Membrane-flocculation-adsorption hybrid system in wastewater treatment: micro and nano size organic matter removal .

Cross flow microfiltration with in-line flocculation reduces the fouling of membranes thus leading to high quality product water. A detailed experimental study conducted with an artificial suspension (particle size distribution similar to that of surface water) revealed that the filtration rate can be increased by several times by adopting in-line flocculation. In-line flocculation-microfiltration is therefore an attractive technique to reduce internal clogging while improving the permeate flux significantly. A detailed ultrafiltration (UF) study was conducted with biologically treated sewage effluent with pretreatment by flocculation and powdered activated carbon adsorption. The TOC removal by the NTR 7410 UF membrane alone was 43.6%. The TOC removal increased significantly by the use of pretreatment: 69.3% by flocculation and 91% by flocculation followed by adsorption. The organic colloidal portion (between 3,500 dalton and 0.45 microm) in the biologically treated effluent was removed up to more than 65% by the pretreatment of flocculation. The molecular weight of the biologically treated effluent ranged from 250 to about 3,573 dalton with the highest fraction in the range of 250-845 dalton. By the incorporation of pretreatment, the majority of both large and small molecular weight organic matter was removed. This hybrid system led to practically no filtration flux decline in membrane filtration.     

Organic colloids and their influence on low-pressure membrane filtration.

Wastewater treatment by low-pressure membrane filtration (MF and UF) is affected to a large extent by macromolecules and colloids. In order to investigate the influence of organic colloids on the membrane filtration process, colloids were isolated from a wastewater treatment plant effluent using a rotary-evaporation pre-concentration step followed by dialysis. Stirred cell tests were carried out using redissolved colloids, with and without additional glass fiber filtration. After constant pressure membrane filtration of 190 L/m2, the initial flux had declined by 50% for colloids > 6-8 kD (glass fiber filtered) with a hydrophilic MF membrane and for colloids > 12-14 kD (glass fiber filtered) with a hydrophobic MF membrane. For the non-filtered colloidal solutions, the flux decline was even steeper with the flux being below 10% of the initial flux after 190 L/m2 were passed through the membranes. As with larger particles, colloids form a filtration cake layer on top of the membrane surface when used as isolates without prior filtration. This filtration cake is easily removed during backwashing. However, polysaccharides as a macromolecular component of the colloid isolate cause severe fouling by the formation of a gel layer on the membrane surface that is difficult to remove completely.     

Membrane fouling and selectivity mechanisms in effluent ultrafiltration coupled with flocculation.

Membrane filtration is adequate for producing disinfected clear water suitable for various kinds of applications. However, fouling of membranes is the main limitation. The scope of the present study is to examine the effect of iron coagulation of primary wastewater effluent on membrane filtration, in parallel to fouling characterization of the iron itself. The fouling of ultrafiltration membranes by colloidal iron hydroxide-oxide has been studied by measuring the pore streaming potential of PES UF membrane. pH 5.5 (charge neutralization zone) provided better removal and lower fouling intensity than pH 7.8 (sweep coagulation zone), but the internal clogging at acidic pH was higher. Fouling of the membrane as measured by flux reduction was usually accompanied by a positive change in zeta potential and iso-electric point (IEP) of the membrane. An initially large change in zeta potential (without charge reversal) was seen even after relatively small amounts of iron solution were filtered through the membrane. A control experiment showed this is not due to iron adsorption equilibrium, but should probably be attributed to fouling. Change in zeta potential, can be used as an indicator for commencement of fouling even for small flux reductions. UF membrane critical flux after iron filtration can be evaluated more accurately by zeta potential than pressure drop or change in iron concentration.     

Evaluation of a MF membrane system composed of pre coagulation-sedimentation and chlorination for water reuse.

In this research, we investigated the variation of transmembrane pressure and permeate water quality in pre-coagulation and sedimentation with iron based coagulant, and chlorination of feed water for PVDF (Polyvinylidene fluoride) based MF membrane filtration. NaCIO was fed to the membrane module at a dosage of 0.5 mg/L and maintained during filtration. To observe the effect of raw water, three types of raw and processed waters, including river surface water, coagulated water and coagulated-settled water, were employed. In the case of river surface water, the transmembrane pressure increased abruptly in 500 hours operation. On the contrary, no significant increase in transmembrane pressure was observed for coagulated water and coagulated-settled water for 1200 hours operation. The turbidity of permeate was lower than the detection limit for all applied waters. The removal efficiency for humic substances in coagulated water and coagulated-settled water was approximately ten times higher than that in surface river water. And, the removal efficiency for TOC and DOC was approximately two times higher than that in surface river water. From the results of the operation, it can be observed that it is possible to maintain stable operation at 0.9 m(3)/m(2)-day filtration flux through a combination of pre-coagulation and pre-chlorination. However, the water quality of permeate was the best when the pre-coagulation-sedimentation process was combined with pre-chlorination. With respect to fouling reduction and operation efficiency increase in membrane filtration, the pre-coagulation/sedimentation process is a promising alternative.     

垃圾渗滤液膜浓缩液超声强化直接接触膜蒸馏处理工艺EI北大核心CSCD

为提高膜蒸馏在处理垃圾渗滤液膜浓缩液时渗透通量的稳定性,设计了一种新型的超声强化直接接触膜蒸馏(US-DCMD)装置,试验研究了超声对膜渗透通量的影响,并采用电子显微镜、X射线能量色散光谱等手段分析超声对膜面污染层的影响。试验结果表明:在60W的超声辐照条件下,渗透通量最高提升19.4%,并在膜溶液浓缩系数达到4时,相对渗透通量最高维持在77.1%,而未施加超声的相对渗透通量在膜溶液浓缩系数为2时降至20.7%;膜面的主要污染物为CaCO_(3)及腐殖酸,其中CaCO_(3)是限制膜渗透通量的主要因素;超声使污染层钙的质量分数从25.6%降至15.0%,并且不会引起有机物的降解或改性;超声辐照使膜面污染层不均匀且存在裂隙,减少了污染层厚度,维持了渗透通量的稳定。     

Resources and nutrients oriented greywater treatment for non-potable reuses

This paper evaluated the performance and suitability of a resources and nutrients oriented decentralized greywater treatment system which uses a submerged spiral wound module. This greywater treatment system is aimed at treating and recovering the resources present in the wastewater. The study revealed that the UF membrane filtration system was able to maintain a permeate flux between 6 and 10 L/m2/h. TOC can be reduced from the influent value of 161 to 28.6 mg/L in the permeate, meaning an average elimination rate of 83.4%. In addition, soluble nutrients such as ammonia and phosphorus can pass through the UF membrane and remain in the permeate. The total nitrogen and total phosphorus in the permeate were 16.7 and 6.7 mg/L respectively. The permeate was low in turbidity (below 1 NTU) and free of suspended solids and E. coli and had an excellent physical appearance. The permeate can be used in gardening and agriculture for irrigation and soil fertilization or alternatively for toilet flushing after disinfection. The retentate generated in this system can be treated with blackwater and kitchen waste in an anaerobic digester at a later stage for producing biogas or compost.     

KNT-artificial neural network model for flux prediction of ultrafiltration membrane producing drinking water.

This paper describes the prediction of flux behavior in an ultrafiltration (UF) membrane system using a Kalman neuro training (KNT) network model. The experimental data was obtained from operating a pilot plant of hollow fiber UF membrane with groundwater for 7 months. The network was trained using operating conditions such as inlet pressure, filtration duration, and feed water quality parameters including turbidity, temperature and UV254. Pre-processing of raw data allowed the normalized input data to be used in sigmoid activation functions. A neural network architecture was structured by modifying the number of hidden layers, neurons and learning iterations. The structure of KNT-neural network with 3 layers and 5 neurons allowed a good prediction of permeate flux by 0.997 of correlation coefficient during the learning phase. Also the validity of the designed model was evaluated with other experimental data not used during the training phase and nonlinear flux behavior was accurately estimated with 0.999 of correlation coefficient and a lower error of prediction in the testing phase. This good flux prediction can provide preliminary criteria in membrane design and set up the proper cleaning cycle in membrane operation. The KNT-artificial neural network is also expected to predict the variation of transmembrane pressure during filtration cycles and can be applied to automation and control of full scale treatment plants.     

Gas-phase photocatalytic oxidation of motor fuel oxygenated additives.

Methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) were oxidized in the gas phase by photocatalytic oxidation (PCO). Transient PCO was carried out at room temperature on TiO2 (Degussa P25), 0.2% Pt-TiO2, and 2% Pt-TiO2 catalysts. Surface-adsorbed reaction by-products were characterized by temperature-programmed desorption (TPD) and oxidation (TPO). Continuous flow PCO was also carried out at 373 K on TiO2. Acetone, H2O, and CO2 were the gas-phase products for PCO of TBA and MTBE, and formic acid was adsorbed on the TiO2 surface. Temperature-programmed desorption of TBA and MTBE formed 2-methyl-1-propene, water (TBA), and methanol (MTBE). During continuous-flow PCO, acetone desorbed in molar amounts equal to the amount of decomposed TBA and MTBE. The Pt/TiO2 catalysts had higher rates of complete oxidation during PCO and TPO. Injection of water during transient PCO increased the rates of oxidation of adsorbed TBA, formic acid, and acetone. Photocatalytic oxidation of TBA proceeded faster in humid air than dry air, but MTBE oxidation was less sensitive to humidity. The TiO2 catalyst was stable for MTBE, TBA, and acetone PCO at 373 K. The PCO at low conversions followed the Langmuir-Hinshelwood model.     

Photocatalytic degradation of di(2-ethylhexyl)phthalate adsorbed by chitin A.

Di(2-ethylhexyl)phthalate (DEHP) is a ubiquitous environmental contaminant due to its extensive use as a plasticiser and its persistence. Currently, there is no cost-effective treatment method for its removal from industrial wastewater. In a previous study, DEHP was effectively adsorbed from aqueous solution by biosorption onto chitinous materials. Biosorption can pre-concentrate DEHP from the aqueous phase for further treatment. As biosorption cannot degrade DEHP, in this study the degradation (and detoxification) of DEHP adsorbed onto chitinous material by photocatalytic oxidation (PCO) is attempted. PCO relies on hydroxyl radical (.OH), which is a strong oxidising agent, for the oxidative degradation of pollutants. It is a non-selective process which can degrade DEHP adsorbed onto chitinous material. The first part of this study is the optimisation of the degradation of adsorbed DEHP by PCO. Adsorption was carried out in the physicochemical conditions optimised in the previous study, with 500 mg/L chitin A and 40 mg/L DEHP at initial pH 2, 22+/-2 degrees C and 150 rpm agitation for 5 min. After optimisation of PCO, a 61% removal efficiency of 10 mg/L of DEHP was achieved within 45 min under 0.65 mW/cm2 of UV-A with 100 mg/L TiO2, and 10 mM of H2O2 at initial pH 12. The optimisation study showed that UV-A and TiO(2) are essential for the degradation of DEHP by PCO. The degradation intermediates/products were identified by GC-MS analysis. GC-MS results showed that the di(2-ethylhexyl) side chain was first degraded, producing phthalates with shorter side chains. Further reaction produced phathalic anhydride and aliphatic compounds such as alkanol and ester. The toxicities of parental and degradation intermediates in the solution phase and on chitinous materials were followed by the Microtox test. Results indicated that toxicity can be removed after 4 h treatment by PCO. Thus the decontamination of DEHP by integrating biosorption and PCO is feasible.     

Factors causing PAC cake fouling in PAC-MF (powdered activated carbon-microfiltration) water treatment systems.

Two pilot-scale powdered activated carbon-microfiltration (PAC-MF) reactors were operated using river water pretreated by a biofilter. A high permeate flux (4 m/d) was maintained in two reactors with different particle sizes of PAC. High concentration (20 g/L) in the PAC adsorption zone demonstrated 60-80% of organic removal rates. Analysis on the PAC cake fouling demonstrated that attached metal ions play more important role than organic matter attached on PAC to the increase of PAC cake resistance. Effects of factors which may cause PAC cake fouling in PAC-MF process were investigated and evaluated by batch experiments, further revealing that small particulates and metal ions in raw water impose prominent influence on the PAC cake layer formation. Fe (II) precipitates after being oxidized to Fe (III) during PAC adsorption and thus Fe(ll) colloids display more significant effect than other metal ions. At a high flux, PAC cake layer demonstrated a higher resistance with larger PAC due to association among colloids, metals and PAC particles, and easy migration of small particles in raw water into the void space in the PAC cake layer. Larger PAC possesses much more non-uniform particle size distribution and larger void space, making it easier for small colloids to migrate into the voids and for metal ions to associate with PAC particles by bridge effect, hence speeding up and intensifying the of PAC cake fouling on membrane surface.     

Photocatalytic removal of cyanide with illuminated TiO(2)

Effects of TiO(2) dosage, pH and initial cyanide concentration on the removal efficiency of cyanide from aqueous solutions with illuminated TiO(2) have been investigated. Adsorption and oxidation were recognized as significant processes for the elimination of cyanide. From the Langmuir isotherm, the maximum adsorption capacity was determined as 17.24 mg/g at pH 7. Adsorbed amount of cyanide slightly increased as the TiO(2) dosage increased. However, as no significant increase was observed above 1 g/L TiO(2), an optimum TiO(2) dosage was determined as 1 g/L. Photocatalytic oxidation efficiency of cyanide was greatly affected by the solution pH. It increased as the solution pH decreased. The photocatalytic oxidation efficiency after 120 min was 80.4% at pH 3 while it was only 20.4% at pH 11. Photocatalytic oxidation of cyanide was well described by the second-order kinetics. Photocatalytic reaction with illuminated TiO(2) can be effectively applied to treat industrial wastewater contaminated with cyanide.     

Membrane Process Design for the Reduction of Wastewater Color of the Mazandaran Pulp-Paper Industry, Iran

The aim of this study is evaluate the use of membrane bioreactor for wastewater treatment Mazandaran pulp and paper Industry. The qualification of wastewater is case study and Characteristics of this industry wastewater were determined by different experiments such as: COD, BOD, Color, densitometry, viscometry and TG/DTA analyzer. Also, the color creating agents in the investigated wastewater was characterized. Then In this study, flux, retention, and permeate quality of various Nanofiltration and low-pressure reverse osmosis membranes were investigated at two temperatures and by using a low shear (DSS Labstak M20®) and a high shear (CR250/2) filter. The overall aim was to study the suitability of Nanofiltration in purification of the discharge water from external activated sludge processes in the pulp and paper industry for reuse in the paper manufacturing process and to compare the results to Nanofiltration of paper machine process waters. The discharge waters were nanofiltered at a higher flux than paper machine process waters. The permeate was almost free of color and organic compounds but contained significantly more inorganic compounds than the permeate from the filtration of process waters. To successfully remove monovalent anions and inorganic carbon from the discharge water a low-pressure reverse osmosis membrane such as the TFC ULP membrane is needed. With that membrane the permeate flux is lower than for Nanofiltration membranes but the permeate quality is significantly better when considering inorganic ions such as sodium, chloride, nitrate and inorganic carbon (bicarbonate). The permeate flux was two times higher in the high shear filter than in the low shear filter but the retentions were significantly lower. The result of this study: decrease pollutants parameter in Tajan Rivers that is effluent because attention to surface water quality has limited in Iran.     

Optimization study of a hybrid alum coagulation-membrane filtration system for virus removal

Due to the intrinsically small sizes of enteric viruses (20-100 nm) and their relatively high resistance to most disinfectants, detection of viruses in treated drinking water is not a rare phenomenon. This study therefore evaluates various aspects involved in a hybrid alum coagulation-ultrafiltration (UF) system for virus removal. Coagulant doses (0, 1 and 10 mg Al(3+)/L) and pH conditions relevant to drinking water (pH 6-8) were investigated. With this hybrid system, removal was not attributable merely to MS2 adsorption to flocs and subsequent retention by UF membranes. MS2 removal comprises of inactivation by the effect of pH and coagulant and subsequently, rejection of virus-associated flocs by UF membrane. Coagulation with 1 mg Al(3+)/L at pH 6 and 7 resulted in an overall reduction brought about by an average of 0.62 log inactivation via the pH effect, 1.2 log inactivation by alum coagulant, and >5.4 log rejection by the 100 kDa polyethersulfone UF membrane. In contrast, negligible upstream inactivation was noted with a coagulant dose of 1 mg Al(3+)/L at pH 8, but 5.8 log rejection was attained with downstream UF filtration. By optimizing the conditions appropriate for upstream inactivation and subsequent membrane rejection, virus removal efficiencies can be enhanced.     

The adsorption and photodegradation of oxalic acid at the TiO2 surface.

ATR-FTIR measurements in combination with quantum chemical calculations were performed to study chemical reactions taking place at the surface of a thin TiO2 layer immersed in an aqueous oxalic acid solution under UV(A) illumination. It was found that the adsorption of oxalic acid on TiO2 in the dark can be explained in terms of two surface complexes for the anatase phase. Under UV(A) illumination, one of the adsorbed species on the anatase phase preferably undergoes photo-degradation and at the same time more molecules of oxalic acid are adsorbed at the TiO2 surface which is thus enriched in the second complexation mode. The spectral changes observed under UV(A) illumination are explained in the light of different theories: photo-desorption of water molecules as a thermal mechanism induced by the absorption of photons, surface reconstruction, and newly exposed surface area provided by the de-aggregation of the TiO2 particles.     

Membrane filtration for tertiary treatment of biologically treated effluents from the pulp and paper industry.

Discharge waters from activated sludge processes in the pulp and paper industry and from a municipal wastewater treatment plant were filtered with various nanofiltration (NF) and low pressure reverse osmosis (RO) membranes. The purpose was to study flux, retention, and permeate quality after membrane filtration by using a high shear (CR-250/2) filter. The suitability of the achieved permeates for reuse at the industrial site is also discussed. The NF permeate was practically free from colour and organic compounds but contained significant amount of inorganic compounds e.g. chloride ions, especially when a high amount of sulphate containing discharge waters were filtered, in which case a low pressure RO membrane was needed to successfully remove monovalent anions. Organic compounds were almost completely retained by NF and RO membranes and organic carbon in the permeate was less than 10 mg/dm3 on average. The achieved permeate can easily be reused in paper production. Nanofiltration has a significantly higher flux and also a lower fouling tendency than reverse osmosis but it passes through monovalent ions when there is a high sulphate concentration in the water. Therefore, RO might be needed in such cases to produce excellent process water.     

Modification of granular activated carbon using low molecular weight polymer for enhanced removal of Cu(2+) from aqueous solution.

Palm shell activated carbon was modified via surface impregnation with polyethyleneimine (PEI) to enhance removal of Cu(2+) from aqueous solution in this study. The effect of PEI modification on batch adsorption of Cu(2+) as well as the equilibrium behavior of adsorption of metal ions on activated carbon were investigated. PEI modification clearly increased the Cu(2+) adsorption capacities by 68% and 75.86% for initial solution pH of 3 and 5 respectively. The adsorption data of Cu(2+) on both virgin and PEI-modified AC for both initial solution pH of 3 and 5 fitted the Langmuir and Redlich-Peterson isotherms considerably better than the Freundlich isotherm.     

Membrane bioreactors for water reclamation.

Singapore has been using dual membrane technology (MF/UF RO) to produce high-grade water (NEWater) from secondary treated sewage. Membrane bioreactor (MBR) has very high potential and will lead to the further improvement of the productivity and quality of high-grade water. This study was focused on the technical feasibility of MBR system for water reclamation in Singapore, making a comparison between various membrane systems available and to get operational experience in terms of membrane cleaning and other issues. Three MBR plants were built at Bedok Water Reclamation Plant with a design flow of 300 m3/day each. They were commissioned in March 2003. Three different types of submerged membranes were tested. They are Membrane A, plate sheet membrane with pore size of 0.4 microm; Membrane B, hollow fibre membrane with pore size of 0.4 microm; and Membrane C, hollow fibre membrane with pore size of 0.035 microm. The permeate quality of all the three MBR Systems were found equivalent to or better than that of the conventional tertiary treatment by ultrafiltration. MBR permeate TOC was about 2 mg/l lower than UF permeate TOC. GC-MS, GC-ECD and HPLC scan results show that trace organic contaminants in MBR permeate and UF permeate were in the same range. MBR power consumption can be less than 1 kwh/m3. Gel layer or dynamic membrane generated on the submerged membrane surface played an important role for the lower MBR permeate TOC than the supernatant TOC in the membrane tank. Intensive chemical cleaning can temporarily remove this layer. During normal operation conditions, the formation of dynamic membrane may need one day to obtain the steady low TOC levels in MBR permeate.     

Nanofiltration process of glyphosate simulated wastewater

Nanofiltration separation of glyphosate simulated wastewater was investigated using a DK membrane. The effects of operating parameters and the addition of impurities on membrane performance were studied in detail. It was found that at 20 °C, with a glyphosate concentration of 500 mg/L and pH of 2.96, the glyphosate retention rate and the membrane permeate flux increased slightly with increasing transmembrane pressure. With an increase in operating temperature, the permeate flux increased linearly while the retention rate decreased. The permeate flux and glyphosate retention rate decreased with increasing feed concentration. Within the pH range of 3-5, the glyphosate retention rate decreases with increasing pH and reaches a minimum at the isoelectric point of the membrane, while the permeate flux reaches a maximum level at this point. In the pH range of 5-11, with the increases of pH, the glyphosate retention rate increases and the permeate flux decreases. Glyphosate retention decreases slightly with increasing NaCl and phosphite concentrations. This can be explained in terms of the shielding phenomenon.     

An integrated wastewater reuse concept combining natural reclamation techniques, membrane filtration and metal oxide adsorption.

In a Sino-German research project, a sustainable water reclamation concept was developed for different applications of municipal water reuse at the Olympic Green 2008 in Beijing, China. Results from pilot-scale experiments in Beijing and Berlin show that selective nutrient removal by adsorption onto granular ferric hydroxide (GFH) after a membrane bioreactor (MBR) can maintain a total phosphorus concentration of <0.03 microg L(-1) P, thus preventing eutrophication of artificial lakes. Operation time of GFH adsorption columns can be extended by regeneration using sodium hydroxide solution. A subsequent ultrafiltration (UF) membrane after bank filtration creates an additional barrier for pathogens and allows for further urban reuse applications such as toilet flushing. Short term bank / bio-filtration prior to UF is shown to effectively remove biopolymers and reduce membrane fouling.     

Particle count and size alteration for membrane fouling reduction in non-conventional water filtration.

If coagulation is not completely successful and produces aggregates which are too small, fouling may increase. In some cases, a deep-bed filter could perhaps provide a solution. The paper examines these effects using experimental results for different waters. Activated sludge effluents, stormy seawater containing microalgae and spent filter backwash water (SFBW) were coagulated by alum or ferric chloride. Sand filtration tests were carried out. Tests were performed in a membrane filtration stirred cell, filtration pilot plant equipped with SDI analyzer (seawater) and pilot UF plant (SFBW). For activated sludge effluent, alum residual ratio curves of turbidity and total particle count (TPC) followed one another. With ferric chloride, low coagulant dosage showed negative turbidity removal. Contact granular filtration reduced membrane fouling intensity. Increasing the dose resulted in higher improvement in membrane flux. For seawater, a filter run period under storm conditions reached 35 hours with satisfactory filtrate quality. An iron chloride dose of 0.3 mg/l during normal conditions and 0.5 mg/l for stormy condition should be injected, mixed well before the filters, while maintaining 10 m/hr filtration rate and pH 6.8 value. For SFBW, alum flocculation pretreatment of SFBW was effective in reducing turbidity, TPC, viruses and protozoa. SFBW settling prior to flocculation did not enhance turbidity and TPC removal. The largest remaining particle fraction after alum flocculation was 3-10 microm in size, both Cryptosporidium and Giardia are found in this size range. Coagulation enhanced the removal of small size particles, a positive impact on reducing membrane fouling potential.