrophobic distribution. Electropositive and electronegative repulsion between TC and CHA400-(10%)Fe(III) at lowly pH(2) and highly pH(8–10) respectively, leaded to the relatively low adsorption capacity and more notable influence of ion concentration. When the pH was between 4 and 8, TC mainly existed in neutral molecules (TCH₂), so the influence of ion concentration was not obvious. The dynamic adsorption results showed that the CHA400-(10%)Fe(III) could continuously treat about 2.4 L TC(27 mg·L⁻¹) wastewater with the effluent concentration as low as 0.068 mg·L⁻¹. Our study suggested a broad application prospect of a new, effective, low-cost and environment-friendly adsorbent CHA400-(10%)Fe(III) for treatment of low-concentration TC polluted wastewater.     

饮用水除砷吸附剂的研究进展

砷在水体中主要以As(Ⅲ)和As(Ⅴ)的无机酸形式存在,对人体的危害很大,吸附法是国内外研究最广泛的饮用水除砷技术之一.详细说明了饮用水除砷的吸附剂类型,指出:复合材料效率高、费用低,目前应用最为广泛;纳米材料与砷结合后性质稳定,除砷效率最高,是今后的主要发展方向;生物吸附材料以其高吸附率、低成本成为研究的热点.     

Surfactant-modified bentonite as adsorbent for the removal of humic acid from wastewaters

The effectiveness of surfactant-modified bentonite (SMB) in removing humic acid (HA) from wastewaters was evaluated. Hexadecyl trimethylammonium (HDTMA) chloride was used to modify the surface of the clay mineral. The SMB exhibits very high adsorption potential for HA and at pH 3.0 more than 99% removal was achieved from an initial concentration of 25 μmol/L. The experimental kinetic data were analyzed using the pseudo-first-order kinetic model. Adsorption occurs through film diffusion at low as well as at higher concentrations and temperatures. The adsorption of HA using SMB was an exothermic process. HA adsorption was found to decrease with increase of ionic strength due to the formation of outer-sphere surface complexes on SMB. The equilibrium isotherms were determined and data were analysed using the Langmuir isotherm model. The maximum adsorption capacity, Q° was 73.52 μmol/g with binding constant, b = 0.155 L/μmol at 30 °C and pH 3.0. The adsorbent was suitable for repeated use (more than 3 cycles) without any noticeable loss of capacity.     

饮用水除砷技术研究新进展

重点介绍了近年来各种除砷新技术的研究进展,内容包括:强化混凝、吸附、离子交换、膜法、预氧化除砷技术。评价了各除砷技术的优缺点与适用范围,并认为饮用水除砷技术的发展将呈现出以下特点:As(Ⅲ)和As(V)同步去除技术的开发;易于取得或制备、生物化学稳定性高、吸附容量大、选择性高、再生能力强的新型除砷吸附剂的开发;多种除砷技术联合,多重去除机理协同的除砷流程的开发;低能耗、低成本除砷技术的开发;生物除砷技术的开发。     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Enhanced removal of humic acid from water by micelle-montmorillonite composites: Comparison to granulated activated carbon

Removal of humic acid (HA) from water by octadecyltrimethyl-ammonium (ODTMA) micelle–montmorillonite (MMT) composites and by granulated activated carbon (GAC) was studied in dispersion and by filtration. FTIR measurements emphasized that the ODTMA micelle–clay-mineral composite differs from the ODTMA monomer-clay-mineral one. HA adsorption by GAC in dispersion was moderately reduced from 100% initially to 75% with an increase in HA concentrations. In contrast, the fractions adsorbed by the composite increased monotonically with HA concentrations from very low adsorption up to 80%. This effect was explained by the presence of a small concentration of ODTMA monomers in dispersion, which adsorbed on the negatively charged HA and partially neutralized it, or caused charge reversal, which in turn inhibited HA adsorption by the positively charged composite. This effect was verified by mobility measurements and was found to be more pronounced at low HA concentrations. This trend of increase in HA removal with an increase in HA concentration (3 and 10 ppm) was also observed in filtration (50% and 85% removal, respectively), when employing columns of the composite mixed with sand (to improve flow). Throughout the experiment the removal of high HA concentration (10 ppm) by the composite filter remained ~ 80% whereas, the removal by the GAC filter decreased from an initial 80% removal to a complete recovery of the HA (no removal) after the passage of 20 L (200 pore volumes). Upon applying sand of higher quality in the columns the removal of low HA concentrations was nearly complete by the composite column while the GAC only slightly contributed to its removal (for a passage of 100 L (1000 pore volumes)).     

Cyclodextrin‐dendrimer functionalized polysulfone membrane for the removal of humic acid in water

Commercial polysulfone (PSf) membranes were crosslinked with a β‐cyclodextrin‐poly (propyleneimine) (β‐CD‐PPI) conjugate which had β‐CD pendant arms using trimesoyl chloride (TMC) by interfacial polymerization. The morphology and physicochemical properties of the nanofiltration membranes were characterized using Fourier transform infrared/attenuated total reflectance (FT‐IR/ATR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and cross‐flow filtration system. Water‐contact angle, water‐intake capacity, and rejection capacities of the membranes were evaluated. The β‐CD‐G4 (generation 4)‐PPI‐PSf and β‐CD‐G3 (generation 3)‐PPI‐PSf membranes both exhibited high humic acid rejection of 72% as compared to the commercial PSf which exhibited 57%. The modified membranes were also more hydrophilic (36° to 41°) than PSf (76°). These results suggest that β‐CD‐PPI nanostructures are promising materials for the synthesis of membranes for the removal of humic acid from water. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4428–4439, 2013     

Chelating water-soluble polymers associated with ultrafiltration membranes for metal ion removal

This article describes the retention properties of commercial chelating water-soluble polymers, for different metal ions in aqueous solution using a liquid-phase polymer-based retention (LPR) technique. The polymers studied were poly(ethyleneimine) or P(EI) (water-free and a 50?% aqueous solution) and poly(ethyleneimine epichlorohydrin) or P(EIE) (a 17?% aqueous solution). These commercial polymers were fractionated by ultrafiltration membranes and then characterized by Fourier-transformed infrared spectroscopy. The extraction process was performed using the following metal ions: Cu²⁺, Cd²⁺, Co²⁺, Ni²⁺, Zn²⁺, Pb²⁺ and Cr³⁺. In the washing studies, we varied the pH (3, 5 and 7) and retention time. The results showed that P(EI) showed high retention for all the metal ions at pH 7 and for selective retention of Cu²⁺ at pH 5, while P(EIE) showed selective retention of Cu²⁺ ions at pH 7. Using the enrichment method, the maximum retention capacity of Cu²⁺ and Cd²⁺ was achieved using a 50?% aqueous solution of P(EI) at pH 5 and 7, respectively. Finally, charge–discharge experiments for Cu²⁺ were analysed by changing the pH from basic to acidic over three cycles. These results showed that it is possible to remove metal ions and regenerate the removal capacity of the polychelatogens using the LPR technique.     

自来水深度处理超滤膜的选择

试验设计、运行了聚砜中空纤维超滤(UF)膜,直接将未经预处理的某自来水管网输出水,处理成优质供水。结果表明,随着UF膜的切割分子量从0.6万增大到5万,产水量提高,对主要水质指标的去除率下降,净化水的水质优良,即使原水的水质突然恶化,UF膜能有效地将被严重污染的高浊度和色度的异常自来水转化成为符合饮用水水质指标的卫生洁净水。