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Membrane science and technology is growing rapidly worldwide and continues to play an increasingly important role in diverse fields by offering high separation efficiency with low energy consumption. Membranes have also shown great promise for “green” separation. A majority of the investigations in the field are devoted to the membrane fabrication and modification with the ultimate goals of enhancing the properties and separation performance of membranes. However, less attention has been paid to membrane life cycle management, particularly at the end of service. This is becoming very important, especially taking into account the trends toward sustainable development and carbon neutrality. On the contrary, this can be a great opportunity considering the large variety of membrane processes, especially in terms of the size and capacity of plants in operation. This work aims to highlight the prominent aspects that govern membrane life cycle management with special attention to life cycle assessment (LCA). While fabrication, application, and recycling are the three key aspects of LCA, we focus here on membrane (module) recycling at the end of life by elucidating the relevant aspects, potential criteria, and strategies that effectively contribute to the achievement of green development and sustainability goals.

The relationship between the solvent–solute interaction and permeation properties is fundamental in the development of the forward osmosis (FO) membrane. In this study, we report on the quantitative reproduction of the permeation flux, which has different solvent–solute interactions, through the modeled FO membrane by non-equilibrium molecular dynamics (NEMD). The interaction effect was investigated by changing the interatomic interaction between the solute and the solvent. The calculated permeation through the semi-permeable modeled FO membrane, in which the interaction between solvent and solution is equal to that between solutions, was consistent with the theoretical curve derived from the combination of the permeation flux and Van’t Hoff equations. These results validate the NEMD for the evaluation of permeation in FO. On the other hand, the permeation is much derived from the theoretical values when the interaction between the solvent and solute atoms is relatively large. However, the simulated permeation was consistent with the theoretical curve, correcting the solution concentration by the coordination number of the solvent atoms to the solute atoms. Our results imply that permeation flux through the FO membrane is significantly changed by the interaction between the solute and the solvent and can be theoretically predicted by calculating the coordination number of the solvent to the solute, which can be readily estimated by equilibrium molecular dynamics simulation.

In this study, a technical scheme of an ammonium recovery process from diluted municipal or industrial wastewaters was developed, and the main operational parameters of adsorption/desorption and air-stripping/acid-scrubbing or membrane units were examined. The proposed approach combines the removal of ammonium nitrogen by an ion-exchange mechanism on metakaolin-based geopolymers (MKGPs) followed by adsorbent regeneration. A regeneration agent was purified by the air-stripping technique or membrane technology. A ready-to-use market-grade fertilizer or industrial-grade ammonia water could be obtained as the final product. The properties and regeneration ability of MKGP, prepared from activated kaolinite clay, were compared with new geopolymer adsorbents based on papermill sludge (FS MKGP). Adsorption fixed-bed column experiments with continuously circulated regeneration solution purified by air-stripping or the membrane approach were conducted to determine the limits of the regeneration solution’s application. Sodium and potassium salts were tested as regeneration agents, and the influence of regeneration solution composition on ammonium removal and recovery rates was investigated. Based on a breakthrough curve analysis, the removal rate of ammonium N by FS MKGP was found to be 3.2 times higher than that by MKGP for actual wastewater samples. Moreover, there were substantial differences in the regeneration regime between the two adsorbents. For the air-stripping technique, a liquid-phase temperature of 45°C was minimal and enough for efficient ammonia transfer to the gaseous phase. For the membrane technique, a feed-phase temperature of 40°C was enough for removing ammonia from the regeneration solution, while no heating of a receiving phase was required.

The co-deposition between polyphenols and amines has been demonstrated in order to prepare positively charged nanofiltration (NF) membranes for multivalent cation rejection in recent years; however, the low reactivities of the involved polyphenols usually cause a long co-deposition time and unsatisfactory rejection. Herein, a novel plant polyphenol (PG) was co-deposited with tetraethylenepentamine (TEPA) in a much shorter time period to prepare positively charged NF with high multivalent cation rejection membranes. The performance of the co-deposition membranes can be easily controlled by adjusting the mass ratio of PG and TEPA, reaction time, and pH value of the buffer solution. The optimal membrane, prepared under a polyphenol and polyamine mass ratio of 1:1, coating time of 2 h, and pH value of 8.0, shows a decent pure water permeability of 8.43 L m−2 h−1 bar−1 while maintaining a superior 96.24% MgCl2 rejection. More importantly, the universality of this method was corroborated by employing other amines with different molecular weights in the co-deposition. This work provides new insights for the preparation of high-performance positively charged NF membranes.

The decomposition of volatile organic compounds by photocatalytic oxidation (PCO) has been widely studied. However, the technological development of this oxidative technique has to address how to handle the formation of transformation products. The work presented here investigates the original combination of a dense membrane separation process and PCO to intensify the trapping and reduction of PCO transformation products. Specific monitoring of toluene PCO transformation products, such as benzene and formaldehyde, in the outflow of both permeate and retentate compartments was proposed. The influence of operating parameters on the process, i.e., light intensity, pressure, membrane type, and catalyst mass, was also studied. The results reveal that membrane separation-PCO hybridization is particularly effective for reducing the presence of benzene and formaldehyde in the effluent treated. The benzene concentration in the outflow of the hybrid module can be reduced by a factor of 120 compared to that observed during the PCO of toluene alone.

This work was aimed at researching and developing a computer model, as well as an optimization and control algorithm for calculating pore shapes for separating membranes in separation processes. Two types of flow fluid rates through separation membranes with various pores configurations were considered. Here, the first type of pores had the form of a tortuous channel with sharp narrowing endings, which, in turn, could be assumed as “zero” wall thickness holes. The second type of pores had conical narrowing at the ends, which is closer to the real shape of the pores. As a result of the analysis of the performed calculations and models, data were obtained on the effect of the thickness of the selective layer on the performance of the membrane. In computer calculations, it was determined that the optimal volumetric porosity should be limited to 0.15, which affects the mechanical strength of the membrane. Calculations were also carried out on the Chemcad software product, which resulted in graphs of the optimal permeability of various liquids, depending on the differ curvature and pore volume of the separation membranes.

Separating carbon dioxide (CO2) from gaseous streams released into the atmosphere is becoming critical due to its greenhouse effect. Membrane technology is one of the promising technologies for CO2 capture. SAPO-34 filler was incorporated in polymeric media to synthesize mixed matrix membrane (MMM) and enhance the CO2 separation performance of this process. Despite relatively extensive experimental studies, there are limited studies that cover the modeling aspects of CO2 capture by MMMs. This research applies a special type of machine learning modeling scenario, namely, cascade neural networks (CNN), to simulate as well as compare the CO2/CH4 selectivity of a wide range of MMMs containing SAPO-34 zeolite. A combination of trial-and-error analysis and statistical accuracy monitoring has been applied to fine-tune the CNN topology. It was found that the CNN with a 4-11-1 topology has the highest accuracy for the modeling of the considered task. The designed CNN model is able to precisely predict the CO2/CH4 selectivity of seven different MMMs in a broad range of filler concentrations, pressures, and temperatures. The model predicts 118 actual measurements of CO2/CH4 selectivity with an outstanding accuracy (i.e., AARD = 2.92%, MSE = 1.55, R = 0.9964).

A key problem associated with the design of graphene oxide (GO) materials and their tuning for nanoscale separations is how specific functional groups influence the competitive adsorption of solvated ions and water at liquid/graphene interfaces. Computation accompanied by experiment shows that OH and COOH exert an influence on water adsorption properties stronger than that of O and H functional groups. The COO– anions, following COOH deprotonation, stabilize Pb(II) through strong electrostatic interactions. This suggests that, among the functional groups under study, COOH offers the best Pb(II) adsorption capacity and the ability to regenerate the sorbent through a pH swing. In line with computation, striking experimental observations revealed that a substantial increase in Pb(II) adsorption occurs with increasing pH. Our findings provide a systematic framework for controlled design and implementation of regenerable C-based sorbents used in separations and desalination.

Ag+ was introduced into *BEA‐type zeolite membrane by an ion‐exchange method to enhance olefin selectivity. Ag−*BEA membrane exhibited superior olefin separation performance for both ethylene/ethane and propylene/propane mixtures. Particularly, the separation factor for ethylene at 373 K reached 57 with the ethylene permeance of 1.6×10−7 mol m−2 s−1 Pa−1. Adsorption properties of olefin and paraffin were evaluated to discuss contribution of Ag+ to separation performance enhancement. A strong interaction between olefin and Ag+ in the membrane caused preferential adsorption of olefin against paraffin, leading to selective permeation of olefin. Ag−*BEA membrane also exhibited high olefin selectivities from olefin/N2 mixtures. The affinity‐based separation through Ag−*BEA membrane showed a high potential for olefin recovery and purification from various gas mixtures., Ag−*BEA membrane for olefin recovery: Ag+ was introduced into *BEA‐type zeolite membrane. We found that such a membrane exhibited superior ethylene and propylene selectivities. Ag−*BEA membrane had a high potential for olefin recovery from various gas mixtures.

In this paper, the effect of time, aeration scheme, aeration rate, and mixed liquor suspended solid (MLSS) concentration on the permeate flux in membrane bioreactors have been studied. Aeration rates of 0.5, 1.0, and 1.5 LPM were tested with MLSS concentrations of 5, 10, and 15 g/L. Furthermore, a continuous and pulsed aeration scheme (5 min on and 5 min off) was tested. The experimental data were used to develop an artificial neural network (ANN) model, which showed excellent agreement (R2 = 0.9963) with the data. The average normalized flux decreased as the MLSS concentration increased from 5 to 15 g/L and increased as the aeration rate increased from 0.5 to 1.5 LPM. No clear correlation was found between the aeration schemes and the average normalized flux. ANN weights analysis revealed the order of importance was time > aeration rate > MLSS concentration > aeration scheme. 2021 Desalination Publications. All rights reserved. Scopus

To handle the rising amount of plastic waste in the environment, new technologies are necessary to recover the value of this resource. Chemical recycling is one option to treat mixed and multi-layer plastic waste streams. Emerging technologies works e.g. with pyrolysis (via thermal or catalytic cracking) of the plastic waste streams and results in multi-material output streams. Membranes are a widely adopted and a relevant technology for bulk separations, within chemical recycling operations. Based on a different separation principle, they need less thermal energy than e.g. distillation columns. However, when it comes to their contribution to the environmental impact of the whole process chain, membranes need special attention. Compared to installed process units, such as pyrolysis and catalytic upgrading reactors, membranes have a shortened life time (non-permanent) compared to the whole process chain and need extra treatments to avoid fouling and maintain their efficiency. These points make it challenging to integrate a LCA model representing membranes within the whole LCA process model. In this paper a framework for the LCA of membranes will be presented regarding their impact in a chemical recycling process and how a shortened life time model can be integrated into a longer life LCA process model with focus on the handling of the different time scales.

We analysed the effectiveness of transvaginal ultrasonographic and foetal/maternal pulse Doppler findings as predictors of labour onset within 1 week. We included 22 single normal pregnancies and evaluated the one-point and short- and long-term differences in uterine artery pulsatility index (PI), umbilical artery PI, middle cerebral artery PI (MCA-PI), peak systolic velocity, and cervical length (CL). Presence of funnelling and membrane separation over the internal cervical os was evaluated. Significant changes were observed in the one-point measurement of and short-term and long-term differences in CL, the one-point measurement of and long-term difference in MCA-PI, and the presence of membrane separation (Grade 2). In multivariate analysis, the significant predictors were short-term differences in CL (odds ratio [OR]: 5.27), long-term differences in MCA-PI (OR: 13.3), and presence of membrane separation (Grade 2) (OR: 5.38). Transvaginal ultrasonographic and foetal pulse Doppler findings were effective predictors of labour onset within 1 week., Impact statement, What is already known on this subject? Parameters reported to predict labour onset include the Bishop score, cervical length, decreased long-term cervical length, funnelling of the internal cervical os, and adrenal gland volume., What do the results of this study add?Short-term changes in cervical length, long-term changes in middle cerebral artery pulsatility index, and the presence of membrane separation Grade 2 were found to be useful predictive factors of labour onset in this study., What are the implications of these findings for clinical practice and/or further research? The prediction of labour onset enables clinicians to properly manage pregnancy and delivery considering maternal and foetal conditions.

Carbon capture has been an important topic of the twenty-first century because of the elevating carbon dioxide (CO2) levels in the atmosphere. CO2 in the atmosphere is above 420 parts per million (ppm) as of 2022, 70 ppm higher than 50 years ago. Carbon capture research and development has mostly been centered around higher concentration flue gas streams. For example, flue gas streams from steel and cement industries have been largely ignored due to lower associated CO2 concentrations and higher capture and processing costs. Capture technologies such as solvent-based, adsorption-based, cryogenic distillation, and pressure-swing adsorption are under research, but many suffer from higher costs and life cycle impacts. Membrane-based capture processes are considered cost-effective and environmentally friendly alternatives. Over the past three decades, our research group at Idaho National Laboratory has led the development of several polyphosphazene polymer chemistries and has demonstrated their selectivity for CO2 over nitrogen (N2). Poly[bis((2-methoxyethoxy)ethoxy)phosphazene] (MEEP) has shown the highest selectivity. A comprehensive life cycle assessment (LCA) was performed to determine the life cycle feasibility of the MEEP polymer material compared to other CO2-selective membranes and separation processes. The MEEP-based membrane processes emit at least 42% less equivalent CO2 than Pebax-based membrane processes. Similarly, MEEP-based membrane processes produce 34–72% less CO2 than conventional separation processes. In all studied categories, MEEP-based membranes report lower emissions than Pebax-based membranes and conventional separation processes.

Metal-organic framework (MOF) membranes have demonstrated high efficiency for CO2 capture due to their wide range of pore sizes, high surface area, high porosity, and open metal sites. In this work, we propose a multi-scale design framework of MOF-based membrane separation for CO2/CH4 mixture via integration of molecular simulation, machine learning, and process modelling and simulation. The GCMC and MD molecular simulation is first used to evaluate adsorption isotherms, isosteric adsorption heat, self-diffusivity, activation energy, permeability, and selectivity of a MOF-based membrane (e.g., IRMOF-1) for CO2/CH4 separation at different operating conditions. It is found that the simulated isotherms at 298 K are consistent with experimental results. CO2 permeability can range from 4.090 × 104 to 3.818 × 105 barrer with variation in operating conditions. The same phenomenon is also reflected in the selectivity. We then establish prediction models of adsorption capacity and self-diffusivity using machine learning methods such as artificial neural network (ANN), which are used to calculate the permeability. The mean squared error is 0.0086, and the coefficient of determination is 0.9822. The proposed ANN models are integrated with the tanks-in-series model of a hollow fiber membrane separation process, which is simulated using the finite volume method. Three case studies illustrate the feasibility and superiority of the proposed integrated framework.

The widely used dyes in the pharmaceutical, chemical, and medical industries have brought about an intensive concern for the sustainable development of the environment. Membrane separation offers a versatile method for classified recycling and the reuse of residual components. In this work, polyimide membranes were synthesized via the polymerization of 4,4′-(hexafluor-isopropylidene) diphthalic anhydride and 1,4-bis (4-aminophenoxy) benzene diamine. The organic solvent nanofiltration membrane was prepared by casting onto a glass plate and precipitating in the non-solvent phase. The properties of the membranes were recorded by FTIR, 1HNMR, TGA, and GPC. The molecular simulations were carried out to analyze the affinity between the membrane and different solvents. The membrane was used in the removal of Rose Bengal, methyl blue, Victoria blue B, and crystal violet from methanol. The effects of the feed liquid concentration, operating pressure, swelling degree, organic solvent resistance, and long-term running on the membrane performance were studied. Results showed that membranes prepared in this work demonstrated high solvent permeation and dye rejection due to the sieving effect and solvent affinity. For methyl blue, the solvent performance achieved a permeability of 2.18 L∙m−2∙h−1∙bar−1 corresponding to a rejection ratio of 94.2%. Furthermore, the membrane exhibited good stability over 60 h of continued testing. These results recommend a potential strategy in the development of a suitable monomer to prepare a polyimide membrane for dye separation.

PEGylated proteins are usually purified using chromatographic methods, which are limited in terms of both speed and scalability. In this paper, we describe a microfiltration membrane-based hybrid method for purifying PEGylated proteins. Polyethylene glycol (or PEG) is a lower critical solution temperature polymer which undergoes phase transition in the presence of a lyotropic salt and forms micelle-like structures which are several microns in size. In the proposed hybrid method, the PEGylated proteins are first converted to their micellar form by the addition of a lyotropic salt (1.65 M ammonium sulfate). While the micelles are retained using a microfiltration membrane, soluble impurities such as the unmodified protein are washed out through the membrane. The PEGylated proteins thus retained by the membrane are recovered by solubilizing them by removing the lyotropic salt. Further, by precisely controlling the salt removal, the different PEGylated forms of the protein, i.e., mono-PEGylated and di-PEGylated forms, are fractionated from each other. Hybrid separation using two different types of microfiltration membrane devices, i.e., a stirred cell and a tangential flow filtration device, are examined in this paper. The membrane-based hybrid method for purifying PEGylated proteins is both fast and scalable.

In this research, the membrane separation process was used to separate helium from methane gas. In order to do this, computational fluid dynamics (CFD) was used, and the effect of process parameters on the performance of the membrane separation process was studied by this method. To simulate the hydrodynamics of flow in the channel, the Navier-Stokes equation was used, and the Maxwell-Stefan equation was applied to simulate the mass transfer phenomenon. In addition, Fick’s law was utilized to simulate mass transfer in the membrane domain. The impacts of significant parameters such as feed pressure, feed flow rate, and feed concentration on parameters such as He/CH4 separation factor, methane and helium membrane flux and helium mole fraction in permeate stream were studied. The results of the simulation indicated that the feed pressure of 10 bar, feed flow rate of 120 cm3 min–1, and feed mole fraction of 0.0254 had the best membrane performance in He/CH4 separation. This work is licensed under a Creative Commons Attribution 4.0 International License.

The concentration of dairy products is widely applied in dairy manufacturing due to obtaining products with the high dry matter, added value, reduced volume, and an increase in shelf-life. Traditional thermal concentration processes are the most applied in dairy industries, however, high temperatures can damage the bioactive compounds in milk, in addition to modifying the physicochemical, sensory, and nutritional characteristics of concentrated products. This review summarizes the importance of replacing traditional concentration methods with unconventional non-thermal processes, which can bring an option to dairy industries due to the concentration enabling the preservation of proteins, enzymes, vitamins, color, and flavor of the product. Alternative methods, such as freeze concentration, membrane separation processes, and freeze-drying, compose recent works about new methodologies to concentrate dairy products without changing specific properties and increase the quality, which is one of the main purposes for the dairy industries. Through a comparative study with recent researches, this overview highlights some alternative concentration processes that can improve the yield and increase the quality of concentrated dairy products. With new environmentally sustainable methods and the possibility of reducing the costs of the concentration process, these emerging concentration methods become attractive for dairy industries from a technological and economic perspective. PRACTICAL APPLICATION: Improving the quality of concentrated dairy products by non-thermal emerging technologies. Made available in DSpace on 2022-07-26T18:22:07Z (GMT). No. of bitstreams: 1 FST-2022-ConventionalAlternativeConcentrationProcessesMilkManufacturing.pdf: 1550466 bytes, checksum: 3e7936c63a4beba51b31adbcfca286a3 (MD5) Previous issue date: 2022

Propylene is industrially produced in a mixture with propane and generally separated from the mixture via distillation. However, because distillation is an energy-consuming process, a more efficient separation process should be developed to mitigate both carbon dioxide (CO2) emissions and production costs. In this study, a two-stage membrane-separation process was designed, and its CO2 emission and production costs were evaluated. The separation processes were designed to minimize energy consumption using different membrane combinations (two recently developed membranes each). To evaluate the separation processes using various membrane combinations, two indicators, i.e., CO2 emissions and total annual costs (TACs), were estimated based on the process simulation (Pro/II, version 10.1.1) results, including energy consumptions, operation expenditure, and capital expenditure. These results were compared to the distillation processes as benchmarks, and the advantages of the membrane-separation process were discussed. In the comparison, carbon taxes were implemented for assessing these two independent indicators as a single indicator, i.e., TAC with carbon tax. Furthermore, using the same scheme, model membranes were also employed in the two-stage membrane-separation process as case studies of technological forecasts.

Carbon dioxide (CO2) is the single largest contributor to climate change due to its increased emissions since global industrialization began. Carbon Capture, Storage, and Utilization (CCSU) is regarded as a promising strategy to mitigate climate change, reducing the atmospheric concentration of CO2 from power and industrial activities. Post-combustion carbon capture (PCC) is necessary to implement CCSU into existing facilities without changing the combustion block. In this study, the recent research on various PCC technologies is discussed, along with the membrane technology for PCC, emphasizing the different types of membranes and their gas separation performances. Additionally, an overall comparison of membrane separation technology with respect to other PCC methods is implemented based on six different key parameters?CO2 purity and recovery, technological maturity, scalability, environmental concerns, and capital and operational expenditures. In general, membrane separation is found to be the most competitive technique in conventional absorption as long as the highly-performed membrane materials and the technology itself reach the full commercialization stage. Recent updates on the main characteristics of different flue gas streams and the Technology Readiness Levels (TRL) of each PCC technology are also provided with a brief discussion of their latest progresses. This research was partially funded for A.K., Z.T., and S.R. by Erasmus+ KA107 International Credit Mobility (2020-1-ES01-KA107-078199 and 2019-1-ES01-KA107-061847) and the Ministry of Innovational Development of the Republic of Uzbekistan (Rector’s order 2/13).

Membrane properties are highly affected by the composition of the polymer solutions that make up the membrane material and their influence in the filtration performance on the separation or purification process. This paper studies the effects of the addition of pluronic (Plu) and patchouli oil (PO) in a polyethersulfone (PES) solution on the membrane morphology, membrane hydrophilicity, and filtration performance in the pesticide removal compound in the water sample. Three types of membranes with the composition of PES, PES + Plu, and PES + Plu + patchouli oil were prepared through a polymer phase inversion technique in an aqueous solvent. The resulting membranes were then analyzed and tested for their mechanical properties, hydrophilicity, antimicrobial properties, and filtration performance (cross-flow ultrafiltration). The results show that all of the prepared membranes could reject 75% of the pesticide. The modification of the PES membrane with Plu was shown to increase the overall pore size by altering the pore morphology of the pristine PES, which eventually increased the permeation flux of the ultrafiltration process. Furthermore, patchouli oil added antimicrobial properties, potentially minimizing the biofilm formation on the membrane surface. Published version Universitas Syiah Kuala (Contract Number: 268/UN11/SPK/PNBP/2020) via “Penelitian Professor” Scheme.

Orientador: Maria Regina Wolf Maciel Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica Resumo: Neste trabalho de tese, foi realizado um estudo do potencial do processo de pervaporação como um processo de separação de misturas azeotrópicas. Foram realizados o estudo, a avaliação e a comparação de dois modelos matemáticos selecionados da literatura par o processo de pervaporação, que têm como base o mecanismo solução-difusão. Forma desenvolvidos dois programas computacionais, o PERKAT e o PERBRUN, que pemitiram avaliar, segundo estes modelos, qualquer tipo de mistura binária, aqui exemplificados pelos sistemas etanol/água e acetato de metila/água. Foi proposto um modelo matemático a partir do mecanismo solução-difusão procurando minimizar a necessidade de dados experimentais e assim, possibilitar a avaliação rápida em estágios iniciais de projetos de processos. Foi , ainda, elaborado um algoritmo de calculo para o processo de pervaporação. Afim de obter um modelo mais robusto, minimizando a necessidade de dados experimentais, foram realizados e estudo da predição do coeficiente de difusão na membrana, a determinação do parâmetro de interação binário solvente/polímero, a validação do método de predição com dados experimentais e uma análise de sensibilidade paramétrica. Com isso, foi desenvolvido o simulador ¿PERVAP¿ a partir do modelo matemático proposto neste trabalho. A intenção foi possibilitar ao engenheiro de processos tomadas de decisão rápidas a respeito da possibilidade de usar o processo de pervaporação para a separação de uma mistura binária qualquer ...Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital Abstract: In this work, a study of the potential of pervaporation process for the separation of azeotropic mixtures was carries out. Two mathematical models were chosen from the literature for pervaporation process based on solution diffusion mechanism and a study, an evaluation and a comparison between these models were made. Two computational programs were developed, PERKAT and PERBRUN, which allow the evaluation, according to these models, of any type of binary mixture, here exemplified by the system ethanol/water and methyl acetate/water. A mathematical model was proposed based on the solution-diffusion mechanism with the aim of minimizing the necessity of experimental data and, thus, to make possible the fast evaluation in early stages of process design.Furthermore, it was elaborated a calculation algorithm for the pervaporation process. In order to get a more robust model, minimizing the necessity of experimental data, the study of the prediction of the diffusion coefficient in the membrane, the determination of the binary interaction parameter of solvent/polymer, the validation of the prediction method with experimental data and a parametric sensitivity analysis were carried out. With this, the "PERVAP" simulator was developed from the mathematical model proposed in this work. The intention was to make possible for engineers to take rapid decisions regarding the possibility for using the pervaporation process for separating any binary mixture ...Note: The complete abstract is available with the full electronic digital thesis or dissertations Doutorado Desenvolvimento de Processos Químicos Doutor em Engenharia Química

Orientador: Luiz Antonio Viotto Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos Resumo: A aplicação do processo de microfiltração para clarificação de certos sucos de frutas tem demonstrado resultados economicamente viáveis. Inúmeros sucos de frutas típicas do Brasil ainda não foram testados neste tipo de processo, visando a sua clarificação. Suco de tamarindo (Tamarindus indica L.) reconstituído na proporção de 1 de polpa para 3 de água foi microfiltrado a 35ºC, em membrana tubular de polipropileno de diâmetro médio de poro de 0,2 µm, variando-se as condições de pressão transmembrana, velocidade de escoamento e utilizando ou não um pré-tratamento enzimático da polpa. Foram observados fluxos finais de permeado de 70 a 115 kg/m2h. O aumento da pressão transmembrana aumentou o fouling, mas resultou em altos valores de fluxo de permeação, tanto iniciais quanto finais. Alta pressão associada ao uso de enzima pectinolítica na concentração de 100 ppm apresentou o melhor resultado de fluxo final, a um fator de concentração igual a dois e, conseqüentemente, no menor tempo de processamento. O aumento da velocidade de escoamento e uso de baixas pressões melhorou o fluxo de modo geral, e o uso concomitante de enzima, melhorou ainda mais o fluxo. Ao usar alta velocidade e alta pressão, o fluxo foi elevado no processamento em que não foi feito o tratamento enzimático. Entretanto, no processamento em que foi realizado o tratamento enzimático, o fluxo diminui em 26%, possivelmente devido ao aumento do fouling na membrana. O permeado obtido apresentou uma coloração amarelo ouro, límpido e sem presença de sólidos insolúveis. Houve também retenção de sólidos solúveis (açúcares e pectinas, entre outros) e, conseqüentemente, dos sólidos totais (diminuição da umidade no retentado). Os resultados de fluxo de permeado em diversas condições de operação permitiram uma análise da influência da camada gel e do fouling de acordo com a teoria de resistências em série. Os dados obtidos para a construção da curva de permação foram ajustados a um modelo matemático, baseado na teoria de renovação de superfície, e calcularam-se os valores da constante de declínio de fluxo. Estes foram maiores nos experimentos em que se fez uso de altas pressões e tratamento enzimático Abstract: Clarification of a lot of fruit juices using microfiltration process has been showing viable economic results. Countless juices of typical fruits of Brazil aren't studied yet in membrane separation process. Tamarind juice (Tamarindus indica L.) reconstituted at 35ºC was microfiltred using a polypropylene tubular membrane of 0,2 µm average diameter poro. The operating conditions of transmembrane pressure, crossflow velocity and enzymatic treatment were evaluated. Final fluxes values of 70 until 115 kg/m2h was observed. The increase in transmembrane pressure resulted in high fouling, but increased the values of inicial and final permeates fluxes. Associated of enzyme pectinolitic at 100 ppm, this experiment presents the best result of final flux and, consequently, the smaller time processing. The increase in crossflow velocity and use of low transmembrane pressure improved the fluxes in general, and using enzymes at the same time, improved the fluxes even more. High crossflow velocities and high transmembrane pressures results in high fluxes just in the experiment without enzymatic treatment. In the experiment where enzymatic treatment was done, the flux reduce 26%, possible due to increase of the fouling on membrane. The permeate presents a gold yellow colour, cloudless and without insoluble solids. There was soluble solids (sugar, pectin etc.) retention and, consequently, total solids retention (reducing of humidity in retentate). The influence of polarized layer and the fouling in several operating conditions results of fluxes allow an analysis by resistance in series theory. The experimental data picked to permeate curve was ajusted to mathematical model based on surface renewal theory and the flux decay constant were calculated. There were higher on experiments with high pressure and enzymatic treatment Mestrado Mestre em Engenharia de Alimentos

Ion concentration polarization (ICP) is a promising mechanism for concentrating and/or separating charged molecules. This work simulates the extraction of Li+ ions in a diluted high Mg2+/Li+ ratio salt lake brines based on free flow ICP focusing (FF-ICPF). The model solution of diluted brine continuously flows through the system with Li+ slightly concentrated and Mg2+ significantly removed by ICP driven by external pressure and perpendicular electric field. In a typical case, our results showed that this system could focus Li+ concentration by ~1.28 times while decreasing the Mg2+/Li+ ratio by about 85% (from 40 to 5.85). Although Li+ and Mg2+ ions are not separated as an end product, which is preferably required by the lithium industry, this method is capable of decreasing the Mg2+/Li+ ratio significantly and has great potential as a preprocessing technology for lithium extraction from salt lake brines.

Orientadores: Teresa Massako Kakuta Ravagnani, Leila Peres Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química Resumo: O biodiesel além de ser biodegradável e obtido de fontes renováveis, apresenta propriedades físico-químicas muito semelhantes ao diesel de petróleo, não necessitando de um novo motor para utilização do mesmo. A rota química mais comumente usada para obtenção do biodiesel é a transesterificação. Nesta, pela reação de um álcool com os triacilgliceróis (TAG) presentes principalmente em óleos vegetais e gordura animal, são produzidos o biodiesel e, como produto secundário, o glicerol em grandes quantidades. A presença deste glicerol é indesejada, pois além de diminuir a produtividade do biodiesel pelo equilíbrio termodinâmico estabelecido no processo, também aumenta seu custo pelo alto tempo de decantação e/ou uso de centrífugas para remover o glicerol do biodiesel. Devido a este inconveniente, o presente trabalho propõe rota alternativa para separação do glicerol, utilizando membrana de microfiltração (TiO2/Al2O3). Vários sistemas foram analisados, focando a separação do glicerol, o aumento do fluxo permeado e da conversão de TAG na catálise heterogênea. Inicialmente estudou-se a permeabilidade e seletividade dos reagentes e produtos obtidos na síntese do biodiesel com a membrana, através de experimentos binários. A partir destes resultados, estabeleceu-se uma nova configuração do sistema para então analisar estes fatores em misturas compostas pelos quatro constituintes do processo através de um planejamento fatorial. Os resultados apresentados geraram modelos que descrevem com 95% de confiabilidade o coeficiente de rejeição ao glicerol e o fluxo permeado frente aos fatores analisados (nível de emulsificação, razão molar óleo/etanol e conversão de TAG). Selecionou-se então, uma melhor faixa destes fatores que resultem em um máximo de rejeição ao glicerol com máximo fluxo permeado, obtendo um resultado bastante representativo do processo que apresentou um bom fluxo permeado (90,11kg/h.m2) com alta rejeição de glicerol (98,69%). Posteriormente propôs-se um estudo do processo simultâneo de reação e separação (leito fixo catalítico envolto em membrana), sendo selecionado para a reação de síntese um catalisador heterogêneo (SrO suportado em alumina), visando facilitar o processo de separação e reduzir significativamente o número de etapas de purificação dos produtos. Os resultados de conversão do TAG foram baixos, impossibilitando uma análise completa do sistema com esta configuração do ponto de vista de reação e separação concomitante Abstract: In addition to being biodegradable and renewable, Biodiesel presents physicochemical properties very similar to those of petroleum-based diesel, so a new engine is not required for its use. The most commonly used chemical process for obtaining biodiesel is transesterification. In this process, through the reaction of an alcohol with triacylglycerols (TAG) present mainly in vegetable oils and animal fat, biodiesel is formed with large quantities of glycerol as a byproduct. The presence of glycerol is unwanted because besides reducing the productivity of biodiesel through the thermodynamic equilibrium established in the process, it also increases the cost due to the long time for settling and/or use of centrifuges for removing the glycerol from biodiesel. Taking into account this inconvenience, this paper proposes an alternative process for the separation of glycerol, using TiO2/Al2O3 membranes. Various systems were analyzed, focusing on the separation of glycerol, the increase of the permeate flux, and the increase in the TAG productivity in heterogeneous catalysis. At first we studied the permeability and selectivity of reagents and products obtained in the biodiesel synthesis with a membrane through binary experiments. From these results a new configuration of the system was established, with subsequent analysis of the new interaction in mixtures of the four components of the process (oil, Ethanol, Biodiesel, glycerol) using a factorial design as tool. Results presented in the factorial design generated models that describe with 95% reliability the glycerol rejection coefficient and the permeate flux compared to the analyzed factors (level of emulsification, molar ratio of oil/ethanol and TAG conversion). A best range of factors that result in a maximum glycerol rejection with maximum permeate flux was selected, obtaining a fairly representative result of the process showing a good permeate flux (90.11 kg/h.m2) with high glycerol rejection rate (98.69%). Subsequently, the study of the reaction and separation simultaneous process was proposed (fixed catalytic bed involved in a membrane) selecting an heterogeneous catalyst (SrO on alumina) to facilitate the separation process and significantly reduce the number of purification steps of products. Results of biodiesel conversion were low, preventing a full assessment of the system with this configuration considering simultaneous reaction and separation Doutorado Sistema de Processos Químicos e Informatica Doutor em Engenharia Química

Drinking water softening is often implemented to increase consumer convenience e.g. by reducing lime scaling and soap use. Softening reduces hardness, but changes also the overall mineral composition of the water, depending on the technology. A broad spectrum of effects from softening has to be considered in relation to e.g. health and corrosion when selecting softening technology and design, otherwise adverse effects may be overlooked in the attempt to increase consumer convenience. We here provided a framework for evaluating softening technologies using water quality indicators for lime scaling, soap use, corrosion, human health, taste and removal of contaminants. None of the evaluated softening technologies scored positive on all the included water quality indicators. Precipitation technologies (lime/soda-ash softening and pellet softening) reduce the predicted copper and lead release, but negatively affect stainless steel corrosion expressed by the Larson Ratio. Pellet softening does not remove magnesium, which may limit the achievable softening depth, but maintains a protective effect against cardio-vascular diseases. Strong-acid cation exchange is not expected to affect the included corrosion indicators, whereas the effects from membrane separation (nanofiltration and reverse osmosis) and weak-acid cation exchange depend on the specific source water and process design. All the evaluated technologies reduce hardness, calcium carbonate precipitation potential (CCPP) and atopic eczema, but have potential adverse effects on dental carries (expressed by DMF-S). Our framework provides a better understanding of softening and can prepare water utility planners and managers for better decisions that balance the positive and adverse effects from drinking water softening.

MXenes have recently been recognized as potential materials based on their unique physical and chemical characteristics. The widely growing family of MXenes is rapidly expanding their application domains since their first usage as energy materials was reported in 2011. The inherent chemical nature, high hydrophilicity, and robust electrochemistry regard MXenes as a promising avenue for environment-remediation technologies such as adsorption, membrane separation, photocatalysis and the electrocatalytic sensor designed for pollutant detection. As the performance of MXenes in these technologies is on a continuous path to improvement, this review intends to cumulatively discuss the diversity and chemical abilities of MXenes and their hybrid composites in the fields mentioned above with a focus on MXenes improving surface-characteristics. The review is expected to promote the diversity of MXenes and their hybrid configuration for advanced technologies widely applied for environmental remediation.

Fabrication of the ZSM-22/Polyethersulfone (ZSM-22/PES) membranes as selective salt filters represent a growing membrane technological area in separation with the potential of high economic reward based on its low energy requirements. The incorporation of ZSM-22 zeolite material as additives into the PES polymer matrix has the prospective advantage of combining both the zeolite and polymer features while overcoming the limitations associated with both materials. This work investigated the influence of the nature of the silica precursor on ZSM-22 zeolite hydrothermally synthesised using colloidal (C60) and fumed (C60) silica to Si/Al of 60. The successful synthesis of the highly crystalline zeolitic materials was confirmed through XRD, FTIR, and SEM with EDX. The ZSM-22 additives were directly dispersed into a PES polymeric matrix to form a casting solution for the preparation of the ZSM-22/PES selective substrate layers via a phase inversion method for salts rejection. The polymeric PES was selected as an organic network in which the content of the ZSM-22 zeolite (ranging between 0 and 1.0 wt.%), was obtained and characterised by XRD, FTIR, and SEM analysis, as well as water contact angle (WCA) measurement and dead-end filtration cell. The phase inversion preparation method has induced the resulting ZSM-22/PES NF substrates anisotropy, as attributed to a high water flux to the above 700 L·m−2·h−1; high selectivity and rejection of salts to above 80% is revealed by the obtained results. The materials also exhibited improved antifouling behavior to above 70% flux recovery ratios. As such, the nature of the silica precursor influences ZSM-22 zeolite synthesis as a potential additive in the PES polymer matrix and led to the enhanced performance of the pure PES ultrafiltration membrane.

Recovering nitrogen from source-separated urine is an important part of the sustainable nitrogen management. A novel bipolar membrane electrodialysis with membrane contactor (BMED���MC) process is demonstrated here for efficient recovery of ammonia from synthetic source-separated urine (���3772 mg N L���1). In a BMED���MC process, electrically driven water dissociation in a bipolar membrane simultaneously increases the pH of the urine stream and produces an acid stream for ammonia stripping. With the increased pH of urine, ammonia transports across the gas-permeable membrane in the membrane contactor and is recovered by the acid stream as ammonium sulfate that can be directly used as fertilizer. Our results obtained using batch experiments demonstrate that the BMED���MC process can achieve 90% recovery. The average ammonia flux and the specific energy consumption can be regulated by varying the current density. At a current density of 20 mA cm���2, the energy required to achieve a 67.5% ammonia recovery in a 7 h batch mode is 92.8 MJ kg���1 N for a bench-scale system with one membrane stack and can approach 25.8 MJ kg���1 N for large-scale systems with multiple membrane stacks, with an average ammonia flux of 2.2 mol m���2 h���1. Modeling results show that a continuous BMED���MC process can achieve a 90% ammonia recovery with a lower energy consumption (i.e., 12.5 MJ kg���1 N). BMED���MC shows significant potential for ammonia recovery from source-separated urine as it is relatively energy-efficient and requires no external acid solution.

The restrictions imposed to the production of high-global warming potential refrigerant gases have boosted the search of novel separation processes for the selective recovery of hydrofluorocarbons (HFCs) and hydrofluoroolefins (HFO) from exhausted refrigerant mixtures. Membrane materials functionalized with ionic liquids can offer an effective techno-economical response to the challenging separation of HFC/HFO blends. In this work, we provide for the first time a thorough characterization of the gas solubility and permeation properties of three of the most relevant compounds for the future of the refrigeration and air conditioning sector, that is, difluoromethane (HFC-R32), 1,1,1,2-tetrafluoroethane (HFC-R134a), and 2,3,3,3-tetrafluoropropene (HFO-R1234yf), through composite ionic liquid-polymer membranes (CILPMs) that were prepared combining the Pebax 1657 copolymer with several ILs, [C2mim][SCN], [C2mim][BF4], [C2mim][OTf], and [C2mim][Tf2N], varying the IL content in the range of 20?60 wt %. The CILPMs with the best separation performance and mechanical stability against feed pressure were those with 40 wt % of [C2mim][BF4] and [C2mim][SCN]. For the 40 wt % [C2mim][BF4] CILPM, the addition of IL promoted the permeability of the smallest molecules R32 and R134a and reduced the permeability of the largest molecule R1234yf, which resulted in 120 and 75% selectivity enhancement relative to that of the pristine polymer for R32/R1234yf and R134a/R1234yf mixtures, respectively. Finally, this CILPM was stable in the separation of two commercial HFC/HFO refrigerant blends (R513A and R454B) over a wide pressure range (up to 12 bar). These results indicate that CILPMs can be used for separating azeotropic and near-azeotropic exhausted HFC/HFO mixtures, which could stimulate the recovery and reuse of their components and thus avoid their emissions and pull down the demand for virgin refrigerants. Authors fully acknowledge the financial support received from Project KET4F-Gas-SOE2/P1/P0823, which is cofinanced by the European Regional Development Fund within the framework of Interreg Sudoe Programme, and project PID2019-105827RB-I00—Agencia Estatal de Investigación, Spain. F.P. acknowledges the postdoctoral fellowship (FJCI-2017-32884 Juan de la Cierva Formación) awarded by the Spanish Ministry of Science, Innovation and Universities.

Drinking water resources, such as groundwater, are threatened by pollution. The pesticide metabolite 2,6-dichlorobenzamide (BAM) is one of the compounds frequently found in groundwater. Studies have attempted to add specific BAM-degrading bacteria to sand-filters at drinking water treatment facilities. This biotechnology has shown great potential in removing BAM from contaminated water. However, the degradation potential was formerly lost after approximately 2-3 weeks due to a decrease of the degrader population over time.The aim of the present study was to overcome the constraints leading to loss of degraders from inoculated filters. Our approach was threefold: 1) Development of a novel inoculation strategy, 2) lowering the flowrate to reduce washout of cells, and 3) increasing the concentration of nutrients hereunder the pollutant in a smaller inlet water stream. The two latter were achieved via modifications of the inlet water by applying membrane treatment which, besides producing an ultra-pure water fraction, produced a residual water stream with nutrients including BAM concentrated in an approximately 10-fold reduced volume. This was done to alleviate starvation of degrader bacteria in the otherwise oligotrophic sand-filters and to enable a decreased flowrate.By this approach, we achieved 100% BAM removal over a period of 40 days in sand-filter columns inoculated with the BAM-degraderAminobactersp. MSH1. Molecular targeting of the degrader strain showed that the population of degrader bacteria persisted at high numbers throughout the sand-filter columns and over the entire timespan of the experiment. 16S rRNA gene amplicon sequencing confirmed that MSH1 dominated the bacterial communities.IMPORTANCEMany countries rely partly or solely on groundwater as the source of drinking water. Here groundwater contamination by pesticide residues poses a serious threat to the production of high quality drinking water. Since scarcity of clean groundwater may occur in progressively larger areas both locally and globally, the need for efficient purification technologies is growing. This study shows that a novel system combining membrane treatment and bioaugmented sand-filters can efficiently remove pesticide residues in laboratory columns when applying specific inoculation and flow conditions. Once upscaled, this system can be used directly for pump-and-treat of contaminated groundwater wells or at drinking water treatment plants.

Poly(ionic liquid)s are an innovative class of materials with promising properties in gas separation processes that can be used to boost the neat polymer performances. Nevertheless, some of their properties such as stability and mechanical strength have to be improved to render them suitable as materials for industrial applications. This work explored, on the one hand, the possibility to improve gas transport and separation properties of the block copolymer Pebax® 1657 by blending it with poly[3-ethyl-1-vinyl-imidazolium] diethyl phosphate (PEVI-DEP). On the other hand, Pebax® 1657 served as a support for the PIL and provided mechanical resistance to the samples. Pebax® 1657/PEVI-DEP composite membranes containing 20, 40, and 60 wt.% of PEVI-DEP were cast from solutions of the right proportion of the two polymers in a water/ethanol mixture. The PEVI-DEP content affected both the morphology of the dense membranes and gas transport through the membranes. These changes were revealed by scanning electron microscopy (SEM), time-lag, and gravimetric sorption measurements. Pebax® 1657 and PEVI-DEP showed similar affinity towards CO2, and its uptake or solubility was not influenced by the amount of PIL in the membrane. Therefore, the addition of the PIL did not lead to improvements in the separation of CO2 from other gases. Importantly, PEVI-DEP (40 wt.%) incorporation affected and improved permeability and selectivity by more than 50% especially for the separation of light gases, e.g., H2/CH4 and H2/CO2, but higher PEVI-DEP concentrations lead to a decline in the transport properties.

Graphene oxide (GO) membranes have great potential for separation applications due to their low-friction water permeation combined with unique molecular sieving ability. However, the practical use of deposited GO membranes is limited by the inferior mechanical robustness of the membrane composite structure derived from conventional deposition methods. Here, we report a nanostructured GO membrane that possesses great permeability and mechanical robustness. This composite membrane consists of an ultrathin selective GO nanofilm (as low as 32 nm thick) and a postsynthesized macroporous support layer that exhibits excellent stability in water and under practical permeability testing. By utilizing thin-film lift off (T-FLO) to fabricate membranes with precise optimizations in both selective and support layers, unprecedented water permeability (47 L·m-2·hr-1·bar-1) and high retention (>98% of solutes with hydrated radii larger than 4.9 Å) were obtained.

A membrane-based system with a retentate recycle process in tandem with an enriching cascade was studied for >90% carbon capture from coal flue gas. A highly CO2-selective facilitated transport membrane (FTM) was utilized particularly to enhance the CO2 separation efficiency from the CO2-lean gases for a high capture degree. A techno-economic analysis showed that the retentate recycle process was advantageous for ≤90% capture owing to the reduced parasitic energy consumption and membrane area. At >90% capture, the enriching cascade outperformed the retentate recycle process since a higher feed-to-permeate pressure ratio could be applied. An overall 99% capture degree could be achieved by combining the two processes, which yielded a low capture cost of USD47.2/tonne, whereas that would be USD 42.0/tonne for 90% capture. This FTM-based approach for deep carbon capture and storage can direct air capture for the mitigation of carbon emissions in the energy sector.

Firstly, 2,3-butanediol (2,3-BDO) is a chemical platform used in several applications. However, the pathogenic nature of its producers and the expensive feedstocks used limit its scale production. In this study, cane molasses was used for 2,3-BDO production by a nonpathogenic Clostridium ljungdahlii. It was found that cane molasses alone, without the addition of other ingredients, was favorable for use as the culture medium for 2,3-BDO production. Compared with the control (i.e., the modified DSMZ 879 medium), the differential genes are mainly involved in the pathways of carbohydrate metabolism, membrane transport, and amino acid metabolism in the case of the cane molasses alone. However, when cane molasses alone was used, cell growth was significantly inhibited by KCl in cane molasses. Similarly, a high concentration of sugars (i.e., above 35 g/L) can inhibit cell growth and 2,3-BDO production. More seriously, 2,3-BDO production was inhibited by itself. As a result, cane molasses alone with an initial 35 g/L total sugars was suitable for 2,3-BDO production in batch culture. Finally, an integrated fermentation and membrane separation process was developed to maintain high 2,3-BDO productivity of 0.46 g·L−1·h−1. Meanwhile, the varied fouling mechanism indicated that the fermentation properties changed significantly, especially for the cell properties. Therefore, the integrated fermentation and membrane separation process was favorable for 2,3-BDO production by C. ljungdahlii using cane molasses.

The comparison study of CO2 removal efficiency from flue gases at low pressures and temperatures is presented, based on commonly used methods and materials. Our own experimental results were compared and analyzed for different methods of CO2 removal from flue gases: absorption in a packed column, adsorption in a packed column and membrane separation on polymeric and ceramic membranes, as well as on the developed supported ionic liquid membranes (SILMs). The efficiency and competitiveness comparison of the investigated methods showed that SILMs obtained by coating of the polydimethylsiloxane (PDMS) membrane with 1-ethyl-3-methylimidazolium acetate ([Emim][Ac]) exhibit a high ideal CO2/N2 selectivity of 152, permeability of 2400 barrer and long term stability. Inexpensive and selective SILMs were prepared applying commercial membranes. Under similar experimental conditions, the absorption in aqueous Monoethanolamine (MEA) solutions is much faster than in ionic liquids (ILs), but gas and liquid flow rates in packed column sprayed with IL are limited due to the much higher viscosity and lower diffusion coefficient of IL. For CO2 adsorption on activated carbons impregnated with amine or IL, only a small improvement in the adsorption properties was achieved. The experimental research was compared with the literature data to find a feasible solution based on commercially available methods and materials.

Due to the growth in the human population globally, it is noted that various industries have also grown. The need for an excess supply of water and the generation of high effluent quality upon proper treatment technologies has become a necessity. These two crucial needs can be achieved with the aid of membrane bioreactor (MBR) that has been proven to be effective in removing organic and inorganic matters as a biological unit for wastewater treatment. MBR plants are created by integrating the biological process with membrane filtration which possesses numerous benefits if compared with conventional methods such as activated sludge; MBR is widely used for municipal and industrial wastewater treatment. This review addresses basic concepts of MBRs plants and subsequently provides information on the recent developments of each part related to MBR plants. The characteristics of the bioreactor treatment process is discussed in detail, and then a comprehensive review of the membrane separation process is examined. The fouling phenomena as a main obstacle to widespread MBRs plant is presented in detail with recent fouling mitigation methods. The efforts of a number of novel MBR processes are summarized. In order to tackle the existing limitation of MBRs to be practical on a larger scale, the existing challenges and future research efforts are proposed.

Interest in recovering and reclaiming refrigerant gases is growing as a consequence of increasing concern about the high global warming potential of some hydrofluorocarbons (HFCs). However, advanced separation processes, like extractive distillation, are required to selectively separate azeotropic and close-boiling refrigerant mixtures. In this regard, ionic liquids (ILs) arise as promising entrainers because of their favorable properties, including nonvolatility and good HFC solubility selectivity. The aim of this review is to become a reference text for the research and design of novel separation processes for mixtures of fluorinated gases based on the use of ILs. We include an extensive compilation of publications on equilibrium, mass transport, and absorption and membrane separation related to the use of ILs to selectively separate, not only the most relevant refrigerants employed nowadays, namely, HFCs, hydrofluoroolefins, and hydrochlorofluoroolefins, but also other relevant refrigerant families, such as chlorofluorocarbons, hydrochlorofluorocarbons, and perfluorocarbons. The UC-RAIL database provided as Supplementary Information compiles more than 5000 data points that are comprehensively analyzed in the review focusing on process design. Finally, we provide a set of directions that lead to the recovery of fluorinated refrigerant gases, to shift the refrigeration and air conditioning sector towards a more circular economy. The authors fully acknowledge the financial support received from Project KET4F-Gas-SOE2/P1/P0823, which is co-financed by the European Regional Development Fund within the framework of Interreg Sudoe Programme, and project PID2019-105827RB-I00 – Agencia Estatal de Investigacion, Spain. S. A.-D. and F. P. acknowledge the FPU grant (18/03939) and the post-doctoral fellowship (FJCI-2017-32884 Juan de la Cierva Formacion), respectively, awarded by the Spanish Ministry of Science and Innovation. Marta Romay’s graphical abstract is gratefully acknowledged.

This study proposed a hybrid modeling framework for membrane separation processes where lithium from batteries is recovered. This is a pertinent problem nowadays as lithium batteries are popularized in hybrid and electric vehicles. The hybrid model is based on an artificial intelligence (AI) structure to model the mass transfer resistance of several experimental separations found in the literature. It is also based on a phenomenological model to represent the transient system regime. An optimization framework was designed to perform the AI model training and simultaneously solve the Ordinary Differential Equation (ODE) system representing the phenomenological model. The results demonstrate that the hybrid model can better represent the experimental validation sets than the phenomenological model alone. This strategy opens doors for further investigations of this system.

α-Lactalbumin is an essential protein with multiple roles in physiological and the nutritional functionalities, such as diabetic prevention, blood pressure stabilization, and cancer cell inhibition. In the present work, polyethersulfone (PES)-based membranes were developed by incorporating Pluronic F127 and carbon nanotubes with single- and multi-walled dimensions (Sw-Cnts and Mw-Cnts) as additives. The resulting membranes were evaluated for use in the filtration of α-lactalbumin protein solution. Four series of membranes, including PES pristine membrane, were fabricated via the phase inversion process. The characteristics of the membrane samples were analyzed in terms of morphology, membrane surface hydrophilicity and roughness, and surface chemistry. The characterization results show that the incorporation of additive increased the surface wettability by reducing the surface water contact angle from 80.4° to 64.1° by adding F127 and Mw-Cnt additives. The highest pure water permeability of 135 L/(m2·h·bar) was also exhibited by the PES/F127/Mw-Cnt membrane. The performance of the modified membranes was clearly better than the pristine PSF for α-lactalbumin solution filtration. The permeability of α-lactalbumin solution increased from 9.0 L/(m2·h·bar) for the pristine PES membrane to 10.5, 11.0 and 11.5 L/(m2·h·bar) for membranes loaded with Pluronic F127, Sw-Cnts, and Mw-Cnts, respectively. Those increments corresponded to 17, 22, and 28%. Such increments could be achieved without altering the α-lactalbumin rejections of 80%. Remarkably, the rejection for the membrane loaded with Sw-Cnts even increased to 89%. Published version This research was funded by the Indonesian Ministry of Education, Culture, Research, and Technology with grant contract number 46/UN11.2.1/PT.01.03/DRPM/2021 (Penelitian Dasar)

Nanofiltration has been shown to be effective in removing pharmaceutical compounds from water and wastewater, so different mechanisms can influence treatment performance. In the present work, we carried out a case study evaluating the performance of two nanofiltration membranes in the removal of Atenolol (ATN)—a pharmaceutical compound widely used for the treatment of arterial hypertension—under different conditions such as operating pressure, ATN concentration, and solution pH. By determining the B parameter, which quantifies the solute/membrane affinity, we verified that the solution pH influenced the performance of the membranes, promoting attraction or repulsion between the ATN and the membranes. At pH 2.5, both membranes and ATN were positively charged, causing electrostatic repulsion, showing lower values of the B parameter and, consequently, higher ATN rejections. At such a pH, the mean ATN rejection for the loose membrane (NF270) was 82%, while for the tight membrane (NF90) it was 88%. On the other hand, at 12 bar pressure, the NF70 membrane (5.1 × 10 −5 m s−1) presented mean permeate fluxes about 2.8 times greater than the NF90 membrane (1.8 × 10−5 m s−1), indicating that NF270 is the most suitable membrane for this application.

Plasma Enhancement Gases (PEGs), i.e. N2 and noble gases, are used to mitigate the heat load over plasma facing components. Therefore, in DEMO, the tokamak exhaust stream will contain a certain amount of these PEGs which require a dedicated purification and separation unit. In the last years, PEG separation using microporous ceramic membranes has been studied at ENEA Frascati laboratories in the framework of the EUROfusion programme. The experiments conducted with a binary gas mixture have revealed the poor separation capability of the multi-channel membranes as a consequence of their high permeance. In this activity, the behaviour of a commercial microporous single-channel membrane made of alpha alumina has been theoretically studied to evaluate its efficacy in separating H2 from PEGs. The analysis has considered a total feed flow rate of 20 L min−1 (at STP) having an equimolar composition of H2 with one of the following species: PEG (Ar or N2), D2 or He. The separation capability has been evaluated by assuming the upstream pressure in the range 200−1000 kPa and keeping the downstream pressure at 100 kPa. Considering the values of the permeances assessed in our previous work for single gas tests, the membrane length needed to achieve a given target of separation has been evaluated as a function of the H2 mole fraction in the retentate stream.

RESUMO O objetivo deste trabalho foi utilizar a ultrafiltração (UF) para o tratamento de água de chuva, ajustando seus parâmetros físico-químicos e microbiológicos para a potabilidade. Para tal, duas membranas de UF foram testadas em duas pressões diferentes para tratar água de chuva coletada em um prédio da Universidade de Passo Fundo (UPF). A água de chuva apresentou uma moderada concentração de sólidos suspensos, cor, turbidez, matéria orgânica e contaminação por coliformes e uma baixa concentração de nitritos, nitratos e sulfatos. As duas membranas de UF utilizadas (com diâmetro de corte de 4 e 50 kDa) permitiram o ajuste desses parâmetros à potabilidade, sendo que a membrana de 50 kDa de fibra oca apresentou fluxos superiores a 130 L.h-1.m-2 (a 2 bar). Logo, a captação de água de chuva e sua UF é uma promissora alternativa para um abastecimento descentralizado de água potável. ABSTRACT The aim of this work was to use the ultrafiltration (UF) for the treatment of rainwater, adjusting their physicochemical and microbiological parameters for the drinking water quality. Two UF membranes were tested at two different pressures to treat the rainwater collected in a building of the University of Passo Fundo. Rainwater showed a moderate concentration of suspended solids, color, turbidity, organic matter and coliform contamination and a low concentration of nitrites, nitrates and sulfates. The two UF membranes used (with molecular weight cutoff of 4 and 50 kDa) allowed the adjustment of these parameters to the potability, and the permeate flux of hollow fiber (50 kDa) membrane was above 130 L.h-1.m-2 (at 2 bar). Therefore, rainwater harvesting and its UF is a promising alternative for a decentralized supply of drinking water.

In the course of dark fermentative hydrogen production, a complex gaseous mixture with significant quantity of CO2 is formed. Hence, proper separation of H2 and CO2 is required for adequate utilization of hydrogen gas in fuel cell applications. Technological solutions for the removal of CO2 can be designed by using gas separation membranes. Nevertheless, contemporary systems should be concerned with the consecutive valorization of carbon dioxide, as well. In this review article, the membrane-based technologies aiming at the effective separation of CO2 and biohydrogen (bioH2) will be evaluated, along with concise discussion and perspectives of integrative schemes offering alternatives for the biologically-mediated (fermentative, bioelectrochemical and algal) conversion of carbon dioxide into value-added substances, such as methane, hydrocarbons, etc. With this analysis, the objective was to bring the most important aspects of membrane-assisted biohydrogen downstream technology under one cover and give insights to recent advancement and possible future research directions.

Grado en Ingeniería Química

Purpose Amyloid-β protein (Aβ) is one of the causative proteins of Alzheimer’s disease. We have been developing extracorporeal blood Aβ-removal systems as a method for enhancing Aβ clearance from the brain. We reported previously that medical adsorbents and hemodialyzers removed Aβ monomers from peripheral blood, which was associated with influx of Aβ monomers from the brain into the bloodstream. Our intent here was to develop a method to promote clearance of Aβ oligomers and to provide an estimate of the molecular size of intact Aβ oligomers in plasma. Methods Two hollow-fiber devices with different pore sizes (Membranes A and B) were evaluated as removers of Aβ oligomers with human plasma in vitro. The concomitant removal of Aβ oligomers and monomers was investigated by using Membrane B and hexadecyl alkylated cellulose beads or polysulfone hemodialyzers. Double-filtration plasmapheresis with Membrane A was investigated as an approach for the removal of plasma Aβ oligomers in humans. Results Aβ oligomers were effectively removed by both Membranes A and B. The increase of Aβ oligomers in plasma was observed just after the removal of plasma Aβ oligomers in humans. The intact molecular size of major Aβ oligomers in the plasma was estimated to be larger than albumin at approximately 60 kDa or more. Additionally, the concomitant removal of Aβ monomers and oligomers evoked dissociation of larger Aβ oligomers into smaller ones and monomers. Conclusion Aβ oligomers were cleared from plasma both in vitro and in human subjects by using hollow-fiber membranes with large pores, indicating that their intact sizes were mostly larger than 60 kDa. Aβ oligomers in peripheral circulation were increased after some clearances in human. Further investigation will determine whether the Aβ oligomers detected in circulation after clearance were via influx from the brain.

Membrane fouling is the bottleneck limiting the wide application of membrane processes. Herein, we adopted an electroactive polyether sulfone (PES) membrane capable of mitigating fouling by various negatively charged foulants. To evaluate anti-fouling performance and the underlying mechanism of this electroactive PES membrane, three types of model foulants were selected rationally (e.g., bovine serum albumin (BSA) and sodium alginate (SA) as non-migratory foulants, yeast as a proliferative foulant and emulsified oil as a spreadable foulant). Water flux and total organic carbon (TOC) removal efficiency in the filtering process of various foulants were tested under an electric field. Results suggest that under electrochemical assistance, the electroactive PES membrane has an enhanced anti-fouling efficacy. Furthermore, a low electrical field was also effective in mitigating the membrane fouling caused by a mixture of various foulants (containing BSA, SA, yeast and emulsified oil). This result can be attributed to the presence of electrostatic repulsion, which keeps foulants away from the membrane surface. Thereby it hinders the formation of a cake layer and mitigates membrane pore blocking. This work implies that an electrochemical control might provide a promising way to mitigate membrane fouling.

Although it is still a great challenge, developing oil-/water-separating membranes that combine the advantages of high separation efficiency, salty environments tolerance, and fouling resistance are highly demanded for marine oil spill cleanups and oil-/gas-produced water treatment. Here, we report a new type of all-inorganic nanostructured membrane, which is composed of titanate nanofibers and SiO2 particulate gel for efficient and stable oil/saltwater separation. The nanoporous and interconnected network structure constructed with titanate nanofibers is the key to ensure the high separation efficiency and high water flux of the new membrane. The SiO2 gel is used as a binder to offer mechanical flexibility and integrity for this type of all-inorganic membrane. The new membrane displays a high oil/water separation efficiency of above 99.5% with oil content in treated effluent lower than US environmental discharge standards (42 ppm) and high water permeation flux of 1600 LMH/bar under low operation pressure. The new membrane also demonstrates outstanding durability in the environment of different salinities, and it has a good resistance for oil fouling due to its excellent underwater superoleophobicity with an oil contact angle above 150 °. Most importantly, the underwater superoleophobic properties can be well maintained after being repeatedly reused. The excellent environmental durability, oil-fouling resistance, high separation efficiency, and facile fabrication process for this new type of membrane render great potential for industrial application in treating produced water. Electronic supplementary material The online version of this article (10.1007/s11356-020-08021-x) contains supplementary material, which is available to authorized users.

Bovine milk oligosaccharides (BMOs) that resemble human milk oligosaccharides are found in whey permeate, indicating that dairy streams can be used as a potential source of bioactive oligosaccharides. Recovery of oligosaccharides from whey permeate is hindered by their low abundance and high concentration of lactose. In the present work, lactose in bovine colostrum whey permeate was hydrolyzed by Aspergillus oryzae β-galactosidase to facilitate subsequent monosaccharide removal by membrane separation. Chromatographic separation coupled with high-resolution mass spectrometry revealed β-galactosidase degradation of several β-linkage-containing BMOs and production of novel oligosaccharides that ranged in size from 5 to 11 monosaccharide units containing several galactose repeating units and N-acetylhexosamine at their reducing ends. Optimization of BMO hydrolysis and separation methodology could generate high amounts of hetero-oligosaccharides for improved recovery of potentially biotherapeutic oligosaccharides.

Ethanol is considered as a renewable transport fuels and demand is expected to grow. In this work, trends related to bio-ethanol production are described using Thailand as an example. Developments on high-temperature fermentation and membrane technologies are also explained. This study focuses on the application of membranes in ethanol recovery after fermentation. A preliminary simulation was performed to compare different process configurations to concentrate 10 wt% ethanol to 99.5 wt% using membranes. In addition to the significant energy reduction achieved by replacing azeotropic distillation with membrane dehydration, employing ethanol-selective membranes can further reduce energy demand. Silicalite membrane is a type of membrane showing one of the highest ethanol-selective permeation performances reported today. A silicalite membrane was applied to separate a bio-ethanol solution produced via high-temperature fermentation followed by a single distillation. The influence of contaminants in the bio-ethanol on the membrane properties and required further developments are also discussed.