Ionic liquids in carbon capture

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The use of ionic liquids in carbon capture is a potential application of ionic liquids as absorbents for use in carbon capture and sequestration. Ionic liquids, which are salts that exist as liquids near room temperature, are polar, nonvolatile materials that have been considered for many applications. The urgency of climate change has spurred research into their use in energy-related applications such as carbon capture and storage.

Contents

Carbon capture using absorption

Ionic liquids as solvents

Amines are the most prevalent absorbent in postcombustion carbon capture technology today. In particular, monoethanolamine (MEA) has been used in industrial scales in postcombustion carbon capture, as well as in other CO2 separations, such as "sweetening" of natural gas. [1] However, amines are corrosive, degrade over time, and require large industrial facilities. Ionic liquids on the other hand, have low vapor pressures . This property results from their strong Coulombic attractive force. Vapor pressure remains low through the substance's thermal decomposition point (typically >300 °C). [2] In principle, this low vapor pressure simplifies their use and makes them "green" alternatives. Additionally, it reduces risk of contamination of the CO2 gas stream and of leakage into the environment. [3]

The solubility of CO2 in ionic liquids is governed primarily by the anion, less so by the cation. [4] The hexafluorophosphate (PF6) and tetrafluoroborate (BF4) anions have been shown to be especially amenable to CO2 capture. [4]

Ionic liquids have been considered as solvents in a variety of liquid-liquid extraction processes, but never commercialized. [5] Beside that, ionic liquids have replaced the conventional volatile solvents in industry such as absorption of gases or extractive distillation. Additionally, ionic liquids are used as co-solutes for the generation of aqueous biphasic systems, or purification of biomolecules.

Process

A typical amine gas treating process flow diagram. Ionic liquids for use in CO2 capture by absorption could follow a similar process. AmineTreating.png
A typical amine gas treating process flow diagram. Ionic liquids for use in CO2 capture by absorption could follow a similar process.

A typical CO2 absorption process consists of a feed gas, an absorption column, a stripper column, and output streams of CO2-rich gas to be sequestered, and CO2-poor gas to be released to the atmosphere. Ionic liquids could follow a similar process to amine gas treating, where the CO2 is regenerated in the stripper using higher temperature. However, ionic liquids can also be stripped using pressure swings or inert gases, reducing the process energy requirement. [3] A current issue with ionic liquids for carbon capture is that they have a lower working capacity than amines. Task-specific ionic liquids that employ chemisorption and physisorption are being developed in an attempt to increase the working capacity. 1-butyl-3-propylamineimidazolium tetrafluoroborate is one example of a TSIL. [2]

Research

In 2023, a research team composed of Chuo University, Nihon University, Kanazawa University, and the Research Institute of Innovative Technology for the Earth utilized electronic state informatics to design and synthesize ionic liquids. [6] Subsequently, they conducted precise measurements of CO2 solubility and successfully developed ionic liquids with the highest physical absorption capacity for CO2 to date. [6]

Drawbacks

Selectivity

In carbon capture an effective absorbent is one which demonstrates a high selectivity, meaning that CO2 will preferentially dissolve in the absorbent compared to other gaseous components. In post-combustion carbon capture the most salient separation is CO2 from N2, whereas in pre-combustion separation CO is primarily separated from H2. Other components and impurities may be present in the flue gas, such as hydrocarbons, SO2, or H2S. Before selecting the appropriate solvent to use for carbon capture it is critical to ensure that at the given process conditions and flue gas composition CO2 maintains a much higher solubility in the solvent than the other species in the flue gas and thus has a high selectivity.

The selectivity of CO2 in ionic liquids has been widely studied by researchers. Generally, polar molecules and molecules with an electric quadrupole moment are highly soluble in liquid ionic substances. [7] It has been found that at high process temperatures the solubility of CO2 decreases, while the solubility of other species, such as CH4 and H2, may increase with increasing temperature, thereby reducing the effectiveness of the solvent. However, the solubility of N2 in ionic liquids is relatively low and does not increase with increasing temperature so the use of ionic liquids in post-combustion carbon capture may be appropriate due to the consistently high CO2/N2 selectivity. [8] The presence of common flue gas impurities such as H2S severely inhibits CO2 solubility in ionic liquids and should be carefully considered by engineers when choosing an appropriate solvent for a particular flue gas. [9]

Viscosity

A primary concern with the use of ionic liquids for carbon capture is their high viscosity compared with that of commercial solvents. Ionic liquids which employ chemisorption depend on a chemical reaction between solute and solvent for CO2 separation. The rate of this reaction is dependent on the diffusivity of CO2 in the solvent and is thus inversely proportional to viscosity. The self diffusivity of CO2 in ionic liquids are generally to the order of 10−10 m2/s, [10] approximately an order of magnitude less than similarly performing commercial solvents used on CO2 capture. The viscosity of an ionic liquid can vary significantly according to the type of anion and cation, the alkyl chain length, and the amount of water or other impurities in the solvent. [11] [12] Because these solvents can be “designed” and these properties chosen, developing ionic liquids with lowered viscosities is a current topic of research. Supported ionic liquid phases (SILPs) are one proposed solution to this problem. [5]

Tunability

1-butyl-3-propylamineimidazolium tetrafluoroborate is a task-specific ionic liquid for use in CO2 separation. 1-butyl-3-propylamineimidazolium-tetrafluoroborate-balls.png
1-butyl-3-propylamineimidazolium tetrafluoroborate is a task-specific ionic liquid for use in CO2 separation.

As required for all separation techniques, ionic liquids exhibit selectivity towards one or more of the phases of a mixture. 1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) is a room-temperature ionic liquid that was identified early on as a viable substitute for volatile organic solvents in liquid-liquid separations. [13] Other [PF6]- and [BF4]- containing ionic liquids have been studied for their CO2 absorption properties, as well as 1-ethyl-3-methylimidazolium (EMIM) and unconventional cations like trihexyl(tetradecyl) phosphonium ([P66614]). [3] Selection of different anion and cation combinations in ionic liquids affects their selectivity and physical properties. Additionally, the organic cations in ionic liquids can be "tuned" by changing chain lengths or by substituting radicals. [5] Finally, ionic liquids can be mixed with other ionic liquids, water, or amines to achieve different properties in terms of absorption capacity and heat of absorption. This tunability has led some to call ionic liquids "designer solvents." [14] 1-butyl-3-propylamineimidazolium tetrafluoroborate was specifically developed for CO2 capture; it is designed to employ chemisorption to absorb CO2 and maintain efficiency under repeated absorption/regeneration cycles. [2] Other ionic liquids have been simulated or experimentally tested for potential use as CO2 absorbents.

Proposed industrial applications

Currently, CO2 capture uses mostly amine-based absorption technologies, which are energy intensive and solvent intensive. Volatile organic compounds alone in chemical processes represent a multibillion-dollar industry. [13] Therefore, ionic liquids offer an alternative that prove attractive should their other deficiencies be addressed.

During the capture process, the anion and cation play a crucial role in the dissolution of CO2. Spectroscopic results suggest a favorable interaction between the anion and CO2, wherein CO2 molecules preferentially attach to the anion. Furthermore, intermolecular forces, such as hydrogen bonds, van der Waals bonds, and electrostatic attraction, contributes to the solubility of CO2 in ionic liquids. This makes ionic liquids promising candidates for CO2 capture because the solubility of CO2 can be modeled accurately by the regular solubility theory (RST), which reduces operational costs in developing more sophisticated model to monitor the capture process.

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<span class="mw-page-title-main">Solubility</span> Capacity of a substance to dissolve in a homogeneous way

In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.

Extractive metallurgy is a branch of metallurgical engineering wherein process and methods of extraction of metals from their natural mineral deposits are studied. The field is a materials science, covering all aspects of the types of ore, washing, concentration, separation, chemical processes and extraction of pure metal and their alloying to suit various applications, sometimes for direct use as a finished product, but more often in a form that requires further working to achieve the given properties to suit the applications.

A supercritical fluid (SCF) is a substance at a temperature and pressure above its critical point, where distinct liquid and gas phases do not exist, but below the pressure required to compress it into a solid. It can effuse through porous solids like a gas, overcoming the mass transfer limitations that slow liquid transport through such materials. SCFs are superior to gases in their ability to dissolve materials like liquids or solids. Near the critical point, small changes in pressure or temperature result in large changes in density, allowing many properties of a supercritical fluid to be "fine-tuned".

<span class="mw-page-title-main">Ionic liquid</span> Salt in the liquid state

An ionic liquid (IL) is a salt in the liquid state at ambient conditions. In some contexts, the term has been restricted to salts whose melting point is below a specific temperature, such as 100 °C (212 °F). While ordinary liquids such as water and gasoline are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions. These substances are variously called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.

<span class="mw-page-title-main">Piperazine</span> Chemical compound

Piperazine is an organic compound that consists of a six-membered ring containing two nitrogen atoms at opposite positions in the ring. Piperazine exists as small alkaline deliquescent crystals with a saline taste.

<span class="mw-page-title-main">Membrane gas separation</span> Technology for splitting specific gases out of mixtures

Gas mixtures can be effectively separated by synthetic membranes made from polymers such as polyamide or cellulose acetate, or from ceramic materials.

<span class="mw-page-title-main">Amine gas treating</span> Removal of impurities from gases by scrubbing them in aqueous solutions of various alkylamines

Amine gas treating, also known as amine scrubbing, gas sweetening and acid gas removal, refers to a group of processes that use aqueous solutions of various alkylamines (commonly referred to simply as amines) to remove hydrogen sulfide (H2S) and carbon dioxide (CO2) from gases. It is a common unit process used in refineries, and is also used in petrochemical plants, natural gas processing plants and other industries.

<span class="mw-page-title-main">Liquid–liquid extraction</span> Method to separate compounds or metal complexes

Liquid–liquid extraction, also known as solvent extraction and partitioning, is a method to separate compounds or metal complexes, based on their relative solubilities in two different immiscible liquids, usually water (polar) and an organic solvent (non-polar). There is a net transfer of one or more species from one liquid into another liquid phase, generally from aqueous to organic. The transfer is driven by chemical potential, i.e. once the transfer is complete, the overall system of chemical components that make up the solutes and the solvents are in a more stable configuration. The solvent that is enriched in solute(s) is called extract. The feed solution that is depleted in solute(s) is called the raffinate. Liquid–liquid extraction is a basic technique in chemical laboratories, where it is performed using a variety of apparatus, from separatory funnels to countercurrent distribution equipment called as mixer settlers. This type of process is commonly performed after a chemical reaction as part of the work-up, often including an acidic work-up.

Deep eutectic solvents or DESs are solutions of Lewis or Brønsted acids and bases which form a eutectic mixture. Deep eutectic solvents are highly tunable through varying the structure or relative ratio of parent components and thus have a wide variety of potential applications including catalytic, separation, and electrochemical processes. The parent components of deep eutectic solvents engage in a complex hydrogen bonding network, which results in significant freezing point depression as compared to the parent compounds. The extent of freezing point depression observed in DESs is well illustrated by a mixture of choline chloride and urea in a 1:2 mole ratio. Choline chloride and urea are both solids at room temperature with melting points of 302 °C and 133 °C respectively, yet the combination of the two in a 1:2 molar ratio forms a liquid with a freezing point of 12 °C. DESs share similar properties to ionic liquids such as tunability and lack of flammability yet are distinct in that ionic liquids are neat salts composed exclusively of discrete ions. In contrast to ordinary solvents, such as volatile organic compounds, DESs are non-flammable, and possess low vapour pressures and toxicity.

<span class="mw-page-title-main">1-Butyl-3-methylimidazolium hexafluorophosphate</span> Chemical compound

1-Butyl-3-methylimidazolium hexafluorophosphate, also known as BMIM-PF6, is a viscous, colourless, hydrophobic and non-water-soluble ionic liquid with a melting point of -8 °C. Together with 1-butyl-3-methylimidazolium tetrafluoroborate, BMIM-BF4, it is one of the most widely studied ionic liquids. It is known to very slowly decompose in the presence of water.

<span class="mw-page-title-main">Hexafluorophosphate</span> Anion with the chemical formula PF6–

Hexafluorophosphate is an anion with chemical formula of [PF6]. It is an octahedral species that imparts no color to its salts. [PF6] is isoelectronic with sulfur hexafluoride, SF6, and the hexafluorosilicate dianion, [SiF6]2−, and hexafluoroantimonate [SbF6]. In this anion, phosphorus has a valence of 5. Being poorly nucleophilic, hexafluorophosphate is classified as a non-coordinating anion.

<span class="mw-page-title-main">Carbon dioxide scrubber</span> Device which absorbs carbon dioxide from circulated gas

A carbon dioxide scrubber is a piece of equipment that absorbs carbon dioxide (CO2). It is used to treat exhaust gases from industrial plants or from exhaled air in life support systems such as rebreathers or in spacecraft, submersible craft or airtight chambers. Carbon dioxide scrubbers are also used in controlled atmosphere (CA) storage and carbon capture and storage processes.

<span class="mw-page-title-main">Zeolitic imidazolate framework</span> Class of metal-organic frameworks

Zeolitic imidazolate frameworks (ZIFs) are a class of metal-organic frameworks (MOFs) that are topologically isomorphic with zeolites. ZIFs are composed of tetrahedrally-coordinated transition metal ions connected by imidazolate linkers. Since the metal-imidazole-metal angle is similar to the 145° Si-O-Si angle in zeolites, ZIFs have zeolite-like topologies. As of 2010, 105 ZIF topologies have been reported in the literature. Due to their robust porosity, resistance to thermal changes, and chemical stability, ZIFs are being investigated for applications such as carbon dioxide capture.

<span class="mw-page-title-main">1-Methylimidazole</span> Chemical compound

1-Methylimidazole or N-methylimidazole is an aromatic heterocyclic organic compound with the formula CH3C3H3N2. It is a colourless liquid that is used as a specialty solvent, a base, and as a precursor to some ionic liquids. It is a fundamental nitrogen heterocycle and as such mimics for various nucleoside bases as well as histidine and histamine.

<span class="mw-page-title-main">Methyldiethanolamine</span> Chemical compound

Methyldiethanolamine, also known as N-methyl diethanolamine and more commonly as MDEA, is the organic compound with the formula CH3N(C2H4OH)2. It is a colorless liquid with an ammonia odor. It is miscible with water, ethanol and benzene. A tertiary amine, it is widely used as a sweetening agent in chemical, oil refinery, syngas production and natural gas.

Post-combustion capture refers to the removal of carbon dioxide (CO2) from a power station flue gas prior to its compression, transportation and storage in suitable geological formations, as part of carbon capture and storage. A number of different techniques are applicable, almost all of which are adaptations of acid gas removal processes used in the chemical and petrochemical industries. Many of these techniques existed before World War II and, consequently, post-combustion capture is the most developed of the various carbon-capture methodologies.

<span class="mw-page-title-main">Ammonium carbamate</span> Chemical compound

Ammonium carbamate is a chemical compound with the formula [NH4][H2NCO2] consisting of ammonium cation NH+4 and carbamate anion NH2COO. It is a white solid that is extremely soluble in water, less so in alcohol. Ammonium carbamate can be formed by the reaction of ammonia NH3 with carbon dioxide CO2, and will slowly decompose to those gases at ordinary temperatures and pressures. It is an intermediate in the industrial synthesis of urea (NH2)2CO, an important fertilizer.

Solid sorbents for carbon capture include a diverse range of porous, solid-phase materials, including mesoporous silicas, zeolites, and metal-organic frameworks. These have the potential to function as more efficient alternatives to amine gas treating processes for selectively removing CO2 from large, stationary sources including power stations. While the technology readiness level of solid adsorbents for carbon capture varies between the research and demonstration levels, solid adsorbents have been demonstrated to be commercially viable for life-support and cryogenic distillation applications. While solid adsorbents suitable for carbon capture and storage are an active area of research within materials science, significant technological and policy obstacles limit the availability of such technologies.

Dioxide Materials was founded in 2009 in Champaign, Illinois, and is now headquartered in Boca Raton, Florida. Its main business is to develop technology to lower the world's carbon footprint. Dioxide Materials is developing technology to convert carbon dioxide, water and renewable energy into carbon-neutral gasoline (petrol) or jet fuel. Applications include CO2 recycling, sustainable fuels production and reducing curtailment of renewable energy(i.e. renewable energy that could not be used by the grid).

<span class="mw-page-title-main">Direct air capture</span> Method of carbon capture from carbon dioxide in air

Direct air capture (DAC) is the use of chemical or physical processes to extract carbon dioxide directly from the ambient air. If the extracted CO2 is then sequestered in safe long-term storage (called direct air carbon capture and sequestration, the overall process will achieve carbon dioxide removal and be a "negative emissions technology".

References

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Further reading

  1. Blanchard, Lynnette A.; Hancu, Dan; Beckman, Eric J.; Brennecke, Joan F. (1999). "Green processing using ionic liquids and CO2". Nature. 399 (6731): 28–29. Bibcode:1999Natur.399...28B. doi:10.1038/19887. ISSN   0028-0836. S2CID   26690265.
  2. Camper, Dean; Bara, Jason E.; Gin, Douglas L.; Noble, Richard D. (2008). "Room-Temperature Ionic Liquid−Amine Solutions: Tunable Solvents for Efficient and Reversible Capture of CO2". Industrial & Engineering Chemistry Research. 47 (21): 8496–8498. doi:10.1021/ie801002m. ISSN   0888-5885.