High-flux whisker layer ceramic membrane prepared by gel spin-coating method for low-pressure oil/water emulsion filtration

Insufficient permeability and membrane fouling significantly influence the efficiency of ceramic microfiltration (MF) membranes in oil/water emulsion treatment. In this study, a high-flux whisker layer ceramic MF membrane with super-hydrophilicity was successfully fabricated through gel-spin coating method and a low-temperature oxidation method, which was used to separate oil/water emulsion. The effects of the whisker layer and surface wettability were systematically investigated, and the mechanism of in-situ gelling and pore size distribution was proposed. The super-hydrophilic ceramic MF membrane with an average pore size of 250 nm exhibited a high gas flux of 934 m³/(m²·h·bar) and excellent pure water flux of 9754 L/(m² h bar). Even after a long-term circulating filtration process, the super-hydrophilic ceramic MF membrane still maintained a high water flux of over 50 L/(m²·h) at a transmembrane pressure of 5 KPa during the treatment of oil-in-water emulsion with a concentration of 1000 mg/L. Overall, the developed ceramic MF membrane demonstrated high permeability and excellent anti-fouling performance, making it a promising candidate for oil/water emulsion wastewater treatment.     

致密超细球形氧化铝制备性能良好的陶瓷超滤膜

热等离子体制备的超细球形氧化铝具有表面致密光滑、分散性好等特点,本工作以超细球形氧化铝为原料,通过浸渍提拉烧结法,制备了孔径分布窄、渗透通量高的陶瓷超滤膜,研究了烧结温度对陶瓷膜微孔结构的演化、孔径分布和渗透通量的影响。随后对1250℃下烧结的陶瓷膜进行了纳米硅水分散液过滤处理,采用不同堵塞模型分析了陶瓷膜过滤纳米硅水分散液的膜污染过程。结果表明,通过调节烧结温度调控陶瓷膜的微孔结构,当烧结温度为1250℃时,陶瓷膜的孔径分布较窄,孔径大小为25?65 nm,渗透通量为986.4 L/(m2?h)。超细球形氧化铝粒径分布较窄及表面致密光滑有助于1250℃下烧结形成均匀的烧结颈,提供了陶瓷膜较窄的孔径分布。对1250℃下烧结的陶瓷膜进行了纳米硅水分散液过滤处理后其浊度下降为0.231 NTU,浊度去除率达99.96%。采用不同堵塞模型分析了陶瓷膜过滤纳米硅水分散液的膜污染过程,结果表明,纳米硅水分散液的堵塞模型是滤饼过滤,属于可逆污染。     

Gas permeation and thermomechanical properties for macroporous alumina focused on necking size at grain boundaries

The gas permeation and thermomechanical properties of macroporous alumina used as a support substrate for microporous ceramic permselective membranes were investigated. The porosity, pore size, and apparent necking size between grains of macroporous alumina were systematically varied, and the relationships between the porous microstructure and material properties were examined. The grain necking size at alumina grain boundaries was evaluated by microstructural observations. The nitrogen gas permeance of the porous alumina increased with increasing pore size. All the measured thermal and mechanical properties decreased with increasing porosity. The properties of porous alumina samples with extensive grain necking showed higher values even in samples with the largest pore size. The high thermal conductivity of porous alumina with extensive grain necking was due to the low interfacial thermal resistance at grain boundaries. Porous alumina with extensive grain necking had high thermal shock strength due to the higher thermal conductivity. It was demonstrated that a porous structure combining high gas permeability and excellent fracture resistance could be successfully achieved.     

The structure and permeability of the disordered layer prepared by freeze-casting

Asymmetric ceramic membranes with disordered layer prepared by directional freeze-casting can be used as filter materials. However, there are few research achievements on the structural and permeability of disordered layers. Here, we obtained alumina asymmetric ceramic membranes with different disordered layer by adjusting the amount of alumina in the ceramic slurry. The results show that there are two kinds of structures in the disordered layer: spherical micropores and interconnected meshy pores, which lead to the change of airflow state. With the increase of the alumina content, the pore size of the disordered layer decreases and the network structure becomes complex, resulting in the decrease of the velocity of the inertial flow. The filter resistance of disordered layer increases obviously, but its proportion in the total filter resistance increases first and then decreases. The permeability is related to the pore size, specific surface area and channel complexity of the membrane.     

Spheroidization of low-cost alumina powders for the preparation of high-flux flat-sheet ceramic membranes

Two kinds of low-cost alumina powders with irregular morphology were pretreated by spheroidization and the two spherical powders were used to prepare high-flux flat-sheet support and microfiltration (MF) membrane with high separation accuracy, respectively. It was found that the spheroidization pretreatment not only unified the morphology of alumina powder particles into spherical shape, but also narrowed the particle size distribution of the powders, which both were conducive to optimizing the performance of the as-prepared ceramic membranes. After sintering at 1350 °C, the open porosity, bending strength, average pore diameter and pure water permeability of alumina flat-sheet support from spheroidized alumina coarse powder were 44.3%, 36.3 MPa, 3.3 μm and 3240 L/h m² bar, respectively. The slurry derived from spheroidized alumina fine powder was dip-coated on the flat-sheet support to prepare MF membrane. The crack-free MF membrane with a thickness of 23.5 μm had a pore diameter of 0.12 μm and pure water permeability of 850 L/h m² bar. Additionally, the elaborated MF membrane was used to clarify aqueous suspension of carbon black with the maximum rejection rate of up to 99.7%, exhibiting excellent cleaning performance at the same time by completely restore the virgin permeate flux after backwash.     

Elaboration and characterization of tubular macroporous ceramic support for membranes from kaolin and dolomite

A low cost macroporous support for ceramic membranes was prepared by in situ reaction sintering from local natural mineral kaolin with dolomite as sintering inhibitor. The characterization focused on the phase evolution, microstructure, pore structure, mechanical strength and water permeability at various compositions and sintering temperatures. The sintering of kaolin was improved with 5 wt% dolomite, but clearly inhibited with ≥10 wt% dolomite. For the 20 wt% dolomite samples, the crystalline phases were mainly composed of mullite, cordierite and anorthite after sintering between 1,150 and 1,300 °C. Moreover, both mean pore size and mechanical strength increased with increasing sintering temperature from 1,100 to 1,300 °C, but the water permeability and porosity decreased. The 1,250 °C sintered macroporous support with 20 wt% dolomite exhibited good performances such as porosity 44.6%, mean pore size 4.7 μm, bending strength 47.6 MPa, water permeability 10.76 m³ m⁻² h⁻¹ bar⁻¹, as well as good chemical resistance. This work provides opportunities to develop cost-effective ceramic supports with controllable pore size, porosity, and high strength for high performance membranes.     

Preparation of fused silica membrane with high performance for high temperature gas filtration by sealing and spray coating

In order to improve the gas permeability and thermal shock resistance of the ceramic membranes applied in high temperature gas-solid separation techniques, fused silica and graphite particles were used as the primary raw material and pore-former agent, and the spray coating based-on PVA sealing was applied to prepare the separation membrane. These approaches remarkably decreases filtration resistance by increasing support permeability and reducing the intrusion of ceramic membrane forming particles into the support as well as the thickness of the membrane. The fabricated membrane had an average pore diameter of 9.85?μm and a gas permeability value of 8.2?×?10⁴?m³/(m² h bar), its dust removal efficiency reached 98.6%.     

A Fully Automated System for the Determination of Pore Size Distribution in Microfiltration and Ultrafiltration Membranes

Abstract

An automated system controlled by a Amstrad CPC 6128 microcomputer was designed. The apparatus can be used for a fast characterization of MF and UF membranes by the bubble point method. The theory for a modified bubble-point method is reviewed. The system determines pore size, pore size distribution, and surface porosity for the membranes of pore radii not less than 45 nm. The whole experiment takes 3–5 h to complete. The apparatus was tested on various MF and UF membranes (Nuclepore, Synpor, PVC UF, PAN UF, CA UF).     

Manufacture and characterization of ultra and microfiltration ceramic membranes by isostatic pressing

This paper describes the manufacture of tubular UF and MF porous and supported ceramic membranes to oil/water emulsions demulsification. For such a purpose, a rigorous control was realized over the distribution and size of pores. Suspensions at 30 vol.% of solids (zirconia or alumina powder and sucrose) and 70 vol.% of liquids (isopropyl alcohol and PVB) were prepared in a jar mill varying the milling time of the sucrose particles, according to the pores size expected. The membranes were prepared by isostatic pressing method and structurally characterized by SEM, porosimetry by mercury intrusion and measurements of weight by immersion. The morphological characterization of the membranes identified the formation of porous zirconia and alumina membranes and supported membranes. The results of porosimetry analysis by mercury intrusion presented an average pore size of 1.8 μm for the microfiltration porous membranes and for the ultrafiltration supported membranes, pores with average size of 0.01-0.03 μm in the top-layer and 1.8 μm in the support. By means of the manufacture method applied, it was possible to produce ultra and microfiltration membranes with high potential to be applied to the separation of oil/water emulsions.     

Separation of bovine serum albumin (BSA) using γ‐Al2O3–clay composite ultrafiltration membrane

BACKGROUND: Ceramic membranes have received more attention than polymeric membranes for the separation and purification of bio‐products owing to their superior chemical, mechanical and thermal properties. Commercially available ceramic membranes are too expensive. This could be overcome by fabricating membranes using low‐cost raw materials. The aim of this work is to fabricate a low‐cost γ‐Al₂O₃–clay composite membrane and evaluate its potential for the separation of bovine serum albumin (BSA) as a function of pH, feed concentration and applied pressure. To achieve this, the membrane support is prepared using low‐cost clay mixtures instead of very expensive alumina, zirconia and titania materials. The cost of the membrane can be further reduced by preparing a γ‐alumina surface layer on the clay support using boehmite sol synthesized from inexpensive aluminium chloride instead of expensive aluminium alkoxide using a dip‐coating technique. RESULTS: The pore size distribution of the γ‐Al₂O₃‐clay composite membrane varied from 5.4–13.6 nm. The membrane was prepared using stable boehmite sol of narrow particle size distribution and mean particle size 30.9 nm. Scanning electron microscopy confirmed that the surface of the γ‐Al₂O₃–clay composite membrane is defect‐free. The pure water permeability of the support and the composite membrane were found to be 4.838 × 10^?6 and 2.357 × 10^?7 m³ m^?2 s^?1 kPa^?1, respectively. The maximum rejection of BSA protein was found to be 95%. It was observed that the separation performance of the membrane in terms of flux and rejection strongly depends on the electrostatic interaction between the protein and charged membrane. CONCLUSION: The successively prepared γ‐Al₂O₃‐clay composite membrane proved to possess good potential for the separation of BSA with high yield and could be employed as a low cost alternate to expensive ceramic membranes. Copyright © 2009 Society of Chemical Industry     

湿式催化氧化/膜过滤组合工艺膜过滤机理

采用湿式催化氧化/膜过滤组合工艺,以Mo-Zn-Al-O粉末作为催化剂降解阳离子红GTL模拟染料废水,探讨在膜过滤过程中平均孔径为0.1 μm的微滤和0.022 μm的超滤聚偏氟乙烯(PVDF)中空纤维膜的过滤机理。实验结果表明,两种膜过滤组合工艺对染料的降解效果均优于单独湿式催化氧化,0.01 MPa恒压条件下运行120 min后微滤和超滤的膜通量分别衰减了26.63%和16.48%,其原因是粉末催化剂可在微滤膜孔内部沉积形成中间阻塞过滤,后在表面形成滤饼层;而在超滤膜表面仅形成滤饼层。通过实验结果对膜阻力进行计算,可知在相同反应过程后微滤膜产生的不可逆阻力大于超滤膜。在不同反应条件下,催化剂的沉积量与膜阻力呈现线性相关。     

β-SiAlON ceramic membranes modified with SiO2 nanoparticles with high rejection rate in oil-water emulsion separation

Porous ceramic membranes with high mechanical strength are suitable for oil-water emulsion separation. Nonetheless, it is difficult to prepare ceramic membranes with a small pore size and a good antifouling ability. In this work, SiO₂ nanoparticles were used to modify β-SiAlON ceramic membranes, which were successfully utilized to remove small oil droplets from oil-water emulsion. The modified membranes displayed a narrow pore size (the average pore size decreased from 1.05?µm, in the unmodified membrane, to 0.65?µm), and gas and water fluxes which are suitable for oil-water separation. Oil rejection rate was always higher than 90% under various pressures (1.0–2.0?bar) and flow velocities (1.0?3.0?L?min^?1) tested, which is considerably higher (60%) than the rejection rate of the unmodified membrane (which was 39.8%). Moreover, the modified membranes exhibited a good antifouling ability, since flux declined by only 7.0% after three recoveries via a simple ultrasonic treatment, over a total running period of 10?h. Accordingly, the produced membranes can be qualified for further consideration in oily wastewater treatment.     

Gel Casting of Free‐Shapeable Ceramic Membranes with Adjustable Pore Size for Ultra‐ and Microfiltration

The growing demand of reliable high‐performance membrane materials for separation processes requires new simple, straightforward, environmental friendly, sustainable approaches for membrane fabrication. In this study, we present an environmentally friendly gel‐casting, one‐pot process based on ionotropic‐gelation for obtaining alumina membranes. A slurry of alumina particles and the biopolymer alginate, which acts in combination with calcium iodate like a resin, was gelled in a controllable temperature dependent manner. Alumina membranes are obtained by three different shaping routes (extrusion, free‐forming, casting). The suitability of extruded capillaries in a polymer‐ceramic hybrid state (green body) and after sintering (1150°C for 2 h) for potential application in micro‐ and ultrafiltration is evaluated by monitoring the chemical and mechanical stability, permeability and separation behavior. Varying the initial alumina particle size from 200 to 900 nm, membranes with a narrow pore size distribution, predictable and tunable average pore diameters from 70 up to 480 nm and a constant open porosity of ~40%, are obtained. The permeability behavior is tested with fluorescence labeled submicron‐ and nano‐particles. Our novel colloidal processing route represents a very versatile tool for designing and manufacturing ceramic membranes with complex shapes for micro‐ (>0.1 μm) and ultrafiltration (0.1–0.01 μm).     

Fabrication of super flux and high thermal shock resistance ceramic membrane support

Ceramic membranes play an important role in high temperature gas-solid filtration. However, the thermal stability of the ceramic support at high temperatures has always been a problem. In this study, porous fused silica ceramic supports were fabricated with hexagonal boron nitride as a sintering aid. The results shown that hexagonal boron nitride could inhibit the crystallization of fused silica ceramic particles at high temperature and act as a sintering addictive to reduce firing temperature. The obtained supports have an average pore size of 72?µm, an open porosity of 42%, a bending strength of 16.5?MPa, a Weibull modulus of 8.67 and a gas permeability of 4.23?×?10⁵ m³/(m² h bar). The bending strength of the support remained 16?MPa after 30 cold-hot cycles, exhibiting high thermal shock resistance. After corrosion in 20?vol% H₂SO₄ solution for 8?h, the weight and the bending strength of the support were diminished by 0.6% and 24.32%, respectively. So, the ceramic support showed good acid corrosion resistance.     

Microfiltration of Milk with Third Generation Ceramic Membranes

The objective of this study was to compare the behavior of different ceramic membranes during skimmed milk microfiltration. Permeate flow rates, protein rejection, and decimal reduction of bacteria were compared for three different 1.4-µm pore size ceramic membranes, one of which was considered traditional (ceramic multichannel membrane) while the other two had a modified structure (on either the macroporous support or the filtering layer). Permeate flux ranged from 400 to 530 Lm^?2h^?1 at 0.5 bar of transmembrane pressure. Protein rejection values between 0.8 and 2.9% were obtained. Temperature (21–45°C) did not have a significant effect. Membranes showed decimal reduction in total bacterial count between 3.5 and 5.2, with Isoflux® membranes showing higher values. The lifespan of microfiltered milk was extended to 10 days in the absence of heat treatment.     

Three-dimensional printing of high-flux ceramic membranes with an asymmetric structure via digital light processing

In this study, a novel method was proposed for preparing high-flux ceramic membranes via digital light processing (DLP) three-dimensional (3D) printing technology. Two different alumina powders were well dispersed in a photosensitive resin to form a UV-curable slurry for DLP 3D printing. The effects of the grading ratio on the viscosity of the slurry and the porosity, pore size distribution, mechanical strength, roughness, and permeability of the ceramic membranes were systematically investigated. The thermal treatment conditions were also studied and optimized. The obtained ceramic membranes exhibited a uniform pore size distribution, a high porosity, a low tortuosity factor, and an asymmetric structure. The combination of these factors led to a high flux for the 3D-printed ceramic membranes. DLP 3D printing exhibited a good potential to be a strong candidate for the next generation of ceramic membrane fabrication technology.     

Preparation processes and characterizations of alumina-coated alumina support layers and alumina-coated natural material-based support layers for microfiltration

Recently, porous ceramic membranes have become a subject of significant interest due to their outstanding thermal and chemical stability. To reduce the high manufacturing costs of these porous ceramic membranes, recent research has focused on the utilization of inexpensive natural materials. However, there have not been any well-established direct comparisons of the membrane properties between typical alumina-based membranes and novel natural material-based membranes. Therefore, we compared alumina-coated alumina support layers (with average pore sizes ranging from 0.10 µm ~0.18 µm), alumina-coated diatomite-kaolin composite support layers (with an average pore size of 0.12 µm), and alumina-coated pyrophyllite-diatomite composite support layers (with an average pore size of 0.11 µm) via the dip-coating method and subsequent heat treatment ranging from 1200 °C–1400 °C for 1 h. The pure water permeability of the alumina-coated diatomite-kaolin composite support layer and the alumina-coated pyrophyllite-diatomite composite support layer was found to be approximately 2.0×10² L m⁻² h⁻¹ bar⁻¹, which is similar to that of an alumina-coated alumina support layer. Therefore, we suggest that the average pore size of an alumina-coated natural material-based support layer can be effectively controlled while exhibiting acceptable water permeability.     

Preparation of alumina membranes for micro- and ultrafiltration applications

Abstract

A very thin disc type ceramic membrane (0·3-0·8 mm thickness, 25-30 mm diameter) made of pure alumina and suitable for microfiltration applications has been prepared by a tape casting process. A sol coating was applied to the disc to form an ultrafiltration membrane. T he pore size of the membrane could be varied in the range 0·1-0·7 μ m and porosity in the range 25-55% by optimising the ex perimental parameters. The most important factor for determining the pore size of the membrane was found to be the initial particle size distribution of the ceramic powder. Firing temperature and soaking time are other crucial parameters affecting volumetric porosity. Water permeability through the membrane under suction and under positive pressure is comparable with that of ceramic membranes prepared by conventional methods. In addition, a typical membrane shows a very narrow pore size distribution in the range 0·1-0·4 μm, with a median pore size of 0·28 μm. A very sharp drop in the pore size distribution pattern around 0·4 μm indicates that no pores larger than this exist. This implies that all particles with radius > 0·4 μm are trapped in the membrane, providing excellent separation efficiency. Results of microbial separation tests confirmed the possibility of micro-organism separation through these membranes.     

Effect of sintering temperature on functional properties of alumina membranes

Supported membranes were prepared from different submicron alumina powders. The evolution of pore size, hardness and permeability were monitored after sintering the films at temperatures ranging from 1000 to 1400 °C. These functional properties and the microstructure of the films were compared with the free-standing membranes. Sintering at temperature range from 1000 to 1200 °C maintained the narrow, monomodal pore size distribution of the supported membranes. The effect of sintering temperature on the hardness of the membranes was weak. The permeability was also independent on the sintering temperature. When sintering temperature was raised up to 1300 and 1400 °C, the pore size increased significantly and distribution was changed to bimodal containing fraction of large pores. The hardness of the membranes increased while significant densification was not observed. Permeability increased due to the large pore size and the high porosity. In sintering of the free-standing membranes pore size remained almost unchanged, density increased when sintering temperature was raised, hardness was dependent on the density and permeability decreased continuously. The substrate did not have effect on the grain growth, which was dependent on the sintering temperature. Evolution of the properties of the free-standing membranes suggests local densification. The rigid substrate restricts the sintering shrinkage leading to densification of small areas. This local densification opens large flow channels between agglomerates. This increases the pore size, broadens the pore size distribution and increases the permeability. The macroscopic densification of the film is small.     

Microstructural characterization and gas permeation performance of freeze-cast alumina supports

One of the major challenges for obtaining asymmetric membranes has been the preparation of ceramic supports with tailored pore structures. The methods commonly used for processing these materials do not allow a fine control of the support structure, which may decrease their mass transport capacity. As a consequence, freeze-casting is a promising technique for obtaining supports with tailored pore structures and permeation behaviors. This work deals with the preparation of freeze-cast alumina macroporous supports. Different freezing routes and alumina powders were used in this study. It was correlated the effect of these parameters on the pore structure and permeation capacity of the obtained supports. It was shown that the isotropic layer observed at the samples bottom side plays a key role in their non-Darcian permeability. As far as we know, this is the first time that this approach is reported in the literature for freeze-cast samples.