Fatty acid fouling of forward osmosis membrane: Effects of pH, calcium, membrane orientation, initial permeate flux and foulant composition

Octanoic acid (OA) was selected to represent fatty acids in effluent organic matter (EOM). The effects of feed solution (FS) properties, membrane orientation and initial permeate flux on OA fouling in forward osmosis (FO) were investigated. The undissociated OA formed a cake layer quickly and caused the water flux to decline significantly in the initial 0.5 hr at unadjusted pH 3.56; while the fully dissociated OA behaved as an anionic surfactant and promoted the water permeation at an elevated pH of 9.00. Moreover, except at the initial stage, the sudden decline of water flux (meaning the occurrence of severe membrane fouling) occurred in two conditions: 1. 0.5 mmol/L Ca^2 +, active layer facing draw solution (AL-DS) and 1.5 mol/L NaCl (DS); 2. No Ca^2 +, active layer-facing FS (AL-FS) and 4 mol/L NaCl (DS). This demonstrated that cake layer compaction or pore blocking occurred only when enough foulants were absorbed into the membrane surface, and the water permeation was high enough to compact the deposit inside the porous substrate. Furthermore, bovine serum albumin (BSA) was selected as a co-foulant. The water flux of both co-foulants was between the fluxes obtained separately for the two foulants at pH 3.56, and larger than the two values at pH 9.00. This manifested that, at pH 3.56, BSA alleviated the effect of the cake layer caused by OA, and OA enhanced BSA fouling simultaneously; while at pH 9.00, the mutual effects of OA and BSA eased the membrane fouling.     

Advanced treatment of municipal wastewater by nanofiltration: Operational optimization and membrane fouling analysis

Municipal sewage from an oxidation ditch was treated for reuse by nanofiltration (NF) in this study. The NF performance was optimized, and its fouling characteristics after different operational durations (i.e., 48 and 169 hr) were analyzed to investigate the applicability of nanofiltration for water reuse. The optimum performance was achieved when transmembrane pressure = 12 bar, pH = 4 and flow rate = 8 L/min using a GE membrane. The permeate water quality could satisfy the requirements of water reclamation for different uses and local standards for water reuse in Beijing. Flux decline in the fouling experiments could be divided into a rapid flux decline and a quasi-steady state. The boundary flux theory was used to predict the evolution of permeate flux. The expected operational duration based on the 169-hr experiment was 392.6 hr which is 175% longer than that of the 48-hr one. High molecular weight (MW) protein-like substances were suggested to be the dominant foulants after an extended period based on the MW distribution and the fluorescence characteristics. The analyses of infrared spectra and extracellular polymeric substances revealed that the roles of both humic- and polysaccharide-like substances were diminished, while that of protein-like substances were strengthened in the contribution of membrane fouling with time prolonged. Inorganic salts were found to have marginally influence on membrane fouling. Additionally, alkali washing was more efficient at removing organic foulants in the long term, and a combination of water flushing and alkali washing was appropriate for NF fouling control in municipal sewage treatment.     

Drinking water treatment using a submerged internal-circulation membrane coagulation reactor coupled with permanganate oxidation

A submerged internal circulating membrane coagulation reactor(MCR) was used to treat surface water to produce drinking water. Polyaluminum chloride(PACl) was used as coagulant,and a hydrophilic polyvinylidene fluoride(PVDF) submerged hollow fiber microfiltration membrane was employed. The influences of trans-membrane pressure(TMP), zeta potential(ZP) of the suspended particles in raw water, and KMnO_4 dosing on water flux and the removal of turbidity and organic matter were systematically investigated. Continuous bench-scale experiments showed that the permeate quality of the MCR satisfied the requirement for a centralized water supply, according to the Standards for Drinking Water Quality of China(GB 5749-2006), as evaluated by turbidity(1 NTU) and total organic carbon(TOC)(5 mg/L)measurements. Besides water flux, the removal of turbidity, TOC and dissolved organic carbon(DOC) in the raw water also increased with increasing TMP in the range of 0.01–0.05 MPa. High ZP induced by PACl, such as 5–9 mV, led to an increase in the number of fine and total particles in the MCR, and consequently caused serious membrane fouling and high permeate turbidity.However, the removal of TOC and DOC increased with increasing ZP. A slightly positive ZP, such as 1–2 mV, corresponding to charge neutralization coagulation, was favorable for membrane fouling control. Moreover, dosing with KMnO_4 could further improve the removal of turbidity and DOC, thereby mitigating membrane fouling. The results are helpful for the application of the MCR in producing drinking water and also beneficial to the research and application of other coagulation and membrane separation hybrid processes.     

Preparation of high concentration polyaluminum chloride by chemical synthesis-membrane distillation method with self-made hollow fiber membrane

A method of direct contact membrane distillation (DCMD) with a self-made hollow polyvinylidene fluoride membrane was applied to prepare high concentration polyaluminum chloride (PACl) with high Al_b content based on chemical synthesis. The permeate flux and Al species distribution were investigated. The experimental results showed that the permeate flux decreased from 14 to 6 kg/(m²·hr) at the end of the DCMD process, which can be mainly attributed to the formation of NaCl deposits on the membrane surface. The Al_b content decreased slightly, only from 86.3% to 84.4%, when the DCMD experiment finished, correspondingly the Al_c content increased slightly from 7.2% to 8.5%, and the Al_a content remained at 7% during the whole DCMD process. A PACl with Al_b content of 84% at total aluminum concentration 2.2 mol/L was successfully prepared by the chemical synthesis-DCMD method.     

A fouling suppression system in submerged membrane bioreactors using dielectrophoretic forces

A novel method was developed to suppress membrane fouling in submerged membrane bioreactors. The method is based on the dielectrophoretic (DEP) motion of particles in an inhomogeneous electrical field. Using a real sample of biomass as feed, the fouling-suppression performance using DEP with different electrical field intensities (60–160 V) and different frequencies (50–1000 Hz) was investigated. The fouling-suppression performance was found to relate closely with the intensity and frequency of the electrical field. A stronger electrical field was found to better recover the filtrate flux. This is because of a stronger DEP force acting on the biomass particles close to the membrane's surface. Above an intensity and frequency value of 130 V and 1 kHz, respectively the permeate flux was reduced due to an electrothermal effect.     

Membrane fouling controlled by coagulation/adsorption during direct sewage membrane filtration (DSMF) for organic matter concentration

Unlike the role of the membrane in a membrane bioreactor, which is designed to replace a sediment tank, direct sewage membrane filtration (DSMF), with the goal of concentrating organic matters, is proposed as a pretreatment process in a novel sewage treatment concept. The concept of membrane-based pretreatment is proposed to divide raw sewage into a concentrated part retaining most organics and a filtered part with less pollutant remaining, so that energy recovery and water reuse, respectively, could be realized by post-treatment. A pilot-scale experiment was carried out to verify the feasibility of coagulant/adsorbent addition for membrane fouling control, which has been the main issue during this DSMF process. The results showed that continuous coagulant addition successfully slowed down the increase in filtration resistance, with the resistance maintained below 1.0 × 10¹³ m^− 1 in the first 70 hr before a jump occurred. Furthermore, the adsorbent addition contributed to retarding the occurrence of the filtration resistance jump, achieving simultaneous fouling control and chemical oxygen demand (COD) concentration improvement. The final concentrated COD amounted to 7500 mg/L after 6 days of operation.     

Effect of non-solvent additives on the morphology, pore structure, and direct contact membrane distillation performance of PVDF-CTFE hydrophobic membranes

Four common types of additives for polymer membrane preparation including organic macromolecule and micromolecule additives, inorganic salts and acids, and the strong non-solvent H2 O were used to prepare poly(vinylidene fluoride-co-chlorotrifluoroethylene)(PVDF-CTFE) hydrophobic flat-sheet membranes. Membrane properties including morphology, porosity, hydrophobicity, pore size and pore distribution were investigated, and the permeability was evaluated via direct contact membrane distillation(DCMD) of 3.5 g/L Na Cl solution in a DCMD configuration. Both inorganic and organic micromolecule additives were found to slightly influence membrane hydrophobicity. Polyethylene glycol(PEG),organic acids, Li Cl, Mg Cl2, and Li Cl/H2 O mixtures were proved to be effective additives to PVDF-CTFE membranes due to their pore-controlling effects and the capacity to improve the properties and performance of the resultant membranes. The occurrence of a pre-gelation process showed that when organic and inorganic micromolecules were added to PVDF-CTFE solution, the resultant membranes presented a high interconnectivity structure. The membrane prepared with dibutyl phthalate(DBP) showed a nonporous surface and symmetrical cross-section. When H2 O and Li Cl/H2 O mixtures were also used as additives, they were beneficial for solid–liquid demixing, especially when Li Cl/H2 O mixed additives were used. The membrane prepared with 5% Li Cl + 2% H2 O achieved a flux of24.53 kg/(m2·hr) with 99.98% salt rejection. This study is expected to offer a reference not only for PVDF-CTFE membrane preparation but also for other polymer membranes.     

Fluoride removal from brackish groundwater by direct contact membrane distillation

The direct contact membrane distillation applied for fluoride removal from brackish groundwater was investigated.The self-prepared polyvinylidene fluoride membrane exhibited high rejection of inorganic salt solutes.The maximum permeate flux 35.6 kg/(m2 ·hr) was obtained with the feed solution at 80°C and the cold distillate water at 20°C.The feed concentration had no significant impact on the permeate flux and the rejection in fluoride.The precipitation of CaCO3 would clog the hollow fiber inlets and foul the membrane surface with increasing concentration factor when natural groundwater was used directly as the feed,which resulted in a rapid decline in the module efficiency.This phenomenon was diminished by acidification of the feed.The experimental results showed that the permeate flux and the quality of obtained distillate kept stable before concentration factor reached 5.0 with the acidified groundwater as feed.The membrane module efficiency began to decline gradually when the feed continued to be concentrated,which can be mainly attributed to the formation of CaF2 deposits on the membrane surface.In addition,a 300 hr continuous fluoride removal experiment of acidified groundwater was carried out with concentration factor at 4.0,the permeate flux kept stable and the permeate fluoride was not detected.     

HLB-MR反应器直接处理城市污水及回收有机物

采用中空纤维超滤膜组件构建了高负荷生物絮凝-膜反应器（HLB-MR）,对其直接处理城市污水及回收有机物进行了研究.结果表明：当水力停留时间（HRT）为1.0h,固体停留时间（SRT）为0.2d时,该工艺可回收进水总COD的60.8%,据估算约有39%的进水总COD可通过中温厌氧消化转化为甲烷能源回收,有机物的甲烷转化率为活性污泥法剩余污泥的2倍以上,能实现污水中有机物的高效回收和利用;经过有机物回收后膜出水的COD能稳定保持在30mg/L左右,且出水中氮、磷营养物保有值均较高又不含固体杂质和病原体,可将其用作灌溉用水,实现水资源回用;SRT分别为0.2,0.6,1.0d时,反应器对胶体COD絮凝效率分别为81.9%、95.1%、96.8%,絮凝效率越高,膜污染越轻,良好的生物絮凝效果可有效减轻膜污染,保证工艺的稳定运行.     

Treatment of phosphate-containing oily wastewater by coagulation and microfiltration

The oily wastewater generated from pretreatment unit of electrocoating industry contains oils, phosphate, organic solvents, and surfactants. In order to improve the removal efficiencies of phosphate and oils, to mitigate the membrane fouling, coagulation for ceramic membrane microfiltration of oily wastewater was performed. The results of filtration tests show that the membrane fouling decreased and the permeate flux and quality increased with coagulation as pretreatment. At the coagulant Ca （OH）2 dosage of 900 mg/L, the removal efficiency of phosphate was increased from 46.4% without coagulation to 99.6%; the removal of COD and oils were 97.0% and 99.8%, respectively. And the permeate flux was about 70% greater than that when Ca（OH）2 was not used. The permeate obtained from coagulation and microfiltration can be reused as make-up water, and the recommended operation conditions for pilot and industrial application are transmembrane pressure of 0.10 MPa and cross-flow velocity of 5 m/s. The comparison results show that 0.2 μm ZrO2 microfilter with coagulation could be used to perform the filtration rather than conventional ultrafilter, with very substantial gain in flux and removal efficiency of phosphate.     

The nitritation performance of biofilm reactor for treating domestic wastewater under high dissolved oxygen

The objective of this study was to investigate the nitritation performance in a biofilm reactor for treating domestic wastewater.The reactor was operated in continuous feed mode from phases 1 to 3.The dissolved oxygen(DO)was controlled at 3.5–7 mg/L throughout the experiment.The biofilm reactor showed excellent nitritation performance after the inoculation of nitrifying sludge,with the hydraulic retention time being reduced from 24 to 7 hr.Above 90%nitrite accumulation ratio(NAR)was maintained in phase 1.Afterwards,nitratation occurred with the low NH_4~+–N concentration in the reactor.The improvement of NH_4~+–N concentration to 20–35 mg/L had a limited effect on the recovery of nitritation.However,nitritation recovered rapidly when sequencing batch feed mode was adopted in phase 4,with the effluent NH_4~+-N concentration above 7 mg/L.The improvement of ammonia oxidizing bacteria(AOB)activity and the combined inhibition effect of free ammonia(FA)and free nitrous acid(FNA)on the nitrite oxidizing bacteria(NOB)were two key factors for the rapid recovery of nitritation.Sludge activity was obtained in batch tests.The results of batch tests had a good relationship with the long term operation performance of the biofilm reactor.     

高温厌氧膜生物反应器处理餐厨废水的启动

以除油后的实际餐厨废水为原料,在高温（50±1）℃条件下利用浸没式纤维膜生物反应器（AnMBR）进行连续厌氧消化试验,以水力停留时间（HRT）20d启动,HRT 15d运行,直到发生膜污染,试验共进行了50d.研究了反应器启动和运行期间的发酵特性和膜过滤性能.研究表明,反应器30d完成了启动,在HRT 15d条件下,甲烷产量达到578L/kgVS_in,COD和挥发性固体（VS）去除率均达到94%以上,膜出水总挥发性脂肪酸（TVFA）浓度为（103±77） mg/L,其中乙酸浓度为（98±28） mg/L.系统pH 8.26,具有良好的稳定性.膜通量设定为9L/（m²·h）,运行30d后发生了明显的膜污染,伴随着反应器内挥发性悬浮固体（VSS）浓度由8.1g/L逐渐增加到18/L.在处理高浓度餐厨废水时,AnMBR可以短时间启动且在8.5kgCOD/（m³·d）的高负荷条件下稳定运行,反应器中污泥浓度和溶解性微生物产物的增加导致膜过滤性能下降是导致膜污染的主要因素.     

Positively charged microporous ceramic membrane for the removal of Titan Yellow through electrostatic adsorption

To develop a depth filter based on the electrostatic adsorption principle, positively charged microporous ceramic membrane was prepared from a diatomaceous earth ceramic membrane.The internal surface of the highly porous ceramic membrane was coated with uniformly distributed electropositive nano-Y_2O_3 coating. The dye removal performance was evaluated through pressurized filtration tests using Titan Yellow aqueous solution. It showed that positively charged microporous ceramic membrane exhibited a flow rate of 421 L/(m~2·hr) under the trans-membrane pressure of 0.03 bar. Moreover it could effectively remove Titan Yellow with feed concentration of 10 mg/L between pH 3 to 8. The removal rate increased with the enhancement of the surface charge properties with a maximum rejection of 99.6%. This study provides a new and feasible method of removing organic dyes in wastewater. It is convinced that there will be a broad market for the application of charged ceramic membrane in the field of dye removal or recovery from industry wastewater.     

印染废水反渗透脱盐系统运行性能及膜污堵特性

反渗透(RO)脱盐工艺对实现印染废水再生利用具有重要的意义.膜污堵却制约了RO工艺应用.对广东省某工业园区印染废水RO脱盐系统运行性能及膜污堵特性进行了研究.结果表明,印染废水生化处理出水经臭氧氧化-砂滤-超滤(UF)预处理后,RO进水COD平均浓度为12.4 mg·L~(-1),浊度1 NTU.RO系统脱盐率稳定在98%,RO产水高锰酸盐指数约为0.7 mg·L~(-1),浊度约为0.12 NTU.但RO系统运行3 a后,跨膜压差高达0.6 MPa,产水量下降至120 m~3·h~(-1),且不能通过化学清洗恢复,在RO膜面沉积了不可逆的污堵物.RO膜面的有机物占总污堵物干重的(53.5±0.2)%,无机物占(46.5±0.2)%,RO膜面有机污堵与无机污堵贡献相近.Si、Al与Ca是RO膜面主要的无机元素.碱液(Na OH溶液)对沉积在RO膜面的Si与Al及有机物提取效果较好.     

Towards a better hydraulic cleaning strategy for ultrafiltration membrane fouling by humic acid: Effect of backwash water composition

As a routine measurement to alleviate membrane fouling, hydraulic cleaning is of great significance for the steady operation of ultrafiltration (UF) systems in water treatment processes. In this work, a comparative study was performed to investigate the effects of the composition of backwash water on the hydraulic cleaning performance of UF membranes fouled by humic acid (HA). Various types of backwash water, including UF permeate, Milli-Q water, NaCl solution, CaCl₂ solution and HA solution, were compared in terms of hydraulically irreversible fouling index, total surface tension and residual HA. The results indicated that Milli-Q water backwash was superior to UF permeate backwash in cleaning HA-fouled membranes, and the backwash water containing Na⁺ or HA outperformed Milli-Q water in alleviating HA fouling. On the contrary, the presence of Ca^2 + in backwash water significantly decreased the backwash efficiency. Moreover, Ca^2 + played an important role in foulant removal, and the residual HA content closely related to the residual Ca^2 + content. Mechanism analysis suggested that the backwash process may involve fouling layer swelling, ion exchange, electric double layer release and competitive complexation. Ion exchange and competitive complexation played significant roles in the efficient hydraulic cleaning associated with Na⁺ and HA, respectively.     

Fouling distribution in forward osmosis membrane process

Fouling behavior along the length of membrane module was systematically investigated by performing simple modeling and lab-scale experiments of forward osmosis （FO） membrane process. The flux distribution model developed in this study showed a good agreement with experimental results, validating the robustness of the model. This model demonstrated, as expected, that the permeate flux decreased along the membrane channel due to decreasing osmotic pressure differential across the FO membrane. A series of fouling experiments were conducted under the draw and feed solutions at various recoveries simulated by the model. The simulated fouling experiments revealed that higher organic （alginate） fouling and thus more flux decline were observed at the last section of a membrane channel, as foulants in feed solution became more concentrated. Furthermore, the water flux in FO process declined more severely as the recovery increased due to more foulants transported to membrane surface with elevated solute concentrations at higher recovery, which created favorable solution environments for organic adsorption. The fouling reversibility also decreased at the last section of the membrane channel, suggesting that fouling distribution on FO membrane along the module should be carefully examined to improve overall cleaning efficiency. Lastly, it was found that such fouling distribution observed with co-current flow operation became less pronounced in counter- current flow operation of FO membrane process.     

微塑料对膜蒸馏处理含锑高盐废水性能影响研究

研究了微塑料在膜蒸馏过程中不同温度、pH、微塑料浓度和微塑料粒径条件下对含锑高盐废水的处理性能及机理.结果表明,随着进料液温度的升高,饱和蒸汽压的增加提高了传质动力,不含微塑料时膜通量由17.4 L·m^-2·h^-1提高至20.7 L·m^-2·h^-1,通量提升了18.9%,含有微塑料时膜通量由15.6 L·m^-2·h^-1提高至18.5 L·m^-2·h^-1,提升了18.6%;pH由3增大至11时,由于重金属锑在不同pH条件下的价态变化及静电排斥作用,重金属锑截留率由98.2%提升至99.6%;微塑料浓度的增加会降低膜通量,提高锑截留效果,这可能是微塑料对溶液中重金属锑的吸附作用及微塑料在膜表面的积聚产生的筛分效应引起的.     

高温厌氧膜生物反应器处理餐厨废水的启动

以除油后的实际餐厨废水为原料,在高温（50±1）℃条件下利用浸没式纤维膜生物反应器（AnMBR）进行连续厌氧消化试验,以水力停留时间（HRT）20d启动,HRT 15d运行,直到发生膜污染,试验共进行了50d.研究了反应器启动和运行期间的发酵特性和膜过滤性能.研究表明,反应器30d完成了启动,在HRT 15d条件下,甲烷产量达到578L/kgVS_in,COD和挥发性固体（VS）去除率均达到94%以上,膜出水总挥发性脂肪酸（TVFA）浓度为（103±77） mg/L,其中乙酸浓度为（98±28） mg/L.系统pH 8.26,具有良好的稳定性.膜通量设定为9L/（m²·h）,运行30d后发生了明显的膜污染,伴随着反应器内挥发性悬浮固体（VSS）浓度由8.1g/L逐渐增加到18/L.在处理高浓度餐厨废水时,AnMBR可以短时间启动且在8.5kgCOD/（m³·d）的高负荷条件下稳定运行,反应器中污泥浓度和溶解性微生物产物的增加导致膜过滤性能下降是导致膜污染的主要因素.     

Denitrification and biofilm growth in a pilot-scale biofilter packed with suspended carriers for biological nitrogen removal from secondary effluent

Tertiary denitrification is an effective method for nitrogen removal from wastewater. A pilot-scale biofilter packed with suspended carriers was operated for tertiary denitrification with ethanol as the organic carbon source. Long-term performance, biokinetics of denitrification and biofilm growth were evaluated under filtration velocities of 6, 10 and 14 m/hr. The pilot-scale biofilter removed nitrate from the secondary effluent effectively, and the nitrate nitrogen (NO₃-N) removal percentage was 82%, 78% and 55% at the filtration velocities of 6, 10 and 14 m/hr, respectively. At the filtration velocities of 6 and 10 m/hr, the nitrate removal loading rate increased with increasing influent nitrate loading rates, while at the filtration velocity of 14 m/hr, the removal loading rate and the influent loading rate were uncorrelated. During denitrification, the ratio of consumed chemical oxygen demand to removed NO₃-N was 3.99–4.52 mg/mg. Under the filtration velocities of 6, 10 and 14 m/hr, the maximum denitrification rate was 3.12, 4.86 and 4.42 g N/(m²·day), the half-saturation constant was 2.61, 1.05 and 1.17 mg/L, and the half-order coefficient was 0.22, 0.32 and 0.24 (mg/L)^1/2/min, respectively. The biofilm biomass increased with increasing filtration velocity and was 2845, 5124 and 7324 mg VSS/m² at filtration velocities of 6, 10 and 14 m/hr, respectively. The highest biofilm density was 44 mg/cm³ at the filtration velocity of 14 m/hr. Due to the low influent loading rate, biofilm biomass and thickness were lowest at the filtration velocity of 6 m/hr.     

混凝对微滤膜处理含磷废水的影响

采用直接微滤和混凝-微滤2种工艺对高浓度含磷废水进行了处理.结果表明,混凝预处理减轻了膜孔堵塞污染,改善了膜表面沉积层的存在形态,提高了膜的渗透通量;与原水直接微滤相比,混凝-微滤组合工艺改进了出水水质,磷酸盐的去除率从11.0%提高到99.7%,出水满足国家一级排放标准;经过相同方法清洗后,混凝-微滤工艺的膜通量能恢复到初始通量的90%以上,而直接微滤工艺的膜通量只能恢复到初始通量的72%.