Supercritical carbon dioxide

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Carbon dioxide pressure-temperature phase diagram Carbon dioxide pressure-temperature phase diagram.svg
Carbon dioxide pressure-temperature phase diagram
This video shows the property of carbon dioxide to go into a supercritical state with increasing temperature

Supercritical carbon dioxide (sCO
2
) is a fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure.

Contents

Carbon dioxide usually behaves as a gas in air at standard temperature and pressure (STP), or as a solid called dry ice when cooled and/or pressurised sufficiently. If the temperature and pressure are both increased from STP to be at or above the critical point for carbon dioxide, it can adopt properties midway between a gas and a liquid. More specifically, it behaves as a supercritical fluid above its critical temperature (304.128 K, 30.9780 °C, 87.7604 °F) [1] and critical pressure (7.3773 MPa, 72.808 atm, 1,070.0 psi, 73.773 bar), [1] expanding to fill its container like a gas but with a density like that of a liquid.

Supercritical CO
2
is becoming an important commercial and industrial solvent due to its role in chemical extraction, in addition to its relatively low toxicity and environmental impact. The relatively low temperature of the process and the stability of CO
2
also allows compounds to be extracted with little damage or denaturing. In addition, the solubility of many extracted compounds in CO
2
varies with pressure, [2] permitting selective extractions.

Applications

Solvent

Carbon dioxide is gaining popularity among coffee manufacturers looking to move away from classic decaffeinating solvents. sCO
2
is forced through green coffee beans which are then sprayed with water at high pressure to remove the caffeine. The caffeine can then be isolated for resale (e.g., to pharmaceutical or beverage manufacturers) by passing the water through activated charcoal filters or by distillation, crystallization or reverse osmosis. Supercritical carbon dioxide is used to remove organochloride pesticides and metals from agricultural crops without adulterating the desired constituents from plant matter in the herbal supplement industry. [3]

Supercritical carbon dioxide can be used as a solvent in dry cleaning. [4]

Supercritical carbon dioxide is used as the extraction solvent for creation of essential oils and other herbal distillates. [5] Its main advantages over solvents such as hexane and acetone in this process are that it is non-flammable and does not leave toxic residue. Furthermore, separation of the reaction components from the starting material is much simpler than with traditional organic solvents. The CO
2
can evaporate into the air or be recycled by condensation into a recovery vessel. Its advantage over steam distillation is that it operates at a lower temperature, which can separate the plant waxes from the oils. [6]

In laboratories, sCO
2
is used as an extraction solvent, for example for determining total recoverable hydrocarbons from soils, sediments, fly-ash, and other media, [7] and determination of polycyclic aromatic hydrocarbons in soil and solid wastes. [8] Supercritical fluid extraction has been used in determining hydrocarbon components in water. [9]

Processes that use sCO
2
to produce micro and nano scale particles, often for pharmaceutical uses, are under development. The gas antisolvent process, rapid expansion of supercritical solutions, and supercritical antisolvent precipitation (as well as several related methods) process a variety of substances into particles. [10]

Due to its ability to selectively dissolve organic compounds and assist enzyme functioning, sCO
2
has been suggested as a potential solvent to support biological activity on Venus- or super-Earth-type planets. [11]

Manufactured products

Environmentally beneficial, low-cost substitutes for rigid thermoplastic and fired ceramic are made using sCO
2
as a chemical reagent. The sCO
2
in these processes is reacted with the alkaline components of fully hardened hydraulic cement or gypsum plaster to form various carbonates. [12] The primary byproduct is water.

sCO
2
is used in the foaming of polymers. Supercritical carbon dioxide can saturate the polymer with solvent. Upon depressurization and heating, the carbon dioxide rapidly expands, causing voids within the polymer matrix, i.e., creating a foam. Research is ongoing on microcellular foams.

An electrochemical carboxylation of a para-isobutyl benzyl chloride to ibuprofen is promoted under sCO
2
. [13]

Working fluid

sCO
2
is chemically stable, reliable, low-cost, non-flammable and readily available, making it a desirable candidate working fluid for transcritical cycles. [14]

Supercritical CO2 is used as the working fluid in domestic water heat pumps. Manufactured and widely used, heat pumps are available for domestic and business heating and cooling. [14] While some of the more common domestic water heat pumps remove heat from the space in which they are located, such as a basement or garage, CO2 heat pump water heaters are typically located outside, where they remove heat from the outside air. [14]

Power generation

The unique properties of sCO
2
present advantages for closed-loop power generation and can be applied to power generation applications. Power generation systems that use traditional air Brayton and steam Rankine cycles can use sCO
2
to increase efficiency and power output.

The relatively new Allam power cycle uses sCO2 as the working fluid in combination with fuel and pure oxygen. The CO2 produced by combustion mixes with the sCO2 working fluid. A corresponding amount of pure CO2 must be removed from the process (for industrial use or sequestration). This process reduces atmospheric emissions to zero.

sCO2 promises substantial efficiency improvements. Due to its high fluid density, sCO2 enables compact and efficient turbomachinery. It can use simpler, single casing body designs while steam turbines require multiple turbine stages and associated casings, as well as additional inlet and outlet piping. The high density allows more compact, microchannel-based heat exchanger technology. [15]

For concentrated solar power, carbon dioxide critical temperature is not high enough to obtain the maximum energy conversion efficiency. Solar thermal plants are usually located in arid areas, so it is impossible to cool down the heat sink to sub-critical temperatures. Therefore, supercritical carbon dioxide blends, with higher critical temperatures, are in development to improve concentrated solar power electricity production.

Further, due to its superior thermal stability and non-flammability, direct heat exchange from high temperature sources is possible, permitting higher working fluid temperatures and therefore higher cycle efficiency. Unlike two-phase flow, the single-phase nature of sCO
2
eliminates the necessity of a heat input for phase change that is required for the water to steam conversion, thereby also eliminating associated thermal fatigue and corrosion. [16]

The use of sCO
2
presents corrosion engineering, material selection and design issues. Materials in power generation components must display resistance to damage caused by high-temperature, oxidation and creep. Candidate materials that meet these property and performance goals include incumbent alloys in power generation, such as nickel-based superalloys for turbomachinery components and austenitic stainless steels for piping. Components within sCO
2
Brayton loops suffer from corrosion and erosion, specifically erosion in turbomachinery and recuperative heat exchanger components and intergranular corrosion and pitting in the piping. [17]

Testing has been conducted on candidate Ni-based alloys, austenitic steels, ferritic steels and ceramics for corrosion resistance in sCO
2
cycles. The interest in these materials derive from their formation of protective surface oxide layers in the presence of carbon dioxide, however in most cases further evaluation of the reaction mechanics and corrosion/erosion kinetics and mechanisms is required, as none of the materials meet the necessary goals. [18] [19]

In 2016, General Electric announced a sCO2-based turbine that enabled a 50% efficiency of converting heat energy to electrical energy. In it the CO2 is heated to 700 °C. It requires less compression and allows heat transfer. It reaches full power in 2 minutes, whereas steam turbines need at least 30 minutes. The prototype generated 10 MW and is approximately 10% the size of a comparable steam turbine. [20] The 10 MW US$155-million Supercritical Transformational Electric Power (STEP) pilot plant was completed in 2023 in San Antonio. It is the size of a desk and can power around 10,000 homes. [21]

Other

Work is underway to develop a sCO
2
closed-cycle gas turbine to operate at temperatures near 550 °C. This would have implications for bulk thermal and nuclear generation of electricity, because the supercritical properties of carbon dioxide at above 500 °C and 20 MPa enable thermal efficiencies approaching 45 percent. This could increase the electrical power produced per unit of fuel required by 40 percent or more. Given the volume of carbon fuels used in producing electricity, the environmental impact of cycle efficiency increases would be significant. [22]

Supercritical CO
2
is an emerging natural refrigerant, used in new, low carbon solutions for domestic heat pumps. Supercritical CO
2
heat pumps are commercially marketed in Asia. EcoCute systems from Japan, developed by Mayekawa, develop high temperature domestic water with small inputs of electric power by moving heat into the system from the surroundings. [23]

Supercritical CO
2
has been used since the 1980s to enhance recovery in mature oil fields.

"Clean coal" technologies are emerging that could combine such enhanced recovery methods with carbon sequestration. Using gasifiers instead of conventional furnaces, coal and water is reduced to hydrogen gas, carbon dioxide and ash. This hydrogen gas can be used to produce electrical power In combined cycle gas turbines, CO
2
is captured, compressed to the supercritical state and injected into geological storage, possibly into existing oil fields to improve yields. [24] [25] [26]

Supercritical CO
2
can be used as a working fluid for geothermal electricity generation in both enhanced geothermal systems [27] [28] [29] [30] and sedimentary geothermal systems (so-called CO
2
Plume Geothermal). [31] [32] EGS systems utilize an artificially fractured reservoir in basement rock while CPG systems utilize shallower naturally-permeable sedimentary reservoirs. Possible advantages of using CO
2
in a geologic reservoir, compared to water, include higher energy yield resulting from its lower viscosity, better chemical interaction, and permanent CO
2
storage as the reservoir must be filled with large masses of CO
2
. As of 2011, the concept had not been tested in the field. [33]

Aerogel production

Supercritical carbon dioxide is used in the production of silica, carbon and metal based aerogels. For example, silicon dioxide gel is formed and then exposed to sCO
2
. When the CO
2
goes supercritical, all surface tension is removed, allowing the liquid to leave the aerogel and produce nanometer sized pores. [34]

Sterilization of biomedical materials

Supercritical CO
2
is an alternative for thermal sterilization of biological materials and medical devices with combination of the additive peracetic acid (PAA). Supercritical CO
2
does not sterilize the media, because it does not kill the spores of microorganisms. Moreover, this process is gentle, as the morphology, ultrastructure and protein profiles of inactivated microbes are preserved. [35]

Cleaning

Supercritical CO
2
is used in certain industrial cleaning processes.

See also

Related Research Articles

<span class="mw-page-title-main">Heat engine</span> System that converts heat or thermal energy to mechanical work

A heat engine is a system that converts heat to usable energy, particularly mechanical energy, which can then be used to do mechanical work. While originally conceived in the context of mechanical energy, the concept of the heat engine has been applied to various other kinds of energy, particularly electrical, since at least the late 19th century. The heat engine does this by bringing a working substance from a higher state temperature to a lower state temperature. A heat source generates thermal energy that brings the working substance to the higher temperature state. The working substance generates work in the working body of the engine while transferring heat to the colder sink until it reaches a lower temperature state. During this process some of the thermal energy is converted into work by exploiting the properties of the working substance. The working substance can be any system with a non-zero heat capacity, but it usually is a gas or liquid. During this process, some heat is normally lost to the surroundings and is not converted to work. Also, some energy is unusable because of friction and drag.

<span class="mw-page-title-main">Rankine cycle</span> Model that is used to predict the performance of steam turbine systems

The Rankine cycle is an idealized thermodynamic cycle describing the process by which certain heat engines, such as steam turbines or reciprocating steam engines, allow mechanical work to be extracted from a fluid as it moves between a heat source and heat sink. The Rankine cycle is named after William John Macquorn Rankine, a Scottish polymath professor at Glasgow University.

A supercritical fluid (SCF) is any 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. SCF are superior to gases in their ability to dissolve materials like liquids or solids. Also, 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">Cogeneration</span> Simultaneous generation of electricity and useful heat

Cogeneration or combined heat and power (CHP) is the use of a heat engine or power station to generate electricity and useful heat at the same time.

<span class="mw-page-title-main">Fossil fuel power station</span> Facility that burns fossil fuels to produce electricity

A fossil fuel power station is a thermal power station which burns a fossil fuel, such as coal or natural gas, to produce electricity. Fossil fuel power stations have machinery to convert the heat energy of combustion into mechanical energy, which then operates an electrical generator. The prime mover may be a steam turbine, a gas turbine or, in small plants, a reciprocating gas engine. All plants use the energy extracted from the expansion of a hot gas, either steam or combustion gases. Although different energy conversion methods exist, all thermal power station conversion methods have their efficiency limited by the Carnot efficiency and therefore produce waste heat.

Supercritical fluid extraction (SFE) is the process of separating one component (the extractant) from another (the matrix) using supercritical fluids as the extracting solvent. Extraction is usually from a solid matrix, but can also be from liquids. SFE can be used as a sample preparation step for analytical purposes, or on a larger scale to either strip unwanted material from a product (e.g. decaffeination) or collect a desired product (e.g. essential oils). These essential oils can include limonene and other straight solvents. Carbon dioxide (CO2) is the most used supercritical fluid, sometimes modified by co-solvents such as ethanol or methanol. Extraction conditions for supercritical carbon dioxide are above the critical temperature of 31 °C and critical pressure of 74 bar. Addition of modifiers may slightly alter this. The discussion below will mainly refer to extraction with CO2, except where specified.

<span class="mw-page-title-main">Thermal power station</span> Power plant that generates electricity from heat energy

A thermal power station is a type of power station in which heat energy is converted to electrical energy. In a steam-generating cycle heat is used to boil water in a large pressure vessel to produce high-pressure steam, which drives a steam turbine connected to an electrical generator. The low-pressure exhaust from the turbine enters a steam condenser where it is cooled to produce hot condensate which is recycled to the heating process to generate more high pressure steam. This is known as a Rankine cycle.

A binary cycle is a method for generating electrical power from geothermal resources and employs two separate fluid cycles, hence binary cycle. The primary cycle extracts the geothermal energy from the reservoir, and secondary cycle converts the heat into work to drive the generator and generate electricity.

<span class="mw-page-title-main">Steam-electric power station</span>

The steam-electric power station is a power station in which the electric generator is steam driven. Water is heated, turns into steam and spins a steam turbine which drives an electrical generator. After it passes through the turbine, the steam is condensed in a condenser. The greatest variation in the design of steam-electric power plants is due to the different fuel sources.

Enhanced oil recovery, also called tertiary recovery, is the extraction of crude oil from an oil field that cannot be extracted otherwise. Although the primary and secondary recovery techniques rely on the pressure differential between the surface and the underground well, enhanced oil recovery functions by altering the chemical composition of the oil itself in order to make it easier to extract. EOR can extract 30% to 60% or more of a reservoir's oil, compared to 20% to 40% using primary and secondary recovery. According to the US Department of Energy, carbon dioxide and water are injected along with one of three EOR techniques: thermal injection, gas injection, and chemical injection. More advanced, speculative EOR techniques are sometimes called quaternary recovery.

An integrated gasification combined cycle (IGCC) is a technology using a high pressure gasifier to turn coal and other carbon based fuels into pressurized gas—synthesis gas (syngas). It can then remove impurities from the syngas prior to the electricity generation cycle. Some of these pollutants, such as sulfur, can be turned into re-usable byproducts through the Claus process. This results in lower emissions of sulfur dioxide, particulates, mercury, and in some cases carbon dioxide. With additional process equipment, a water-gas shift reaction can increase gasification efficiency and reduce carbon monoxide emissions by converting it to carbon dioxide. The resulting carbon dioxide from the shift reaction can be separated, compressed, and stored through sequestration. Excess heat from the primary combustion and syngas fired generation is then passed to a steam cycle, similar to a combined cycle gas turbine. This process results in improved thermodynamic efficiency, compared to conventional pulverized coal combustion.

<span class="mw-page-title-main">Turboexpander</span> Type of turbine for high-pressure gas

A turboexpander, also referred to as a turbo-expander or an expansion turbine, is a centrifugal or axial-flow turbine, through which a high-pressure gas is expanded to produce work that is often used to drive a compressor or generator.

Supercritical fluid chromatography (SFC) is a form of normal phase chromatography that uses a supercritical fluid such as carbon dioxide as the mobile phase. It is used for the analysis and purification of low to moderate molecular weight, thermally labile molecules and can also be used for the separation of chiral compounds. Principles are similar to those of high performance liquid chromatography (HPLC); however, SFC typically utilizes carbon dioxide as the mobile phase. Therefore, the entire chromatographic flow path must be pressurized. Because the supercritical phase represents a state whereby bulk liquid and gas properties converge, supercritical fluid chromatography is sometimes called convergence chromatography. The idea of liquid and gas properties convergence was first envisioned by Giddings.

<span class="mw-page-title-main">Transcritical cycle</span> Closed thermodynamic cycle involving fluid

A transcritical cycle is a closed thermodynamic cycle where the working fluid goes through both subcritical and supercritical states. In particular, for power cycles the working fluid is kept in the liquid region during the compression phase and in vapour and/or supercritical conditions during the expansion phase. The ultrasupercritical steam Rankine cycle represents a widespread transcritical cycle in the electricity generation field from fossil fuels, where water is used as working fluid. Other typical applications of transcritical cycles to the purpose of power generation are represented by organic Rankine cycles, which are especially suitable to exploit low temperature heat sources, such as geothermal energy, heat recovery applications or waste to energy plants. With respect to subcritical cycles, the transcritical cycle exploits by definition higher pressure ratios, a feature that ultimately yields higher efficiencies for the majority of the working fluids. Considering then also supercritical cycles as a valid alternative to the transcritical ones, the latter cycles are capable of achieving higher specific works due to the limited relative importance of the work of compression work. This evidences the extreme potential of transcritical cycles to the purpose of producing the most power with the least expenditure.

<span class="mw-page-title-main">Geothermal power</span> Power generated by geothermal energy

Geothermal power is electrical power generated from geothermal energy. Technologies in use include dry steam power stations, flash steam power stations and binary cycle power stations. Geothermal electricity generation is currently used in 26 countries, while geothermal heating is in use in 70 countries.

Lower-temperature fuel cell types such as the proton exchange membrane fuel cell, phosphoric acid fuel cell, and alkaline fuel cell require pure hydrogen as fuel, typically produced from external reforming of natural gas. However, fuels cells operating at high temperature such as the solid oxide fuel cell (SOFC) are not poisoned by carbon monoxide and carbon dioxide, and in fact can accept hydrogen, carbon monoxide, carbon dioxide, steam, and methane mixtures as fuel directly, because of their internal shift and reforming capabilities. This opens up the possibility of efficient fuel cell-based power cycles consuming solid fuels such as coal and biomass, the gasification of which results in syngas containing mostly hydrogen, carbon monoxide and methane which can be cleaned and fed directly to the SOFCs without the added cost and complexity of methane reforming, water gas shifting and hydrogen separation operations which would otherwise be needed to isolate pure hydrogen as fuel. A power cycle based on gasification of solid fuel and SOFCs is called an Integrated Gasification Fuel Cell (IGFC) cycle; the IGFC power plant is analogous to an integrated gasification combined cycle power plant, but with the gas turbine power generation unit replaced with a fuel cell power generation unit. By taking advantage of intrinsically high energy efficiency of SOFCs and process integration, exceptionally high power plant efficiencies are possible. Furthermore, SOFCs in the IGFC cycle can be operated so as to isolate a carbon dioxide-rich anodic exhaust stream, allowing efficient carbon capture to address greenhouse gas emissions concerns of coal-based power generation.

<span class="mw-page-title-main">Non ideal compressible fluid dynamics</span>

Non ideal compressible fluid dynamics (NICFD), or non ideal gas dynamics, is a branch of fluid mechanics studying the dynamic behavior of fluids not obeying ideal-gas thermodynamics. It is for example the case of dense vapors, supercritical flows and compressible two-phase flows. With the term dense vapors, we indicate all fluids in the gaseous state characterized by thermodynamic conditions close to saturation and the critical point. Supercritical fluids feature instead values of pressure and temperature larger than their critical values, whereas two-phase flows are characterized by the simultaneous presence of both liquid and gas phases.

The Allam Cycle or Allam-Fetvedt Cycle is a process for converting carbonaceous fuels into thermal energy, while capturing the generated carbon dioxide and water. This zero emissions cycle was validated at a 50 MWth natural gas fed test facility in La Porte, Texas in May 2018. This industrial plant is owned and operated by NET Power LLC, a privately held technology licensing company. NET Power is owned by Constellation Energy Corporation, Occidental Petroleum Corporation (Oxy) Low Carbon Ventures, Baker Hughes Company and 8 Rivers Capital, the company holding the patents for the technology. The key inventors behind the process are English engineer Rodney John Allam, American engineer Jeremy Eron Fetvedt, American scientist Dr. Miles R Palmer, and American businessperson and innovator G. William Brown, Jr. The Allam-Fetvedt Cycle was recognized by MIT Technology Review on the 2018 list of 10 Breakthrough Technologies.

<span class="mw-page-title-main">Solar augmented geothermal energy</span> Solar-heated artificial underground lake

Solar augmented geothermal energy (SAGE) is an advanced method of geothermal energy that creates a synthetic geothermal storage resource by heating a natural brine with solar energy and adding enough heat when the sun shines to generate power 24 hours a day. The earth is given enough energy in one hour to provide all electrical needs for a year. Available energy is not the issue, but energy storage is the problem and SAGE creates effective storage and electrical power delivery on demand. This technology is especially effective for geothermal wells that have demonstrated inconsistent heat or idle oil or gas fields that have demonstrated the proper geology and have an abundance of solar.

<span class="mw-page-title-main">Supercritical carbon dioxide blend</span> Homogeneous mixture of CO2

Supercritical carbon dioxide blend (sCO2 blend) is an homogeneous mixture of CO2 with one or more fluids (dopant fluid) where it is held at or above its critical temperature and critical pressure.

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Further reading