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This paper reviews research progress on metal organic framework membranes which have demonstrated ability to separate carbon dioxide from different light gases. We focus on CO₂/N₂, CO₂/CH₄, and CO₂/H₂, gas separations which are highly relevant compositions in flue gas treatment, natural gas purification, and hydrogen purification, respectively.
A process for separating a carbon dioxide from a gas stream is disclosed. The process can include passing the gas stream over a sorbent that adsorbs the carbon dioxide by concentration swing adsorption and adsorptive displacement. The sorbent can be regenerated and the carbon dioxide recaptured by desorbing the carbon dioxide from the sorbent using concentration swing adsorption and desorptive displacement. A carbon dioxide separation system is also disclosed. Neither the system nor the process rely on temperature swing or pressure swing adsorption.
uelCell Energy, Inc. (FCE) has developed a novel system concept for separation of carbon dioxide (CO2) from greenhouse gas (GHG) emission sources using an electrochemical membrane (ECM). The salient feature of the ECM is its capability to produce electric power while capturing CO2 from flue gas, such as from an existing pulverized coal (PC) plant. Laboratory scale testing of the ECM has verified the feasibility of the technology for CO2 separation from simulated flue gases of PC plants as well as combined cycle power plants and other industrial facilities. Recently, FCE was awarded a contract (DE-FE0007634) from the U.S. Department of Energy to evaluate the use of ECM to efficiently and cost effectively separate CO2 from the emissions of existing coal fired power plants. The overarching objective of the project is to verify that the ECM can achieve at least 90% CO2 capture from flue gas of an existing PC plant with no more than 35% increase in the cost of electricity (COE) produced by the plant. The specific objectives and related activities planned for the project include: 1) conduct bench scale tests of a planar membrane assembly consisting of ten or more cells of about 0.8 m2 area each, 2) develop the detailed design for an ECM-based CO2 capture system applied to an existing PC plant, and 3) evaluate the effects of impurities (pollutants such as SO2, NOx, Hg) present in the coal plant flue gas by conducting laboratory scale performance tests of the membrane. The results of this project are anticipated to demonstrate that the ECM is an advanced technology, fabricated from inexpensive materials, based on proven operational track records, modular, scalable to large sizes, and a viable candidate for >90% carbon capture from existing PC plants. In this paper, the fundamentals of ECM technology including: material of construction, principal mechanisms of operation, carbon capture test results and the benefits of applications to PC plants will be presented.
The Department of Energy (DOE) seeks to develop carbon capture materials specifically tailored for Direct Air Capture (DAC) processes. Related to this, they require recipients to develop novel DAC materials such as: solvents, membranes, or sorbents that demonstrate high affinities or capacities for carbon dioxide (CO2) at concentrations typically available in air and at near ambient conditions. Toward this, InnoSense LLC (ISL) is developing High-Performance, Hybrid Polymer Membranes (HypoMemTM) for Carbon Dioxide Separation from Ambient Air. HypoMem consists of two major layers. The first layer is the active layer which contains the active ingredients that help to separate CO2 from ambient air. The second is the support layer that provides good mechanical support to have a free-standing membrane without interfering with the properties of the active layer.
Approximately six trillion standard cubic feet (scf) of hydrogen are produced each year by steam reforming light hydrocarbons. The water gas shift portion of the process yields a hydrogen product containing significant quantities of by-products such as carbon dioxide. The hydrogen must be purified for further use and carbon dioxide, a primary global warming agent, should be captured for other applications or sequestration. Pressure swing adsorption (PSA) is often used to produce high-purity hydrogen. However, the tail gas coming out of PSA contains about 15% of the hydrogen produced from reforming, and is currently used as fuel for reformers. The overall goal of this DOE-funded SBIR project was to develop a membrane process to recover hydrogen from PSA tail gas. This process also produces liquid carbon dioxide for sequestration. In the Phase I project, polyamide polyether based membranes were developed and evaluated with pure gases and model mixed hydrogen containing gases. Two bench scale modules were fabricated from these membranes, and evaluated with pure gases. These membranes and modules provided high carbon dioxide permeance and high carbon dioxide/hydrogen selectivity. In the Phase II project, a modified polyamide polyether based membrane, Polaris (TM), was successfully developed, and the membrane permeances were greatly improved. Bench scale modules prepared from this membrane were tested in the laboratory. Industrial scale 8-inch diameter modules were prepared and tested at BP's Pascagoula Gas Processing Plant. The modules were exposed to high-pressure natural gas for three months in a long-term integrity test. The promising results in the laboratory and field tests have generated great interest in using Polaris (TM) membranes for carbon dioxide/hydrogen separations. The membranes and processes developed in this project are in the early stage of commercialization. This work has already resulted in the sale of one commercial membrane unit for carbon dioxide removal and hydrogen purification.
A gas separation process for treating flue gases from combustion processes, and combustion processes including such gas separation. The invention involves routing a first portion of the flue gas stream to be treated to an absorption-based carbon dioxide capture step, while simultaneously flowing a second portion of the flue gas across the feed side of a membrane, flowing a sweep gas stream, usually air, across the permeate side, then passing the permeate/sweep gas to the combustor.
The invention is a process involving membrane-based gas separation for separating and recovering carbon dioxide emissions from combustion processes in partially concentrated form, and then transporting the carbon dioxide and using or storing it in a confined manner without concentrating it to high purity. The process of the invention involves building up the concentration of carbon dioxide in a gas flow loop between the combustion step and a membrane separation step. A portion of the carbon dioxide-enriched gas can then be withdrawn from this loop and transported, without the need to liquefy the gas or otherwise create a high-purity stream, to a destination where it is used or confined, preferably in an environmentally benign manner.
The invention is a process involving membrane-based gas separation for separating and recovering carbon dioxide emissions from combustion processes in partially concentrated form, and then transporting the carbon dioxide and using or storing it in a confined manner without concentrating it to high purity. The process of the invention involves building up the concentration of carbon dioxide in a gas flow loop between the combustion step and a membrane separation step. A portion of the carbon dioxide-enriched gas can then be withdrawn from this loop and transported, without the need to liquefy the gas or otherwise create a high-purity stream, to a destination where it is used or confined, preferably in an environmentally benign manner.
This project explored the viability of a Ni(OH) 2 based hydroxide exchange membrane carbon capture (HEMCC) device for direct air capture. It is built off an H 2 fuel cell based HEMCC previously developed in the Yushan Yan group at University of Delaware. Taking the same membrane-based, electrochemically driven pH gradient concept, similar flux performance was able to be seen in the Ni(OH) 2 system as the H 2 system when using comparable current densities. The project produced two types of membrane electrode assemblies (MEA). The first was a traditional MEA with two electrodes and a membrane, the second was a flow-through membrane MEA. Consistent performance was achieved with the traditional MEA with an energy cost of 1.1 MWh∙ton -1 and flux of 82 kg∙m -2 ∙yr -1 . This was the most stable of the two designs. This project investigated strategies to improve performance with a flow-through membrane design. Two designs were made, one with a cast phase inversion membrane, and one with powdered membrane layer. The template phase inversion membrane achieved low pressure drop but had performance limitations due to a skin layer of membrane limiting CO 2 gas transport. The powdered membrane layer had better performance but higher pressure drop. Finally, using the powdered membrane, commercial battery materials were able to be used in order to achieve higher flux. This showed that the flow through membrane design does have the capability to overcome flux inefficiencies in the traditional MEA. Moreover, the process design of the system is proposed and given in this project. The process mass and energy balances were calculated for a reference plant of 1000 t/yr CO 2 capture, which contains several subsystems, e.g. air processing subsystem, electrical subsystem, and CO 2 purification and compression subsystem is designed and evaluated. Based on our calculation, When the power consumption for stack is 1 MWh t -1 CO 2 , Additional 382 kWh t -1 CO 2 will be consumed by other subsystem of the plant, i.e. The total power consumption of 1.38 MWh t -1 CO 2 , lower than the final milestone of 1.5 MWh t -1 CO 2 in this project.
1,3-Substituted imidazolium bis(trifluoromethylsulfonyl)imide (Tf 2 N) ionic liquids (ILs) were incorporated at 40 and 60 vol % loading into a cross-linked poly(ethylene oxide) polymer network to create ion gels for carbon dioxide (CO 2 )-selective gas separation membranes. The ILs plasticize the poly(ethylene oxide)-based polymer to increase its gas permeability. Compared to the base polymer, with a CO 2 permeability of 145 barrer and a CO 2 against nitrogen (N 2 ) selectivity of 47, the highest CO 2 permeability achieved was 530 barrer coupled with a CO 2 /N 2 selectivity of 31 by having 60 vol % [1-ethyl-3-methylimidazolium][Tf 2 N]. The extent of gas permeability improvement depends on the cation’s terminal substituent. Substituents that promote additional noncovalent intermolecular interactions, such as hydroxyl, benzyl, and nitrile, can reduce the gas diffusivity by reducing the polymer chain mobility. Here, while n -alkyl, branched alkyl, and oligo(ethylene glycol) substituents can significantly increase the gas permeability, the shortest substituents (such as ethyl) were the most effective because they promote high ionic charge density.
Compositions and methods of preparing the compositions are disclosed for sorbents and other surfaces that can adsorb and desorb carbon dioxide. A sorbent or surface can include a metal compound such as an alkali or alkaline earth compound and a support. The sorbent can be prepared by several methods, including an incipient wetness technique. The sorbents have a CO 2 adsorption and desorption profile. A sorbent having high levels of a metal compound and adsorbed CO 2 is disclosed.
An adsorption material is disclosed that comprises a metal-organic framework and a plurality of ligands. The metal-organic framework comprising a plurality of metal ions. Each respective ligand in the plurality of ligands is amine appended to a respective metal ion in the plurality of metal ions of the metal-organic framework. Each respective ligand in the plurality of ligands comprises a substituted 1,3-propanediamine. The adsorbent has a CO 2 adsorption capacity of greater than 2.50 mmol/g at 150 mbar CO 2 at 40° C. Moreover, the adsorbent is configured to regenerate at less than 120° C. An example ligand is diamine 2,2-dimethyl-1,3-propanediamine. An example of the metal-organic framework is Mg 2 (dobpdc), where dobpdc 4− is 4,4′-dioxidobiphenyl-3,3′-dicarboxylate. Example applications for the adsorption material are removal of carbon dioxide from flue gas and biogasses.
A membrane useful in gas separation, the membrane comprising a cross-linked polysiloxane structure having a cross-link density of about 0.1.times.10.sup.-5 mol/cm.sup.3 to about 6.times.10.sup.-5 mol/cm.sup.3, where, in particular embodiments, the cross-linked polysiloxane structure has the following general structure: ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are independently selected from hydrocarbon groups having at least 1 and up to 6 carbon atoms; A.sup.1 and A.sup.2 are independently selected from cyclic hydrocarbon groups; L.sup.1 and L.sup.2 are linking groups or covalent bonds; n is an integer of at least 1; r and s are independently selected from integers of at least 1; and p is an integer of at least 10. The invention also includes methods for making and using the above-described membranes for gas separation.
Carbon capture from industrial point sources is an essential component of the global effort to mitigate climate risks. However, traditional approaches require significant energy input—often provided, counterproductively, by fossil fuel combustion. Using sunlight directly as the energy source would significantly improve the energy efficiency of carbon capture processes. Herein, we report the first fully visible-light-driven CO 2 separation system, in which carbon capture is achieved via the photoenolization/addition reaction of inexpensive 2-methylbenzophenone with CO 2 , and CO 2 release is realized through an intramolecular photodecarboxylation reaction. Finally, this system operates isothermally, works with natural sunlight, and facilitates CO 2 removal from natural gas flue emissions, providing a blueprint for other non-thermal chemical separations.
Membrane and membrane process have been widely considered as one of the best candidates for mitigating CO 2 emissions from the combustion or utilization of fossil fuels. Various amine-containing polymers constitute an important class of membranes, where the highly selective CO 2 transport is achieved by the facilitated transport mechanism. In this review, the amine–CO 2 chemistry is discussed in conjunction with the mechanism of the reaction-mediated CO 2 transport. A wide variety of amine-containing polymers are discussed based on two synthesis motifs: (a) polyamines with amino groups covalently bound to the polymer backbone and (b) small molecule amines embedded in a polymer matrix. This review concludes with the remarks on the facilitated transport membranes for post-combustion carbon capture (CO 2 /N 2 ) and hydrogen purification (CO 2 /H 2 ).
Ionic liquids (ILs) have emerged as highly tunable sorbents and membranes for gas separation, especially in the purification of CO 2 -containing gas streams such as air, natural gas, biogas, and syngas. Their negligible volatility, high thermal stability, and chemical versatility position them as promising alternatives to conventional amine and alkaline metal derivative-based systems, effectively addressing key challenges such as volatility, stability, and high regeneration energy. Here, this Review explores IL-derived systems for CO 2 -related gas separation across dense, porous, and supported categories. At the dense liquid level, we discuss strategies for tailoring IL properties to optimize CO 2 sorption, focusing on the correlation between IL-CO 2 interaction strength, uptake capacity, and regeneration energy. Key advancements in carbon capture, including amino-functionalized (AILs) and superbase-derived ILs (SILs), are highlighted, along with strategies such as chemical structure engineering, multiple binding site integration, alternative driving force exploration, and stability enhancement. Then, the porous liquids (PLs) scale focuses on the emerging field integrating IL properties with permanent porosity engineering, spanning ultramicropores (<5 Å) to macropores (around 100 nm). These innovations improve gas uptake capacity, accelerate transport kinetics, introduce the gating effect, and enable the coexistence of active sites with antagonistic properties within a single IL medium. At the supported IL scale, the discussion shifts to IL- and ionic pair-modified sorbents and membranes, emphasizing the modulation of cations and anions, confinement effects from porous supports, and the IL–interface interaction to enhance CO 2 separation performance, particularly in diluted gas streams. Beyond separation, this Review highlights IL-based integrated processes for CO 2 capture and conversion into value-added chemicals via thermocatalytic, electrocatalytic, and photocatalytic pathways. At each scale, advanced computational and experimental tools for IL design are also discussed, providing insights into stability enhancement, sorption efficiency, and process integration. The Review concludes by addressing existing challenges and outlining future directions for IL-driven innovations in gas separation technologies.
The development of high performance materials for CO 2 separation and capture will significantly contribute to a solution for climate change. In this work, (bicycloheptenyl) ethyl terminated polydimethylsiloxane (PDMSPNB) membranes with varied cross-link densities were synthesized via ring-opening metathesis polymerization. The developed polymer membranes show higher permeability and better selectivity than those of conventional cross-linked PDMS membrane. The achieved performance (CO 2 permeability ~ 6800 Barrer and CO 2 /N 2 selectivity ~ 14) is very promising for practical applications. The key to achieving this high performance is the use of an in-situ cross-linking method of the difunctional PDMS macromonomers, which provides lightly cross-linked membranes. By combining positron annihilation lifetime spectroscopy, broadband dielectric spectroscopy and gas solubility measurements, we have elucidated the key parameters necessary for achieving their excellent performance.
The separation of CO 2 from N 2 using polymeric membranes has proven a particularly challenging task. One promising class of polymers for this application is alkoxysilyl-substituted vinyl-added polynorbornenes (VAPNBs), which are high T g materials that often exhibit notable CO 2 /N 2 separation performance. This performance is believed to arise from their anomalous behavior in which they display high levels of solubility selectivity, a trait more commonly encountered in rubbery polymers than high T g glassy materials. While this trait has been documented in literature, no systematic investigations have been reported that probe the relationship between alkoxysilyl-substituted VAPNB structure and their resultant gas separation behavior. Here, we describe the synthesis and evaluation of three sets of alkoxysilyl-substituted VAPNBs that are designed to probe distinct facets of their structure-transport relationship. This includes investigations into the effect that alkoxysilyl branching, chain length, and carbon linker length have on CO 2 /N 2 permeability, solubility, and diffusivity.