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Supercritical drying, also known as critical point drying, is a process to remove liquid in a precise and controlled way. [1] It is useful in the production of microelectromechanical systems (MEMS), the drying of spices, the production of aerogel, the decaffeination of coffee and in the preparation of biological specimens. [2]
As the substance in a liquid body crosses the boundary from liquid to gas (see green arrow in phase diagram), the liquid changes into gas at a finite rate, while the amount of liquid decreases. When this happens within a heterogeneous environment, surface tension in the liquid body pulls against any solid structures the liquid might be in contact with. Delicate structures such as cell walls, the dendrites in silica gel, and the tiny machinery of microelectromechanical devices, tend to be broken apart by this surface tension as the liquid–gas–solid junction moves by.
To avoid this, the sample can be brought via two possible alternate paths from the liquid phase to the gas phase without crossing the liquid–gas boundary on the phase diagram. In freeze-drying, this means going around to the left (low temperature, low pressure; blue arrow). However, some structures are disrupted even by the solid–gas boundary. Supercritical drying, on the other hand, goes around the line to the right, on the high-temperature, high-pressure side (red arrow). This route from liquid to gas does not cross any phase boundary, instead passing through the supercritical region, where the distinction between gas and liquid ceases to apply. Densities of the liquid phase and vapor phase become equal at critical point of drying.
Fluids suitable for supercritical drying include carbon dioxide (critical point 304.25 K at 7.39 MPa or 31.1 °C at 1072 psi) and freon (≈300 K at 3.5–4 MPa or 25–0 °C at 500–600 psi). Nitrous oxide has similar physical behavior to carbon dioxide, but is a powerful oxidizer in its supercritical state. Supercritical water is inconvenient due to possible heat damage to a sample at its critical point temperature (647 K, 374 °C) and corrosiveness of water at such high temperatures and pressures (22.064 MPa, 3,212 psi).
In most such processes, acetone is first used to wash away all water, exploiting the complete miscibility of these two fluids. The acetone is then washed away with high pressure liquid carbon dioxide, the industry standard now that freon is unavailable. The liquid carbon dioxide is then heated until its temperature goes beyond the critical point, at which time the pressure can be gradually released, allowing the gas to escape and leaving a dried product.
In the physical sciences, a phase is a region of material that is chemically uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air is a third phase over the ice and water. The glass of the jar is another separate phase.
A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions at which thermodynamically distinct phases occur and coexist at equilibrium.
Dry cleaning is any cleaning process for clothing and textiles using a solvent other than water.
In thermodynamics, the phase rule is a general principle governing "pVT" systems, whose thermodynamic states are completely described by the variables pressure, volume and temperature, in thermodynamic equilibrium. If F is the number of degrees of freedom, C is the number of components and P is the number of phases, then
Sublimation is the transition of a substance directly from the solid to the gas state, without passing through the liquid state. Sublimation is an endothermic process that occurs at temperatures and pressures below a substance's triple point in its phase diagram, which corresponds to the lowest pressure at which the substance can exist as a liquid. The reverse process of sublimation is deposition or desublimation, in which a substance passes directly from a gas to a solid phase. Sublimation has also been used as a generic term to describe a solid-to-gas transition (sublimation) followed by a gas-to-solid transition (deposition). While vaporization from liquid to gas occurs as evaporation from the surface if it occurs below the boiling point of the liquid, and as boiling with formation of bubbles in the interior of the liquid if it occurs at the boiling point, there is no such distinction for the solid-to-gas transition which always occurs as sublimation from the surface.
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 much 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".
Supercritical may refer to:
A coolant is a substance, typically liquid, that is used to reduce or regulate the temperature of a system. An ideal coolant has high thermal capacity, low viscosity, is low-cost, non-toxic, chemically inert and neither causes nor promotes corrosion of the cooling system. Some applications also require the coolant to be an electrical insulator.
In thermodynamics, a critical point is the end point of a phase equilibrium curve. One example is the liquid–vapor critical point, the end point of the pressure–temperature curve that designates conditions under which a liquid and its vapor can coexist. At higher temperatures, the gas cannot be liquefied by pressure alone. At the critical point, defined by a critical temperatureTc and a critical pressurepc, phase boundaries vanish. Other examples include the liquid–liquid critical points in mixtures, and the ferromagnet–paramagnet transition in the absence of an external magnetic field.
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.
Supercritical carbon dioxide is a fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure.
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 in which liquid and gas properties converge, supercritical fluid chromatography is sometimes called convergence chromatography.
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, an 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.
An oil production plant is a facility which processes production fluids from oil wells in order to separate out key components and prepare them for export. Typical oil well production fluids are a mixture of oil, gas and produced water. An oil production plant is distinct from an oil depot, which does not have processing facilities.
Supercritical adsorption also referred to as the adsorption of supercritical fluids, is the adsorption at above-critical temperatures. There are different tacit understandings of supercritical fluids. For example, “a fluid is considered to be ‘supercritical’ when its temperature and pressure exceed the temperature and pressure at the critical point”. In the studies of supercritical extraction, however, “supercritical fluid” is applied for a narrow temperature region of 1-1.2 or to +10 K, which is called the supercritical region.
In fluid dynamics, the Frenkel line is a proposed boundary on the phase diagram of a supercritical fluid, separating regions of qualitatively different behavior. Fluids on opposite sides of the line have been described as "liquidlike" or "gaslike", and exhibit different behaviors in terms of oscillation, excitation modes, and diffusion.
Carbon dioxide cleaning (CO2 cleaning) comprises a family of methods for parts cleaning and sterilization, using carbon dioxide in its various phases. Due to being non-destructive, non-abrasive, and residue-free, it is often preferred for use on delicate surfaces. CO2 cleaning has found application in the aerospace, automotive, electronics, medical, and other industries. Carbon dioxide snow cleaning has been used to remove particles and organic residues from metals, polymers, ceramics, glasses, and other materials, and from surfaces including hard drives and optical surfaces.
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.
Liquid carbon dioxide is the liquid state of carbon dioxide, which cannot occur under atmospheric pressure. It can only exist at a pressure above 5.1 atm, under 31.1 °C (88.0 °F) and above −56.6 °C (−69.9 °F). Low-temperature carbon dioxide is commercially used in its solid form, commonly known as "dry ice". Solid CO
2 sublimes at 194.65 K at Earth atmospheric pressure — that is, it transitions directly from solid to gas without an intermediate liquid stage. The uses and applications of liquid carbon dioxide include decaffeinating coffee, extracting virgin olive oil from olive paste, in fire extinguishers, and as a coolant.
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.