Development of Multiple Unit-Fluid Processes and Bio-refineries Using Critical Fluids

  • Jerry W. KingEmail author
  • Keerthi Srinivas
Part of the Food Engineering Series book series (FSES)


Supercritical fluids and their liquefied analogues have been traditionally used in single unit operations, i.e. extraction, fractionation, using neat supercritical carbon dioxide (SCCO2) or with appropriate modifiers. Many of the supercritical fluid extraction processes have been devoted to extraction of food and natural products. Beginning in the mid-1980s, columnar and chromatographic techniques followed by reactions in supercritical fluids were developed to facilitate supercritical fluid derived extracts or products, thereby extending the application of a critical fluids processing platform beyond SFE. These newer developments were investigated in part due to the complexity of many natural product matrices and the desire to concentrate specific target components for food and other industrial uses.

In this chapter the advantages of coupling processing options using critical fluids are discussed and pertinent examples provided. Hence by combining different unit processes and sequencing them with the use of multiple fluids utilized at different temperatures and pressures, one can obtain multiple products and optimize the extraction or reaction process. Several specific options are illustrated for the cases of processing lipid-based materials such as concentrates of tocopherols, sterols, and phospholipids. Sequential isolation of both non-polar and polar ingredients is documented using a combination of fluids and/or unit processes. Finally the merits and difficulties in integrating critical fluid technology into the concept of a “bio-refinery” are provided.


High pressure multiple units Integrated high pressure processes Multi-fluid plants Natural matter processing Critical fluid bio-refineries 


  1. Antal MJ Jr, Allen SG, Schulman D et al (2000) Biomass gasification in supercritical water. Ind Eng Chem Res 39(11):4040–4053CrossRefGoogle Scholar
  2. Ayala RS, de Castro MDL (2001) Continuous subcritical water extraction as a useful tool for isolation of edible essential oils. Food Chem 75(1):109–113CrossRefGoogle Scholar
  3. Baig MN, Alenezi R, Leeke GA et al (2008) Critical fluids as a process environment for adding value and functionality to sunflower oil; a model system for biorefining. In: Proceedings of the 11th Meeting on supercritical fluids, Barcelona, Spain, May 4–7, 2008Google Scholar
  4. Baig MN, Santos RCD, King JW et al (2013) Evaluation and modeling of continuous flow sub-critical water hydrolysis of biomass-derived components: lipids and carbohydrates. Chem Eng Res Des 91(12):2663–2670CrossRefGoogle Scholar
  5. Barneby HL, Brown AC (1948) Continuous fat splitting plants using the Colgate-Emery process. J Am Oil Chem Soc 25(3):95–99CrossRefGoogle Scholar
  6. Bogel-Lukasik E, Bogel-Lukasis R, Kriaa K et al (2008) Limonene hydrogenation in high-pressure CO2: effect of hydrogen pressure. J Supercrit Fluids 45(2):225–230CrossRefGoogle Scholar
  7. Brunner G (2000) Fractionation of fats with supercritical carbon dioxide. Eur J Lipid Sci Technol 102(3):240–245CrossRefGoogle Scholar
  8. Bunyakiat K, Makmee S, Ngamprasertsith S et al (2006) Continuous production of biodiesel via transesterification from vegetable oils in supercritical methanol. Energy Fuels 20:812–817CrossRefGoogle Scholar
  9. Cao X, Ito Y (2003) Supercritical fluid extraction of grape seed oil and subsequent separation of free fatty acids by high speed counter-current chromatography. J Chromatogr 1021:117–124CrossRefGoogle Scholar
  10. Catchpole OJ, Durling NE, Grey JB (2006) Improvements in or related separation technology. New Zealand Patent NZ545146, World Patent WO2007091901Google Scholar
  11. Catchpole OJ, Tallon S, Dyer P et al (2012) Integrated supercritical fluid extraction and bioprocessing. Am J Biochem Biotechnol 8:263–287CrossRefGoogle Scholar
  12. Chuang M-H, Brunner G (2006) Concentration of minor componentsin crude palm oil. J Supercrit Fluids 37:151–156CrossRefGoogle Scholar
  13. Ciftci ON, Temelli F (2013) Continuous biocatalytic conversion of the oil of corn distiller’s dried grains with solubles to fatty acid methyl esters in supercritical carbon dioxide. Biomass Bioenergy 54:140–146CrossRefGoogle Scholar
  14. Clifford MN (2000) Anthocyanins- nature, occurrence and dietary burden. J Sci Food Agric 80:1063–1072CrossRefGoogle Scholar
  15. Clifford AA, Basile M, Jimenes-Carmona M et al (1999) Extraction of natural products with superheated water. In: Proceedings of the 6th Meeting on supercritical fluids, Nottingham, pp 485–490Google Scholar
  16. Eckert C, Liotta C, Ragauskas A et al (2007) Tunable solvents for fine chemicals from the biorefinery. Green Chem 9:545–548CrossRefGoogle Scholar
  17. Eggers R (1996) Supercritical fluid extraction of oilseeds/lipids in natural products. In: King JW, List GR (eds) Supercritical fluid technology in oil and lipid chemistry. AOCS, Champaign, pp 35–65Google Scholar
  18. Eller FJ, Taylor SL, Compton DL et al (2008) Counter-current liquid carbon dioxide purification of a model reaction mixture. J Supercrit Fluids 43:510–514CrossRefGoogle Scholar
  19. Fang T, Goto M, Sasaki M et al (2007) Extraction and purification of natural tocopherols by supercritical CO2. In: Martinez JL (ed) Supercritical fluid extraction of nutraceuticals and bioactive compounds. CRC, Boca Raton, pp 103–141CrossRefGoogle Scholar
  20. Foidl N (1999) Device and process for the production of oils or other extractable substances. US Patent 5,939,571Google Scholar
  21. Galbe M, Zacchi G (2007) Pretreatment of lignocellulosic materials for efficient bioethanol production. Adv Biochem Eng Biotechnol 108:41–65Google Scholar
  22. Garcia-Marino M, Rivas-Gonzalo JC, Ibanez E et al (2006) Recovery of catechins and proanthocyanidins from winery by-products by using subcritical water extraction. Anal Chim Acta 563(1–2):44–50CrossRefGoogle Scholar
  23. Giezen, F Dijkink, B, Perrut M et al (2005) Continuous supercritical fluid extraction using a twin screw extruder. In: Proceedings of International symposium on supercritical fluids, Orlando, FL, May 1–4, 2005, Abstract #350Google Scholar
  24. Gomez AM, Lopez CP, de la Ossa EM (1996) Recovery of grape seed oil by liquid and supercritical carbon dioxide extraction: a comparison with conventional solvent extraction—short communication. Chem Eng J 61:227–231Google Scholar
  25. Goto M, Tanaka M, Quitain AT et al (2012). Recovery of phytochemicals by hybrid extraction process using supercritical CO2 and water. In: Proceedings of 10th International symposium on supercritical fluids (ISSF-2012), San Francisco, CA, May 13–16, 2012, pp 626–632Google Scholar
  26. Gupta RB, Shim J-J (2007) Solubility in supercritical carbon dioxide. CRC, Boca RatonGoogle Scholar
  27. Gupta MN, Sharma S, Shaw S (2004) Biodiesel preparation by lipase-catalyzed transesterification of jatropha oil. Energy Fuels 18:154–159CrossRefGoogle Scholar
  28. Hansen CM (2007) Hansen solubility parameters: a user’s handbook, 2nd edn. CRC, Boca RatonCrossRefGoogle Scholar
  29. Hawthorne SB, Yang Y, Miller DJ (1994) Extraction of organic pollutants from environmental solids with sub- and supercritical water. Anal Chem 66:2912–2920CrossRefGoogle Scholar
  30. Jackson MA, King JW (1996) Methanolysis of seed oils in flowing supercritical carbon dioxide. J Am Oil Chem Soc 73(3):353–356CrossRefGoogle Scholar
  31. Ju ZY, Howard LR (2005) Subcritical water and sulfured water extraction of anthocyanins and other phenolics from dried red grape skin. J Food Sci 70(4):S270–S276CrossRefGoogle Scholar
  32. Kamm B, Gruber PR, Kamm M (eds) (2006) Biorefineries—industrial processes and products, vols 1 & 2. Wiley-VCH, WeinheimGoogle Scholar
  33. Kim KH, Hong J (2001) Supercritical CO2 pretreatment of lignocellulose enhances enzymatic cellulose hydrolysis. Bioresour Technol 77:139–144CrossRefGoogle Scholar
  34. King JW (2000a) Sub- and supercritical fluid processing of agrimaterials: extraction, fractionation and reaction modes. In: Kiran E, Debenedetti PG, Peters CJ (eds) Supercritical fluids: fundamentals and applications. Kluwer, Dordrecht, pp 451–488CrossRefGoogle Scholar
  35. King JW (2000b) Advances in critical fluid technology for food processing. Food Sci Technol Int 14(4):186–191Google Scholar
  36. King JW (2002) Critical fluid options for isolating and processing agricultural and natural products. In: Proceedings of the 1st International symposium on supercritical fluid technology for energy and environmental applications super green, Suwon, South Korea, November 3–6, 2002, pp 61–66Google Scholar
  37. King JW (2003) Coupled processing options for agricultural materials using supercritical carbon dioxide. In: Gopalan AS, Wai CM, Jacobs HK (eds) Supercritical carbon dioxide: separations and processes. American Chemical Society, Washington, pp 104–130CrossRefGoogle Scholar
  38. King JW (2004a) Critical fluid technology for the processing of lipid-related natural products. Compt Rendus Chem 7:647–659CrossRefGoogle Scholar
  39. King JW (2004b) Development and potential of critical fluid technology in the nutraceutical industry. In: York P, Kompella UB, Shekunov BY (eds) Supercritical fluids technology for drug product development. Marcel Dekker, New York, pp 579–614Google Scholar
  40. King JW (2006) Pressurized water extraction: resources and techniques for optimizing analytical applications. In: Turner C (ed) Modern extraction techniques: food and agricultural samples. American Chemical Society, Washington, DC, pp 79–95CrossRefGoogle Scholar
  41. King JW (2012) Supercritical fluid-based extraction/processing: then and now. INFORM 23(2):124–127Google Scholar
  42. King JW (2014) Modern supercritical fluid technology for food applications. Annu Rev Food Sci Technol 5:215–238CrossRefGoogle Scholar
  43. King JW, Dunford NT (2002) Phytosterol-enriched triglyceride fractions from vegetable oil deodorizer distillates utilizing supercritical fluid fractionation technology. Sep Sci Tech 37(2):451–462CrossRefGoogle Scholar
  44. King JW, Grabiel RD (2007) Isolation of polyphenolic compounds from fruits or vegetables utilizing sub-critical water extraction. US Patent 7,208,181Google Scholar
  45. King JW, Srinivas K (2009) Multiple unit fluid processing using sub- and supercritical fluids. J Supercrit Fluids 47:598–610CrossRefGoogle Scholar
  46. King JW, Taylor SL, Snyder JM et al (1998) Total fatty acid analysis of vegetable oil soapstocks by supercritical fluid extraction/reaction (SFE/SFR). J Am Oil Chem Soc 75:1291–1295CrossRefGoogle Scholar
  47. King JW, Holliday RL, List GR et al (2001) Hydrogenation of vegetable oils using mixtures of supercritical carbon dioxide and hydrogen. J Am Oil Chem Soc 78(2):107–113CrossRefGoogle Scholar
  48. King JW, Srinivas K, del Valle JM et al (2006) Design and optimization for the use of sub-critical fluids in biomass transformation, bio-fuel production, and bio-refinery utilization—I. In: Proceedings of the 8th International symposium of supercritical fluids, Kyoto, Japan, November 5–8, 2006 Proceeding #OC-2-17, pp 1–8Google Scholar
  49. King JW, Howard LR, Srinivas K et al (2007) Pressurized liquid extraction and processing of natural products. In: Proceedings of the 5th International symposium on supercritical fluids, Seoul, South Korea, November 28–December 1, 2007, Proceedings # KL04, pp 1–8Google Scholar
  50. King JW, Zhang D, Schlagenhauf A et al (2008) Greening biomass/bioenergy conversion processes using analytical instrumentation. In: Proceedings of Pittcon conference and expo 2008, New Orleans, LA, March 2–7, 2008, Abstract #2150-4Google Scholar
  51. King JW, Srinivas K, Zhang D (2010) Advances in critical fluid processing. In: Proctor A (ed) Alternatives to conventional food processing. Royal Society of Chemistry, Cambridge, pp 93–144CrossRefGoogle Scholar
  52. King JW, Srinivas K, Guevara O et al (2012) Reactive high pressure carbonated water pretreatment prior to enzymatic saccharification of biomass substrates. J Supercrit Fluids 66:221–231CrossRefGoogle Scholar
  53. Kusdiana D, Saka S (2004) Two-step preparation for catalyst-free biodiesel fuel production. Appl Biochem Biotechnol 115(1–3):781–791CrossRefGoogle Scholar
  54. Lascaray L (1949) Mechanism of fat splitting. Ind Eng Chem Res 41(4):786–790CrossRefGoogle Scholar
  55. Lee Y-W (2012) Supercritical fluid technology—key to the future. In: Proceedings of 10th International symposium on supercritical fluids (ISSF-2012), San Francisco, CA, May 10–13, 2012, Proceeding #407_004Google Scholar
  56. Licence P, Litchfield D, Dellar MP et al (2004) Supercriticality; a dramatic but safe demonstration of the critical point. Green Chem 6:352–354CrossRefGoogle Scholar
  57. Mantell C, Casas L, Rodriguez M et al (2013) Supercritical fluid extraction. In: Ramaswamy S, Huang H-J, Ramarao BV (eds) Separation and purification technologies in biorefineries. Wiley, West Sussex, pp 79–100CrossRefGoogle Scholar
  58. McHugh MA, Krukonis VJ (1994) Supercritical fluid extraction: principles and practice, 2nd edn. Butterworth-Heinemann, BostonGoogle Scholar
  59. Moreschi SRM, Petenate AJ, Meireles MAA (2004) Hydrolysis of ginger bagasse starch in subcritical water and carbon dioxide. J Agric Food Chem 52(6):1753–1758CrossRefGoogle Scholar
  60. Moreschi SRM, Leal JC, Braga MEM et al (2006) Ginger and turmeric starches hydrolysis using subcritical water + CO2: effect of SFE pre-treatment. Braz J Chem Eng 23(2):235–242CrossRefGoogle Scholar
  61. Murga R, Ruiz R, Beltran S et al (2000) Extraction of natural complex phenols and tannins from grape seeds by using supercritical mixtures of carbon dioxide and alcohol. J Agric Food Chem 48:3408–3412CrossRefGoogle Scholar
  62. Nagesha GK, Manohar B, Udayasankar K (2003) Enrichment of tocopherols in modified soy deodorizer distillate using supercritical carbon dioxide extraction. Eur Food Res Technol 217(5):427–433CrossRefGoogle Scholar
  63. Panayiotou C (1997) Solubility parameter revisited: an equation-of-state approach for its estimation. Fluid Phase Equilibria 131:21–35CrossRefGoogle Scholar
  64. Pasquel A, Meireles MAA, Marques MOM et al (2000) Extraction of stevia glycosides with CO2 + water, CO2 + ethanol, and CO2 + water + ethanol. Braz J Chem Eng 17(3):271–282CrossRefGoogle Scholar
  65. Pettinello G, Bertucco A, Pallado P et al (2000) Production of EPA enriched mixtures by supercritical fluid chromatography: from the laboratory scale to the pilot plant. J Supercrit Fluids 19:51–60CrossRefGoogle Scholar
  66. Quancheng Z, Guihua S, Hong J et al (2004) Concentration of tocopherols by supercritical carbon dioxide with cosolvents. Eur Food Res Technol 219:398–402CrossRefGoogle Scholar
  67. Rayner CM, Oakes R, Sakakura T et al (2005) Supercritical carbon dioxide. In: Mikami K (ed) Green reaction media in organic synthesis. Royal Society of Chemistry, Cambridge, pp 125–182Google Scholar
  68. Rayner CM, Clifford AA, Brough S et al (2006) Exploiting the potential of supercritical CO2 in synthetic organic chemistry. In: Proceedings of the 8th International symposium of supercritical fluids, Kyoto, Japan, November 5–8, 2006, Proceeding #OC-2-17Google Scholar
  69. Reverchon E (1997) Supercritical fluid extraction and fractionation of essential oils and related products. J Supercrit Fluids 10:1–37CrossRefGoogle Scholar
  70. Rizvi SSH, Mulvaney SJ, Sokhey AS (1995) The combined application of supercritical fluid and extrusion technology. Trends Food Sci Technol 6(7):232–240CrossRefGoogle Scholar
  71. Sabirzyanov AN, Il'in AP, Akhunov AR et al (2002) Solubility of water in supercritical carbon dioxide. High Temp 40(2):203–206CrossRefGoogle Scholar
  72. Sarmento LAV, Machado RAF, Petrus JCC et al (2008) Extraction of polyphenols from cocoa seeds and concentration through polymeric membranes. J Supercrit Fluids 45:64–69CrossRefGoogle Scholar
  73. Sarrade S, Perre CC, Vignet P (1999) Process and installation for the separation of heavy and light compounds by extraction using a supercritical fluid and nanofiltration. US Patent 5,961,835Google Scholar
  74. Savage PE, Gopalan S, Mizan TI et al (1995) Reactions at supercritical conditions—applications and fundamentals. AIChE J 47(7):1723–1778CrossRefGoogle Scholar
  75. Schacht C, Zetzil C, Brunner G (2008) From plant materials to ethanol by means of supercritical fluid technology. J Supercrit Fluids 46:299–321CrossRefGoogle Scholar
  76. Snyder JM, King JW, Jackson MA (1997) Analytical supercritical fluid extraction with lipase catalysis: conversion of different lipids to methyl esters and effect of moisture. J Am Oil Chem Soc 74(5):585–588CrossRefGoogle Scholar
  77. Srinivas K, King JW (2010) Supercritical carbon dioxide and subcritical water: complimentary agents in the processing of functional foods. In: Smith J, Charter E (eds) Functional food product development. Wiley-Blackwell, New York, pp 39–78CrossRefGoogle Scholar
  78. Srinivas K., King J.W, Hansen CM (2008) Prediction and modeling of solubility phenomena in subcritical fluids using an extended solubility parameter approach. Abstracts ACS-AIChE National Meeting, New Orleans, April 6–10, 2008, Abstract #174hGoogle Scholar
  79. Stewart PB, Munjal P (1970) Solubility of carbon dioxide in pure water, synthetic sea water, and synthetic sea water concentrates at −5° to 25°C and 10- to 45-atm. pressure. J Chem Eng Data 15(1):67–71CrossRefGoogle Scholar
  80. Taylor SL, King JW (2001) Fatty and resin acid analysis in tall oil products via SFE/SFR using enzymatic catalysis. J Chromatogr 39(7):269–272Google Scholar
  81. Temelli F (2009) Perspectives on supercritical fluid processing of fats and oils. J Supercrit Fluids 47:583–590CrossRefGoogle Scholar
  82. Temelli F, King JW, List GR (1996) Conversion of oils to monoglycerides by glycerolysis in supercritical carbon dioxide media. J Am Oil Chem Soc 73(6):699–706CrossRefGoogle Scholar
  83. Teng H, Yamasaki A (1998) Solubility of liquid CO2 in synthetic sea water at temperatures from 278 K to 293 K and pressures from 6.44 MPa to 29.49 MPa, and densities of the corresponding aqueous solutions. J Chem Eng Data 43(1):2–5CrossRefGoogle Scholar
  84. Toews K, Shroll R, Wai CM et al (1995) pH-defining equilibrium between water and supercritical CO2. Influence on SFE of organics and metal chelates. Anal Chem 67:4040–4043CrossRefGoogle Scholar
  85. Towsley RW, Turpin J, Sims M et al (1999) Porocritical fluid extraction using carbon dioxide for industrial recovery and recycle. In: Proceedings of the 6th Meeting on supercritical fluids, NottinghamGoogle Scholar
  86. Valcarcel M, Tena MT (1997) Applications of supercritical fluid extraction in food analysis. J Anal Chem 358:561–573CrossRefGoogle Scholar
  87. Van Walsum GP, Shi H (2004) Carbonic acid enhancement of hydrolysis in aqueous pretreatment of corn stover. Bioresour Technol 93:217–226CrossRefGoogle Scholar
  88. Wai CM, Lang Q (2003) Pressurized water extraction. US Patent 6,524,628 Google Scholar
  89. Weibe R, Gaddy VL (1934) The solubility of carbon dioxide in water at various temperatures from 12 to 40° and at pressures to 500 atmospheres. critical phenomena. J Am Chem Soc 62:815–817CrossRefGoogle Scholar
  90. Yang Y, Bowadt S, Hawthorne SB et al (1995) Subcritical water extraction of polychlorinated biphenyls from soil and sediment. Anal Chem 67:4571–4576CrossRefGoogle Scholar
  91. Yoshida H (2012) Development of pilot scale continuous sub-critical water plant to produce valuable materials and energy from organic wastes and their dynamic and kinetic analyses. In: Proceedings of 10th International symposium on supercritical fluids (ISSF-2012), San Francisco, CA, May 10–13, 2012, Proceeding #464_004Google Scholar

Copyright information

© Springer International Publishing Switzerland 2015

Authors and Affiliations

  1. 1.CFS—University of ArkansasFayettevilleUSA
  2. 2.Center for Bioproducts and BioenergyWashington State University Tri-citiesRichlandUSA

Personalised recommendations