光催化协同TiO2动态膜去除水中腐植酸及膜污染特性

针对物理扰动模式控制动态膜污染使涂膜层脱落方面的局限性,提出光催化氧化技术协同动态膜降低膜污染,对比了陶瓷微滤膜、动态膜、光催化协同动态膜处理含腐植酸废水及含腐植酸/TiO₂混合废水过程中的膜通量、污染物去除率及膜污染阻力分布的变化趋势。结果表明:光催化协同作用可有效提高动态膜过滤腐植酸溶液过程中的膜通量、总有机碳(TOC)及UV₂₅₄的去除率,并同时降低可逆污染阻力及不可逆污染阻力,其中可逆污染阻力明显大于其他部分阻力,可逆污染是造成膜通量衰减的主要原因。光催化预处理时间越长,稳态膜通量、TOC及UV₂₅₄去除率增幅越显著,控制膜污染越有效。光催化预处理2h和8h再动态膜过滤时TOC去除率分别可达到80%和90%以上,UV₂₅₄去除率都可达95%以上。     

Study of reverse osmosis membranes fouling by inorganic salts and colloidal particles during seawater desalination

Fouling phenomenon is considered among the major reasons that cause significant increase of operating cost of desalination plants equipped with reverse osmosis (RO) membranes. This phenomenon is studied in the present work in the case of RO polyamide aromatic membranes using model seawater containing inorganic salts and colloidal compounds. Different solubility conditions of CaCO₃ and CaSO₄ were applied to study RO performances with and without colloid presence. During experiments, the membrane permeate fluxes were continuously monitored. Moreover, studies of chemical composition, structure, and morphology of the materials deposited on the membrane surface were conducted using energy dispersive microanalysis (EDS) X-ray diffraction and scanning electronic microscopy (SEM). Results show that in conditions of calcium carbonate oversaturation there is a reduction in the permeate flow of 11.2% due to fouling of the membrane by the precipitation of this compound. While in the same conditions of calcium sulphate oversaturation the reduction of the flow is 5%, so we can conclude that in conditions of oversaturation of both salts, calcium carbonate produces a greater fouling of the membrane that in its view causes greater decrease in the flow of permeate. All this based on the results of the test with both salts in oversaturated conditions. Resulting in the formation of calcite and gypsum crystals onto the membranes as XRD analyses stated. Additional presence of colloidal silica in those conditions intensifies strongly the fouling, leading until to 24.1% of permeate flux decrease.     

Forward-osmosis strategy and chemical cleaning of seawater desalination reverse osmosis membranes

In order to settle the membrane fouling of reverse osmosis membranes in seawater desalination process, this study reported a novel strategy based on forward-osmosis process and discussed the effects of different factors like different cleaning combination among reverse osmosis product, simulated reverse osmosis concentrate and simulated seawater, as well as cleaning time on the membrane permeate flux and salt rejection. For irreversible fouling, the effects of different chemical cleaning agents, immersion time and concentration were also investigated in this study. The results exhibited that the cleaning combination between diluted water and simulated reverse osmosis concentrate possessed the best cleaning performance in the process of forward-osmosis cleaning. Such approach also enhanced normalized flux from 9.48 L/(m²·h·MPa) to 13.6 L/(m²·h·MPa) and enhanced NaCl rejection from 80.59% to 92.80%. Furthermore, the normalized flux was enhanced from 9.48 L/(m²·h·MPa) to 14.3 L/(m²·h·MPa) and NaCl rejection was also enhanced from 80.59% to 96.27% after soaking in 2%(mass) citric acid solution for 2h, soaking with 1%(mass) ethylenediamine tetra-acetic acid tetrasodium salt and 0.3%(mass) sodium tripolyphosphate solution for 1.5 h. According to the result of SEM images and AFM images, the forward-osmosis cleaning strategy could not cause the damage of selective layer of membrane surface and caused the drop of inorganic and organic fouling on the membrane surface. Hence, cleaning fouled RO membranes by such approach could prolong the chemical cleaning cycle and reduce the amount of chemical cleaning agent, which has certain industrial application perspectives.     

正渗透策略和化学清洗海水淡化反渗透膜

为解决海水淡化过程中反渗透膜的污染问题,研究了基于正渗透策略的反渗透产水、模拟反渗透浓水、模拟海水不同的组合清洗和清洗时间对膜通量和截留率的影响。针对不可逆污染,研究了不同化学清洗药剂、浸泡时间、浓度对膜通量和截留率的影响。结果表明,正渗透策略清洗方式中,淡水/模拟反渗透浓水的组合清洗方式效果最佳,其归一化通量从9.48 L/(m²·h·MPa)提升至13.6 L/(m²·h·MPa),截留率从80.59%提升至92.80%。此外,经质量分数为2%的柠檬酸溶液浸泡2 h后,再使用质量分数为1%的乙二胺四乙酸四钠盐和0.3%的三聚磷酸钠溶液浸泡1.5 h,其归一化通量从9.48 L/(m²·h·MPa)提升至14.3 L/(m²·h·MPa),截留率从80.59%提升至96.27%。从SEM和AFM图可以看出,正渗透清洗策略并未对膜表面选择层造成损坏,且可以清洗膜表面的有机污染物和无机污染物,因此,应用这种方法对污染的反渗透膜进行清洗,可延长化学清洗周期,减少化学清洗剂用量,具有一定的工业应用前景。     

Influence of filtration conditions on the performance of nanofiltration and reverse osmosis membranes in dairy wastewater treatment

Filtration performance and fouling of nanofiltration (NF) and reverse osmosis (RO) membranes in the treatment of dairy industry wastewater were investigated. Two series of experiments were performed. The first one involved a NF membrane (TFC-S) for treating the chemical-biological treatment plant effluents. The second one used a RO membrane (TFC-HR) for treating the original effluents from the dairy industry. The permeate flux was higher at higher transmembrane pressures and higher feed flowrates. The curves of permeate flux exhibited a slower increase while the feed flowrate decreased and the pressure increased. Membrane fouling resulted in permeate flux decline with increasing the feed COD concentration. Furthermore, the flux decline due to the COD increase was found higher at higher pressures for both NF and RO membranes.     

Effects of ultrasound parameters on ultrasound-assisted ultrafiltration using cross-flow hollow fiber membrane for Radix astragalus extracts

In this study, the effects of ultrasonic parameters on permeate flux and fouling resistances in the ultrasound-assisted ultrafiltration (UAUF) process of Radix astragalus extracts with hollow fiber membrane (HFM) was investigated. Ultrasonic parameters such as frequency, power and irradiation mode all can significantly affect the flux and fouling during the UAUF process, though the ultrasound power intensity was attenuated to be 10% only from generator. Concentration polarization and cake layer were decreased effectively by the ultrasound irradiation, resulting in a high flux performance. Meanwhile, HFM was susceptible to the irradiation at high power and low frequency compared with a flat sheet membrane. Ultrasound can not only enhance the permeate flux in UAUF but also cause breakage of HFM at an unsuited ultrasound field. It can be applied to the ultrafiltration process with HFM at an appropriate power and frequency.     

超细TiO_2粉体洗涤过程中膜污染和再生方法研究

针对陶瓷膜洗涤超细TiO2粉体中Cl-的过程,确定了适合的跨膜压差和膜表面流速,并采用阻力系列模型分析膜污染机理,确定有效的膜再生方法。此过程渗透通量随跨膜压差和膜表面流速的增长而增长,但是增长幅度减缓。合适的跨膜压差和膜表面流速分别为0.10—0.15 MPa和2.0 m/s;主要的膜污染来自粉体在膜表面的沉积;单一的化学和物理清洗方法无法达到理想的清洗效果,采用纯水浸泡、超声波清洗和质量分数0.5%的HCl清洗可使纯水通量恢复至新膜的72%以上,且多次的清洗效果稳定。     

垃圾渗滤液生化出水絮凝-纳滤处理及过程机理

垃圾焚烧发电厂渗滤液是一种含高浓度腐殖酸类物质和高盐含量的复杂有机废水, 传统生化处理后仍难达标排放。本工作围绕垃圾渗滤液生化出水的特性, 开展了Ca(OH)₂絮凝、臭氧氧化预处理与NF处理相结合的处理工艺, 并对处理过程的机理进行了探讨。研究表明, 渗滤液生化出水经过Ca(OH)₂絮凝处理, 可以有效地去除其中的杂环类化合物。生化出水经8 g·L^-1的Ca(OH)₂絮凝处理后, 比MBR出水产水通量提高达8.2%。对Ca(OH)₂絮凝出水进行臭氧氧化处理, 虽然降低了它的COD, 但并未进一步提高其NF膜通量, 其主要原因可能是臭氧氧化生成的硅氧烷类物质造成了膜的污染;与RO处理垃圾渗滤液生化出水相比较, NF膜无法分离废水中的酮类、胺和酰胺类、杂环类化合物, 使得NF产水的COD处在100~160 mg·L^-1。NF平均膜通量的增大可导致产水COD略有上升;垃圾渗滤液生化出水及其预处理水在NF处理过程中, 都没有表现出严重的膜污染。     

Influence of colloidal fouling and feed water recovery on salt rejection of RO and NF membranes

The influence of colloidal fouling and feed water recovery (or concentration factor, CF) on salt rejection of thin-film composite reverse osmosis (RO) and nanofiltration (NF) membranes was investigated. Fouling experiments were carried out using a laboratory-scale crossflow test unit with continuous permeate disposal to simulate the CF and recovery as commonly observed in full-scale RO/NF systems. For feed waters containing only salt (NaCl), permeate flux declined linearly as CF was increased and salt rejection was nearly constant for both RO and NF membranes. On the other hand, a sharp decrease in permeate flux and significant decline in salt rejection with increasing CF were observed under conditions where colloidal fouling takes place. For both RO and NF membranes, the marked permeate flux decline was attributed to the so-called “cake-enhanced osmotic pressure”. The decline in salt rejection when colloidal fouling predominated was much more substantial for NF than for RO membranes. In all cases, the decline in salt rejection was higher under conditions of more severe colloidal fouling, namely at higher ionic strength and initial permeate flux.     

Application of ultrafiltration hybrid membrane processes for reuse of secondary effluent

This study evaluates the factors affecting pretreatment conditions for hybrid UF membrane processes for reuse of secondary effluent from the sewage treatment plant. The experimental results obtained from the ultrafiltration (UF) membrane process showed that the particles of the size range between 0.2 and 1.2 μm caused a significant impact on membrane fouling in all cases even with or without the coagulation process. As pretreatment of UF membrane process, the coagulation significantly improved the permeate flux. Optimal flux improvement was seen at an alum dose of 50 mg/L. In addition, it was found that the permeate flux was least declined under the coagulation condition of charge neutralization (pH 5.0). Also, the powdered activated carbon (PAC) adsorption enhanced the permeate flux. Application of the direct filtration as a pretreatment of UF membrane process was also very effective in reducing the UF membrane fouling.     

Simultaneous recovery of phosphorus and nitrogen from liquid digestate by vacuum membrane distillation with permeate fractional condensation

A vacuum membrane distillation(VMD) process with permeate fractional condensation on membrane downstream has been developed for simultaneous recovery of phosphorus and nitrogen from liquid digestate. The polytetrafluoroethylene(PTFE) membrane flux could reach 6000 g·m~(-2)·h~(-1) with the rejection efficiency of total phosphorus(TP) over 0.99, under the condition of flowrate being 120 L·h~(-1) and temperature being 40°C. Membrane fouling occurred with a film of organics and microorganism deposited on the surface of the membrane. Membrane flux could be reversed after the membrane was rinsed by water. Higher feed temperature and flowrate could improve the membrane flux, while hardly affect the rejection efficiency of total phosphorus. The concentration of TP could reach 1600 mg·L~(-1) after membrane distillation, which is about 5 times of that in initial liquid digestate. On the downstream of the membrane, some of the permeate vapor was condensed under the vacuum condition and most of water was collected here. The remaining vapor enriched with total nitrogen(TN) was compressed and pumped to the atmospheric condition to condense. The TN concentration in atmospheric condensate was as high as 7000 mg·L~(-1) with the process separation factor for ammonia being enhanced to 114.     

微纳米气泡对超滤膜过滤腐植酸污染影响研究

为有效解决超滤过程中因有机物堵塞膜孔导致的膜污染和渗透通量下降问题，提出在对腐植酸（HA）溶液超滤传输及反洗过程中引入微纳米气泡水处理工艺，以强化超滤过程，实验研究了微纳米气泡对超滤膜渗透通量和截留效率的影响以及膜污染去除效果。结果表明在纯水和HA溶液中鼓入微纳米气泡后其归一化通量增大到1.1~1.3，截留效率提高了2.5%~22.0%，微纳米气泡水清洗和反洗后膜通量恢复分别高于纯水21%和25%。     

Seawater desalination by direct contact membrane distillation

Membrane fouling still posts as one of the major obstacles in membrane distillation (MD). This is why the MD approach still cannot successfully compete with other conventional seawater desalination methods. In this study, both the NaCl solution and real seawater are used as the feed of MD processes to investigate the differences in permeate flux, product water quality and membrane fouling. The results indicate the accumulation rate of membrane scale can be depressed by reducing the degree of polarization if NaCl solution is used as the feeding fluid, however, this kind of depression effect is not so obvious when real seawater is used as the feeding fluid. An ultrasonic cleaning technique is found to be an effective way to restore the flux rate for these MD processes and extend the life span of MD membrane.     

Hydrodynamic factors affecting flux and fouling during reverse osmosis of seawater

In this paper results are presented obtained from investigations on a polyamide reverse osmosis membrane fouled by precipitation of materials which exist in seawater. In these studies the effect of different hydrodynamic factors on fouling of the membrane was investigated. Operating conditions such as temperature, pressure, crossflow velocity and pH, which could play an important role in the fouling processes, were selected for the studies. The results show that increasing temperature, pressure and crossflow velocity enhance fouling of the membrane, but on the other hand, increase permeate flux. Thus, optimization of the parameters was found to be necessary and optimum values of them and pH were determined.     

纳米TiO_2复合膜光催化和膜分离的耦合作用

以微孔陶瓷管为载体,采用阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)辅助的溶胶-凝胶法制备了纳米TiO2复合超滤膜。以1 g/L聚丙烯酰胺(PAM)为料液(目标污染物),以膜截留率及膜通量为实验参数,研究了复合膜的光催化-膜分离耦合作用,耦合时的膜通量较单一膜分离的膜通量提高了60%;以0.5 g/L牛血清白蛋白(BSA)为模拟天然大分子料液,采用无光照料液过膜-紫外光照清水过膜的交替间歇运行方法,膜通量可恢复60%以上。     

往复旋转管式陶瓷膜超滤脱脂奶水溶液的研究

往复旋转管式陶瓷膜过滤系统通过膜组件往复旋转在膜表面反复产生高剪切率,达到减缓膜污染的效果。在相同操作条件下,与单向旋转过滤和死端过滤相比较,往复旋转过滤具有更好的减缓膜污染的作用。本实验利用往复旋转膜过滤装置超滤脱脂奶水溶液,考察了各种参数对该膜系统过滤特性的影响。实验结果表明,料液浓度增大,膜通量减小;过高的操作压差将会抑制膜通量增加;旋转速度增大,膜表面剪切强化作用增强,膜通量相应增大;膜稳态通量随往复旋转周期增大呈现先增大后减小的趋势。当料液速度达到膜组件转速时,瞬时反方向旋转膜组件,膜表面产生最大的剪切率,膜稳态通量也达到最大值。能耗分析表明,往复旋转过滤较单向旋转过滤单位通量能耗低。     

纳米ZrO2修饰Al2O3微滤膜处理废冷却液的实验研究

膜分离技术处理含油废水表现出明显的技术优势,其应用还应解决膜表面易被污染,分离效果逐渐下降的问题,主要原因是由于油滴的易变形性引起的膜堵塞。为解决膜渗透通量与膜选择性的矛盾,本文在市售Al2O3微滤膜孔道表面制备纳米ZrO2涂层,利用纳米涂层改变微滤膜的表面亲水憎油性,阻止油滴的变形。研究了陶瓷膜修饰条件和膜过滤操作参数对膜渗透通量的影响,结果表明:纳米涂层能有效提高微滤膜的渗透通量。膜面流速的增加在一定程度上能提高膜渗透通量,但超过一定程度后,增加不明显。当膜面流速为7m/s,修饰陶瓷膜的最大渗透通量为280 L.m-2.h-1,油截留率为96.4%。纳米涂层修饰微滤膜具有良好的抗油滴污染性能,能有效实现稳定含油废水的油水分离。     

The effects of performance and cleaning cycles of new tubular ceramic microfiltration membrane fouled with a model yeast suspension

The efficiency of crossflow microfiltration processes is limited by membrane fouling and concentration polarization leading to permeate flux decline during operation. The experiments that were carried out in the laboratory were conducted to determine and investigate the performance, behaviour and the fouling susceptibility of new ceramic tubular microfiltration membranes during the crossflow filtration of yeast suspensions. The tubular membranes of nominal pore size 0.5 microns were fouled over a varied range of concentration, temperatures, pH, crossflow velocities and system pressures. The typical filtration conditions were at a temperature of 25°C, a system pressure of 1.5 bar and a concentration of 0.03 g/L yeast suspension. These parameters varied during subsequent investigations. After each experiment, the membrane and the rig were cleaned using a three stage cleaning process and was reused in order to replicate industrial filtration conditions. The effects of repeated fouling and cleaning cycles upon membrane flux over time and cleaning efficiency are investigated and their influence over time is also documented. For every experiment, the flux data was recorded over a 50 min period and the membrane was changed after the PWF declined considerably due to excessive fouling over time. Chemical cleaning consisted of a sequential application of a 1% caustic solution through the rig followed by a 2% hypochlorite solution and a 2% nitric solution, all at 50°C. The permeate flux was shown to decrease with filtration time during the development of the fouling layer. Once the fouling layer was developed and established, there appeared to be a leveling of permeate flux. The experimental results are presented in the report and the flux values at different conditions are presented.     

Control of scale formation in reverse osmosis by membrane rotation

Scale formation of soluble salts is one of the major factors limiting the application of reverse osmosis (RO) membranes. In this study, rotating RO, which takes advantage of Taylor-Couette flow instabilities to reduce concentration polarization and membrane fouling, was investigated as a novel method to control CaSO₄ scale formation. The permeate flux for rotating RO at ω = 180 rpm remains constant up to a volume concentration factor (VCF) of 4.2, while the permeate flux declines steadily with increasing VCF for no rotation. This is probably because vortices in rotating RO induce bulk crystallization and prevent scale particle deposition on the membrane surface. The anti-scaling effect in rotating RO increases with increasing rotational speed and depends to some extent on transmembrane pressure.     

Insight into fouling behavior of poly(vinylidene fluoride) (PVDF) hollow fiber membranes caused by dextran with different pore size distributions

Membrane fouling is the key problem that occurs in membrane process for water treatment. However, how membrane microstructure influences the fouling behavior is still not clear. In this study, fouling behavior caused by dextran was deeply and systematically investigated by employing four poly(vinylidene fluoride)(PVDF)membranes with different pore sizes, ranging from 24 to 94 nm. The extent of fouling by dextran was accurately characterized by pore reduction, flux decline, and the change of critical flux. The result shows that membrane with the smallest pore size of 24 nm experienced the smallest fouling rate and the lowest fouling extent. As the membrane pore size increased, the critical flux ranges were 105-114, 63-73, 38-44 and 34-43 L·m~(-2)·h~(-1),respectively. The critical flux and fouling resistances indicated that the fouling propensity increases with the increase of membrane pore size. Two pilot membrane modules with mean pore size of 25 nm and 60 nm were applied in membrane filtration of surface water treatment. The results showed that serious irreversible membrane fouling occurred on the membrane with pore size of 60 nm at the permeate flux of40.5 L·m~(-2)·h~(-1).On the other hand, membrane with pore size of 25 nm exhibited much better anti-fouling performance when permeate flux was set to 40.5,48 and 60 L·m~(-2)·h~(-1).