Effects of Alkaline Cleaning Agents on the Long-Term Performance and Aging of Polyethersulfone Ultrafiltration Membranes Applied for Treatment of Car Wash Wastewater.

The commercial ultrafiltration polyethersulfone (PES) membranes (10 and 100 kDa) blended with polyvinylpyrrolidone (PVP) were applied for the filtration of car wash wastewater. Periodical membrane rinsing with water did not prevent fouling and a decrease in permeate flux was observed. Fouling was reduced by washing the membranes with cleaning agents, which are used in car washes to clean wheels and remove insects. In addition to surfactants, these agents contain NaOH, hence the pH value of cleaning solutions was over 11. Long-term contact with such solutions resulted in the removal of PVP from the membrane matrix and an increase in pore size. The PES membranes were soaked in an alkaline solution (pH = 11.5) for 20 months, after which the 200 kDa dextran rejection decreased from 95% to 80%. To compare with the static degradation conditions, 8 weeks of alkaline agent filtration was realized, after which the dextran (200 kDa) rejection decreased below 50%. This indicated that the cross-flow of alkaline agents can accelerate the removal of components building the membrane matrix. Despite membrane degradation, the separation efficiency (the rejection of chemical oxygen demand-COD, turbidity, and surfactants) during the treatment of synthetic car wash wastewater was similar to that obtained for pristine membranes.

Biogas Upgrading Using a Single-Membrane System: A Review.

In recent years, the use of biogas as a natural gas substitute has gained great attention. Typically, in addition to methane (CH4), biogas contains carbon dioxide (CO2), as well as small amounts of impurities, e.g., hydrogen sulfide (H2S), nitrogen (N2), oxygen (O2) and volatile organic compounds (VOCs). One of the latest trends in biogas purification is the application of membrane processes. However, literature reports are ambiguous regarding the specific requirement for biogas pretreatment prior to its upgrading using membranes. Therefore, the main aim of the present study was to comprehensively examine and discuss the most recent achievements in the use of single-membrane separation units for biogas upgrading. Performing a literature review allowed to indicate that, in recent years, considerable progress has been made on the use of polymeric membranes for this purpose. For instance, it has been documented that the application of thin-film composite (TFC) membranes with a swollen polyamide (PA) layer ensures the successful upgrading of raw biogas and eliminates the need for its pretreatment. The importance of the performed literature review is the inference drawn that biogas enrichment performed in a single step allows to obtain upgraded biogas that could be employed for household uses. Nevertheless, this solution may not be sufficient for obtaining high-purity gas at high recovery efficiency. Hence, in order to obtain biogas that could be used for applications designed for natural gas, a membrane cascade may be required. Moreover, it has been documented that a significant number of experimental studies have been focused on the upgrading of synthetic biogas; meanwhile, the data on the raw biogas are very limited. In addition, it has been noted that, although ceramic membranes demonstrate several advantages, experimental studies on their applications in single-membrane systems have been neglected. Summarizing the literature data, it can be concluded that, in order to thoroughly evaluate the presented issue, the long-term experimental studies on the upgrading of raw biogas with the use of polymeric and ceramic membranes in pilot-scale systems are required. The presented literature review has practical implications as it would be beneficial in supporting the development of membrane processes used for biogas upgrading.

The Resistance of Polyethersulfone Membranes on the Alkaline Cleaning Solutions.

Polyethersulfone (PES) is a polymer popularly used to produce ultrafiltration (UF) membranes. PES is relatively hydrophobic; thus, hydrophilic ingredients are added to the membrane matrix to reduce the fouling intensity. Ingredients such as polyvinylpyrrolidone (PVP) reduce the resistance of PES to NaOH solutions. This study investigated the possibility of using PES membranes for the separation of alkaline cleaning solutions. For this purpose, self-made PES membranes and commercial ultrafiltration PES membranes (UE10-10 kDa and UE50-100 kDa) containing PVP additive were used. The membranes were soaked for 18 months in alkaline (pH = 11.3-11.5) solutions of car washing fluids. It has been found that long-term contact with these solutions caused changes in the structure of the surface layer, especially of membranes containing PVP. As a result, the separation of dextran (100-200 kDa) decreased by 30-40% for PES membranes, 30-40% for UE10 and 40-60% for UE50. Despite these changes, the separation efficiency (rejection of COD, NTU and anionic surfactants) of synthetic car wash wastewater (mixture of surfactants and hydrowax) was similar to the results obtained for pristine membranes.

The Application of Polyethersulfone Ultrafiltration Membranes for Separation of Car Wash Wastewaters: Experiments and Modelling.

The wastewater generated as a result of car washes is considered a new source of water. However, recovered water must meet the required quality criteria for reuse. For this purpose, the ultrafiltration (UF) process can be successfully used. The main aim of the present work was to investigate the influence of the membrane's molecular weight cut-off (MWCO) on the UF performance in terms of the fouling phenomenon and retention degree of car wash wastewater. Moreover, for a better understanding of the fouling mechanisms, Hermia's model was used. The experimental studies were conducted with the use of two polyethersulfone (PES) membranes (MWCO of 10 kDa and 100 kDa). It has been noted that the used membranes provided a high-quality permeate and excellent turbidity removal, up to 99%. Moreover, it has been noted that the MWCO membrane has a significant impact on the fouling mechanism. Generally, a much greater intensity of fouling for the membrane with MWCO of 100 kDa was observed. Results obtained in the present study showed that both real wastewaters and the clean solutions used for washing cars cause the fouling phenomenon. It has been proven that rinsing the membranes with water is not sufficient to recover the initial membrane's performance. Hence, periodic chemical cleaning of the membranes was required. Fitting the experimental data to Hermia's model allowed us to indicate that membranes with MWCO of 100 kDa are more prone to intermediate blocking. To sum up, the findings suggest that for the UF of the car wash wastewater, the use of membranes with MWCO equal to 10 kDa is recommended.

Long-Term Performance of Ultrafiltration Membranes: Corrosion Fouling Aspect.

The past decade has seen a rise in the importance of the ultrafiltration (UF) technique in the separation of various complex solutions. However, the fouling phenomenon is the main limitation to faster process development. To the best of the authors' knowledge, the present paper is the first to aim to identify the role of corrosion fouling in long-term UF. For this purpose, polyvinylidene fluoride (PVDF) and polyethersulfone (PES) membranes were used. The investigations were carried out with the use of both pilot-scale and laboratory-scale units. Results obtained in the present study have clearly demonstrated that the oil concentration has a significant impact on the process performance. Indeed, it has been noted that a reduction in oil concentration from 160 to 100 mg/L resulted in an increase in the PVDF membrane flux from 57 to 77 L/m2h. In addition, it has been shown that the feed temperature has a significant influence on the UF performance. Importantly, it has been shown that corrosion fouling is of vital importance in UF membranes. Indeed, corrosion products such as iron oxides contaminated the membrane surface leading to an irreversible decrease in the UF process performance. In addition, it has been found that repeating the chemical cleaning of the membrane units significantly reduced the intensity of the fouling phenomenon. However, the complete elimination of its effects was not achieved. Therefore, it has been indicated that cleaning agents recommended by membrane manufacturers do not remove corrosion products deposited on the membrane surface. Undoubtedly, the obtained results can be used in the design of UF units leading to the extension of membrane installation lifetime.

Wettability Studies of Capillary PTFE Membranes Applied for Membrane Distillation.

In the present study, the membrane distillation (MD) process was studied with the use of commercial polytetrafluoroethylene (PTFE) capillary membranes. For this purpose, both solutions with NaCl concentrations up to 300 g/L and brines contaminated with oil (70-120 mg/L) were used as feeds. The membrane's wetting resistance was tested by conducting long-term experiments for over 3500 h. Using detailed studies, it has been shown that increasing the salt concentration from 35 to 300 g/L resulted in a 50% reduction in the permeate flux. Nevertheless, the membranes retained 100% of the salt rejection after 2000 h of the module's operation. Moreover, it has been found that performing the MD process with brines contaminated with oil (120 mg/L) led to the wetting of some membranes pores, which it turn resulted in an increase in the distillate's conductivity to 450 µS/cm after 700 h running the process. The mechanism of pore wetting by oil droplets adsorbed on the membrane's surface was presented. Finally, the proposed method of membrane cleaning with the use of a solvent allowed restoring the initial MD module's performance. Consequently, both the permeate flux and distillate conductivity were stable during the MD of the feed containing 35 g/L of NaCl over the next 280 h.

The Application of Cellulose Acetate Membranes for Separation of Fermentation Broths by the Reverse Osmosis: A Feasibility Study.

Recently, there has been a special research focus on the bioconversion of glycerol to 1,3-propanediol (1,3-PD) due to its significance in the chemical industry. However, the treatment and separation of fermentation broths is a great challenge. Currently, the reverse osmosis (RO) process is a reliable state-of-the-art technique for separation of biological solutions. This study (as the first to do so) investigated the feasibility of separation of 1,3-PD broths with the use of cellulose acetate (CA) membrane by the RO process. The experiments were carried out using the installation equipped with the plate module, under the transmembrane pressure (TMP) and temperature of 1 MPa and 298 K, respectively. It was found that the used membrane was suitable for broth separation. Indeed, it was noted that 1,3-PD, as a target product, migrated through the membrane; meanwhile, other broth components were rejected in various degrees. Moreover, it was proven that retention of carboxylic acids tended to increase with increasing molecular weight, according to the following order: succinic acid > lactic acid > acetic acid > formic acid. With regards to ions, retention degree increased with the increase of ionic radius and decrease of diffusion coefficient. Finally, it was demonstrated that the CA membrane is resistant to irreversible fouling, which has a positive effect on the economic viability of the process.

The Impact of Operational Parameters on Polypropylene Membrane Performance during the Separation of Oily Saline Wastewaters by the Membrane Distillation Process.

In the present study, membrane distillation (MD) was applied for the treatment of oily saline wastewaters produced on ships sailing the Baltic Sea. For comparison purposes, experiments were also carried out with model NaCl solutions, the Baltic Seawater and oil in water emulsions. The commercial Accurel PP V8/2 membranes (Membrana GmbH, Germany) were used. In order to investigate the impact of the operational parameters on the process performance, the experiments were conducted under various values of the feed flow velocity (from 0.03 to 0.12 m/s) and the feed temperature (from 323 to 343 K). The obtained results highlight the potential of PP membranes application for a stable and reliable long-term treatment of oily wastewater. It was demonstrated that the permeate flux increased significantly with increasing feed temperature. However, the lower temperature ensured the limited scaling phenomenon during the treatment of oily wastewaters. Likewise, increasing the feed flow velocity was beneficial to the increase in the flux. Moreover, it was found that performing a cyclic rinsing of the module with a 3% HCl solution is an effective method to maintain a satisfactory module performance. The present study sheds light on improving the MD for the treatment of oily wastewaters.

Membrane Distillation Crystallizer Applied for Separation of NaCl Solutions Contaminated with Oil.

In the present study, the membrane crystallizer was used to separate a saturated NaCl solution contaminated with an oil emulsion. The crystallizer was connected via a mesh separator with a feed tank in which capillary submerged modules were assembled. The effect of scaling and oil sorption on the wetting of polypropylene (PP) membranes has been investigated during the long-term studies. It has been found that cooling the solution in the crystallizer by 15 K below the feed temperature resulted in intensive NaCl crystallization in the zone below the mesh separator. A result, the salt crystallization on the membrane surface was eliminated. Contamination of saturated brines with oil in the concentration exceeding 100 mg/L caused the oil penetration into the membrane pores. The application of a PP net assembled on the capillary membranes surface reduced the intensity of wetting phenomenon caused by scaling and the oil sorption, which provides a stable membrane module performance during 1300 h test.

Membrane Distillation of Saline Water Contaminated with Oil and Surfactants.

Application of the membrane distillation (MD) process for the treatment of high-salinity solutions contaminated with oil and surfactants represents an interesting area of research. Therefore, the aim of this study is to investigate the effect of low-concentration surfactants in oil-contaminated high-salinity solutions on the MD process efficiency. For this purpose, hydrophobic capillary polypropylene (PP) membranes were tested during the long-term MD studies. Baltic Sea water and concentrated NaCl solutions were used as a feed. The feed water was contaminated with oil collected from bilge water and sodium dodecyl sulphate (SDS). It has been demonstrated that PP membranes were non-wetted during the separation of pure NaCl solutions over 960 h of the module exploitation. The presence of oil (100-150 mg/L) in concentrated NaCl solutions caused the adsorption of oil on the membranes surface and a decrease in the permeate flux of 30%. In turn, the presence of SDS (1.5-2.5 mg/L) in the oil-contaminated high-salinity solutions slightly accelerated the phenomenon of membrane wetting. The partial pores' wetting accelerated the internal scaling and affected degradation of the membrane's structure. Undoubtedly, the results obtained in the present study may have important implications for understanding the effect of low-concentration SDS on MD process efficiency.

The Use of NaOH Solutions for Fouling Control in a Membrane Bioreactor: A Feasibility Study.

Nowadays, the microbial production of 1,3-propanediol (1,3-PD) is recognized as preferable to the chemical synthesis. However, finding a technological approach allowing the production of 1,3-PD in the membrane bioreactor (MBR) is a great challenge. In the present study, a ceramic ultrafiltration (UF) membrane (8 kDa) for treatment of 1,3-PD broths was used. It has been demonstrated that the membrane used provides the stable permeate flux that is necessary to ensure the stability of the fermentation process in MBR technology. It was noticed that the broth pH has a significant impact on both the final 1,3-PD concentration and permeate flux. Moreover, the feasibility of using NaOH for fouling control in the MBR was evaluated. It has been shown that 1% NaOH solution is effective in restoring the initial membrane performance. To the best of our knowledge, this study is the first to shed light onto the possibility of reducing the amount of the alkaline solutions generated during the MBR operation. Indeed, it has been found that 1% NaOH solution can be successfully used several times for both membrane cleaning and to stabilize the broth pH. Finally, based on the results obtained, the technological conceptions of the MBR technology were designed.

Resistance of Polypropylene Membrane to Oil Fouling during Membrane Distillation.

The influence of oil emulsion presence in the water on the course of water desalination by membrane distillation was studied. The feed water was contaminated by oil collected from the bilge water. The impact of feed composition on the wetting resistance of hydrophobic polypropylene membranes was evaluated during long-term studies. Two types of the capillary membranes fabricated by thermally induced phase separation method were tested. It has been found that these membranes were non-wetted during the separation of NaCl solutions over a period of 500 h of modules exploitation. The addition of oil (5-100 mg/L) to the feed caused a progressive decline of the permeate flux up to 30%; however, the applied hydrophobic membranes retained their non-wettability for the consecutive 2400 h of the process operation. It was indicated that several compounds containing the carbonyl group were formed on the membranes surface during the process. These hydrophilic compounds facilitated the water adsorption on the surface of polypropylene which restricted the oil deposition on the membranes used.

Stability of Ar/O2 Plasma-Treated Polypropylene Membranes Applied for Membrane Distillation.

In the present work, Ar/O2 plasma treatment was used as a surface modification tool for polypropylene (PP) membranes. The effect of the plasma conditions on the properties of the modified PP surface has been investigated. For this purpose, the influence of gas composition and its flow rate, plasma power excitation as well as treatment time on the contact angle of PP membranes has been investigated. The properties of used membranes were determined after various periods of time: immediately after the modification process as well as after one, four and five years of storage. Moreover, the used membranes were evaluated in terms of their performance in long-term MD process. Through detailed studies, we demonstrated that the performed plasma treatment process effectively enhanced the performance of the modified membranes. In addition, it was shown that the surface modification did not affect the degradation of the membrane matrix. Indeed, the used membranes maintained stable process properties throughout the studied period.

Comparison of Polypropylene and Ceramic Microfiltration Membranes Applied for Separation of 1,3-PD Fermentation Broths and Saccharomyces cerevisiae Yeast Suspensions.

In recent years, microfiltration (MF) has gained great interest as an excellent technique for clarification of biological suspensions. This paper addresses a direct comparison of efficiency, performance and susceptibility to cleaning of the ceramic and polymeric MF membranes applied for purification of 1,3-propanediol (1,3-PD) fermentation broths and suspensions of yeast Saccharomyces cerevisiae. For this purpose, ceramic, titanium dioxide (TiO2) based membranes and polypropylene (PP) membranes were used. It has been found that both TiO2 and PP membranes provide sterile permeate during filtration of 1,3-PD broths. However, the ceramic membrane, due to the smaller pore diameter, allowed obtaining a better quality permeate. All the membranes used were highly susceptible to fouling with the components of the clarified broths and yeast suspensions. The significant impact of the feed flow velocity and fermentation broth composition on the relative permeate flux has been demonstrated. Suitable cleaning agents with selected concentration and duration of action effectively cleaned the ceramic membrane. In turn, the use of aggressive cleaning solutions led to degradation of the PP membranes matrix. Findings of this study add to a growing body of literature on the use of ceramic and polypropylene MF membranes for the clarification of biological suspensions.

Clarification of 1,3-Propanediol Fermentation Broths by Using a Ceramic Fine UF Membrane.

This work examined the use of a ceramic fine ultrafiltration (UF) membrane for the pre-treatment of 1,3-propanodiol (1,3-PD) fermentation broths. It has been demonstrated that the membrane used provides obtaining a high-quality, sterile permeate, which can be sequentially separated by other processes such as nanofiltration (NF) and membrane distillation (MD). Special attention was paid to the impact of the operational parameters on the membrane performance. The series of UF experiments under transmembrane pressure (TMP) from 0.1 to 0.4 MPa and feed flow rate (Q) from 200 to 400 dm3/h were performed. Moreover, the impact of the feed pH, in the range from 5 to 10, on the flux was investigated. It has been demonstrated that for fine UF, increasing the TMP is beneficial, and TMP equal to 0.4 MPa and Q of 400 dm3/h ensure the highest flux and its long-term stability. It has been shown that in terms of process efficiency, the most favorable pH of the broths is equal to 9.4. An effective and simple method of membrane cleaning was presented. Finally, the resistance-in-series model was applied to describe resistances that cause flux decline. Results obtained in this study can assist in improving the cost-effectiveness of the UF process of 1,3-PD fermentation broths.

Mitigation of Membrane Wetting by Applying a Low Temperature Membrane Distillation.

The formation of deposits on the membrane surface during membrane distillation is considered as one of the main reasons for membrane wetting. To assess the intensity of this phenomenon, long-term studies were performed comparing the membrane wettability with non-fouling feed (NaCl solutions) and feeds containing various foulants (lake and Baltic Sea water). The polypropylene membranes used were non-wetted by NaCl solutions during several hundred hours of water desalination. However, the occurrence of CaCO3 or other salt crystallization caused the membranes to be partially wetted, especially when periodical membrane cleaning was applied. The scaling intensity was significantly reduced by lowering the feed temperature from 353 to 315 K, which additionally resulted in the limitation of the degree of membrane wetting.

Cross-Flow Microfiltration of Glycerol Fermentation Broths with Citrobacter freundii.

This paper reports the study of the cross-flow microfiltration (MF) of glycerol fermentation broths with Citrobacter freundii bacteria. A single channel tubular ceramic membrane with a nominal pore size of 0.14 µm was used. It has been demonstrated that the MF ceramic membrane has been successfully applied to bacteria cell removal and to effectively eliminate colloidal particles from glycerol fermentation broths. However, due to fouling, the significant reduction of the MF performance has been demonstrated. In order to investigate the impact of transmembrane pressure (TMP) and feed flow rate (Q) on MF performance, 24 experiments have been performed. The highest steady state permeate flux (138.97 dm3/m2h) was achieved for 0.12 MPa and 1000 dm3/h. Fouling analysis has been studied based on the resistance-in series model. It has been found that the percentage of irreversible fouling resistance during the MF increases with increasing TMP and Q. The permeate flux regeneration has been achieved by membrane cleaning with 3 wt % NaOH and 3 wt % H3PO4 at 45 °C. The results of this study are expected to be useful in industrially employing the MF process as the first step of glycerol fermentation broth purification.

The Application of Submerged Modules for Membrane Distillation.

This paper deals with the efficiency of capillary modules without an external housing, which were used as submerged modules in the membrane distillation process. The commercial hydrophobic capillary membranes fabricated for the microfiltration process were applied. Several constructional variants of submerged modules were discussed. The influence of membrane arrangement, packing density, capillary diameter and length on the module performance was determined. The effect of process conditions, i.e., velocity and temperature of the streams, on the permeate flux was also evaluated. The submerged modules were located in the feed tank or in the distillate tank. It was found that much higher values of the permeate flux were obtained when the membranes were immersed in the feed with the distillate flowing inside the capillary membranes. The efficiency of submerged modules was additionally compared with the conventional membrane distillation (MD) capillary modules and a similar performance of both constructions was achieved.

The Influence of Talc Addition on the Performance of Polypropylene Membranes Formed by TIPS Method.

The effect of talc addition on the morphology of capillary membranes formed by a thermally induced phase separation (TIPS) method was investigated in the presented work. The usability of such formed membranes for membrane distillation was evaluated. Two types of commercial capillary polypropylene membranes, fabricated for microfiltration process, were applied in the studies. A linear arrangement of polymer chains was obtained in the walls of membranes formed without a talc addition. In the case of membranes blended with talc, the linear structure was disordered, and a more porous structure was obtained. The changes in morphology enhanced the mechanical properties of blended membranes, and their lower thermal degradation was observed during 350 h of membrane distillation studies. Long-term studies confirmed the stability of talc dispersion in the membrane matrix. A leaching of talc from polypropylene (PP) membranes was not found during the membrane distillation (MD) process.

The long-term studies of osmotic membrane distillation.

The results of osmotic membrane distillation carried out for 2.5 years were presented in this work. The influence of the process conditions, such as temperature and brine concentration on the permeate flux, was investigated. The saturated NaCl solutions and distilled water were used as a stripping solution and feed, respectively. A continuous regeneration of stripping solution was conducted using a method of natural evaporation from the surface of Bialecki rings to the air surrounding the installation. The possibilities of application of Accurel PP S6/2 hydrophobic polypropylene membranes were tested. It was studied whether a saturation stripping solution does not cause scaling and wettability of membranes. It was found that most of the pores in the used membranes were non-wetted, and the salt retention over 99% was maintained during a study period. However, the obtained permeate flux was decreased by 10-20%. The SEM examinations revealed that it was caused by amorphous deposit, which was formed on the membrane surface on the brine side. The SEM-EDS analysis demonstrated that the deposit composition mainly included Si and O.