The future development of LLE for the biorefinery setting

process requires the handling of large quantities of solvents and, in particular, the 1,3-PD extraction and separation efficiency is too low [58]. An alternative method is to convert 1,3-propanediol with aldehyde to form highly hydrophobic acetals (2-methyl-1,3-dioxane [2MD]) through a cyclic reaction, then extract them using an organic solvent such as o-xylene, toluene, or ethylbenzene, and finally hydrolyze the acetals to 1,3-PD. Liquid-liquid extraction is also used as an alternative enantioseparation for the crystallization approach. Bisnaphthyl phosphoric acid was used as extractant for phenylglycinol separation at a laboratory and industrial scale. After six extraction stages, the purity and yield were 70% and 36%, respectively [59].

The chiral n-protected alpha-amino acid derivatives transfer from an aqueous solution to the organic phase for enantioselective separation by lipophilic carbamylated quinine as chiral selector and phase carrier. The enantiomeric purity of N-(3,5-dinitrobenzoyl)-leucine exceeded 95% enantiomeric excess with 70% overall yield with a single extraction and back-extraction step [60].

of high solubility in organic solute. This technology can therefore be used for high value-added chemicals production. However, supercritical fluid extraction technology requires special machinery, which is the major barrier to its industrial application.

Ionic liquids are salts with melting points lower than 100^◦C; some ionic salts even form at room temperature. Ionic liquids have many unique properties such as exceedingly low vapor pressure and superior stability at wide range of temperature. They can be dissolved into the aqueous phase of LLE for polar change for better separation. Ionic liquids may improve the volatile compound separation through high solubility, and they have been used widely in recent years such as for separation of metal [70] and other materials [71]. Ionics liquids have their own challenges in terms of contamination by ions in the extractant.

Ionic liquids can sometimes decrease the volatility, which can complicate the extractant recovery. Another disadvantage is the high cost of ionic liquid systems.

The application of LLE technology to the biorefinery process presents several challenges. First, many biorefinery systems are involved with bioactive organisms or biological catalysis, which may limit the application of organic extractants. It is therefore necessary to find the right extractant, which has a tolerance for microbes. Second, the LLE process has been conducted either at high temperature or high pressure, which are mostly detrimental conditions for active organisms. The extraction process in a biorefinery setting must be conducted under mild temperature conditions. Future breakthroughs can occur in the development of new extractants, new processes that can handle living organisms, or new active organisms that can endure the harsh conditions of LLE. Finally, biological systems are usually much more complex because they contain many more components and chemicals than regular chemical extraction processes.

A more selective solvent is therefore required. It is more complicated to scale up an LLE technology in the biorefinery process, and the interaction of components in biosystems will be more complex than that of a chemical process. With the development of these new types of extraction processes, the use of LLE in the biorefinery field will have a promising future.

References

1. Stephen, H.S.T.,Solubilities of Inorganic and Organic Compounds, Pergamon Press, 1963.

2. Pena-Pereira, F., I. Lavilla, and C. Bendicho, Miniaturized preconcentration methods based on liquid-liquid extraction and their application in inorganic ultratrace analysis and speciation: A review.Spectrochimica Acta Part B-Atomic Spectroscopy, 2009. 64(1): 1–15.

3. Pereira, E.A. and P.K. Dasgupta, Measurement of atmospheric formaldehyde using a drop collector and in-situ colorimetry.International Journal of Environmental Analytical Chemistry, 1997. 66(3): 201–213.

4. Cardoso, A.A. and P.K. Dasgupta, Analytical-Chemistry in a Liquid-Film Droplet.Analytical Chemistry, 1995.

67(15): 2562–2566.

5. Borges, S.D. and B.F. Reis, An automatic falling drop system based on multicommutation process for photo-metric chlorine determination in bleach.Analytica Chimica Acta, 2007. 600(1–2): 66–71.

6. Jeannot, M.A. and F.F. Cantwell, Mass transfer characteristics of solvent extraction into a single drop at the tip of a syringe needle.Analytical Chemistry, 1997. 69(2): 235–239.

7. Jain, A. and K.K. Verma, Recent advances in applications of single-drop microextraction: A review.Analytica Chimica Acta, 2011. 706(1): 37–65.

8. Lindenburg, P.W.,et al., Online capillary liquid-liquid electroextraction of peptides as fast pre-concentration prior to LC-MS.Electrophoresis, 2010. 31(23–24): 3903–3912.

9. Bonnesen, P.V.,et al., Development of effective solvent modifiers for the solvent extraction of cesium from alkaline high-level tank waste.Solvent Extraction and Ion Exchange, 2003. 21(2): 141–170.

10. Tsalev, D.L.,et al., Permanent modification in electrothermal atomic absorption spectrometry—advances, antic-ipations and reality.Spectrochimica Acta Part B-Atomic Spectroscopy, 2000. 55(5): 473–490.

11. Brunner, G.,Supercritical Fluids as Solvents and Reaction Media, Elsevier, 2004.

12. Alizadeh, N. and K. Ashtari, Coalescence extraction of silver(I) using the temperature-induced phase separation (TIPS) process.Separation and Purification Technology, 2005. 44(1): 79–84.

13. Ullmann, A., Z. Ludmer, and R. Shinnar, Phase-transition extraction using solvent mixtures with critical-point of miscibility.Aiche Journal, 1995. 41(3): 488–500.

14. Persson, J.,et al., Purification of recombinant proteins using thermoseparating aqueous two-phase system and polymer recycling.Journal of Chemical Technology and Biotechnology, 1999. 74(3): 238–243.

15. Bailes, P.J., Solvent-extraction in an electrostatic-field.Industrial and Engineering Chemistry Process Design and Development, 1981. 20(3): 564–570.

16. Sato, M., T. Hatori, and M. Saito, Experimental investigation of droplet formation mechanisms by electrostatic dispersion in a liquid-liquid system.IEEE Transactions on Industry Applications, 1997. 33(6): 1527–1534.

17. M¨uller, E., et al., Liquid–liquid extraction, in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, 2000.

18. Karr, A.E., T.L. Holmes, and R.W. Cusack, Effect of trace contaminants on performance of agitated extraction equipment.Solvent Extraction and Ion Exchange, 1990. 8(3): 515–528.

19. Timothy C., F.L.D.B.S. Holden, William D. Prince, A. Frank Seibert, Loren C., Wilson, Liquid-liquid extraction and other liquid-liquid opertions and equipment, in Perry’s Chemical Engineers’ Handbook, Don W.Green, Robert H. Perry, Editor, McGraw-Hill, 2008.

20. Likidis, Z. and K. Schugerl, Recovery of penicillin by reactive extraction in centrifugal extractors.Biotechnology and Bioengineering, 1987. 30(9): 1032–1040.

21. Croker, J.R. and R.G. Bowrey, Liquid extraction of furfural from aqueous-solution.Industrial and Engineering Chemistry Fundamentals, 1984. 23(4): 480–484.

22. Pei, Y.C., et al., Recovery of furfural from aqueous solution by ionic liquid based liquid-liquid extraction.

Separation Science and Technology, 2008. 43(8): 2090–2102.

23. Vane, L.M., Separation technologies for the recovery and dehydration of alcohols from fermentation broths.

Biofuels Bioproducts and Biorefining-Biofpr, 2008. 2(6): 553–588.

24. Mitchell, R.J., A. Arrowsmith, and N. Ashton, Mixed-solvent systems for recovery of ethanol from dilute aqueous-solution by liquid-liquid-extraction.Biotechnology and Bioengineering, 1987. 30(3): 348–351.

25. Offeman, R.D., et al., Solvent extraction of ethanol from aqueous solutions. I. Screening methodology for solvents.Industrial and Engineering Chemistry Research, 2005. 44(17): 6789–6796.

26. Offeman, R.D., et al., Solvent extraction of ethanol from aqueous solutions. II. Linear, branched, and ring-containing alcohol solvents.Industrial and Engineering Chemistry Research, 2005. 44(17): 6797–6803.

27. Koullas, D.P., O.S. Umealu, and E.G. Koukios, Solvent selection for the extraction of ethanol from aqueous solutions.Separation Science and Technology, 1999. 34(11): 2153–2163.

28. Solimo, H.N., H.E. Martinez, and R. Riggio, Liquid liquid extraction of ethanol from aqueous-solutions with amyl acetate, benzyl alcohol, and methyl isobutyl ketone at 298.15-k. Journal of Chemical and Engineering Data, 1989. 34(2): 176–179.

29. Rahman, M.A., M.S. Rahman, and M.N. Nabi, Extraction of ethanol from aqueous solution by solvent extraction-liquid-liquid equilibrium of ethanol-water-1-butanol, ethanol-water-l-pentanol and ethanol-water-1-hexanol sys-tems.Indian Journal of Chemical Technology, 2001. 8(5): 385–389.

30. Solimo, H.N. and J.L. Zurita, Influence of temperature on the liquid-to-liquid extraction of ethanol from (water plus ethanol plus 1,2-dichloroethane). Canadian Journal of Chemistry-Revue Canadienne de Chimie, 1992.

70(8): 2310–2313.

31. Egan, B.Z., D.D. Lee, and D.A. Mcwhirter, Solvent-extraction and recovery of ethanol from aqueous-solutions.

Industrial and Engineering Chemistry Research, 1988. 27(7): 1330–1332.

32. Gomis, V., et al., Salt effects in extraction of ethanol from aqueous solution: 2-ethylhexanol plus sodium chloride as the solvent.Industrial and Engineering Chemistry Research, 1998. 37(2): 599–603.

33. Habaki, H.,et al., Extraction equilibrium of ethanol for bioethanol production-solvent selection and liquid-liquid equilibrium measurement.Journal of the Japan Petroleum Institute, 2010. 53(3): 135–143.

34. Minier, M. and G. Goma, Production of ethanol by coupling fermentation and solvent-extraction. Biotechnology Letters, 1981. 3(8): 405–408.

35. Rahman, M.A., M.S. Rahman, and M. Asadullah, Production of fuel grade ethanol from dilute-solution by liquid-liquid-extraction using vegetable-oils as solvents. Indian Journal of Chemical Technology, 1995. 2(2):

90–92.

36. Matsumura, M. and H. Markl, Application of solvent-extraction to ethanol fermentation.Applied Microbiology and Biotechnology, 1984. 20(6): 371–377.

37. Arce, A., H. Rodriguez, and A. Soto, Effect of anion fluorination in 1-ethyl-3-methylimidazolium as solvent for the liquid extraction of ethanol from ethyl tert-butyl ether.Fluid Phase Equilibria, 2006. 242(2): 164–168.

38. Crabbe, P.G., C.W. Tse, and P.A. Munro, Effect of microorganisms on rate of liquid extraction of ethanol from fermentation broths.Biotechnology and Bioengineering, 1986. 28(7): 939–943.

39. Gyamerah, M. and J. Glover,Production of ethanol by continuous fermentation and liquid-liquid extraction.

Journal of Chemical Technology and Biotechnology, 1996. 66(2): 145–152.

40. Qian, J.F., Z. Yun, and H.X. Shi, Cogeneration of biodiesel and nontoxic cottonseed meal from cot-tonseed processed by two-phase solvent extraction. Energy Conversion and Management, 2010. 51(12):

2750–2756.

41. Shi, H.X. and Z.H. Bao, Direct preparation of biodiesel from rapeseed oil leached by two-phase solvent extrac-tion.Bioresource Technology, 2008. 99(18): 9025–9028.

42. Offeman, R.D.,et al., Solvent extraction of ethanol from aqueous solutions using biobased oils, alcohols, and esters.Journal of the American Oil Chemists Society, 2006. 83(2): 153–157.

43. Csanyi, E.,et al., Study on ethanol fermentation integrated with simultaneous solvent extraction and enzymatic reaction.Acta Alimentaria, 2004. 33(1): 63–70.

44. (ASTM), A.S.f.T.a.M.,ASTM D6751-02, inStandard Specification for Biodiesel Fuel (B100) Blend Stock for Distillate Fuels.

45. Tizvar, R., et al., Optimal separation of glycerol and methyl oleate via liquid-liquid extraction. Journal of Chemical and Engineering Data, 2009. 54(5): 1541–1550.

46. Adhami, L., et al., Liquid-liquid extraction of butanol from dilute aqueous solutions using soybean-derived biodiesel.Journal of the American Oil Chemists Society, 2009. 86(11): 1123–1128.

47. Achour, D., B. Abdi, and J.R. Molinier, Recovery of lactic and tartaric acid from dilute aqueous effluents by liquid extraction.Afinidad, 2001. 58(492): 112–114.

48. Malmary, G.H.,et al., Recovery of aconitic acid from simulated aqueous effluents of the sugarcane industry through liquid-liquid-extraction.Bioresource Technology, 1995. 52(1): 33–36.

49. Alvarez, M.E.T.,et al., Evaluation of liquid-liquid extraction process for separating acrylic acid produced from renewable sugars.Applied Biochemistry and Biotechnology, 2007. 137: 451–461.

50. Demirci, A., A.L. Pometto, and K.R. Harkins, Rapid screening of solvents and carrier compounds for lactic acid recovery by emulsion liquid extraction and toxicity onLactobacillus casei (ATCC 11443).Bioseparation, 1999. 7(6): 297–308.

51. Kurzrock, T. and D. Weuster-Botz, Recovery of succinic acid from fermentation broth.Biotechnology Letters, 2010. 32(3): 331–339.

52. SanMartin, M., C. Pazos, and J. Coca, Liquid-liquid extraction of lactic acid with alamine 336. Journal of Chemical Technology and Biotechnology, 1996. 65(3): 281–285.

53. Katikaneni, S.P.R. and M. Cheryan, Purification of fermentation-derived acetic acid by liquid-liquid extraction and esterification.Industrial and Engineering Chemistry Research, 2002. 41(11): 2745–2752.

54. Lee, S.C., Extraction of succinic acid from simulated media by emulsion liquid membranes.Journal of Membrane Science, 2011. 381(1–2): 237–243.

55. Frenz, J., C. Largeau, and E. Casadevall, Hydrocarbon recovery by extraction with a biocompatible solvent from free and immobilized cultures of botryococcus-braunii.Enzyme and Microbial Technology, 1989. 11(11):

717–724.

56. Malinowski, J.J., Evaluation of liquid extraction potentials for downstream separation of 1,3-propanediol.

Biotechnology Techniques, 1999. 13(2): 127–130.

57. Boonsongsawat, T., et al., Solvent extraction of biologically derived 1,3-propanediol with ethyl acetate and ethanol cosolvent.Separation Science and Technology, 2010. 45(4): 541–547.

58. Xiu, Z.L. and A.P. Zeng, Present state and perspective of downstream processing of biologically produced 1,3-propanediol and 2,3-butanediol.Applied Microbiology and Biotechnology, 2008. 78(6): 917–926.

59. Schuur, B., et al., Enantioselective liquid-liquid extraction of (R,S)-phenylglycinol using a bisnaphthyl phos-phoric acid derivative as chiral extractant.Tetrahedron, 2011. 67(2): 462–470.

60. Kellner, K.H.,et al., Enantioseparation of N-protected alpha-amino acid derivatives by liquid-liquid extraction technique employing stereoselective ion-pair formation with a carbamoylated quinine derivative.Chirality, 1997.

9(3): 268–273.

61. Ogunsola, O.M. and N. Berkowitz, Extraction of oil shales with sub-critical and near-critical water. Fuel Processing Technology, 1995. 45(2): 95–107.

62. Cassel, E.,et al., Steam distillation modeling for essential oil extraction process.Industrial Crops and Products, 2009. 29(1): 171–176.

63. Ayala, R.S. and M.D.L. de Castro, Continuous subcritical water extraction as a useful tool for isolation of edible essential oils.Food Chemistry, 2001. 75(1): 109–113.

64. Wennrich, L., B. Popp, and J. Breuste, Determination of organochlorine pesticides and chlorobenzenes in fruit and vegetables using subcritical water extraction combined with sorptive enrichment and CGC-MS. Chro-matographia, 2001. 53: S380–S386.

65. Raghavarao, K.S.M.S., M.R. Guinn, and P. Todd, Recent developments in aqueous two-phase extraction in bioprocessing.Separation and Purification Methods, 1998. 27(1): 1–49.

66. Favati, F., J.W. King, and M. Mazzanti, Supercritical carbon-dioxide extraction of evening primrose oil.Journal of the American Oil Chemists Society, 1991. 68(6): 422–427.

67. Levy, J.M., E. Storozynsky, and R.M. Ravey, The use of alternative fluids in online supercritical fluid extraction—capillary gas-chromatography. HRC—Journal of High Resolution Chromatography, 1991. 14(10):

661–666.

68. Alexandrou, N., M.J. Lawrence, and J. Pawliszyn, Cleanup of complex organic mixtures using supercritical fluids and selective adsorbents.Analytical Chemistry, 1992. 64(3): 301–311.

69. Huang, K.J.,et al., Designed polar cosolvent-modified Supercritical CO2 removing caffeine from and retaining catechins in green tea powder using response surface methodology.Journal of Agricultural and Food Chemistry, 2007. 55(22): 9014–9020.

70. Visser, A.E.,et al., Liquid/liquid extraction of metal ions in room temperature ionic liquids.Separation Science and Technology, 2001. 36(5–6): 785–804.

71. Werner, S., M. Haumann, and P. Wasserscheid, Ionic liquids in chemical engineering.Annual Review of Chemical and Biomolecular Engineering, 2010. 1: 203–230.

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