Membrane-aided simultaneous reaction-separation for liquid-phase products and methods

Abstract

A membrane for simultaneous reaction-separation of liquid phase reactants, comprising a membrane body having a plurality of pores, wherein the membrane body is coated with a self-assembly monolayer (SAM). A method for simultaneous reaction-separation of immiscible liquid phase reactants, comprising providing a membrane having a membrane body; wherein the membrane is disposed between a first vessel and a second vessel; placing two or more reactants in the first vessel; and receiving one or more products of the simultaneous reaction-separation in the second vessel.

Description

MEMBRANE-AIDED SIMULTANEOUS REACTION-SEPARATIONFOR LIQUID-PHASE PRODUCTS AND METHODSRELATED APPLICATION

[0001] This application claims priority benefit under 35 U. S. C. § 119(e) of U. S. Provisional Application No.63 / 713,556 filed October 29, 2024, the contents of which are herein incorporated by reference.STATEMENT OF GOVERNMENT SUPPORT

[0002] This invention was made with government support under grant # 2329767 awarded by the National Science Foundation. The government has certain rights in the invention.FIELD OF THE DISCLOSURETechnical field

[0003] The present disclosure generally relates to the field of chemical reaction and separation processes and, more specifically, to simultaneous chemical reaction-separation processes.Background

[0004] Liquid-phase chemical reaction plays a vital role in various industries, ranging from pharmaceuticals to biochemicals. Conventionally, reaction and separation are two separate steps in manufacturing. During the reaction step, the reagents react to form the products. Then, the product is separated from the unreacted reagents, solvent and byproduct in the separation step. To improve efficiency and reduce cost, it is highly desirable to develop a simultaneous reaction-separation process. Previously, different technologies, integrating chemical reactions and separation, have been studied. Reactive distillation combines chemical reactions and distillation in a single unit, allowing simultaneous reaction and separation. However, distillation suffers from high consumption of thermal energy and associated high carbon emission.Adsorption-enhanced reaction involves the use of adsorbents to selectively remove one or more reactants or products from the reaction mixture, thereby driving the reaction towards completion. Here, the challenge is the regeneration and reuse of the adsorbent material. Reactive extraction combines a chemical reaction withliquid-liquid extraction. Similar to conventional extraction, the large amounts of the solvent used and the high operation cost are major concerns.

[0005] Membrane reactors integrate chemical reactions and selective membrane separation. The reaction takes place inside the reactor, while the membrane selectively separates the desired product(s) from the reaction mixture. This approach offers benefits such as improved selectivity, reduced reaction inhibition, and simplified downstream separation. Membrane separation is also a more intensified process compared to conventional extraction or distillation. However, to date, membrane reactor only applies for gas-phase reactions.

[0006] Liquid phase chemical reaction is critical for many industrial applications, ranging from petrochemicals to pharmaceuticals. Conventionally, reaction and separation are two separate steps in manufacturing. During the reaction, the reagents react to form the products, and then the product is separated from the unreacted reagents, solvents and byproducts in the separation step. To improve efficiency and reduce costs, it is highly desirable to integrate these two steps into a simultaneous reaction-separation process.

[0007] Liquid phase chemical reaction is critical to many industries such as pharmaceuticals, petrochemicals, energy production, and wastewater treatment. In such a chemical reaction, raw materials are converted into valuable liquid products which are then separated from the reaction systems consisting of unreacted reagents, solvents and by products. Conventionally, reaction and separation are two separate steps in manufacturing. Process intensification has emerged as a popular subject in Chemical Engineering in past decades, aiming to develop novel technologies which can bring significant improvements to existing manufacturing processes.1Examples of such improvement include reduction of equipment-size / production-capacity ratio, decreasing energy consumption and waste production, as well as integration of multiple operations or functions.1'3For process intensification of chemical reactions, integration of reaction and separation into a simultaneous reaction-separation process will have many benefits such as overcoming equilibrium limitation, reduced costs, complete reactant conversion, etc.1'3

[0008] Previously, different technologies integrating chemical reactions and separation have been studied. Reactive distillation combines chemical reactions and distillation in a single unit, allowing simultaneous reaction and separation based on product volatility.4However, reactive distillation is limited by complex design of distillation column, temperature mismatch between reaction and separation, unfavorably volatile reactants, high consumption of thermal energy and associated high carbon emission.4"6Adsorption-enhanced reaction involves the use of adsorbents to selectively remove byproducts from the reaction mixture, thereby driving the reaction towards completion,7’8which has been researched extensively for CO2adsorption in H2production.9Here, the challenge is the regeneration and reuse of adsorbent material, that requires multiple steps involving high pressure desorption.7’8Reactive extraction involves a chemical reaction between solute and extractant, and it has been recognized as an effective, low-cost and more environmentally friendly production method for carboxylic acid, compared to conventional synthesis from petroleum reserves.10"12However, the application of organic solvent in reactive extraction still has several disadvantages, e.g., solvent toxicity, operation safety, regeneration of the solvent.13

[0009] Membrane reactors integrate chemical reactions and selective membrane separation. The reaction takes place inside the reactor, while the membrane selectively separates the desired product(s) from the reaction mixture. This approach offers benefits such as improved selectivity, reduced reaction inhibition, and simplified downstream separation. Membrane separation is also a more intensified process compared to conventional extraction or distillation. Researchers have investigated different types of membranes, including polymeric, ceramic, and composite membranes, to optimize their performance for simultaneous reaction-separation.14"21However, to date, the application of membrane reactor is largely limited to some gas product, e.g., H2 gas14, 15’19, 21. In liquid phase separation, microfiltration, nanofiltration, ultrafiltration and reverse osmosis membranes have been utilized in biodiesel production22’23and wastewater treatment,24’23where small molecules can be separated via membrane pore size exclusion. However, the efficiency is limited by membrane fouling and external pressure as the driving force imparts additional costs.24Therefore, there exists a gap for membrane-based reactors to achieve simultaneous reaction-separation for liquid phase reaction.

[0010] To date, very few studies have been conducted to integrate the membrane separation into liquid-phase chemical reaction. Xu et al demonstrated a continuous in-situ separation for the product 2-bromo-2-methylpropane (tert-CMBBr) from the reaction between tert-butanol (tert-C4H10O) and hydrobromic acid (HBr) using a hydrophobic / oleophilic porous polytetrafluoroethylene membrane.26Ma et al achieved in-situ separation of a similar reaction system using a pH-responsive fabric with switchable wettability, where TiO2nanoparticles are modified with fluorine polymer and deposited onto a fabric by dip coating.27Wu et al demonstrated simultaneous synthesis and separation in production of hydrophobic ionic liquids (IL) taking advantage of a Janus hollow fiber membrane reactor with a hydrophilic inner surface and hydrophobic outer surface.28However, the complicated membrane preparation process in the above studies makes it not feasible in large-scale real-life applications..

[0011] The present disclosure is directed to a membrane-based reactor in which a reaction takes place, and the membrane selectively separates the desired products from the reagent, which is immiscible with the product. The present disclosure demonstrates the simultaneous reaction-separation of an ionic liquid (IL), i.e., [EMIM][NTf2], through a perfluorocarbon-coated membrane which shows hydrophobicity / oleophilicity, and the major driving force for the separation is the liquid capillary pressure within membrane pores, without external pressure applied. The IL product purity is -100% based on NMR and TGA results, and it does not degrade in multiple cycles of reaction-separation. Our work here highlights the potential of the process intensification in industrial manufacturing of various liquid products.

[0012] To address shortcomings of the prior art, the present disclosure is directed to (1) methods of fabricating membranes, which enable simultaneous reaction-separation of liquid-phase products; and (2) a process and device for conducting simultaneous reaction-separation.BRIEF SUMMARY OF THE DISCLOSURE

[0013] In a preferred aspect, the present disclosure comprises a membrane for simultaneous reactionseparation of liquid phase reactants, comprising a membrane body having a plurality of pores, wherein the membrane body is coated with a self-assembly monolayer (SAM).

[0014] In another preferred aspect of a membrane for simultaneous reaction-separation of liquid phase reactants of the present disclosure, the membrane body comprises one or more of glass, ceramic, metal and / or plastics.

[0015] In yet another preferred aspect of a membrane for simultaneous reaction-separation of liquid phase reactants of the present disclosure, each of the plurality of pores has a diameter of approximately 5-300 pm.

[0016] In another preferred aspect of a membrane for simultaneous reaction-separation of liquid phase reactants of the present disclosure, the SAM has a thickness of about 0.5-1000 nanometers.

[0017] In an additional preferred aspect of a membrane for simultaneous reaction-separation of liquid phase reactants of the present disclosure, the SAM comprises lH,lH,2H,2H-perfluorodecyltrichlorosilane (FDTS), or wherein the SAM is made from a fluorocarbon coupling agent or a hydrocarbon silane coupling agent wherein each of the fluorocarbon or hydrocarbon silane coupling agents has an end group selected from the group of ethanol, methanol and chloride; or wherein the SAM is made from a hydrophobic silane coupling agent selected from the group of CF3(CF2)5(CH2)2Si(OC2H5)3, CF3(CF2)5(CH2)2Si(OCH3)3, CF3(CF2)5(CH2)2SiCl3, CF3(CF2)5(CH2)2Si(CH3)Cl2, CF3(CF2)5(CH2)2Si(CH3)2Cl, CH3(CH2)nSiCl3, and CH3[Si(CH3)2O]nSi(CH3)3.

[0018] In another preferred aspect, the present disclosure comprises a method for simultaneous reactionseparation of immiscible liquid phase reactants, comprising providing a membrane having a membrane body; wherein the membrane is disposed between a first vessel and a second vessel; placing two or more reactants in the first vessel; and receiving one or more products of the simultaneous reaction-separation in the second vessel.

[0019] In another preferred aspect of a method for simultaneous reaction-separation of immiscible liquid phase reactants of the present disclosure, the membrane body has a plurality of pores, wherein the membrane body is coated with a self-assembly monolayer (SAM).

[0020] In yet another preferred aspect of a method for simultaneous reaction-separation of immiscible liquid phase reactants of the present disclosure, the membrane body comprises glass, ceramic, metal or plastic.

[0021] In another preferred aspect of a method for simultaneous reaction-separation of immiscible liquid phase reactants of the present disclosure, each of the plurality of pores has a diameter of approximately 5-300 pm.

[0022] In yet another preferred aspect of a method for simultaneous reaction-separation of immiscible liquid phase reactants of the present disclosure, the SAM has a thickness of about 0.5 to about 1,000 nanometers.

[0023] In an additional preferred aspect of a method for simultaneous reaction-separation of immiscible liquid phase reactants of the present disclosure, the reactants comprise [EMIM][Cl] and [Li][NTf2], the SAM comprises lH,lH,2H,2H-perfluorodecyltrichlorosilane (FDTS) and the one or more products received in the second vessel comprises [EMIM] [NTf2].

[0024] In another preferred aspect of a method for simultaneous reaction-separation of immiscible liquid phase reactants of the present disclosure, one or more of the products is immiscible with one or more of the reactants; wherein an oil-based product will go through the membrane, while the water-based product will not.

[0025] In an additional preferred aspect, the present disclosure comprises a membrane for separation of miscible liquid phase mixtures, comprising a supported ionic liquid membrane (SILM) comprising a polyvinylidene fluoride (PVDF) membrane body impregnated with an ionic liquid.

[0026] In another preferred aspect of a membrane for separation of miscible liquid phase mixtures of the present disclosure, the ionic liquid comprises l-Butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), or another ionic liquid where the basic structure of the cation is based on imidazolium, pyrrolidinium, pyridinium, tetraalkylammonium, or tetraalkylphosphonium, and the anion consists of trifluoromethane sulfonate, tetrafluoro borate, bis(fluorosulfonyl)imide, bis(perfluoroalkyl sulfonyl)imide, or hexafluorophosphate.

[0027] In yet an additional preferred aspect, the present disclosure comprises a method for separation of miscible liquid phase mixtures, comprising providing a membrane comprising a supported ionic liquid membrane (SILM) comprising a polyvinylidene fluoride (PVDF), or other plastic, glass, ceramic or metal membrane body impregnated with an ionic liquid; wherein the membrane is disposed between a first vesseland a second vessel; placing one or more reactants and solvents in the first vessel; and receiving the product that is miscible with one or more of the one or more reactants and solvents in the second vessel.

[0028] In another preferred aspect of a method for separation of miscible liquid phase mixtures of the present disclosure, the ionic liquid comprises l-Butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), or another ionic liquid where the basic structure of the cation is based on imidazolium, pyrrolidinium, pyridinium, tetraalkylammonium, or tetraalkylphosphonium, and the anion consists of trifluoromethane sulfonate, tetrafluoro borate, bis(fluorosulfonyl)imide, bis(perfluoroalkyl sulfonyl)imide, or hexafluorophosphate.

[0029] In yet another preferred aspect, a method for separation of miscible liquid phase mixtures of the present disclosure further comprises adding a stripping solvent to the second vessel.

[0030] In another preferred aspect of a method for separation of miscible liquid phase mixtures of the present disclosure, the reactants in the first vessel produce the miscible products.

[0031] In yet another preferred aspect of a method for separation of miscible liquid phase mixtures of the present disclosure, the reactants in the first vessel produce the miscible products and the stripping solvent comprises aromatic hydrocarbons or linear hydrocarbons or nonpolar solvents or weakly polar solvents.

[0032] In a further preferred aspect of a method for separation of miscible liquid phase mixtures of the present disclosure, (i) the reactants comprise benzene and heptane or (ii) the reactants comprise heptane and dichloromethane where in either (i) or (ii) the stripping solvent comprises hexadecane.BRIEF DESCRIPTION OF THE DRAWINGS

[0033] For the present disclosure to be easily understood and readily practiced, the present disclosure will now be described for purposes of illustration and not limitation in connection with the following figures, wherein:

[0034] FIGS. 1(a) -(e) show the fabrication of FDTS coating on glass substrates and more specifically:

[0035] . FIG. 1(a) shows a schematic of a preferred thermal vapor deposition (TVD) setup according to the present disclosure;

[0036] . FIG. 1(b) shows contact angles on glass slides;

[0037] FIG. 1(c) shows images of contact angle on a FDTS-coated glass membrane;

[0038] FIG. 1(d) shows SEM images of glass membranes;

[0039] FIG. 1(e) shows XPS survey scans of uncoated and FDTS-coated glass membranes;

[0040] FIG. 2 shows a chart showing FDTS film thickness on glass slides at different TVD durations;

[0041] FIGS. 3(a)-(c) show a preferred simultaneous reaction-separation of an IL product of the present disclosure where:

[0042] FIG. 3(a) is a schematic of an ionic liquid reaction in a membrane-based reactor of the present disclosure;

[0043] FIG. 3(b) shows a preferred separation mechanism of an ionic liquid reaction in a membrane-based reactor of the present disclosure;

[0044] FIG. 3(c) shows IL products and aqueous phase byproduct from a preferred ionic liquid reaction from a preferred membrane-based reactor of the present disclosure;

[0045] FIGS. 4(a) and FIG. 4(b) show a simultaneous reaction-separation process for [Li] [Cl] (dyed blue) at the start of the process (FIG. 4(a)) and after 2 hours of going through the coated membrane (FIG. 4(b)), during which [EMIM][NTf2] has been separated.

[0046] FIGS. 5(a) and 5(b) show that in a preferred horizontal setup membrane-based reactor of the present disclosure liquid penetration through a preferred coated membrane in such setup is governed by capillary force only, and therefore, the passage of [EMIM][NTf2] was observed because of a driving-through capillary force (FIG. 5(a)), while [Li] [Cl] was blocked by a repelling capillary force (FIG. 5(b));

[0047] FIGS. 6(a)-(c) show ‘H NMR spectra of [EMIM][NTf2] collected from: commercial purchase (FIG.6(a)), simultaneous reaction-separation (FIG. 6(b)), and (c) reaction-decanting (FIG. 6(c)), where the watercontent in mass percentage in each sample was determined from the peak integration ratio;

[0048] FIGS. 6(d)-(e) show TGA Weight loss (%) of [EMIM][NTf2] collected from: (d) simultaneous reaction-separation, decanting after reaction and commercial purchase (FIG. 6(d)), and (e) from multiple cycles of simultaneous reaction-separation (FIG. 6(e));

[0049] FIG. 7 shows 1H NMR spectra of solvent DMSO-d6;

[0050] FIG. 8(a) is a schematic of the synthesis of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM] [NTf2]) according to a preferred method of the present disclosure;

[0051] . FIG. 8(b) shows a preferred setup of for a preferred simultaneous reaction-separation with a membrane that repels water and attracts ([EMIM] [NTf2]);

[0052] FIG. 8(c) shows 1H-NMR results of [EMIM] [NTf2] prepared by a preferred simultaneous reactionseparation process of the present disclosure (left) and conventional reaction followed by an additional separation step.

[0053] FIG. 9 is a schematic of a preferred Supported Ionic Liquid Membrane (SILM) separation setup according to the present disclosure comprising a feed compartment containing a mixture of benzene and heptane separated from a receiving compartment, which contains hexadecane, by the SILM where each compartment contains a stir bar.DETAILED DESCRIPTION

[0054] In the following detailed description, reference is made to the accompanying examples and figures that form a part hereof, and in which is shown, by way of illustration, specific embodiments in which the inventive subject matter may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice them, and it is to be understood that other embodiments may be utilized and that structural or logical changes may be made without departing from the scope of the inventive subject matter. Such embodiments of the inventive subject matter may be referred to, individually and / or collectively, herein by the term "disclosure" merely for convenience and without intending to voluntarily limit the scope of this application to any single inventive concept if more than one is in fact disclosed.

[0055] The following description is, therefore, not to be taken in a limited sense, and the scope of the inventive subject matter is defined by the appended claims and their equivalents.

[0056] The present disclosure is directed to a low-cost and easy-to-fabricate membrane-based reactor for the synthesis of l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM][NTf2], which is an (IL)involved in many important applications.29The bulk phase of IL product is immiscible with the reagent aqueous phase so that the separation can be driven by different capillary forces of two phases with membrane, which does not require external pressure. Commercial porous glass membranes have been modified by a perfluorocarbon coating: (heptadecafluoro- 1, 1, 2, 2-tetrahydrodecyl)triethoxy silane (FDTS) via thermal vapor deposition, and the coated membrane surface has hydrophobicity / oleophilicity due to the fluorinated surface chemistry of FDTS and the intrinsic roughness of glass membrane surface, which induces more robust simultaneous reaction-separation. In other words, the capillary force will drive the IL phase to pass through the oleophilic membrane, but the passage of aqueous phase is stopped by the membrane hydrophobicity. The [EMIM][NTf2] separated simultaneously in reaction shows high purity based on1H NMR and thermogravimetric analysis (TGA), which does not decrease in multiple cycles of simultaneous reaction-separation. The finding here demonstrates the potential for large-scale synthesis of many liquid products for industrial-level applications.Hydrophobicity / oleophilicity: The effect of coating and surface topography

[0057] The contact angles of water (WCA) and hexadecane (HCA) on uncoated and coated glass slides are shown in FIG. 1(b). WCA and HCA increased from 13.2° and 7° to 106° and 72°, respectively, after flat glass slides are coated with FDTS in a thermal vapor deposition setup shown in FIG. 1(a), indicating that the perfluorocarbon coating has successfully modified the glass surface wettability, and the higher WCA and lower HCA suggest a hydrophobic / oleophilic glass surface. The change in surface wettability is due to the low surface energy of FDTS’ s fluorinated chemistry. This TVD process gives rise to a coating thickness of ~2.6 nm, shown in FIG.2. The FDTS coating thickness is a function of TVD duration, and longer duration leads to a thicker FDTS film, because longer TVD time allows more FDTS molecules to bombard and bond to the glass surfaces. A preferred TVD duration used for glass membranes in simultaneous reactionseparation is 24 hours. The contact angles of [EMIM][NTf2] (ENCA) and [Li] [Cl] (LCCA) were measured because they are the immiscible products formed in the ionic liquid reaction and expected to be separated based on the different capillary forces from their interactions with the coated membrane surface. This capillary-force-driven separation mechanism has been reported previously30, 31and is discussed in detailherein. Here, the hydrophobicity / oleophilicity of glass surface is expected to result in a higher contact angle of aqueous phase [Li][Cl] and a lower contact angle of IL (oil) phase [EMIMJfNTfj]. As shown in FIG. 1(b), the LCCA and ENCA of coated glass slide are 87.6° and 76.8°, respectively.

[0058] For the porous glass membrane with a more complicated surface topography, the surface morphology was characterized by SEM images, which could lead to different CAs compared to that on the flat surface of glass slides. As shown in FIG. 1(d), the surface of uncoated glass membrane exhibits many “small cylinders” which were sintered together into a porous bulk solid, and after FDTS coating, there is no significant change for such surface morphology, suggesting a thin and uniform FDTS layer formed. The fluorine peak at —689 eV emerging in the XPS survey scan of glass membranes in FIG. 1(e) confirms the successful surface modification by FDTS coating. The sintered “cylinders” result in a textured surface with microscale pockets that can trap air. Based on the Cassie-Baxter model, the air trapped at the solid-liquid interface is responsible for either higher or lower CA on the textured surface, which could render a hydrophobic surface superhydrophobic (WCA > 150°).32133There have been recent reports that the re-entrant geometry within those pockets between “cylinders” will govern the wetting behavior of different liquids,34'36and a previous study confirmed the existence of such structure within our glass membranes.30When two cylinders are arranged in parallel ideally, a re-entry angle is formed from cross-section view as shown in FIG. 1(d). A liquid will enter the re-entry space if the contact angle on flat surface is smaller than the reentry angle (LI in FIG. 1(d)), because the capillary and gravity forces both point downward and drive the liquid movement. The liquid will wet the surface and squeeze the trapped air out, and the solid-liquid interface becomes in the Wenzel state.37On the other hand, when a liquid has a contact angle greater than the re-entry angle (L2 in FIG. 1(d)), the capillary force is in counter direction to gravity force, such that the liquid cannot enter the re-entrant space if the capillary force is greater than gravity force. In this case, the trapped air repels the liquid, and the interface is in the Cassie state.32’33The ENCA and LCCA on FDTS-coated glass membrane are ~0° and -130° respectively as shown in FIG. 1(c), which can be attributed to the effect of the re-entrant topography. The “re-entry angle” within the membrane is estimated to be greater than 76.8° and smaller than 87.6°, given by the irregularly textured surface.Membrane-aided simultaneous reaction-separation of an ionic liquid product

[0059] Ionic liquids (ILs) are molten salts with melting temperature below room temperature, and their bulky and asymmetric ions dampen the lattice structure and make them in liquid form.38ILs have attracted a growing research interest during past decades due to their nonvolatility, nonflammability, high thermal and electrochemical stability, and conductivity.38For the synthesis of ILs, a purification step is required after the IL product is decanted from the reaction system, which includes extraction with solvents and drying under vacuum.39However, the isolated separation step from synthesis increases the operational costs, and the intensive consumption of organic solvent in the purification step, especially for scale-up production, is not environmentally friendly. In-situ separation of IL product from solvents is highly desirable in that it can simplify the post reaction procedure by eliminating the extraction and washing steps.

[0060] A preferred membrane-based reactor 111 having membrane 10 according to the present disclosure was established here to separate an ionic liquid product [EMIM][NTfz] simultaneously as the synthesis reaction takes place, as shown in FIG.3(a). The mechanism of separating liquids through porous membrane is shown in FIG.3(b). The liquid movement within a cylindrical pore is regulated by hydraulic pressure (pgh) and capillary pressure (PL), and PL is a function of liquid surface tension (y), liquid contact angle (0) and pore size (r) of the cylindrical pore. A liquid can pass through a pore if 0 is smaller than 90°, because cos 0 is positive so that PL and pgh are driving the liquid downwards together. However, when 0 is greater than 90°, PL and pgh are forcing the liquid in opposite directions, and thus the liquid penetration can be repelled if PL is greater than pgh. Therefore, an ENCA of ~0° and LCCA of -130° on FDTS-coated glass membrane imply that [EMIM][NTfz] and [Li] [Cl] can be separated successfully using membrane 10.

[0061] The irregular surface texture of glass membranes, nevertheless, may not result in a uniform pore size, which means that the liquid PL may not be greater than pgh everywhere within the membrane, indicating possible penetration of the aqueous phase. FIG. 4(a) and FIG.4(b) show an inefficient separation where [Li] [Cl] 21 (dyed blue) started to go through the coated membrane 10 after ~2 h from the onset of separation, during which [EMIM][NTf2] has been separated. As shown in FIG. 3(a), to ensure a more robust separation, the separation setup 111 is tilted from perpendicular so that the gravity force driving liquid movementthrough the membrane 10 is reduced. A coated membrane 10 was integrated into the setup 111 that was tilted to a nearly crossflow mode (-20° to horizontal). After ~4 h from loading reactants into the setup, the liquid passing through the membrane 10 and that staying in the feeding side were collected in separate vials shown in FIG. 3(c). Clearly, there is no blue liquid 20 visible within the separated phase 22, indicating an efficient separation. It is noteworthy that the transparent IL phase can still penetrate the membrane 10, even though the overall driving force is reduced with the tilted setup 111 where capillary force dominates in governing liquid movement. The ~0° ENCA leads to a capillary force driving [EMIMJfNTfi] to go through the membrane 10. On the other hand, the passage of aqueous phase was not allowed because of the higher LCCA (-130°) which results in a repelling capillary force that balances the contribution of the gravity force. This can be evidenced by FIG. 5 where a completely horizontal setup 111 was loaded with [EMIM][NTf2] 24 and [Li] [Cl] 26 separately. The liquid penetration through a coated membrane 10 in such setup is governed by capillary force only, and therefore, the passage of [EMIM][NTf2] 24 was observed because of a driving-through capillary force, while [Li] [Cl] 26 was blocked by a repelling capillary force. Hence, the different capillary forces have enabled efficient separation of IL phase during reaction.IL Product Purity

[0062] ’H NMR spectra of [EMIM][NTf2] from simultaneous reaction-separation is shown in FIG. 6(b). The peak at 2.5 ppm is from the trace impurities of the NMR solvent DMSO-d6, and the peak at 3.3 ppm is from the adsorbed water in the solvent.40The peak shift and peak integral of all assigned peaks are identical to that of a commercially available [EMIM][NTf2] shown in FIG. 6(a), indicating the successful synthesis of [EMIM] NTfz]. The spectra of IL product decanted after reaction as a control is presented in FIG. 6(c), which shows a much higher peak of water, leading to a higher water impurity (~4.9%) than that from simultaneous reaction-separation (-1.1%). This result suggests that [EMIM][NTf2] is not decanted efficiently from the aqueous phase. Although the IL from the commercial purchase has lower water content (-0.7%) shown in FIG. 6(a), the IL separated during reaction shows high product purity without washing and heating afterwards, thus suggesting the effectiveness of membrane-aided separation in repelling the aqueous phase by capillary force.

[0063] The TGA results of [EMIM][NTf2] from reaction-decanting, simultaneous reaction-separation, and commercial purchase are shown in FIG. 6(d). The onset of weight loss for [EMIM][NTf2] is -350 °C,29showing a high thermal stability which can be attributed to the strong electrostatic interactions between IL ions. The weight losses of all 3 types of [EMIM][NTf2] follow the same trend, and there is no considerable weight loss before 350 °C. The IL from decanting has a slightly lower mass fraction (-98.7%) around -100 °C than that from simultaneous reaction-separation (-99.3%), which is attributed to the higher water impurity in decanted IL and consistent with the NMR results. In addition, 10 cycles of membrane-aided simultaneous reaction-separation were conducted to investigate its reusability. The TGA of [EMIMjfNTfz] produced from each cycle was performed, and FIG. 6(e) shows the results from 1st, 5thand 10thcycle. The weight loss of IL remains unchanged during the 10 cycles, indicating an excellent stability of the membrane-aided simultaneous reaction-separation for process intensification of IL synthesis.

[0064] Integration of reaction and separation into a single step is beneficial to process intensification of liquid-phase chemical production. In this work, we have reported a membrane-aided simultaneous reactionseparation process for synthesis of IL [EMIM][NTf2], which was achieved by a commercial porous glass membrane with a perfluorocarbon coating. The textured membrane surface with apparent re-entrant geometry results in more robust surface hydrophobicity / oleophilicity, which enables capillary-force-driven separation of IL phase and aqueous phase during reaction. A tilted membrane-based reactor can ensure -100% separation efficiency, and [EMIM][NTf2] separated in this manner shows lower water impurity, compared to conventionally decanted IL after reaction. This membrane-based reactor is promising to facilitate the process intensification and scale-up of synthesis for not only IL but also many other liquid products at industrial level.Materials and methodsMaterials

[0065] The reagents for synthesizing [EMIM][NTf2] including l-ehyl-3-methylimidazolium chloride [EMIM][C1] and bis(trifluoromethane)sulfonimide lithium salt [Li][NTf2], commercially available [EMIM][NTf2] and hexadecane were purchaseded from Sigma- Aldrich. The coating precursor(heptadecafluoro- 1,1, 2,2-tetrahydrodecyl)triethoxy silane (FDTS) was purchased from Gelest Inc. The chemicals are used as received. Deionized (DI) water was produced from a Millipore Academic A10 system (total organic carbon lower than 40 ppb). Fritted glass discs / membranes with 4-8 ^m pores were purchased from Ace Glass Inc., and 25 x 1 x 75 mm plain glass microscope slides were obtained from Fisher Scientific.TVD coating fabrication

[0066] Glass membranes and slides were washed with acetone, isopropanol and DI water and then dried in a vacuum oven at ~50°C. The dried substrates were treated by UV / Ozone for 10 min at room temperature in a BioForce Nansciences UV / Ozone Procleaner which emits a high-intensity UV light (110VCA, 50 / 60 HZ, 0.5 A and 1 PH) with 185 and 254 nm wavelengths. A simple thermal vapor deposition (TVD) process was utilized to expose glass membranes and slides to the vapor of coating precursor at elevated temperature as shown in FIG. 1(a). After UV / Ozone treatment, the cleaned substrates were placed on stainless-steel mesh in a closed chamber with an open vessel holding ~1 mL of FDTS for a duration of 24 h at 80°C.Simultaneous reaction-separation

[0067] For reaction only as a control, -17.5 mL solution of reactants [EMIM][C1] and [Li][NTf2] was prepared with a concentration of 0.55 M and placed in a centrifuge tube which was then sonicated for 4 h. Afterwards, the top phase product was decanted, and the bottom phase product [EMIM][ NTfz] was washed with 20 mL DI water twice, followed by air dry at room temperature for 24 h.

[0068] For simultaneous reaction-separation, the coated glass membrane was placed between two funnels as described in a previous study.30The setup was tilted -70° relative to perpendicular. The reagent solution of same volume and concentration was prepared and dyed blue and then poured in the top funnel. After 4 h, the simultaneous reaction-separation ended, and the liquid penetrating the membrane and that retained by the membrane were collected separately. This experiment was repeated with 10 cycles without washing the membrane between each cycle, to test the membrane reliability in the long run.Characterizations

[0069] SEM images of uncoated and coated glass membranes were taken using a Zeiss SIGMA VP Scanning Electron Microscope with the electron source of Schottky thermal field emitter under high vacuum. The accelerating voltage utilized was 3 kV.

[0070] The contact angle tests were conducted with a VCA optima XE (AST Production Inc.) system in an ambient lab environment. Probe liquids were utilized including water, hexadecane, [EMIM][NTf2] and [Li] [Cl]. In a contact angle test, an image of the liquid-substrate interface was photographed right after a sessile drop (~luL) was placed on the substrate, and the value of contact angle was determined automatically by the VCA software. All the reported contact angles are the average of at least three repeats at different locations of the tested sample.

[0071] The surface chemistry of uncoated and coated glass membranes was investigated using X-ray photoelectron spectroscopy (PHI GENESIS XPS with a monochromatized Al X-ray source). Each sample was fixed onto a piece of double-sided Scotch tape that was adhered to a stainless-steel sample holder.Pressure in the analytical chamber during spectral acquisition was about 5xl0~7Torr. Pass energies for survey spectra were 110 eV.

[0072] The purity of separated [EMIM][NTf2] from reaction was examined by *H NMR spectroscopy using a Bruker AVANCE III 400 MHz spectrometer with a BBF / 1H broadband observe probe. The 2.50 ppm chemical shift of the trace impurity of the NMR solvent, that is, dimethylsulfoxide (DMSO)-d6, was referenced.40The water content in mass percentage in each sample was determined from the peak integration ratio based in the equations below:Where “n” and “M” are the molar number and molecular weight of water or [EMIMJfNTf?], and “I” is the peak integration of water or IL (peak “a” in FIG. 6) from NMR spectra. IwaterinDMSo isthe integration ratio of water to DMSO, determined from the H1NMR spectra of pure solvent DMSO-d6 (shown in FIG. 7), and it corresponds to the water impurity in DMSO-d6 solvent.

[0073] The purity of separated [EMIM][NTf2] from reaction was further analyzed by TGA using a SEIKO-22 TG / DTA system. For each test, a sample of IL weighing approximately 50 mg was placed in an aluminum pan and heated from room temperature to 550°C at a heating rate of 10 °C / min under air purging.

[0074] For liquid-phase reaction of the present disclosure, the produced liquid mixture could be either immiscible or miscible. For immiscible liquid mixture, membranes 3, 10 (FIGS. 8-9) with special wettability, e.g., simultaneous hydrophilicity / oleophobicity, are preferred under the present disclosure to not only increase the separation efficiency but also to decrease fouling. Taking oil-water separation as an example, since water has higher density than oil, both gravity and capillary forces render water passing through the pores of the hydrophilic membrane 3, 10. Meanwhile, oil is rejected from penetrating the pores as long as oleophobicity-induced capillary force is larger than the gravity. More importantly, membrane 3, 10 is expected to have improved anti-fouling performance since it repels oil. The desired wettability is realized by applying a carefully-designed coating. Such membranes 3, 10 of the present disclosure will enable simultaneous reaction-separation as illustrated with the following example.

[0075] Example 1: Simultaneous reaction-separation of an ionic liquid (IL). As shown in FIG. 8(a), a commonly used ionic liquid, l-ethyl-3-methylimidazolium bis(trifiuoromethylsulfonyl)imide ([EMIM] [NTfi]), was conventionally prepared by an ion exchange reaction. The reaction occurs at room temperature (RT) in water phase and the product ([EMIM] [NTfi]) forms a separate IL phase. Conventionally, after the reaction is complete in 4 hours, the water and IL phase is separated by decanting. Afterwards, the product is washed with water multiple times to remove the impurity. The last step is necessary since decanting will not achieve 100% separation efficiency.

[0076] Here as shown in FIG. 8(b), a membrane 10 according to the present disclosure repels water and attracts ([EMIM] [NTfz]. To achieve this, a commercial glass membrane w / the pore size of approximately100 pm has been coated with a nanometer-thick, preferably ranging from about 0.5 nm to about 1000 nm, self-assembly monolayer (SAM), i.e., lH,lH,2H,2H-perfluorodecyltrichlorosilane (FDTS). The perfluorinated segments repels water and attracts [EMIM] [NTfz]. As a result, the coated membrane 10 is not wettable to water but wettable to [EMIM] [NTfz]. In other words, during the reaction, capillary force will drive the IL through the membrane 10 and stop the water phase from penetrating the membrane 10. Indeed, as shown in FIG. 8(b), the water phase 11 (dyed in blue) does not penetrate the membrane and only [EMIM] [NTf2] 12 (colorless liquid) goes through the membrane. In this way, a simultaneous reaction-separation of the present disclosure has been demonstrated.

[0077] The product yield is 68.1% for this preferred simultaneous reaction-separation process of the present disclosure, which is comparable to that of the conventional reaction plus separation process, i.e., 71.3%. To further characterize the purity of the product, 1H-NMR analysis has been conducted. As shown in FIG. 8(c), the purity of the IL prepared by this preferred simultaneous reaction-separation process of the present disclosure is indeed slightly higher than that prepared via conventional separation after reaction. The result can be attributed to two factors. First, the capillary force stops the water phase from penetrating the membrane 10. Second, a preferred separation setup 111 of the present disclosure is horizontal instead of vertical. As a result, the gravity force, driving the water through the membrane, is also minimized.

[0078] For miscible liquid separation, nanofiltration (NF) and reverse osmosis (RO) membranes have been used. The separation mechanism is preferably size exclusion and / or solution-diffusion. Both polymeric and ceramic membranes have been investigated. Though both NF and RO membranes have been demonstrated to be effective in liquid separation, there are several challenges. First, these membranes operate under several MPa, which requires special equipment and makes the cost high. Moreover, long-term operation under high pressure will deform the membrane and reduce the separation efficiency. Second, NF and OS membranes have the pores in the size of nanometer or below. As a result, fouling is a serious concern; especially in liquid separation (vs. gas separation), which explains why NF and RO membranes have been only applied in membrane reactor for gas products to date.

[0079] According to the present disclosure, Supported Liquid Membranes (SLMs) are preferably used in separating miscible liquid-liquid mixtures. In SLM separation, the extraction occurs inside the membrane and the small amounts of the extraction solvents involved address the issues associated with the large amounts of solvents in conventional bulk extraction. However, conventional SLMs suffer from poor durability due to the loss of liquid phase. According to the present disclosure, an ionic liquid (ILs), i.e., 1-Butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), has been impregnated into commercially available poly vinylidene fluoride (PVDF) membranes 10 (FIG. 8(b)) to separate miscible benzene-heptane mixture with hexadecane as the stripping solvent (FIG. 9). The reason the IL is utilized here is due to its high chemical and thermal stability, which is expected to improve the durability of the SLM. As shown in FIG. 8(c), successful separation has been demonstrated by 1H Nuclear Magnetic Resonance (1H -NMR) results. Moreover, the Supported Ionic Liquid Membrane 3, 10 (SILM) has shown excellent durability with the separation efficiency does not degrade after 144 hours’ operation.

[0080] FIG. 9 is a schematic of a preferred SILM separation setup according to the present disclosure where feed compartment 1, containing a mixture of benzene 5 and heptane 6, is separated from the receiving compartment 2, which contains hexadecane 7, by the SILM 3. Each compartment preferably contains a stir bar 4.

[0081] For any liquid-phase product with miscible liquid mixture, a device / setup similar to the device / setup 111 of FIG. 8(b), with SILM 10 and a carefully selected receiving solvent, is expected to enable the simultaneous reaction-separation of the present disclosure. The process of the present disclosure preferably can be either batch or continuous.References

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[0122] In the foregoing Detailed Description, various features are grouped together in a single embodiment to streamline the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments of the disclosure require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in less than all features of a single disclosed embodiment. Thus, the following claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separate embodiment.

Claims

What is claimed is:

1. A membrane for simultaneous reaction-separation of liquid phase reactants, comprising:a membrane body having a plurality of pores, wherein the membrane body is coated with a selfassembly monolayer (SAM).

2. The membrane of claim 1, wherein the membrane body comprises one or more of glass, ceramic, metal and / or plastics3. The membrane of claim 1, wherein each of the plurality of pores has a diameter of approximately 5-300 pm.

4. The membrane of claim 1, wherein the SAM has a thickness of about 0.5-1000 nanometers.

5. The membrane of claim 1, wherein the SAM comprises 1H,1H,2H,2H-perfluorodecyltrichlorosilane (FDTS), or wherein the SAM is made from a fluorocarbon coupling agent or a hydrocarbon silane coupling agent wherein each of the fluorocarbon or hydrocarbon silane coupling agents has an end group selected from the group of ethanol, methanol and chloride; or wherein the SAM is made from a hydrophobic silane coupling agent selected from the group of CF3(CF2)5(CH2)2Si(OC2H5)3, CF3(CF2)5(CH2)2Si(OCH3)3, CF3(CF2)5(CH2)2SiC13, CF3(CF2)5(CH2)2Si(CH3)Cl2, CF3(CF2)5(CH2)2Si(CH3)2Cl, CH3(CH2)nSiCl3, and CH3[Si(CH3)2O]nSi(CH3)3.

6. A method for simultaneous reaction-separation of immiscible liquid phase reactants, comprising:providing a membrane having a membrane body; wherein the membrane is disposed between a first vessel and a second vessel;placing two or more reactants in the first vessel; andreceiving one or more products of the simultaneous reaction-separation in the second vessel.

7. The method of claim 6, wherein the membrane body has a plurality of pores, wherein the membrane body is coated with a self-assembly monolayer (SAM).

8. The method of claim 7, wherein the membrane body comprises glass, ceramic, metal or plastic.

9. The method of claim 7, wherein each of the plurality of pores has a diameter of approximately 5-300 pm.

10. The method of claim 7, wherein the SAM has a thickness of about 0.5 to about 1,000 nanometers.

11. The method of claim 6, wherein the reactants comprise [EMIM][C1] and [Li][NTf2], the SAM comprises lH,lH,2H,2H-perfluorodecyltrichlorosilane (FDTS) and the one or more products received in the second vessel comprises [EMIM] [NTf?].

12. The method of claim 6, wherein one or more of the products is immiscible with one or more of he reactants; wherein an oil-based product will go through the membrane, while the water-based product will ot.

13. A membrane for separation of miscible liquid phase mixtures, comprising:a supported ionic liquid membrane (SILM) comprising a polyvinylidene fluoride (PVDF) membrane ody impregnated with an ionic liquid.

14. The membrane of claim 13, wherein the ionic liquid comprises l-Butyl-3-methylimidazolium exafluorophosphate ([BMIM][PF6]), or another ionic liquid where the basic structure of the cation is based on midazolium, pyrrolidinium, pyridinium, tetraalkylammonium, or tetraalkylphosphonium, and the anion consists f trifluoromethane sulfonate, tetrafluoro borate, bis(fluorosulfonyl)imide, bis(perfluoroalkyl sulfonyl)imide, or exafluorophosphate.

15. A method for separation of miscible liquid phase mixtures, comprising:providing a membrane comprising a supported ionic liquid membrane (SILM) comprising a olyvinylidene fluoride (PVDF), or other plastic, glass, ceramic or metal membrane body impregnated with an onic liquid; wherein the membrane is disposed between a first vessel and a second vessel;placing one or more reactants and solvents in the first vessel; andreceiving the product that is miscible with one or more of the one or more reactants and solvents in the econd vessel.

16. The method of claim 15, wherein the ionic liquid comprises l-Butyl-3-methylimidazolium exafluorophosphate ([BMIM][PF6]), or another ionic liquid where the basic structure of the cation is based on midazolium, pyrrolidinium, pyridinium, tetraalkylammonium, or tetraalkylphosphonium, and the anion consists f trifluoromethane sulfonate, tetrafluoro borate, bis(fluorosulfonyl)imide, bis(perfluoroalkyl sulfonyl)imide, or exafluoropho sphate.

17. The method of claim 15, further comprising: adding a stripping solvent to the second vessel.

18. The method of claim 15, wherein the reactants in the first vessel produce the miscible products.

19. The method of claim 17, wherein the reactants in the first vessel produce the miscible products and the stripping solvent comprises aromatic hydrocarbons or linear hydrocarbons or nonpolar solvents or weakly polar solvents.

20. The method of claim 17, wherein (i) the reactants comprise benzene and heptane or (ii) the reactants comprise heptane and dichloromethane where in either (i) or (ii) the stripping solvent comprises hexadecane.

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