Impact of gel layer formation on colloid retention in membrane filtration processes

Colloidal particles in the feed streams of membrane filtration processes control membrane fouling rate in many instances. In this study, the non-gelling colloidal Na-alginate and the gelling colloidal Ca-alginate are employed to investigate the significance of gel layer formation in membrane filtration processes in terms of contribution to membrane fouling and supplementary impurity removal. The results show that contribution of colloidal particles to membrane fouling depends on the gelling propensity of the colloids and the operational mode (constant pressure or constant flux) implemented. A small dose of either Na-alginate or Ca-alginate was found to greatly increase membrane fouling rate during constant pressure filtration. Both the resistance to removal by application of shear and the lower susceptibility of the concentration polarization layer to shear resulted in more severe fouling during constant flux filtration in the presence of Ca-alginate assemblages than in the presence of Na-alginate. Apparent channel sizes of the Ca-alginate gel layer were calculated from the material properties of the fouling layer. Incomplete catalase retention highlighted the likely heterogeneity in size of liquid transport pathways. Adsorption also contributed to the trapping of colloidal particles according to the retention behaviour of BSA by the Ca-alginate gel layer. Gel layer formation propensity should be seriously considered for the operation of membrane filtration processes. Two simple methods based on (i) a permeability recovery experiment and (ii) comparison of dead-end filtration behaviour with and without shear application are proposed for evaluation of the gelling propensity of colloidal dispersions.     

DNA microarrays on porous membrane supports with colorimetric detection

The technology of DNA microarrays on porous membrane supports with colorimetric detection on horseradish peroxidase was developed. Comparison of the methods of oligonucleotide immobilization on chemically different membranes was carried out and the conditions of colorimetric detection of biotin in DNA duplexes on microarray surface were optimized. The method that was developed was applied for determining the type of genes encoding extended-spectrum β lactamases.     

Influence of diazonium-induced surface grafting on PES NF membrane fouling reduction in algal-rich water treatment

The algae bloom phenomenon incurs a major challenge to conventional drinking water treatment processes due to the discharges of a large amount of intracellular pollutant and odor compounds in the water sources. Membrane processes have been considered as promising technologies to treatment of algal-rich water due to complete algal cell rejection however, its application has been limited by membrane fouling. In this work, the high-performance loose antifouling PES NF membranes were fabricated using diazonium-induced grafting and applied for treating real algal effluent. The modified membranes exhibited complete algal dye removal and turbidity removal throughout the long-term filtration. Also, the coupling and radically modified membranes can be able to removed COD by up to 90% and 88%, respectively, while a removal efficiency of 24% was observed for bare membrane. It is worth noting that, a relative smooth behavior in permeate flux by loose modified membranes during prolonged algal dye filtration, demonstrating exceptional anti-fouling property of membranes. In addition, the fouled modified membranes were effectively recovered by water flushing. Both loose modified membranes exhibited excellent resistance in the strongly acidic environment. These high performance antifouling NF membranes affords an innovative methodology toward the treatment of algal-rich water.     

Influence of membrane structure on fouling layer morphology during apple juice clarification

The flux behavior of 0.2 μm nylon, polysulfone (PS), polyvinylidene fluoride (PVDF) and polyethersulfone (PES) membranes was examined during dead-end microfiltration of commercial apple juice. On nylon membranes, a 0.1 μm thick surface fouling layer rapidly formed that acted as a secondary membrane. The colloidal particles retained by this surface layer aggregated to form a thick loose gel structure, producing an anisotropic fouling structure. In contrast, the 4 μm thick surface fouling layer of PES was slower to form and had a more open structure with a lower flux resistance per unit thickness. The morphology of the PES surface layer also did not differ dramatically from the loose gel structure that subsequently formed on top of this secondary membrane. The PS surface fouling layer was similar in structure to nylon whereas the PVDF layer more closely resembled that found with PES. The density of the surface fouling layer did not directly correlate to membrane surface hydrophobicity or pure water flux. Atomic force microscopy (AFM) indicated that surface roughness strongly influenced surface fouling layer morphology. The membrane surface appears to act as a template for the fouling process; therefore, smooth membranes (nylon and PS) produce a dense surface fouling layer whereas this same layer on rough membranes (PES and PVDF) is much more open. Consequently, the fluxes of PES and PVDF membranes are less affected by fouling formation.     

In-situ cryo-SEM investigation of porous structure formation of chitosan sponges

Aiming at better understanding of porous structure formation unique in-situ experiments on freeze-drying the chitosan-based solvents were carried out by cryo-SEM method. It allowed us to visualize the lyophilization process and to follow the formation of the porous structure in the chitosan sponge. It was clearly shown that the chitosan solutions just after freezing possess an evident microstructure consisting of the walls of the future pores and of the frozen solvent filling the space between them. The diameter of the pores and their wall thickness are controlled be pre-freezing temperature. An incorporation of nanofillers (chitin nanofibrils and montmorillonite) into the chitosan solution did not affect the pore size and wall thickness. However, they can promote the formation of the layered structure of the pore walls.     

Diffusion into and adsorption of polyethylenimine on porous silica gel

The polyethyleneimine (PEI)–water–silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI–cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state.     

Membrane fouling in a submerged membrane bioreactor (MBR) under sub-critical flux operation: Membrane foulant and gel layer characterization

Membrane foulants and gel layer formed on membrane surfaces were systematically characterized in a submerged membrane bioreactor (MBR) under sub-critical flux operation. The evaluation of mean oxidation state (MOS) of organic carbons and Fourier transform infrared (FT-IR) spectroscopy demonstrated that membrane foulants in gel layer were comprised of not only extracellular polymeric substances (EPS) (proteins, polysaccharides, etc.) but also other kinds of organic substances. It was also found that fine particles in mixed liquor had a strong deposit tendency on the membrane surfaces, and membrane foulants had much smaller size than mixed liquor in the MBR by particle size distribution (PSD) analysis. Gel filtration chromatography (GFC) analysis showed that membrane foulants and soluble microbial products (SMP) had much broader distributions of molecular weight (MW) and a larger weight-average molecular weight (M_w) compared with the influent wastewater and the membrane effluent. Scanning electron microscopy (SEM) and energy-diffusive X-ray (EDX) analysis indicated that membrane surfaces were covered with compact gel layer which was formed by organic substances and inorganic elements such as Mg, Al, Fe, Ca, Si, etc. The organic foulants coupled the inorganic precipitation enhanced the formation of gel layer and thus caused membrane fouling in the MBR.     

多孔玻璃载体自转晶B-Al-MFI型沸石膜的原位合成

在乙胺和水的混合蒸汽相中,首次通过载体自转晶,在多孔玻璃表面原位合成了B-Al-MFI型沸石膜。X射线衍射和扫描电镜观察证明,膜中沸石晶体的取向是随机的。晶体尺寸约为15～25μm,单层晶体厚的膜约为10～20μm。在焙作去有机模板剂后的沸石膜上,O~2和N~2的透过性分别为0.095×10^-^8和0.15×10^-^8mol/(m^2·s·Pa)。计算的O~2/N~2的理想选择值(0.63)明显低于诺森扩散的理想选择性值(0.94)和透过原载体的理想选择性值(0.91)。     

Low-pressure membrane filtration of secondary effluent in water reuse: Pre-treatment for fouling reduction

Fouling in the low-pressure membrane filtration of secondary effluent for water reuse can be severe due to the complex nature of the components in the water. Pre-filtration, coagulation and anion exchange resin were investigated as pre-treatments for reducing fouling of microfiltration (MF) and ultrafiltration (UF) membranes in the treatment of activated sludge-lagoon effluent. The key fouling components were determined using several analytical techniques to detect differences in the organic components between the feed and permeate.Pre-filtration (1.5 μm) enhanced the permeate flux for MF by removing particulates, but had little effect for UF. Marked flux improvement was obtained by coagulation pre-treatment at 5 mg L⁻¹ Al³⁺ with internal membrane fouling being substantially alleviated. Anion exchange resin removed >50% of effluent organic matter but did not improve the flux or reduce irreversible membrane fouling. These results, together with detailed organic compositional analyses, showed that the very high-molecular weight organic materials (40–70 kDa) comprised of hydrophilic components such as soluble microbial products, and protein-like extracellular matter were the major cause of membrane fouling.     

Physisorbed water layer formation on fully hydroxylated mesoporous silicas

Kinetic adsorption isotherms were obtained by gravimetric determination of water adsorption into fully hydroxylated mesoporous silicas using samples exposed to controlled humidity air at 22+/-2 degrees C. Twenty kinetic isotherms at several relative humidities (11, 33, 43, 51, 75, and 85%) were obtained with 11 different batches of silica using this simple procedure to obtain quantitative information on the formation of H2O adsorbates. The H2O surface concentrations obtained from the plateau data of individual kinetic adsorption isotherms at 43 and 51% RH, typically precise to about +/-1%, show that a complete monolayer is formed with negligible second-layer adsorption at these relative humidities. This monolayer has a surface concentration of 7.68+/-0.30 micromol H2O/m2, which is lower than the quasi-equilibrium concentration at these relative humidities obtained by the conventional equilibrium-isotherm procedure. Comparison with the Kiselev-Zhuravlev concentration of silanol groups on fully hydroxylated silicas (7.6+/-0.8 micromol SiOH/m2) confirms 1:1 H2O:SiOH stoichiometry of this monolayer. The presence of partial-layer structures at 2.85+/-0.1 and 5.7+/-0.1 micromol H2O/m2 is suggested by isotherms at 11 and 33% RH, respectively, while a bilayer at approximately 14+/-1 micromol H2O/m2 is suggested by kinetic isotherms at 75 and 85% RH.     

The study on vulcanization fouling behavior of nanocrystalline layer

Mold fouling can degrade the physical properties and reduce the aesthetic value of the molded product. A plethora of research efforts have tried addressing these drawbacks, however, an effective method to prevent the foregoing adverse effects of mold fouling is still a challenge. Here, the fouling performance of aluminum alloy with a nanocrystalline surface layer fabricated by High Pressure Shot Peening (HPSP) during vulcanization has been investigated. Results indicate that an HPSP‐treated sample shows excellent resistance of mold fouling with only 1/8 weight gain after 25 cycles, compared to its HPSP‐free counterpart. The improved release performance can be attributed to the compact passivation layer with a larger thickness and low‐energy surface obtained after HPSP treatment, as well as the strengthened surface with a lower friction coefficient. Copyright © 2011 John Wiley & Sons, Ltd.     

Photocatalytic thin film composite forward osmosis membrane for mitigating organic fouling in active layer facing draw solution mode

As a high-flux operation mode of thin film composite-forward osmosis (TFC-FO) membrane, active layer facing draw solution (AL-DS) mode suffers from the severe membrane fouling tendency, which is not addressed well. Here, we introduced a photocatalyst (Anatase titanium dioxide, A-TiO₂) onto the support layer of TFC-FO membrane via the bonding of polydopamine (PDA) and polytetrafluoroethylene (PTFE), and prepared two photocatalytic membranes, A-TiO₂/PDA@TFC and A-TiO₂/PTFE@TFC. Compared with the pristine TFC-FO membrane, both A-TiO₂/PDA @TFC and A-TiO₂/PTFE@TFC had an improved water permeability (10.5 L m⁻²h⁻¹ and 9.5 L m⁻² h⁻¹, respectively) and reduced reverse NaCl flux salt (0.8 g m⁻² h⁻¹ and 0.7 g m⁻² h⁻¹, respectively) in the AL-DS mode using 1 mol/L NaCl as draw solution and pure water as feed solution. Moreover, in the 16 h fouling experiment using 200 ppm bovine serum albumin (BSA) solution as a representative pollutant, the flux decline rate of both photocatalytic membranes was dramatically alleviated from 39.7% and 21.7% in the darkness to 8.5% and 9.7% under UV irradiation, respectively, indicating a significant anti-fouling capacity of photocatalytic effect. In all, the presence of A-TiO₂ endowed membrane with high permeability, high rejection efficiency and excellent anti-fouling capacity under UV spotlight. As bonding agent, PTFE provided the modified membrane with a high photocatalytic effect and high self-cleaning capacity, while PDA increased the membrane permeability and protected membrane against photocatalytic damage. This work provides a simple and feasible method to improve the anti-fouling capacity of TFC-FO membrane in AL-DS mode.     

p-Nitrophenol permeability and temperature characteristics of an acryloyl-L-proline methyl ester-based porous gel membrane

Thermoresponsive porous gel membranes were synthesized by a simultaneously occurring process consisting of radiation-induced polymerization and crosslinking in aqueous solutions at various concentrations of acryloyl-L -proline methyl ester(A-ProOMe) without a crosslinker. Permeation of p-nitrophenol (PNP) through a thermoresponsive porous gel membrane obtained at a monomer concentration of 80% (w/w) drastically reduced around 14°C, the lower critical solution temperature (LCST) of linear poly(A-ProOMe) in water, from 0.60 × 10⁻³ cm/min at 10°C to no permeation at 18°C, accompanied by changes in both size and shape of pores associated with gel shrinkage. Moreover, it was found that porous gel membranes with a porosity of approximately 60% had a greater PNP permeability constant through porous gel membranes with mutually connected pores obtained at a monomer concentration of 50% (w/w) than individually supported pores obtained at a monomer concentration of 70% (w/w). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1495–1500, 1998     

Preparation of water and alkali durable porous glass membrane coated on porous alumina tubing by sol-gel method

Composite porous glass membranes were prepared by the sol-gel method. A thin porous glass layer, about 2 μm thick, was coated on the surface of the porous ceramic tubing (Al₂O₃:99.9 wt.%, pore diameter: 200 nm). The composition of the porous glass layer of the composite membrane was SiO₂-ZrO₂. Considering from the fact that the desalination ratio of the feed aqueous NaCl solution (NaCl 0.5 wt.%) was about 90% by use of these membranes, they were defect-free. The best composition of the porous glass layer was 70 SiO₂-30 ZrO₂ from the standpoint of preparing membranes. These membranes had a large water and alkali durability. These membranes can be expected to apply to recovering dyes and paints from organic solvents and to be used as a gas separation membrane.     

蛋壳膜原位生长PbS纳米颗粒及其机理初探

基于双扩散原理,在室温条件下,利用活性蛋壳膜具有的特殊渗透功能,成功地在蛋壳膜的活性位点处原位生长出绣球花状的硫化铅纳米颗粒.用X-射线衍射仪(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱仪(FTIR)对硫化铅纳米颗粒的形貌和结构进行了表征,并对蛋壳膜上原位生长硫化铅纳米颗粒的生长机理进行了初步探讨.     

Formation of porous ceramic supports for catalysts by microarc oxidation

Microarc oxidation of aluminum in borate and silicate-alkaline electrolytes in order to form porous ceramic coatings that can be used as catalyst supports was subjected to an integrated study. The advantages of the technological modes of microarc oxidation of aluminum were analyzed. A catalytically active nickel oxide was deposited into pores of a ceramic coating.     

Impact of ultrafiltration operating conditions on membrane irreversible fouling

The main limitation of the ultrafiltration (UF) process identified in drinking water treatment is membrane fouling. Although adsorption of natural organic matter (NOM) is known to cause irreversible fouling, operating conditions also impact the degree of irreversible fouling. This study examined the impact of several operating parameters on fouling including flux, concentrate velocity in hollow fibers, backwash frequency, and transmembrane pressure. A hydrophilic cellulose derivative membrane and a hydrophobic acrylic polymer membrane were used to conduct these tests. Pilot testing showed that when short-term reversible fouling was limited during a filtration cycle by increasing the concentrate velocity, reducing the flux, and increasing the backwash frequency, the evolution of the membrane toward irreversible fouling could be controlled. It appeared that operating parameters should be adjusted to maintain the increase of transmembrane pressure below a certain limit, determined to be approximately 0.85 to 1.0 bar for the tested UF membrane, in order to minimize the rate of irreversible fouling. This threshold for transmembrane pressure was confirmed empirically by compiling data from over 36 pilot studies. Other testing results demonstrated that hydraulic backwash effectiveness decreased as the transmembrane pressure applied in the previous filtration cycle increased. Backwash efficiency in terms of membrane flux recovery after hydraulic backwash was reduced by 50% when the transmembrane pressure was increased from 0.4 bar to 1.4 bar.     

Impact of cation concentrations on fouling in membrane bioreactors

In this study, the interaction of calcium, magnesium, and sodium as well as impact of monovalent to divalent (M/D) cation ratio and magnesium to calcium (Mg/Ca) ratio in the feed wastewater on membrane fouling in submerged membrane bioreactor (MBR) was investigated. The protein and carbohydrate content of soluble microbial products (SMP) and extracellular polymeric substances (EPS) as well as their relative hydrophobicities was examined. The mixed liquor and its components (soluble and suspended solids) were analyzed for their filtration resistance, as reflected by the modified fouling index (MFI). Based on the findings of this study, the optimum conditions with respect to fouling rate were calcium and sodium concentrations of 36 and 140 mg/L, respectively, M/D of 1:1 and Mg/Ca of 5:1, with all parameters on an equivalent basis. High sodium concentration at high M/D ratio was found to decrease the floc size and increase the fouling rate. At the low M/D ratio of 1:1, introduction of magnesium was beneficial in reducing the fouling rate by increasing the EPS concentration and floc size and decreasing the SMP concentration and relative hydrophobicity in the supernatant. The fouling rate was found to be statistically correlated with the concentrations of Ca, Mg, and Na, with both Ca and Na adversely impacting fouling and Mg alleviating fouling propensity.     

Gel layer formation and hollow fiber membrane filterability of polysaccharide dispersions

Gel layer formation on the membrane surface during filtration plays a significant role in membrane fouling that, in many instances, controls water production and energy consumption in the treatment of waters and wastewaters. In this study, alginate is selected as a model of the polysaccharides prevalent in wastewaters which, on membrane filtration, may form a gel on the membrane surface which subsequently limits filtrate throughput. We show that over the range of the applied pressures of 11.7–135 kPa considered here, constant pressure ultrafiltration of alginate follows the behavior of cake filtration. The material properties of the alginate are determined by the employment of the previously developed steady-state filtration approach. The consolidation of the gel layer is found to be controlled by the hydraulic flow resistance rather than the rearrangement of particles. Under these conditions, it is valid to apply the derived material properties for the quantification of both constant pressure and constant flux filtration. The gel layer formed from alginate is very compressible and far from uniform over its depth. Within the range of the applied pressures, the gel layer is very porous with a water content of more than 96% but very low Darcy permeability of less than 1 × 10⁻¹⁷ m². During hollow fiber membrane filtration, the local flux is neither uniform nor constant along the fiber length, resulting in non-uniformity of the growth rate, the average porosity and the thickness of the gel layer. The non-uniformity is most apparent at the start of filtration and then gradually diminishes as the gel layer builds up with ongoing filtration.     

Chemical vapor infiltration method for deposition of gold nanoparticles on porous alumina supports

Knudsen’s effusion method with mass spectral analysis of the composition of the gas phase was used to measure the temperature dependence of the saturated vapor of several (CH₃)₂AuL chelate complexes and to determine the thermodynamic parameters of their sublimation. Based on the results of this study, conditions for chemical vapor deposition of gold using dimethylgold(III) chelates were chosen. Gold nanoparticles were synthesized by chemical vapor deposition (infiltration) of (CH₃)₂Au(acac) on porous granules of γ-Al₂O₃ with subsequent calcination in air at 325°C. Particle size and the chemical state of gold in Au/γ-Al₂O₃ systems were evaluated by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). A vapor infiltration procedure is suggested to prepare metallic gold particles ≤5 nm in diameter from Au/γ-Al₂O₃. It is shown that Au/γ-Al₂O₃ systems obtained by chemical vapor infiltration and containing small gold crystallites possess high catalytic activity in CO oxidation reactions at 40°C.