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In the pursuit of developing advanced nanofiltration membranes with high permeation flux for organic solvents, a TiO2 nanofilm was synthesized via a vapor–liquid interfacial reaction on a flat-sheet α-Al2O3 ceramic support. This process involves the reaction of glycerol, an organic precursor with a structure featuring 1,2-diol and 1,3-diol groups, with TiCl4 vapor to form organometallic hybrid films. Subsequent calcination in air at 250 °C transforms these hybrid films into carbon-doped titanium oxide nanofilms. The unique structure of glycerol plays a crucial role in determining the properties of the resulting nanopores, which exhibit high solvent permeance and effective solute rejection. The synthesized carbon-doped TiO2 nanofiltration membranes demonstrated impressive performance, achieving a pure methanol permeability as high as 90.9 L·m−2·h −1·bar−1. Moreover, these membranes exhibited a rejection rate of 93.2% for Congo Red in a methanol solution, underscoring their efficacy in separating solutes from solvents. The rigidity of the nanopores within these nanofilms, when supported on ceramic materials, confers high chemical stability even in the presence of polar solvents. This robustness makes the carbon-doped TiO2 nanofilms suitable for applications in the purification and recovery of organic solvents.

In the pursuit of developing advanced nanofiltration membranes with high permeation flux for organic solvents, a TiO 2 nanofilm was synthesized via a vapor-liquid interfacial reaction on a flat-sheet α-Al 2 O 3 ceramic support. This process involves the reaction of glycerol, an organic precursor with a structure featuring 1,2-diol and 1,3-diol groups, with TiCl 4 vapor to form organometallic hybrid films. Subsequent calcination in air at 250 °C transforms these hybrid films into carbon-doped titanium oxide nanofilms. The unique structure of glycerol plays a crucial role in determining the properties of the resulting nanopores, which exhibit high solvent permeance and effective solute rejection. The synthesized carbon-doped TiO 2 nanofiltration membranes demonstrated impressive performance, achieving a pure methanol permeability as high as 90.9 L·m -2 ·h -1 ·bar -1 . Moreover, these membranes exhibited a rejection rate of 93.2% for Congo Red in a methanol solution, underscoring their efficacy in separating solutes from solvents. The rigidity of the nanopores within these nanofilms, when supported on ceramic materials, confers high chemical stability even in the presence of polar solvents. This robustness makes the carbon-doped TiO 2 nanofilms suitable for applications in the purification and recovery of organic solvents.

Bottom-up approaches to producing aqueous crystal suspensions of active pharmaceutical ingredients (APIs), such as anti-solvent crystallisation, are gaining interest as they offer better control over surface properties compared to top-down approaches. However, one of the major challenges that needs to be addressed is the removal of organic solvents after the crystallisation step due to strict limitations regarding human exposure. Within this work, we investigated a process concept for the removal of solvent (i.e., ethanol) from the API crystal suspension using membrane-based diafiltration. A four-stage diafiltration process successfully reduced the ethanol concentration in the API (here, naproxen) crystal suspension below 0.5 wt% (the residual solvent limit as per ICH guidelines) with a water consumption of 1.5 g of added water per g of feed. The solvent exchange process had no negative influence on the stability of the crystals in suspension, as their size and polymorphic form remained unchanged. This work is a step towards the bottom-up production of API crystal suspension by applying solvent/anti-solvent crystallisation. It provides the proof of concept for establishing a process of organic solvent removal and offers an experimental framework to serve as the foundation for the design of experiments implementing a solvent exchange in API production processes.

In research on membranes, the addition of co-solvents to the polymer dope solution is a common method for tuning the morphology and separation performance. For organic solvent nanofiltration (OSN) applications, we synthesized polybenzimidazole (PBI) membranes with high separation properties and stability by adding acetonitrile (MeCN) to the dope solution, followed by crosslinking with dibromo-p-xylene. Accordingly, changes in the membrane structure and separation properties were investigated when MeCN was added. PBI/MeCN membranes with a dense and thick active layer and narrow finger-like macrovoids exhibited superior rejection properties in the ethanol solution compared with the pristine PBI membrane. After crosslinking, they displayed superior rejection properties (96.56% rejection of 366-g/mol polypropylene glycol). In addition, the membranes demonstrated stable permeances for various organic solvents, including acetone, methanol, ethanol, toluene, and isopropyl alcohol. Furthermore, to evaluate the feasibility of the modified PBI OSN membranes, ecamsule, a chemical product in the fine chemical industry, was recovered. Correspondingly, the efficient recovery of ecamsule from a toluene/methanol solution using the OSN process with PBI/MeCN membranes demonstrated their applicability in many fine chemical industries.

Poly-(4,4′-oxydiphenylene) pyromellitimide or Kapton is the most widely available polyimide with high chemical and thermal stability. It has great prospects for use as a membrane material for filtering organic media due to its complete insolubility. However, the formation of membranes based on it, at the moment, is an unsolved problem. The study corresponds to the rediscovery of poly(4,4′-oxydiphenylene–pyromellitimide)-based soluble copoly(urethane-imides) as membrane polymers of a new generation. It is shown that the physical structure of PUI films prepared by the solution method becomes porous after the removal of urethane blocks from the polymer, and the pore size varies depending on the conditions of thermolysis and subsequent hydrolysis of the membrane polymer. The film annealed at 170 °C with a low destruction degree of polycaprolactam blocks exhibits the properties of a nanofiltration membrane. It is stable in the aprotic solvent DMF and has a Remasol Brilliant Blue R retention coefficient of 95%. After the hydrolysis of thermally treated films in acidic media, ultrafiltration size 66–82 nm pores appear, which leads to an increase in the permeate flow by more than two orders of magnitude. This circumstance provides opportunities for controlling the membrane polymer structure for further optimization of the performance characteristics of filtration membranes based on it. Thus, we proposed a new preparation method of ultra- and nanofiltration membranes based on poly(4,4′-oxydiphenylene–pyromellitimide) that are stable in aprotic solvents.

Compared to the traditional chemical-crosslinking-based polymer, the porous polytetrafluoroethylene (PTFE) substrate is considered to be an excellent support for the fabrication of thin-film composite (TFC) organic solvent nanofiltration (OSN) membranes. However, the low surface energy and chemical inertness of PTFE membranes presented major challenges for fabricating a polyamide active layer on its surface via interfacial polymerization (IP). In this study, a triple-layered TFC OSN membrane was fabricated via IP, which consisted of a PA top layer on a carbon nanotube (CNT) interlayer covering the macroporous PTFE substrate. The defect-free formation and cross-linking degree of the PA layer can be improved by controlling the CNT deposition amount to achieve a good OSN performance. This new TFC OSN membrane exhibited a high dye rejection (the rejection of Bright blue B > 97%) and a moderate and stable methanol permeated flux of approximately 8.0 L m−2 h−1 bar−1. Moreover, this TFC OSN membrane also exhibited an excellent solvent resistance to various organic solvents and long-term stability during a continuous OSN process.

Membranes with excellent separation performance and stability are needed for organic solvent nanofiltration in industrial separation and purification processes. Here we reported a newly PPSU-MoS2/PA-MIL-101(Cr) composite membrane with high permeance, good selectivity and stability. The MIL-101(Cr) was introduced in the polyamide (PA) layer via the PIP/TMC interfacial polymerization process on a microporous PPSU-MoS2 substrate. At a small doping amount of 0.005 wt% MIL-101(Cr), the PPSU-MoS2/PA-MIL-101(Cr) composite membrane exhibited a high methanol permeance of 12.03 L m−2 h−1 bar−1, twice higher than that of the pristine membrane without sacrificing selectivity. Furthermore, embedding MIL-101(Cr) notably enhanced the stability of the composite membrane, with permeance only decreasing by 8% after a long time operation of 80 h (pristine membrane decreased by 25%). This work demonstrated a composite membrane modified by MIL-101(Cr) with superior separation performance, which provides potential application of MOF materials for high-performance membranes in organic solvent nanofiltration and a theoretical foundation for future research in studying MOF’s influence on membrane properties.

In this work, we combined the non-solvent induced phase separation (NIPS) and further cross-linking by cations towards the preparation of nanofiltration membranes based on sodium alginate, a biodegradable, natural polymer. Acetone, ethanol, toluene, and hexane were used as non-solvents, and cations of calcium, silver, and aluminum—for polymer cross-linking, respectively. Results showed the precipitation strength of non-solvent played a noticeable role in the membrane’s performance; for instance, the toluene permeability changed by four orders of magnitude with the decrease of precipitation strength of the non-solvent: acetone (Ptoluene = 0.1 kg∙m−2∙h−1∙bar−1) < ethanol (3 kg∙m−2∙h−1∙bar−1) < hexane (41 kg∙m−2∙h−1∙bar−1) < toluene (415 kg∙m−2∙h−1∙bar−1). It was shown that simultaneous precipitation and crosslinking in aqueous solutions AlCl3 or AgNO3 must be used in the preparation of alginate membranes for the highly selective recovery of pharmaceutical compounds from organic media. These membranes show rejection R = 90–93% of substances with MW = 626 g/mol and ethanol permeability PEtOH = 1.5–2.5 kg∙m−2∙h−1∙bar−1. For the highly selective recovery of pharmaceutical compounds from water, the method of obtaining membranes must be changed. Precipitation in toluene and then crosslinking in aqueous solutions of AlCl3 or AgNO3 must be used sequentially instead of simultaneous precipitation and crosslinking in aqueous solutions of the same inorganic salts. The permeability of such membranes varied from 0.44 to 7.8 kg∙m−2∙h−1∙bar−1 depending on the crosslinking cation in the alginate. The rejection of model substances with MW 350 and 626 g/mol were on the level of 99%. Alginate membranes can be used to solve separation problems in the pharmaceutical field, for example, to isolate antibiotics from their extractants and remove the same antibiotics from aqueous pharmaceutical waste to prevent their accumulation in the environment and the emergence of resistant genes and bacteria.

Pickering emulsions (PEs) have received increasing interest for their application in catalytic multiphase reactions. Organic solvent nanofiltration of PEs was shown to be a promising procedure for efficient and effective catalyst recycling. In this work, a systematic parameter study to identify the main influencing parameters on PE filtration was conducted for a large variety of PE compositions for the first time. In addition to temperature, only the type of organic solvent significantly influenced the filtration performance, which could be mathematically modeled via a combination of the solution–diffusion and the resistance in the series model. Particle type and concentration, dispersed phase fraction and the presence of reaction (by-)products did not show any significant impact on the permeability. The stirrer speed only became important when emulsions stabilized by particles without the tendency to form 3D network structures were filtered in long-term filtration experiments. These results pave the way towards the application of PE membrane filtration for catalyst recovery in continuous liquid/liquid multiphase reactions and enable broad operation windows. As the mechanical separation of PEs was shown to be a very robust process, the emulsion composition can now be tuned to meet the needs of the reaction without any (significant) loss in filtration performance.

Graphene-based membranes are promising candidates for efficient organic solvent nanofiltration (OSN) processes because of their unique structural characteristics, such as mechanical/chemical stability and precise molecular sieving. Recently, to improve organic solvent permeance and selectivity, nanopores have been fabricated on graphene planes via chemical and physical methods. The nanopores serve as an additional channel for facilitating ultrafast solvent permeation while filtering organic molecules by size exclusion. This review summarizes the recent developments in nanoporous graphene (NG)-based membranes for OSN applications. The membranes are categorized depending on the membrane structure: single-layer NG, multilayer NG, and graphene-based composite membranes hybridized with other porous materials. Techniques for nanopore generation on graphene, as well as the challenges faced and the perspectives required for the commercialization of NG membranes, are also discussed.

Organic solvent nanofiltration (OSN) has been considered as one of the key technologies to improve the sustainability of separation processes. Recently, apart from enhancing the membrane performance, greener fabricate on of OSN membranes has been set as a strategic objective. Considerable efforts have been made aiming to improve the sustainability in membrane fabrication, such as replacing membrane materials with biodegradable alternatives, substituting toxic solvents with greener solvents, and minimizing waste generation with material recycling. In addition, new promising fabrication and post-modification methods of solvent-stable membranes have been developed exploiting the concept of interpenetrating polymer networks, spray coating, and facile interfacial polymerization. This review compiles the recent progress and advances for sustainable fabrication in the field of polymeric OSN membranes.

Bottom-up approaches to producing aqueous crystal suspensions of active pharmaceutical ingredients (APIs), such as anti-solvent crystallisation, are gaining interest as they offer better control over surface properties compared to top-down approaches. However, one of the major challenges that needs to be addressed is the removal of organic solvents after the crystallisation step due to strict limitations regarding human exposure. Within this work, we investigated a process concept for the removal of solvent (i.e., ethanol) from the API crystal suspension using membrane-based diafiltration. A four-stage diafiltration process successfully reduced the ethanol concentration in the API (here, naproxen) crystal suspension below 0.5 wt% (the residual solvent limit as per ICH guidelines) with a water consumption of 1.5 g of added water per g of feed. The solvent exchange process had no negative influence on the stability of the crystals in suspension, as their size and polymorphic form remained unchanged. This work is a step towards the bottom-up production of API crystal suspension by applying solvent/anti-solvent crystallisation. It provides the proof of concept for establishing a process of organic solvent removal and offers an experimental framework to serve as the foundation for the design of experiments implementing a solvent exchange in API production processes.

In research on membranes, the addition of co-solvents to the polymer dope solution is a common method for tuning the morphology and separation performance. For organic solvent nanofiltration (OSN) applications, we synthesized polybenzimidazole (PBI) membranes with high separation properties and stability by adding acetonitrile (MeCN) to the dope solution, followed by crosslinking with dibromo-p-xylene. Accordingly, changes in the membrane structure and separation properties were investigated when MeCN was added. PBI/MeCN membranes with a dense and thick active layer and narrow finger-like macrovoids exhibited superior rejection properties in the ethanol solution compared with the pristine PBI membrane. After crosslinking, they displayed superior rejection properties (96.56% rejection of 366-g/mol polypropylene glycol). In addition, the membranes demonstrated stable permeances for various organic solvents, including acetone, methanol, ethanol, toluene, and isopropyl alcohol. Furthermore, to evaluate the feasibility of the modified PBI OSN membranes, ecamsule, a chemical product in the fine chemical industry, was recovered. Correspondingly, the efficient recovery of ecamsule from a toluene/methanol solution using the OSN process with PBI/MeCN membranes demonstrated their applicability in many fine chemical industries.

Poly-(4,4'-oxydiphenylene) pyromellitimide or Kapton is the most widely available polyimide with high chemical and thermal stability. It has great prospects for use as a membrane material for filtering organic media due to its complete insolubility. However, the formation of membranes based on it, at the moment, is an unsolved problem. The study corresponds to the rediscovery of poly(4,4'-oxydiphenylene-pyromellitimide)-based soluble copoly(urethane-imides) as membrane polymers of a new generation. It is shown that the physical structure of PUI films prepared by the solution method becomes porous after the removal of urethane blocks from the polymer, and the pore size varies depending on the conditions of thermolysis and subsequent hydrolysis of the membrane polymer. The film annealed at 170 °C with a low destruction degree of polycaprolactam blocks exhibits the properties of a nanofiltration membrane. It is stable in the aprotic solvent DMF and has a Remasol Brilliant Blue R retention coefficient of 95%. After the hydrolysis of thermally treated films in acidic media, ultrafiltration size 66-82 nm pores appear, which leads to an increase in the permeate flow by more than two orders of magnitude. This circumstance provides opportunities for controlling the membrane polymer structure for further optimization of the performance characteristics of filtration membranes based on it. Thus, we proposed a new preparation method of ultra- and nanofiltration membranes based on poly(4,4'-oxydiphenylene-pyromellitimide) that are stable in aprotic solvents.

Compared to the traditional chemical-crosslinking-based polymer, the porous polytetrafluoroethylene (PTFE) substrate is considered to be an excellent support for the fabrication of thin-film composite (TFC) organic solvent nanofiltration (OSN) membranes. However, the low surface energy and chemical inertness of PTFE membranes presented major challenges for fabricating a polyamide active layer on its surface via interfacial polymerization (IP). In this study, a triple-layered TFC OSN membrane was fabricated via IP, which consisted of a PA top layer on a carbon nanotube (CNT) interlayer covering the macroporous PTFE substrate. The defect-free formation and cross-linking degree of the PA layer can be improved by controlling the CNT deposition amount to achieve a good OSN performance. This new TFC OSN membrane exhibited a high dye rejection (the rejection of Bright blue B > 97%) and a moderate and stable methanol permeated flux of approximately 8.0 L m−2 h−1 bar−1. Moreover, this TFC OSN membrane also exhibited an excellent solvent resistance to various organic solvents and long-term stability during a continuous OSN process.

Membranes with excellent separation performance and stability are needed for organic solvent nanofiltration in industrial separation and purification processes. Here we reported a newly PPSU-MoS 2 /PA-MIL-101(Cr) composite membrane with high permeance, good selectivity and stability. The MIL-101(Cr) was introduced in the polyamide (PA) layer via the PIP/TMC interfacial polymerization process on a microporous PPSU-MoS 2 substrate. At a small doping amount of 0.005 wt% MIL-101(Cr), the PPSU-MoS 2 /PA-MIL-101(Cr) composite membrane exhibited a high methanol permeance of 12.03 L m -2 h -1 bar -1 , twice higher than that of the pristine membrane without sacrificing selectivity. Furthermore, embedding MIL-101(Cr) notably enhanced the stability of the composite membrane, with permeance only decreasing by 8% after a long time operation of 80 h (pristine membrane decreased by 25%). This work demonstrated a composite membrane modified by MIL-101(Cr) with superior separation performance, which provides potential application of MOF materials for high-performance membranes in organic solvent nanofiltration and a theoretical foundation for future research in studying MOF's influence on membrane properties.

Pickering emulsions (PEs) have received increasing interest for their application in catalytic multiphase reactions. Organic solvent nanofiltration of PEs was shown to be a promising procedure for efficient and effective catalyst recycling. In this work, a systematic parameter study to identify the main influencing parameters on PE filtration was conducted for a large variety of PE compositions for the first time. In addition to temperature, only the type of organic solvent significantly influenced the filtration performance, which could be mathematically modeled via a combination of the solution–diffusion and the resistance in the series model. Particle type and concentration, dispersed phase fraction and the presence of reaction (by-)products did not show any significant impact on the permeability. The stirrer speed only became important when emulsions stabilized by particles without the tendency to form 3D network structures were filtered in long-term filtration experiments. These results pave the way towards the application of PE membrane filtration for catalyst recovery in continuous liquid/liquid multiphase reactions and enable broad operation windows. As the mechanical separation of PEs was shown to be a very robust process, the emulsion composition can now be tuned to meet the needs of the reaction without any (significant) loss in filtration performance. [ABSTRACT FROM AUTHOR]

In this work, we combined the non-solvent induced phase separation (NIPS) and further cross-linking by cations towards the preparation of nanofiltration membranes based on sodium alginate, a biodegradable, natural polymer. Acetone, ethanol, toluene, and hexane were used as non-solvents, and cations of calcium, silver, and aluminum-for polymer cross-linking, respectively. Results showed the precipitation strength of non-solvent played a noticeable role in the membrane's performance; for instance, the toluene permeability changed by four orders of magnitude with the decrease of precipitation strength of the non-solvent: acetone ( P toluene = 0.1 kg∙m -2 ∙h -1 ∙bar -1 ) < ethanol (3 kg∙m -2 ∙h -1 ∙bar -1 ) < hexane (41 kg∙m -2 ∙h -1 ∙bar -1 ) < toluene (415 kg∙m -2 ∙h -1 ∙bar -1 ). It was shown that simultaneous precipitation and crosslinking in aqueous solutions AlCl 3 must be used in the preparation of alginate membranes for the highly selective recovery of pharmaceutical compounds from organic media. These membranes show rejection 3 must be used in the preparation of alginate membranes for the highly selective recovery of pharmaceutical compounds from organic media. These membranes show rejection R = 90-93% of substances with MW = 626 g/mol and ethanol permeability P EtOH = 1.5-2.5 kg∙m -2 . For the highly selective recovery of pharmaceutical compounds from water, the method of obtaining membranes must be changed. Precipitation in toluene and then crosslinking in aqueous solutions of AlCl -1 ∙bar -1 must be used sequentially instead of simultaneous precipitation and crosslinking in aqueous solutions of the same inorganic salts. The permeability of such membranes varied from 0.44 to 7.8 kg∙m 3 or AgNO 3 must be used sequentially instead of simultaneous precipitation and crosslinking in aqueous solutions of the same inorganic salts. The permeability of such membranes varied from 0.44 to 7.8 kg∙m -2 ∙h -1 350 and 626 g/mol were on the level of 99%. Alginate membranes can be used to solve separation problems in the pharmaceutical field, for example, to isolate antibiotics from their extractants and remove the same antibiotics from aqueous pharmaceutical waste to prevent their accumulation in the environment and the emergence of resistant genes and bacteria.-1 depending on the crosslinking cation in the alginate. The rejection of model substances with MW 350 and 626 g/mol were on the level of 99%. Alginate membranes can be used to solve separation problems in the pharmaceutical field, for example, to isolate antibiotics from their extractants and remove the same antibiotics from aqueous pharmaceutical waste to prevent their accumulation in the environment and the emergence of resistant genes and bacteria.

Graphene-based membranes are promising candidates for efficient organic solvent nanofiltration (OSN) processes because of their unique structural characteristics, such as mechanical/chemical stability and precise molecular sieving. Recently, to improve organic solvent permeance and selectivity, nanopores have been fabricated on graphene planes via chemical and physical methods. The nanopores serve as an additional channel for facilitating ultrafast solvent permeation while filtering organic molecules by size exclusion. This review summarizes the recent developments in nanoporous graphene (NG)-based membranes for OSN applications. The membranes are categorized depending on the membrane structure: single-layer NG, multilayer NG, and graphene-based composite membranes hybridized with other porous materials. Techniques for nanopore generation on graphene, as well as the challenges faced and the perspectives required for the commercialization of NG membranes, are also discussed. [ABSTRACT FROM AUTHOR]

Organic solvent nanofiltration (OSN) has been considered as one of the key technologies to improve the sustainability of separation processes. Recently, apart from enhancing the membrane performance, greener fabricate on of OSN membranes has been set as a strategic objective. Considerable efforts have been made aiming to improve the sustainability in membrane fabrication, such as replacing membrane materials with biodegradable alternatives, substituting toxic solvents with greener solvents, and minimizing waste generation with material recycling. In addition, new promising fabrication and post-modification methods of solvent-stable membranes have been developed exploiting the concept of interpenetrating polymer networks, spray coating, and facile interfacial polymerization. This review compiles the recent progress and advances for sustainable fabrication in the field of polymeric OSN membranes. [ABSTRACT FROM AUTHOR]

Organic solvent nanofiltration (OSN) has been considered as one of the key technologies to improve the sustainability of separation processes. Recently, apart from enhancing the membrane performance, greener fabricate on of OSN membranes has been set as a strategic objective. Considerable efforts have been made aiming to improve the sustainability in membrane fabrication, such as replacing membrane materials with biodegradable alternatives, substituting toxic solvents with greener solvents, and minimizing waste generation with material recycling. In addition, new promising fabrication and post-modification methods of solvent-stable membranes have been developed exploiting the concept of interpenetrating polymer networks, spray coating, and facile interfacial polymerization. This review compiles the recent progress and advances for sustainable fabrication in the field of polymeric OSN membranes.