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 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.

The Application of the Nanofiltration Membrane NF270 for Separation of Fermentation Broths.

The potential for nanofiltration (NF) in removing both relatively low molecular weight (MW) organic species and charged solutes from complex media is noteworthy. The main aim of the current work was to improve understanding of the separation mechanisms of fermentation broths components in the NF process. For this purpose, the experimental investigations were performed using the commercial polyamide NF270 membrane. The feed solution was ultrafiltered 1,3-propanediol (1,3-PD) broths. The separation results were analyzed and discussed in light of the detailed characteristics of both the membrane and the broth components. It has been noted that the membrane ensured the complete 1,3-PD permeability and significant rejection of some feed components. A thorough analysis showed that the retention of carboxylic acids was based on both the Donnan effect and sieve mechanism, according to the following order: succinic acid > lactic acid > acetic acid > formic acid. Indeed, acids retention increased with increasing charged acids ions valency, Stokes radius (rS) as well as MW, and decreasing diffusion coefficient (D). In turn, for ions, the following orders retention was determined: SO42− = PO43− > Cl− and Ca2+ > Na+ > NH4+ ~ K+. It indicated that the ions retention increased with increasing ions charge density, hydrated radius (rH), and hydration energy (Eh). It showed that the separation of the ions was based on the Donnan exclusion, sieving effect, and dielectric exclusion.

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 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.

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.

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.