Effects of silica sol on ion exchange membranes: Electrochemical characterization of anion exchange membranes in electrodialysis of silica sol containing-solutions

The fouling potential of the negatively charged silica sol in electrodialysis (ED) by adsorption on the surface of an anion exchange membrane was investigated. Since the fouling potential is related to the physical and electrochemical properties of the silica sol and anion exchange membranes, it is important to characterize the properties of silica sol and membranes. The surface charge of silica sol was investigated by the electrophoretic mobility and its isoelectric point was determined as pH 3. The commercial anion exchange membranes were characterized in terms of exchange capacity, water content, the zeta potential and the electrochemical properties of the membranes using impedance spectroscopy to predict the effects on the electrodialysis performances. Among the characterized properties, exchange capacity and some electrochemical properties of the anion exchange membranes were rather improved after ED experiments. In the electrodialysis of solution containing silica sol, deposition of the silica sol did not decrease the desalting performance of the anion exchange membranes because of loosely packed cake layer on the membrane surface.     

PROTEIN ADSORPTION AND FOULING OF CERAMIC MEMBRANES AS MEASURED BY SCANNING ELECTRON MICROSCOPY WITH DIGITAL X-RAY MAPPING

A technique for studying fouling in ceramic membranes using the energy dispersive x-ray spectroscopy capability of an electron microscope is described. The location and amount of foulant within the membrane are presented on a digital x-ray map showing elements constituent to or stained on the foulant.

Fouling of alumina membranes during filtration of the protein hemoglobin has been studied as a function of filtration time, pH, and membrane pore size. After each filtration run, the protein within a piece of the membrane was stained with phosphotungstic acid and located on a digital map of either phosphorus or tungsten.

For a 0.2 μm pore size membrane, time dependent fouling was observed consistent with an observed flux decline within the first few minutes of filtration. A pH dependence was also observed indicating much greater fouling at pH 6.9 near the protein isoelectric point than at pH 8.5. This observation is consistent with pH dependent adsorption, flux, and rejection studies. No internal fouling was observed for a 40 Å pore size membrane, which is consistent with the size of hemoglobin in solution being larger than the 40 Å pores and with the fact that the 40 Å membrane can be more easily cleaned after use than can the 0.2 μm membrane.     

Critical flux in cross-flow ultrafiltration of protein solutions

The effect of solute size relative to membrane pore size on the critical flux during the ultrafiltration of protein solutions was investigated using the constant pressure method. Hydrophilic regenerated cellulose membranes with a cut-off of 10, 30 and 100 kg mol⁻¹, model proteins and skimmed milk solutions were used. The critical flux mainly increased with the pore size of the ultrafiltration membrane. The lowest critical fluxes, 40-50 L m⁻²h⁻¹, were obtained with the retentive 10 kg mol⁻¹ cut-off membrane. This membrane had a very low permeability and, thus, the critical fluxes were achieved at high transmembrane pressures (TMP): 1.7-2.3 bar. With the 100 kg mol⁻¹ cut-off membrane critical fluxes were obtained at 0.2 bar TMP, which were around 100 L m⁻² h⁻¹, slightly declining with increasing protein molar mass. In skimmed milk experiments the permeate flux decreased when the protein molecules were enzymatically split to peptides. A critical flux for skimmed milk solution could not be found unless the protein concentration was diluted to 0.3-w% or lower. The results with model proteins were then compared to those obtained with skimmed milk resulting in β-lactoglobulin being the worst foulant.     

Influence of hemicellulose aggregate and gel layer formation on flux and retention during nanofiltration of alkaline solutions

Nanofiltration of process liquors from viscose-type textile fibre production was investigated using a laboratoryscale crossflow test apparatus. Feed solutions contained about 200 g/l sodium hydroxide and a high concentration of hemicellulose as a contaminant originating from the raw material wood. The effects of various pretreatments and the addition of reagents on flux, retention and irreversible fouling were studied. Reagent addition affected the solution state of hemicellulose thus purposely provoking aggregate formation. Dynamic light scattering and turbidity measurements were used to track the evolution of hemicellulose aggregates. Aggregation generally coincided with distinct flux decline during nanofiltration thus indicating that this phenomenon may result in the build-up of gel layers at the membrane surface. Partial neutralisation with sulfuric acid caused extremely severe fouling, whereas methanol addition had a minor effect. The impact of heat treatment and oxidative degradation of hemicellulose on nanofiltration performance was attributed to changes in molar mass distribution.     

Color and COD retention by nanofiltration membranes

In the present study the application of the nanofiltration process was investigated mainly in the retention ofcolor and chemical oxygen demand (COD) present in textile industry wastewater. Nanofiltration experiments were carried out in a pilot unit, operating in crossflow. Three different types of spiral wound membranes, DK 1073, NF 45 and MPS 31 were used simultaneously in the same unit. The results of the tests showed that for color retention, the values were around 99% for the DK 1073 and NF 45 membranes and the 87% for COD retention for the DK 1073. The permeate flux for the different wastewaters varied from 30.5 to 70 L/h.m². Fouling was observed in all membranes due to the accumulation of molecular species close to the filtering surface. The process was efficient and promising for the reuse of wastewater from this type of industry.     

Modification of polysulfone ultrafiltration membranes by CO2 plasma treatment

Carbon dioxide plasmas were used to modify hydrophobic polysulfone ultrafiltration membranes to create hydrophilic surfaces throughout the membrane structure. The water contact angle of the upstream side of the membrane (facing the plasma) decreased to zero after treatment and did not change even after several months of aging. The water contact angle of the downstream side decreased with increasing CO₂ plasma treatment time and became zero for treatment times ≥ 1 min (P = 10 W). Functional groups introduced by CO₂ plasma treatment were examined using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). For the treated membranes, the atomic concentration of oxygen increased dramatically and small amounts of nitrogen incorporation were also observed. Membrane performance was tested with water flux measurements as well as protein fouling studies. For treated membranes, the water flux recovery measured after protein fouling was significantly higher than that for control membranes, with nearly 100% recovery after gentle cleaning in water. Moreover, the amount of protein adsorption decreased by over 75% for the treated membranes compared to control membranes. This suggests the protein fouling layer is essentially completely reversible on the CO₂ plasma treated membranes.     

UiO-66/PES混合基质超滤膜的制备及性能

以聚醚砜(PES)为主要膜材料、溶剂热法合成UiO-66并掺入铸膜液中,通过非溶剂相转化法(NIPS)制备了混合基质超滤膜.利用X射线衍射仪(XRD)、傅里叶红外光谱(FTIR)、扫描电镜(SEM)、接触角测量仪及原子力显微镜(AFM)对制备的UiO-66和混合基质膜进行表征.重点考察了UiO-66添加量对膜表面形貌、...     

Ash deposition behavior of upgraded brown coal in pulverized coal combustion boiler

Ash with a low melting point causes slagging and fouling problems in pulverized coal combustion boilers. Ash deposition on heat exchanger tubes reduces the overall heat transfer coefficient due to its low thermal conductivity. The purpose of this study is to evaluate the ash deposition for Upgraded Brown Coal (UBC) and bituminous coal in a 145 MW practical coal combustion boiler. The UBC stands for Upgraded Brown Coal. The melting temperature of UBC ash is relatively lower than that of bituminous coal ashes. Combustion tests were conducted on blended coal consisting 20 wt.% of UBC and 80 wt.% of bituminous coal. Before actual ash deposition tests, the molten slag fractions in those coal ashes were estimated by means of chemical equilibrium calculations. The calculation results showed the molten slag fraction for UBC ash reached approximately 90% at 1523 K. However, that for blended coal ash decreased to 50%. These calculation results mean that blending UBC with bituminous coal played a role in decreasing the molten slag fraction. This phenomenon occurred because the coal blending led to the formation of alumino-silicates compounds as a solid phase. Next, ash deposition tests were conducted using a practical pulverized coal combustion boiler. A water-cooled stainless-steel tube was inserted in locations at both 1523 K and 1273 K in the boiler to measure the amount of ash deposits. The results showed that the mass of ash deposition for blended coal did not greatly increase, compared with that for bituminous coal alone. Therefore, appropriately blending UBC with bituminous coal enabled the use of UBC without any ash deposition problems in practical boilers.     

Numerical and experimental methodology for the development of a new membrane prototype intended to microfiltration bioprocesses. Application to milk filtration

In tangential flow filtration, the non-uniform TransMembrane Pressure (TMP) on the membrane length produces a non homogeneous filtration cake, initiates process selectivity changes and modifies the permeate quality. The purpose of this study is to create a tubular ceramic membrane prototype with a more uniform TMP, intended to filtration of fouling fluids. The principle of this membrane structure is to waterproof the external membrane surface to limit flow circulation in the porous support of the membrane. The production was controlled by sizing «permeation vents». This development was achieved using a CFD modelling tool interacting with experiments. A preliminary modelling study was made with water. This work was afterwards applied to the industrial process of casein micelle separation from skim milk. The influence of operating conditions on the membrane hydrodynamics was highlighted. The modelling results were experimentally confirmed, with a discrepancy smaller than 3% and a reproducible water permeability of 2.3 L h⁻¹ bar⁻¹ for 1 mm-wide vent (TMP = 1 bar, T = 20 °C). Then, milk filtration experiments showed a production ratio milk/water equal to 1/2. The permeate quality parameters were studied and the fouling phenomena were taken into account. A parametric study led to the sizing of a final prototype. Its efficiency was experimentally evaluated.     

防止设备结垢延长乙烯装置运行周期

设备结垢堵塞问题已成为乙烯装置长周期运转的难点。笔者重点论述了急冷油塔和冷箱的结垢问题及防范措施。