Carbon Dioxide Capture: Prospects for New Materials

The escalating level of atmospheric carbon dioxide is one of the most pressing environmental concerns of our age. Carbon capture and storage (CCS) from large point sources such as power plants is one option for reducing anthropogenic CO₂ emissions; however, currently the capture alone will increase the energy requirements of a plant by 25–40 %. This Review highlights the challenges for capture technologies which have the greatest likelihood of reducing CO₂ emissions to the atmosphere, namely postcombustion (predominantly CO₂/N₂ separation), precombustion (CO₂/H₂) capture, and natural gas sweetening (CO₂/CH₄). The key factor which underlies significant advancements lies in improved materials that perform the separations. In this regard, the most recent developments and emerging concepts in CO₂ separations by solvent absorption, chemical and physical adsorption, and membranes, amongst others, will be discussed, with particular attention on progress in the burgeoning field of metal–organic frameworks.     

Molecularly engineering polymeric membranes for H2/CO2 separation at 100–300 °C

Over the last two decades, polymers with superior H₂/CO₂ separation properties at 100–300 °C have gathered significant interest for H₂ purification and CO₂ capture. This timely review presents various strategies adopted to molecularly engineer polymers for this application. We first elucidate the Robeson's upper bound at elevated temperatures for H₂/CO₂ separation and the advantages of high-temperature operation (such as improved solubility selectivity and absence of CO₂ plasticization), compared with conventional membrane gas separations at ~35 °C. Second, we describe commercially relevant membranes for the separation and highlight materials with free volumes tuned to discriminate H₂ and CO₂, including functional polymers (such as polybenzimidazole) and engineered polymers by cross-linking, blending, thermal treatment, thermal rearrangement, and carbonization. Third, we succinctly discuss mixed matrix materials containing size-sieving or H₂-sorptive nanofillers with attractive H₂/CO₂ separation properties.     

Electro‐kinetic Separation of Rare Earth Elements Using a Redox‐Active Ligand

Purification of rare earth elements is challenging due to their chemical similarities. All of the deployed separation methods rely on thermodynamic properties, such as distribution equilibria in solvent extraction. Rare‐earth‐metal separations based on kinetic differences have not been examined. Herein, we demonstrate a new approach for rare‐earth‐element separations by exploiting differences in the oxidation rates within a series of rare earth compounds containing the redox‐active ligand [{2‐(t BuN(O))C₆H₄CH₂}₃N]³⁻. Using this method, a single‐step separation factor up to 261 was obtained for the separation of a 50:50 yttrium–lutetium mixture.     

Hyperthin Membranes for Gas Separations via Layer‐by‐Layer Assembly

Thin film formation via the Layer‐by‐Layer method is now a well‐established and broadly used method in materials science. We have been keenly interested in exploiting this technique in the area of gas separations. Specifically, we have sought to create hyperthin (<100 nm) polyelectrolyte‐based membranes that have practical potential for the separation of CO₂ from N₂ (flue gas) and H₂ from CO₂ (syngas). In this personal account, we summarize recent studies that have been aimed at measuring the influence of a variety of factors that can affect the permeability and permeation selectivity of hyperthin polyelectrolyte multilayers (PEMs).     

Homochiral MOF–Polymer Mixed Matrix Membranes for Efficient Separation of Chiral Molecules

Homochiral metal–organic framework (MOF) membranes have been recently reported for chiral separations. However, only a few high‐quality homochiral polycrystalline MOF membranes have been fabricated due to the difficulty in crystallization of a chiral MOF layer without defects on porous substrates. Alternatively, mixed matrix membranes (MMMs), which combine potential advantages of MOFs and polymers, have been widely demonstrated for gas separation and water purification. Here we report novel homochiral MOF–polymer MMMs for efficient chiral separation. Homochirality was successfully incorporated into achiral MIL‐53‐NH₂ nanocrystals by post‐synthetic modification with amino acids, such as l ‐histidine (l ‐His) and l ‐glutamic acid (l ‐Glu). The MIL‐53‐NH‐l ‐His and MIL‐53‐NH‐l ‐Glu nanocrystals were then embedded into polyethersulfone (PES) matrix to form homochiral MMMs, which exhibited excellent enantioselectivity for racemic 1‐phenylethanol with the highest enantiomeric excess value up to 100 %. This work, as an example, demonstrates the feasibility of fabricating diverse large‐scale homochiral MOF‐based MMMs for chiral separation.     

Light Hydrocarbon Separations Using Porous Organic Framework Materials

Light hydrocarbons (C₁–C₃) are used as basic energy feedstocks and as commodity organic compounds for the production of many industrially necessary chemicals. Due to the nature of the raw materials and production processes, light hydrocarbons are generated as mixtures, but the high-purity single-component products are of vital importance to the petrochemical industry. Consequently, the separation of these C₁–C₃ products is a crucial industrial procedure that comprises a significant share of the total global energy consumption per year. As a complement to traditional separation methods (distillation, partial hydrogenation, etc.), adsorptive separations using porous solids have received widespread attention due to their lower energy costs and higher efficiency. Extensive research has been devoted to the use of porous materials such as zeolites and metal-organic frameworks (MOFs) as solid adsorbents for these key separations, owing to the high porosity, tunable pore structures, and unsaturated metal sites present in these materials. Recently, porous organic framework (POF) materials composed of organic building blocks linked by covalent bonds have also shown excellent properties in light hydrocarbon adsorption and separation, sparking interest in the use of these materials as adsorbents in separation processes. This Minireview summarizes the recent advances in the use of POFs for light hydrocarbon separations, including the separation of mixtures of methane/ethane, methane/propane, ethylene/ethane, acetylene/ethylene, and propylene/propane, while highlighting the relationships between the structural features of these materials and their separation performances. Finally, the difficulties, challenges, and opportunities associated with leveraging POFs for light hydrocarbon separations are discussed to conclude the review.     

INORGANIC POROUS MEMBRANES FOR LIQUID PHASE SEPARATION

Porous ceramic membranes are reviewed with reference to liquid phase separation. Methods for preparing porous ceramic membranes are summarized after a brief introduction to membranes and membrane processes. In the section on liquid phase separation, membrane materials are summarized from the viewpoint of pore size limits, since the pore sizes of porous membranes play an important role in determining separation performance. Various types of metal oxides and composite oxides have been developed by the sol-gel process; typical materials are Al₂O₃, TiO₂, SiO₂, ZrO₂, and composite oxides. The sol-gel process has a great advantage in terms of pore-size controllability over a wide range, from 0.5 ～ several ten nm, and therefore, is suitable for preparing membranes for use in liquid phase separation. Applications of inorganic membranes are reviewed in terms of water treatment, separation of nonaqueous systems, and photocatalysis.     

ORGANIC PERMSELECTIVE PERVAPORATION CHARACTERISTICS OF POLY(SILYLPROPYNE) AND COPOLYMER DENSE MEMBRANES

An investigation into the organic permselective separation through poly [1-trimethylsilyl-1-propyne] (PTMSP) and (1-trimethylsily1)-1-(1-penta-methyl-disilyl)-1-propyne copoly-mer (TMSP-PMDSP) dense membranes was made to gain an insight into the effect ofthe chemical structure of membrane materials on pervaporation (PV) characteristics. Theresults show that the copolymer has a higher separation factor α_(org/water) but with a rela-tively lower value of flux J_t (g/m~2·h) than pure PTMSP. This phenomenon may be at-tributed to the introduction of side chain with large bulk volume in copolymer, whichbrought about a decrease of excess free volume and the improvement of diffesion selectivityto some extent. With the same molar concentration of organic liquids in feed, THF/watersolutions have the highest value of α_(org/water) as well as J_t in comparison with ethanol/water,iso-propanol/water and THF/water mixtures.     

Determination of the upper limits, benchmarks, and critical properties for gas separations using stabilized room temperature ionic liquid membranes (SILMs) for the purpose of guiding future research

The literature reports that supported ionic liquid membranes (SILMs) outperform standard polymers for the separations of CO₂/N₂ and CO₂/CH₄, even under continuous flow mixed gas conditions. Before the expenditure of more resources to develop new room temperature ionic liquids (RTILs) and SILMs, it is time to consider what benchmarks for SILM performance exist and if upper limits could be projected based on the physical chemistry of RTILs. At this juncture, we should ask if the current research efforts are properly focused based on the successes and failures in the literature. We summarize literature data, along with adding new data, on the SILM permeabilities and selectivities for the following gas pairs: CO₂/N₂, CO₂/CH₄, O₂/N₂, ethylene/ethane, propylene/propane, 1-butene/butane, and 1,3-butadiene/butane. The analysis predicts a maximum CO₂-permeability for SILMs and an upper bound for permeability selectivity vs. CO₂-permeability with respect to the CO₂/N₂ and CO₂/CH₄ separations. Also summarized are the representative successes and failures for improving the separation performance of SILMs via functionalization and facilitated transport in the context of the CO₂/N₂, CO₂/CH₄, and olefin/paraffin separations. In the context of the CO₂-separations, the analysis recommends a number of future research foci including research into SILMs cast from RTILs with smaller molar volumes. In the context of olefin/paraffin separations, the preliminary data is encouraging when considering the use of facilitated transport via silver carriers. Since RTIL-solvent/solvent interactions dominate in terminating the overall SILM performance, past attempts at enhancing solute/solvent interactions via the addition of functional groups to the RTILs have not produced SILMs with better separation performance compared to the unfunctionalized RTILs. Future research into functionalized RTILs needs to consider the changes to the dominant solvent/solvent interactions and not just the solute/solvent interactions.     

Electropolymerization of Molecular‐Sieving Polythiophene Membranes for H2 Separation

Membrane technologies that do not rely on heat for industrial gas separation would lower global energy cost. While polymeric, inorganic, and mixed‐matrix separation membranes have been rapidly developed, the bottleneck is balancing the processability, selectivity, and permeability. Reported here is a softness adjustment of rigid networks (SARs) strategy to produce flexible, stand‐alone, and molecular‐sieving membranes by electropolymerization. Here, 14 membranes were rationally designed and synthesized and their gas separation ability and mechanical performance were studied. The separation performance of the membranes for H₂/CO₂, H₂/N₂, and H₂/CH₄ can exceed the Robeson upper bound, among which, H₂/CO₂ separation selectivity reaches 50 with 626 Barrer of H₂ permeability. The long‐term and chemical stability tests demonstrate their potential for industrial applications. This simple, scalable, and cost‐effective strategy holds promise for the design other polymers for key energy‐intensive separations.     

Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks

Reducing anthropogenic CO₂ emission and lowering the concentration of greenhouse gases in the atmosphere has quickly become one of the most urgent environmental issues of our age. Carbon capture and storage (CCS) is one option for reducing these harmful CO₂ emissions. While a variety of technologies and methods have been developed, the separation of CO₂ from gas streams is still a critical issue. Apart from establishing new techniques, the exploration of capture materials with high separation performance and low capital cost are of paramount importance. Metal-organic frameworks (MOFs), a new class of crystalline porous materials constructed by metal-containing nodes bonded to organic bridging ligands hold great potential as adsorbents or membrane materials in gas separation. In this paper, we review the research progress (from experimental results to molecular simulations) in MOFs for CO₂ adsorption, storage, and separations (adsorptive separation and membrane-based separation) that are directly related to CO₂ capture.     

Two‐Dimensional Microporous Material‐based Mixed Matrix Membranes for Gas Separation

Since the discovery of graphene and its derivatives, the development and application of two‐dimensional (2D) materials have attracted enormous attention. 2D microporous materials, such as metal‐organic frameworks (MOFs), covalent organic frameworks (COFs), graphitic carbon nitride (g‐C₃N₄) and so on, hold great potential to be used in gas separation membranes because of their high aspect ratio and homogeneously distributed nanometer pores, which are beneficial for improving gas permeability and selectivity. This review briefly summarizes the recent design and fabrication of 2D microporous materials, as well as their applications in mixed matrix membranes (MMMs) for gas separation. The enhanced separation performances of the membranes and their long‐term stability are also introduced. Challenges and the latest development of newly synthesized 2D microporous materials are finally discussed to foresee the potential opportunities for 2D microporous material‐based MMMs.     

Extraction studies on the group VB–VIIB and VIII elements using 1-(2-pyridylazo)-2-naphthol as chelating reagent

Extraction behaviour of the chelates of group VB–VIIB and VIII elements using 1-(2-pyridylazo)-2-naphthol (PAN) has been studied as a function of pH. Studies have been made to back-extract the metal ions from the organic phase into the aqueous solution containing the optimum concentration of KCN and HClO₄ and buffers of appropriate pH. The masking agents such as citrate, cyanide, thiosulphate, fluoride and thiourea were used to achieve more specific separations. The studies indicate the potentiality of PAN as a useful solvent extracting reagent in devising group chemical separation procedures for activation analysis.     

The role of additives on dope rheology and membrane formation of defect-free Torlon hollow fibers for gas separation

The high demands on high performance membranes for energy, water and life science usages provide the impetus for membrane scientists to search for a comprehensive understanding of membrane formation from molecular level to design membranes with desirable configuration and separation performance. This pioneering work is to elaborate the importance of polymer rheology on hollow fiber formation and reveal the integrated science bridging polymer fundamentals such as polymer cluster size, shear and elongational viscosities, molecular orientation, stress relaxation to membrane microstructure and separation performance for gas separation. Torlon^® poly(amide imide) was employed in this study with various solvent/nonsolvent additives. The effects of additives on polymeric cluster size, hydrogen bonding and dope rheology during the phase inversion have been examined. It is found that hydrogen bonding and strain-hardening characteristics play very important roles in dope rheology and membrane separation performance. Torlon^® possesses strong hydrogen bonds with NMP/water mixtures, the addition of a small amount of water enlarges polymer cluster size, strengthen molecular network (i.e., strain hardening) and facilitate macrovoid-free morphology. However, strong hydrogen bonding may retard chain unfolding during spinning, induce faster relaxation for highly oriented dense-selective skin, and thus reduce gas-pair selectivity. By adjusting dope chemistry and spinning conditions with balanced solubility parameters and dope rheology, we have developed defect-free Torlon^® hollow fiber membranes with an O₂/N₂ selectivity of 8.55 and an ultra-thin layer of 488 Å simply using water as the additive. Fibers spun from dopes containing other additives have the optimal O₂/N₂ selectivity varying from 7.69 to 9.97 at 25 ± 2 °C, and the dense layer thickness varying from 500 Å to 2000 Å. Their corresponding mixed-gas O₂/N₂ selectivity for compressed air varies from 7.12 to 9.00.     

Molecular and Morphological Designs of High Performance Polymeric Membranes

Currently, membrane separation techniques, such as reverse osmosis and ultrafiltration, play an important role in industrial separation technology. To develop high performance polymeric membranes, it is essential to design the molecular and morphological structures of the membranes for their specific applications. In the reverse osmosis field, we have developed several kinds of composite membranes for specific uses. Applications include ultrapure water production, seawater desalination, softening and desalination of brackish water, and recovery of valuable substances. In the course of development, thin-film composite membrane materials and membrane morphology have been analyzed intensively and are becoming clearer. These results enable us to control membrane performance by an optimum combination of membrane materials and membrane morphology. The morphological structure and chemical structure of the composite membranes were designed to optimize the performance of both the ultrathin layer and the supporting substrate layer for each membrane's application. As ultrafiltration is expanding to various fields, requirements for membrane performance have become more severe, especially for 1) sharpness of molecular weight cutoff, 2) solvent and high temperature resistance, and 3) fouling resistance (low nonspecific protein adsorption). To satisfy these requirements, we have developed a new ultrafiltration membrane. Owing to the high resistivity and hydrophilicity of its chemical structure, the membrane shows excellent solvent and high temperature resistance as well as fouling resistance. In addition, sharp molecular cutoff was realized by controlling membrane morphology.     

Using PDMS coated TFC-RO membranes for CO2/N2 gas separation: Experimental study,modeling and optimization

Thin film composite (TFC) reverse osmosis (RO) membranes are semipermeable membranes that are utilized in water purification or water desalination systems. Discarding these membranes after end-of-life leads to environmental problems. Reusing old TFC-RO membranes is one way to solve this problem. For this reason, in this study, used TFC-RO membranes were coated with polydimethylsiloxane (PDMS) for CO₂/N₂ gas separation application. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized to confirm the crosslinking of coated PDMS. The morphology of PDMS/TFC-RO membranes was characterized using scanning electron microscopy (SEM). The parameters that can affect performance of prepared membranes (N₂ permeance and CO₂/N₂ selectivity) are concentration of PDMS solution, coating time, solvent evaporation time and curing temperature and time. Given that the used membranes don't have uniform surfaces, the first step of this study was to investigate the effect of the above mentioned factors on virgin membranes using fractional factorial design (FFD) of experiments. The results obtained showed that PDMS concentration is the most significant factor that has a negative effect on N₂ permeance and positive effect on CO₂/N₂ selectivity. The reported CO₂/N₂ selectivity of PDMS membranes was 11–12, but this selectivity for prepared PDMS/TFC-RO membranes was in the range of 6.7–22.5. After determining optimum conditions, the gas separation performance of PDMS coated used TFC-RO membrane under these conditions was finally determined. The results showed that the used membranes had a better performance than virgin membranes.     

Pushing the limits on possibilities for large scale gas separation: which strategies?

Opportunities abound to extend membrane markets for gas and vapor separations; however, the existing membrane materials, membrane structures and formation processes are inadequate to fully exploit these opportunities. The requirements for viability of membranes vary somewhat with each application. Nevertheless, the key requirements of durability, productivity and separation efficiency must be balanced against cost in all cases. The various ‘contender’ technologies for large scale gas separation membrane applications and the gas transport mechanisms are considered. The current spectrum of applications of gas separation membranes include; nitrogen enrichment, oxygen enrichment, hydrogen recovery, acid gas CO₂, H₂S removal from natural gas and dehydration of air and natural gas. The current status and the limitations faced by the available membrane materials for each of these applications are discussed. Two key technical challenges exist. Achieving higher permselectivity for the relevant application with at least equivalent productivity is the first of these challenges. Maintaining these properties in the presence of complex and aggressive feeds is the second challenge. Attractive avenues to overcome these challenges for each application will be presented. Finally, several new membrane applications with immense potential (e.g. fuel cells and olefin-paraffin separations) are discussed.     

Paper chromatography in the separation of ions

A study has been made of the separation of ions of the alkali metals, alkaline earth metals, elements of groups IIIA and B and of anions, such as arscnate, phosphate, vanadate, molybdate, tungstate and chromate, with solvent mixtures of tert.-butyl alcohol, water and hydrochloric or acetic acid in the ratio of 7:2 1, and with 01 without tartaric, citric or malonic acid. The solvent mixture with hydrochloric acid as one of the components was found to be most effective for the separation of six cations or three anions from their mixtures. The rl and R1 values and the sequences of separations have been recorded     

Thin Layer Chromatography of Synthetic Dyes on Antimonic Acid and on Admixture of Antimonic Acid and Silica Gel ‘G’ in a Mixed Solvent System

Abstract

Thin layer chromatography of synthetic dyes have been performed on antimonic acid and on admixture of antimonic acid and silica gel ‘G’ in a mixed solvent system i. e. Butanol: Acetic acid: water (25:5:10). The separation potential of antimonic acid and silica gel ‘G’ has been explored. Several important separations of closely related dyes have been achieved as a result of such studies.     

渗透汽化优先透醇分离膜

20世纪70年代的能源危机促使了人们对可再生能源-发酵法制备乙醇与节能分离工艺的探求。渗透汽化膜分离技术作为一种新兴的膜分离技术,具有分离效率高、低能耗、易于和发酵装置耦合、易于与其它分离方法联用等显著优点,特别适用于乙醇/水等恒沸混合物体系的分离。本文简要介绍了渗透汽化优先透醇膜的研究背景,总结并分析了用于指导膜材料选择的理论,详细介绍了用于制备优先透醇膜的含硅聚合物、含氟聚合物、有机/无机复合膜材料以及其他聚合物等膜材料的的结构特点、改性方法及膜材料分子结构与渗透汽化性能间的关系,并对不同膜材料对乙醇/水的渗透汽化分离性能进行了总结比较,在此基础上总结了目前渗透汽化乙醇/水分离膜存在的问题,并对其未来的研究方向和发展前景进行了展望。