Supercritical carbon dioxide

Short description: Carbon dioxide above its critical point

Carbon dioxide pressure-temperature phase diagram File:CO2 Supercritical state.webmThis video shows the property of carbon dioxide to go into a supercritical state with increasing temperature

Supercritical carbon dioxide (sCO2[disputed - discuss]) is a fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure.

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 CO2 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 CO2 also allows compounds to be extracted with little damage or denaturing. In addition, the solubility of many extracted compounds in CO2 varies with pressure,[2] permitting selective extractions.

## Contents

* 1 Applications
* 1.1 Solvent
* 1.2 Manufactured products
* 1.3 Working fluid
* 1.3.1 Power generation
* 1.4 Impregnation
* 1.4.1 Other
* 1.5 Aerogel production
* 1.6 Sterilization of biomedical materials
* 1.7 Cleaning of Cork
* 1.8 Cleaning
* 2 See also
* 3 References
* 4 Further reading

## Applications

### Solvent

Main article: Engineering:Supercritical fluid extraction

Carbon dioxide is gaining popularity among coffee manufacturers looking to move away from classic decaffeinating solvents. sCO2 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 CO2 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, sCO2 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 sCO2 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, sCO2 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 sCO2 as a chemical reagent. The sCO2 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.

sCO2 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-isobutylbenzyl chloride to ibuprofen is promoted under sCO2.[13]

### Working fluid

sCO2 is chemically stable, reliable, low-cost, non-flammable and readily available, making it a desirable candidate working fluid for transcritical cycles.[14]

Supercritical CO
2 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, CO
2 heat pump water heaters are typically located outside, where they remove heat from the outside air.[14]

sCO2 has also been considered as a working fluid for enhanced geothermal systems due to its aqueous and gas properties.[15] sCO2 is also favorable for enhanced geothermal due to its high buoyancy, large expansivity and low viscosity.[16]

#### Power generation

The unique properties of sCO2 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 sCO2 to increase efficiency and power output.

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

sCO
2 promises substantial efficiency improvements. Due to its high fluid density, sCO
2 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.[17]

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 sCO2 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.[18]

The use of sCO2 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 sCO2 Brayton loops suffer from corrosion and erosion, specifically erosion in turbomachinery and recuperative heat exchanger components and intergranular corrosion and pitting in the piping.[19]

Testing has been conducted on candidate Ni-based alloys, austenitic steels, ferritic steels and ceramics for corrosion resistance in sCO2 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.[20][21]

In 2016, General Electric announced a sCO
2-based turbine that enabled a 50% efficiency of converting heat energy to electrical energy. In it the CO
2 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.[22] 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.[23]

### Impregnation

Due to its low viscosity while retaining solvent capacities, supercritical carbon dioxide is also used for impregnation of different raw materials. The biggest industrial application in this field is impregnation of wood with biocides. The big advantage is, that the CO2 can penetrate the complete structure of the board, carrying the active ingredient and therefore fully impregnating it. [24]

#### Other

Work is underway to develop a sCO2 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.[25]

Supercritical CO2 is an emerging natural refrigerant, used in new, low carbon solutions for domestic heat pumps. Supercritical CO2 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.[26]

Supercritical CO2 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, CO2 is captured, compressed to the supercritical state and injected into geological storage, possibly into existing oil fields to improve yields.[27][28][29]

Supercritical CO2 can be used as a working fluid for geothermal electricity generation in both enhanced geothermal systems[30][31][32][33] and sedimentary geothermal systems (so-called CO2 Plume Geothermal).[34][35] EGS systems utilize an artificially fractured reservoir in basement rock while CPG systems utilize shallower naturally-permeable sedimentary reservoirs. Possible advantages of using CO2 in a geologic reservoir, compared to water, include higher energy yield resulting from its lower viscosity, better chemical interaction, and permanent CO2 storage as the reservoir must be filled with large masses of CO2. As of 2011, the concept had not been tested in the field.[36]

### 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 sCO2. When the CO2 goes supercritical, all surface tension is removed, allowing the liquid to leave the aerogel and produce nanometer sized pores.[37]

### Sterilization of biomedical materials

Supercritical CO2 is an alternative for thermal sterilization of biological materials and medical devices with combination of the additive peracetic acid (PAA). Supercritical CO2 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.[38]

### Cleaning of Cork

Natural Cork is a suberin based natural polymer foam that can have unpleasant substances which are responsible for the loss of quality in wine. The leading substance is 2,4,6 trichloroanisole (TCA), which can be detected already at 2 ng/l in the wine. Supercritical CO2 is used at industrial scale to remove this substance and guarantee that the wine remains in its full quality. [39]

### Cleaning

Supercritical CO2 is used in certain industrial cleaning processes.

## See also

* Caffeine
* Dry cleaning
* Perfume
* Supercritical fluid
* Atmosphere of Venus, nearly all carbon dioxide, supercritical at the surface

## References

1. ↑ 1.0 1.1 Span, Roland; Wagner, Wolfgang (1996). "A New Equation of State for Carbon Dioxide Covering the Fluid Region from the Triple-Point Temperature to 1100 K at Pressures up to 800 MPa". Journal of Physical and Chemical Reference Data 25 (6): 1509–1596. doi:10.1063/1.555991. Bibcode: 1996JPCRD..25.1509S.
2. ↑ Discovery - Can Chemistry Save The World? - BBC World Service
3. ↑ Department of Pharmaceutical Analysis, Shenyang Pharmaceutical University, Shenyang 110016, China
4. ↑ Stewart, Gina (2003), Joseph M. DeSimone; William Tumas, eds., "Dry Cleaning with Liquid Carbon Dioxide", Green Chemistry Using Liquid and SCO2: 215–227CO2&rft.aulast=Stewart&rft.aufirst=Gina&rft.au=Stewart, Gina&rft.date=2003&rft.pages=215–227&rfr_id=info:sid/en.wikibooks.org:Physics:Supercritical_carbon_dioxide">
5. ↑ Aizpurua-Olaizola, Oier; Ormazabal, Markel; Vallejo, Asier; Olivares, Maitane; Navarro, Patricia; Etxebarria, Nestor; Usobiaga, Aresatz (2015-01-01). "Optimization of supercritical fluid consecutive extractions of fatty acids and polyphenols from Vitis vinifera grape wastes". Journal of Food Science 80 (1): E101–107. doi:10.1111/1750-3841.12715. ISSN 1750-3841. PMID 25471637.
6. ↑ Mendiola, J.A.; Herrero, M.; Cifuentes, A.; Ibañez, E. (2007). "Use of compressed fluids for sample preparation: Food applications". Journal of Chromatography A 1152 (1–2): 234–246. doi:10.1016/j.chroma.2007.02.046. PMID 17353022.
7. ↑ "Test Methods | Wastes - Hazardous Waste | US EPA". http://www.epa.gov/epawaste/hazard/testmethods/index.htm.
8. ↑ U.S.EPA Method 3561 Supercritical Fluid Extraction of Polycyclic Aromatic Hydrocarbons.
9. ↑ Use of Ozone Depleting Substances in Laboratories. TemaNord 2003:516.
10. ↑ Yeo, S.; Kiran, E. (2005). "Formation of polymer particles with supercritical fluids: A review". J. Supercrit. Fluids 34 (3): 287–308. doi:10.1016/j.supflu.2004.10.006.
11. ↑ Budisa, Nediljko; Schulze-Makuch, Dirk (8 August 2014). "Supercritical Carbon Dioxide and Its Potential as a Life-Sustaining Solvent in a Planetary Environment". Life 4 (3): 331–340. doi:10.3390/life4030331. PMID 25370376. Bibcode: 2014Life....4..331B.
12. ↑ Rubin, James B.; Taylor, Craig M. V.; Hartmann, Thomas; Paviet-Hartmann, Patricia (2003), Joseph M. DeSimone; William Tumas, eds., "Enhancing the Properties of Portland Cements Using Supercritical Carbon Dioxide", Green Chemistry Using Liquid and Supercritical Carbon Dioxide: 241–255
13. ↑ Sakakura, Toshiyasu; Choi, Jun-Chul; Yasuda, Hiroyuki (13 June 2007). "Transformation of Carbon dioxide". Chemical Reviews 107 (6): 2365–2387. doi:10.1021/cr068357u. PMID 17564481.
14. ↑ 14.0 14.1 14.2 Ma, Yitai; Liu, Zhongyan; Tian, Hua (2013). "A review of transcritical carbon dioxide heat pump and refrigeration cycles". Energy 55: 156–172. doi:10.1016/j.energy.2013.03.030. ISSN 0360-5442. Bibcode: 2013Ene....55..156M. https://www.researchgate.net/publication/257177350.
15. ↑ Brown, D. W. (2000). A HOT DRY ROCK GEOTHERMAL ENERGY CONCEPT UTILIZING SUPERCRITICAL CO2 INSTEAD OF WATER.
16. ↑ Pruess, K. (2006). Enhanced geothermal systems (EGS) using CO2 as working fluid—A novel approach for generating renewable energy with simultaneous sequestration of carbon. Geothermics, 35(4), 351–367. https://doi.org/10.1016/j.geothermics.2006.08.002
17. ↑ "Supercritical CO2 Power Cycle Developments and Commercialization: Why sCO2 can Displace Steam". http://www.echogen.com/documents/why-sco2-can-displace-steam.pdf.
18. ↑ "Supercritical Carbon Dioxide Power Cycles Starting to Hit the Market". http://breakingenergy.com/2014/11/24/supercritical-carbon-dioxide-power-cycles-starting-to-hit-the-market/.
19. ↑ "Corrosion and Erosion Behavior in sCO2 Power Cycles". Sandia National Laboratories. http://energy.sandia.gov/wp-content/gallery/uploads/SAND-2014-0602C.pdf.CO2+Power+Cycles&rft.atitle=&rft.pub=Sandia+National+Laboratories&rft_id=http://energy.sandia.gov/wp-content/gallery/uploads/SAND-2014-0602C.pdf&rfr_id=info:sid/en.wikibooks.org:Physics:Supercritical_carbon_dioxide">
20. ↑ "THE EFFECT OF TEMPERATURE ON THE sCO2 COMPATIBILITY OF CONVENTIONAL STRUCTURAL ALLOYS". The 4th International Symposium - Supercritical CO2 Power Cycles. http://www.swri.org/4org/d18/sCO2/papers2014/materials/61-Pint.pdf.
21. ↑ J. Parks, Curtis. "Corrosion of Candidate High Temperature Alloys in Supercritical Carbon Dioxide". Ottawa-Carleton Institute for Mechanical and Aerospace Engineering. https://curve.carleton.ca/system/files/etd/e721cac4-dfdd-4490-985c-f519efec6426/etd_pdf/123e849e0ffc3b9bc8249b63b32d1738/parks-corrosionofcandidatehightemperaturealloys.pdf.
22. ↑ Talbot, David (April 11, 2016). "Desk-Size Turbine Could Power a Town". https://www.technologyreview.com/s/601218/desk-size-turbine-could-power-a-town/#/set/id/601246/.
23. ↑ Blain, Loz (2023-11-01). "Supercritical CO2 pilot aims to make steam turbines obsolete" (in en-US). https://newatlas.com/energy/supercritical-co2-turbines/.
24. ↑ "Wood impregnation plant - Natex Prozesstechnologie GesmbH" (in en-US). https://natex.at/projects/wood-impregnation-plant/.
25. ↑ V. Dostal, M.J. Driscoll, P. Hejzlar, "A Supercritical Carbon Dioxide Cycle for Next Generation Nuclear Reactors". https://web.mit.edu/22.33/www/dostal.pdf. MIT-ANP-Series, MIT-ANP-TR-100 (2004)
26. ↑ "Heat Pumps". https://www.mayekawa.com/products/heat_pumps/.
27. ↑ "The Hydrogen Economy: Opportunities, Costs, Barriers, and R&D Needs", p. 84 (2004)
28. ↑ "FutureGen 2.0 Project". http://futuregenalliance.org/futuregen-2-0-project/.
29. ↑ "Øyvind Vessia: "Fischer- Tropsch reactor fed by syngas"". http://www.zero.no/transport/bio/fischer-tropsch-reactor-fed-by-syngas.
30. ↑ K Pruess(2006), "A hot dry rock geothermal energy concept utilizing sCO2 instead of water"
31. ↑ Donald W. Brown(2000), "On the feasibility of using sCO2 as heat transmission fluid in an engineered hot dry rock geothermal system"
32. ↑ K Pruess(2007)Enhanced Geothermal Systems (EGS) comparing water with CO2 as heat transmission fluids"
33. ↑ J Apps(2011), "Modeling geochemical processes in enhanced geothermal systems with CO2 as heat transfert fluid"
34. ↑ Randolph, Jimmy B.; Saar, Martin O. (2011). "Combining geothermal energy capture with geologic carbon dioxide sequestration". Geophysical Research Letters 38 (L10401): n/a. doi:10.1029/2011GL047265. Bibcode: 2011GeoRL..3810401R.
35. ↑ Adams, Benjamin M.; Kuehn, Thomas H.; Bielicki, Jeffrey M.; Randolph, Jimmy B.; Saar, Martin O. (2015). "A comparison of electric power output of CO2 Plume Geothermal (CPG) and brine geothermal systems for varying reservoir conditions". Applied Energy 140: 365–377. doi:10.1016/j.apenergy.2014.11.043.
36. ↑ http://earthsciences.typepad.com/blog/2011/06/achieving-carbon-sequestration-and-geothermal-energy-production-a-win-win.html ESD News and Events "Achieving Carbon Sequestration and Geothermal Energy Production: A Win-Win!"
37. ↑ "Aerogel.org » Supercritical Drying". http://www.aerogel.org/?p=345.
38. ↑ White, Angela; Burns, David; Christensen, Tim W. (2006). "Effective terminal sterilization using supercritical carbon dioxide". Journal of Biotechnology 123 (4): 504–515. doi:10.1016/j.jbiotec.2005.12.033. PMID 16497403.
39. ↑ "Cork cleaning plant Diam 3 - Natex Prozesstechnologie GesmbH" (in en-US). https://natex.at/projects/cork-cleaning-plant-diam-3/.

## Further reading

* Mukhopadhyay M. (2000). Natural extracts using supercritical carbon dioxide. United States: CRC Press, LLC. Free preview at Google Books.

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