改性聚偏氟乙烯中空纤维膜处理压裂返排液研究

针对中空纤维膜应用于水力压裂返排液处理时存在膜污染严重、通量衰减快、影响处理效率等问 题,研究了PVDF（聚偏氟乙烯）固含量、凝固浴温度等因素对PVDF膜性能的影响,通过非溶剂致相分离法制 备PVDF中空纤维膜,并采用表面接枝技术,对PVDF中空纤维膜进行了表面亲水化改性。压裂返排液吸附实 验结果表明,表面接枝降低了PVDF的接触角,提高了膜的亲水性。将亲水性中空纤维膜用于页岩气水力压裂 返排液的过滤处理,应用结果表明其对压裂返排液中的总铁、SS、浊度、细菌去除率达到90％以上,长时间运行 后的通量保持率高,有较好的抗膜污染性。     

氧化石墨烯与纳米TiO_2改性PVDF膜的性能研究

自制氧化石墨烯(GO)与纳米TiO_2复合改性PVDF中空纤维超滤膜(简称GOTiO_2改性PVDF膜),测定其表面功能特性,考察其对微污染物腐殖酸(HA)的截留特性与抗污染性能。结果表明:GO-TiO_2改性PVDF膜的静态水接触角下降为38. 6°±1. 2°(原膜为80. 6°±1. 8°),表面亲水性能得到很大改善。改性后膜表面富含大量的—COOH、—OH等亲水性基团,亲水性表面为GO-聚酰胺-TiO_2复合结构。GO-TiO_2改性PVDF膜的通量衰减率得到显著改善,其通量总衰减率下降到35. 6%(改性前总衰减率为51. 2%);改性膜不可逆衰减率大幅下降,约为原膜的1/4。改性膜抗污染性能明显改善,其对HA的静态吸附量由改性前的295. 0 mg/m2下降到158. 6 mg/m2。水力反冲洗能使GO-TiO_2改性PVDF膜的通量恢复率达到94%,而原膜只有69%。GO-TiO_2改性PVDF膜的截留性能得到显著提升,其对HA的截留率从81. 0%上升到90. 1%,过滤周期延长了约2. 5倍。     

表面改性纳米氧化铝亲水共混膜制备及其水处理效能

经低温等离子体处理后,在纳米氧化铝(Al_2O_3)表面接枝甲基丙烯酸-2-羟乙酯(HEMA)或其聚合物,制备了Al_2O_3-g-HEMA纳米复合颗粒。采用纳米Al_2O_3及Al_2O_3-g-HEMA纳米复合颗粒分别与聚偏氟乙烯(PVDF)共混,制备了PVDF/Al_2O_3膜和PVDF/Al_2O_3-g-HEMA膜,并与未改性PVDF膜进行比较。考察了改性纳米Al_2O_3表面的接枝情况和平均粒径,以及上述3种超滤膜处理聚驱采油废水的通量、出水水质及膜污染情况。结果表明,经表面改性的纳米Al_2O_3,其颗粒团聚得到良好控制,平均粒径大幅下降。PVDF/Al_2O_3膜和PVDF/Al_2O_3-g-HEMA膜的亲水性、纯水通量、处理聚驱采油废水的运行通量及清洗后通量恢复率均大幅提高。3种膜对聚丙烯酰胺、油类和TOC均有良好的去除效果,且共混改性不影响膜对大分子物质的去除。以PVDF/Al_2O_3-g-HEMA纳米复合颗粒作为添加剂制备的共混膜,其通量、去除效果和抗污染能力等综合性能最佳,是深度处理聚驱采油废水的理想膜材料。     

中美页岩气水力压裂返排液环境影响与治理

对比分析中美页岩气水力压裂返排液,发现两者均具有产生量大、成分复杂、难生物降解、高COD、高 TSS、高TDS等特点,若压裂返排液进入到地表水及土壤中,可能造成不利影响,甚至对人类健康造成 影响。目前常用的处理压裂返排液的技术有深井回注法、处理后回用法及处理后排放法。我国页岩气水力压 裂返排液处理技术尚不成熟,部分地区仍沿用石油行业处理采出水的方法;部分页岩气田以借鉴国外压裂返排 液处理技术为主,结合自身返排液情况制定处理流程;返排液回收后重新用于水力压裂的水处理技术还不成 熟,应积极开展压裂返排液处理技术的研究。     

NOM的亲疏水性及分子质量分布对超滤膜污染的影响

采用XAD-8/XAD-4型树脂将松花江水中的有机物分离出强疏水性、弱疏水性和亲水性三种有机组分,分别研究了其对PVDF超滤膜和改性PVDF超滤膜的污染性能。分别过滤强疏水、弱疏水和亲水性有机组分时,PVDF原膜的比通量分别为60.6%、70.8%和82.0%,而改性PVDF膜的比通量为75.1%、77.6%和86.0%。表明有机物的疏水性越强则对膜的污染能力越大;而膜的污染程度与对有机物的去除率并非呈正相关。此外,还研究了不同组分有机物的分子质量分布对膜污染的影响。结果表明,与分子质量相对较大的亲水性天然有机物相比,分子质量相对较小的疏水性天然有机物产生的膜污染较重。     

浸入式中空纤维膜处理净水厂沉淀池排泥试验研究

首次采用浸入式中空纤维膜处理净水厂沉淀池排泥,对膜通量、过滤后水质及膜污染的清洗等问题进行了现场试验、分析和探讨。     

减压膜蒸馏浓缩脱硫液试验研究

采用减压膜蒸馏(VMD)技术浓缩脱硫液,研究了减压膜蒸馏过程中脱硫液浓度、流速、热侧料液温度、冷侧真空度及膜组件装实密度对膜通量和截留率的影响。试验结果表明:当脱硫液浓度较低时,膜通量随脱硫液浓度的升高而下降缓慢,当脱硫液浓度较高时,膜通量随脱硫液浓度的升高呈抛物线式下降;随着热侧料液流速的增加,膜通量略有增加;热侧料液温度升高,膜通量线性增加;随着冷侧真空度的增加,膜通量先略有增加,当冷侧真空度超过一临界值时,膜通量显著增加;膜通量随着组件内膜丝数目的增加而线性减少;试验过程中截留率保持在99.0%以上,表明聚偏氟乙烯(PVDF)中空纤维膜具有良好的疏水性。     

纳米TiO_2改性膜生物反应器处理污水的研究

采用啧涂纳米TiO2的方法对聚偏氟乙烯（PVDF）微滤膜进行改性,用改性膜生物反应器（MBR）和非改性MBR处理污水,对比了两者的出水水质、膜通量和膜过滤阻力。结果表明,两套MBR的出水水质均可达到《生活杂用水水质标准》（CJ25．1—89）的要求;纳米TiO2改善了膜表面的亲水性和粗糙度,从而使改性MBR的清水膜过滤阻力和不同抽吸压力下的膜过滤阻力均低于非改性MBR的,而其在不同抽吸压力下的稳定膜通量则高于非改性MBR的。     

改性聚偏氟乙烯微滤膜深度处理城市污水的研究

采用改良的热诱导化学聚合技术,在聚偏氟乙烯（PVDF）微滤膜表面接枝具有离子交换性能的羧酸基团,并借助X衍射光电子能谱（XPS）和环境扫描电镜（ESEM）对改性PVDF微滤膜进行了表征.采用该改性PVDF（PAA/PVDF）膜深度处理城市污水,探讨了pH值、接触时间对处理效果的影响.试验结果表明：热诱导化学聚合技术在PVDF膜表面成功接枝了羧酸基团,PAA/PVDF膜对水溶性金属离子具有交换去除作用,出水水质优良.     

压裂返排液处理技术现状及展望

针对页岩气压裂返排液的特点、危害,综述了氧化-絮凝-过滤/吸附联合处理工艺、氧化-絮凝-电解-过滤/吸附联合处理工艺、氧化 絮凝-电解-过滤/吸附-生化联合处理工艺的特点、适用性及处理效果,经过多种工艺处理后,压裂返排液中COD等污染物可以有效去除,出水可以达标。并对压裂返排液处理技术的发展前景进行展望,认为回收重复利用是未来压裂返排液处理的发展趋势。     

大型超滤水厂PVC和PVDF膜运行特性差异与优化

超滤技术已广泛应用于城镇给水处理厂,使得饮用水水质得到显著改善。不同材质超滤膜的运行周期、膜通量、跨膜压差(TMP)等的变化规律会有显著的差异,需要根据各自的特点对超滤系统进行运行参数调控与优化,以保证超滤系统的长期稳定运行。分析了山东某大型超滤水厂超滤系统长期运行的特点,对比了PVC膜和PVDF膜孔结构特征、膜通量、跨膜压差变化趋势及膜过滤阻力特性,调控和优化超滤系统运行参数,并进行了长时间的运行验证。结果表明,膜孔径和膜孔结构不同造成的膜污染是PVC膜与PVDF膜过滤特性差异的主要因素,恒定过滤周期运行模式下PVC膜通量加速衰减时段为82~220 min,造成PVC膜通量衰减了9. 14%,并形成了约5%的永久衰减膜通量,而PVDF膜的通量衰减并不明显,使得水厂超滤系统在恒定过滤周期(180min)运行模式下,出现了PVC膜的污染速率明显高于PVDF膜、系统的运行工况出现显著差异的现象。按照恒定过滤阻力模式运行时,PVC膜和PVDF膜的最佳过滤周期范围分别为82~108 min和96~155 min。水厂超滤系统在恒定过滤阻力运行模式下将PVC膜与PVDF膜在高温期和低温期的过滤周期分别调整为110、90 min和150、120 min,TMP的增长速率和化学维护清洗周期均基本一致,超滤系统实现了长期稳定运行。研究成果为我国超滤水厂中不同材质超滤膜的运行参数优化及协同稳定运行提供了参考。     

Analysis of filtration characteristics in submerged microfiltration for drinking water treatment

Hollow fiber membranes have been widely employed for water and wastewater treatments. Nevertheless, understanding the filtration characteristics of hollow fiber membranes is complicated by the axial distributions of transmembrane pressure (TMP) and flux, which are key factors for both fouling control and module design. In this study, model equations to account for different fouling mechanisms were derived to analyze the performance of submerged hollow fiber systems with different conditions in terms of feed water characteristics and membrane material. A series of experiments with synthetic feed and raw water were carried out using hydrophilic and hydrophobic membrane modules. The model successfully fits the experimental results for synthetic feed as well as raw water. The major fouling mechanisms for filtration of raw water using hydrophilic and hydrophobic membranes are identified as cake formation and standard blocking, respectively. The model calculations indicate that the distributions of flux and cake (fouling) resistance are sensitive to the fiber length of the membrane.     

Influence of the characteristics of natural organic matter on the fouling of microfiltration membranes

Natural organic matter (NOM) plays a significant role in fouling microfiltration membranes in drinking water treatment processes even though the NOM is retained only to a small extent. The aim of this study was to obtain a better understanding of the interactions between the fractional components of NOM and microfiltration membranes. Filtration experiments were performed using 0.22 μm hydrophobic and hydrophilic polyvinylidene fluoride (PVDF) membranes in a stirred-cell system on the NOM isolated from three Australian surface waters. As expected, the fouling rate for the hydrophobic membrane was considerably greater than for the hydrophilic membrane. Focusing on the hydrophobic membrane, it was shown that the high molecular weight fraction of NOM (>30 kDa) was responsible for the major flux decline. Filtration tests on the four fractions of NOM isolated on the basis of hydrophobicity and charge using non-functionalised and anionic resins revealed that the fouling potential for the three waters was hydrophilic neutral>hydrophobic acids>transphilic acids>hydrophilic charged. The low-aromatic hydrophilic neutral compounds were the main determinant of the rate and extent of flux decline. This was linked to the colloidal size fraction (>30 kDa) and to the selective concentration of calcium in the fraction leading to organics-Ca²⁺ bridging. It was also shown that the higher the aromaticity of the NOM the greater the flux decline, and the aromatics mainly resided in the hydrophobic acids fraction. Overall, the fouling mechanism controlling the flux decline involved the combined effects of adsorptive and colloidal fouling by the hydrophilic neutral fraction in the internal pore structure of the membrane.     

Surface modification of polypropylene microporous membrane to improve its antifouling characteristics in an SMBR: N2 plasma treatment

Fouling is the major obstacle in membrane processes applied in water and wastewater treatment. The polypropylene hollow fiber microporous membranes (PPHFMMs) were surface modified by N₂ low-temperature plasma treatment to improve the antifouling characteristics. Morphological changes on the membrane surface were characterized by field emission scanning electron microscopy (FE-SEM). The change of surface wettability was monitored by contact angle measurements. The static water contact angle of the modified membrane reduced obviously; the relative pure water flux of the modified membranes increased with the increase of plasma treatment time. To assess the relation between plasma treatment and membrane fouling in a submerged membrane bioreactor (SMBR), filtration of activated sludge was carried out by using synthetic wastewater. After continuous operation in the SMBR for about 90 h, flux recoveries for the N₂ plasma-treated PPHFMM for 8 min were 62.9% and 67.8% higher than those of the virgin membrane after water and NaOH cleaning. The irreversible fouling resistance decreased after plasma treatment.     

疏水性中空纤维微孔膜无泡曝气试验研究

利用疏水性聚偏氟乙烯(PVDF)中空纤维膜及组件开展膜无泡曝气研究.通过检测膜组件的泡点,发现一定浸没深度下静水中膜组件的泡点高于紊流状态下的,且泡点随水流速度的增大而减小.考察水力条件和曝气压力对曝气效果的影响,并与常规曝气头曝气作比较.结果表明:将气压控制在泡点以内时,充氧能力随液体循环流量的增大、气压的升高而增强;而当气压超过泡点时,供氧初期充氧能力显著,但随曝气时间的延长增幅降低.中空纤维膜的曝气性能优于曝气头的.     

Investigation of the effect of coagulation bath composition on PVDF/CA membrane by evaluating critical flux and antifouling properties in lab‐scale submerged MBR

Ultrafiltration membranes were prepared from blends of poly(vinylidene fluoride) (PVDF)/cellulose acetate (CA) via phase inversion method. The effect of different coagulation bath compositions on the morphology and performance of the blend membrane prepared from casting solution of PVDF/CA with ratio of 80/20 was investigated using sewage wastewater. NaCl and ethanol were used as additives of coagulation bath. Fouling analysis was conducted with Bovine Serum Albumin solution and critical flux evaluation was performed using a lab‐scale membrane bioreactor. In terms of morphological structure, the macrovoids decreased and changed to finger‐like structure. The irreversible fouling reduced and the flux recovery ratio (FRR) of the modified membranes increased remarkably while the reversible fouling caused by deposition of foulants on the surface of the membranes increased. The maximum values of FRR and critical flux of irreversibility were reached by the membrane which was prepared in the coagulation bath containing the highest concentration of NaCl.     

Surface modification of polypropylene macroporous membrane to improve its antifouling characteristics in a submerged membrane-bioreactor: H(2)O plasma treatment

To improve the antifouling characteristics of polypropylene hollow fiber macroporous membranes in a submerged membrane-bioreactor for wastewater treatment, the membranes were surface modified by H₂O plasma treatment. Structural and morphological changes on the membrane surface were characterized by X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE-SEM). The change of surface wettability was monitored by contact angle measurement. The static water contact angle of the modified membrane reduced obviously with the increase of plasma treatment time. The total surface free energy and its dispersive component decreased, while the polar component increased with the increase of treatment time. The relative pure water flux for the modified membranes increased gradually with the increase of plasma treatment time. The tensile strength and the tensile elongation at break for the membranes decreased after plasma treatment. After continuous operation in a submerged membrane-bioreactor for about 68 h, flux recovery after water and caustic cleaning, flux ratio after fouling were improved by 2.0, 3.6 and 22.0%, while reduction of flux was reduced by 1.1% for the 1 min H₂O plasma treated membrane, compared to those of the unmodified membrane.     

Fouling indices for low pressure hollow fiber membrane performance assessment

This study evaluated the use of fouling indices to describe low pressure membrane fouling. One critical aspect of this study was the use of a bench-scale hollow fiber membrane system that imitated full-scale operation (constant flux with automatic hydraulic backwash and chemical cleaning). Fouling indices were based on a resistance-in-series model. Two different hollow fiber membrane types (membrane A and B) were tested with water from two water utilities (A and B) and three other natural sources (oligotrophic, algal bloom impacted, and wastewater impaired). The bench-scale testing included use of the same membrane as utilized at Utility B. Most fouling was reversible by hydraulic backwash and chemical cleaning. Specific flux and fouling indices for the bench-scale system were higher than those determined from full-scale data but fouling index ratios were comparable, suggesting a similar fouling nature. At similar organic loading, fouling was specific to water source and membrane type, i.e., no generalization on the impact of water source was possible. Full-scale data were compared with bench-scale data to validate the use of fouling indices. Fouling indices based on a resistance-in-series are useful tools to describe membrane performance data for both raw and pretreated water, for different water sources, and different membrane types.     

Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM)

An understanding of natural organic matter (NOM) as a membrane foulant and the behavior of NOM components in low-pressure membrane fouling are needed to provide a basis for appropriate selection and operation of membrane technology for drinking water treatment. Fouling by NOM was investigated by employing several innovative chemical and morphological analyses.

Source (feed) waters with a high hydrophilic (HPI) fraction content of NOM resulted in significant flux decline. Macromolecules of a relatively hydrophilic character (e.g. polysaccharides) were effectively rejected by low-pressure membranes, suggesting that macromolecular compounds and/or colloidal organic matter in the hydrophilic NOM fraction may be a problematic foulant of low-pressure membranes. Moreover, the significant organic fouling that is contributed by polysaccharides and/or proteins in macromolecular and/or colloidal forms depends on molecular shape (structure) as well as size (i.e. molecular weight). More significant flux decline was observed in microfiltration (MF) compared to ultrafiltration (UF) membrane filtration. MF membrane fouling may be caused by pore blockage associated with large (macromolecular) hydrophilic molecules and/or organic colloids. In the case of UF membranes, the flux decline may be caused by sequential or simultaneous processes of surface (gel layer) coverage during filtration. Morphological analyses support the notion that membrane roughness may be considered as a more important factor in membrane fouling by controlling interaction between molecules and the membrane surface, compared to the hydrophobic/hydrophilic character of membranes. Membrane fouling mechanisms are not only a function of membrane type (MF versus UF) but also depend on source (feed) water characteristics.     

Effect of membrane configuration on bench-scale MF and UF fouling experiments

Hollow fiber and flat sheet membranes were compared in side-by-side bench-scale experiments to evaluate whether the configuration has an impact on the rate of membrane fouling. Both microfiltration (MF) and ultrafiltration (UF) membranes were evaluated. In general, flat sheet membranes fouled more rapidly than hollow fiber membranes. Pretreatment such as coagulation generally affected both configurations similarly, but in some cases coagulation reduced fouling on hollow fiber membranes but increased fouling on flat sheet membranes. Prefiltration to remove foulants above 1microm in size had a consistent effect on both configurations. A bench-scale apparatus employing a single-fiber module that allows testing over multiple filter runs with integral backwashing capabilities was demonstrated to provide more detailed information about fouling, which can be applied to full-scale applications. When bench-scale tests are to be used to screen treatment options for full-scale applications, the use of a backwashable hollow fiber system is recommended.