Are Ionic Liquids Enabling Technology? Startup to Scale-Up to Find Out

  • Julia L. ShamshinaEmail author
  • Robin D. Rogers
Part of the Green Chemistry and Sustainable Technology book series (GCST)


Commercialization of new sustainable technology from academia to industry is based on the technology-enabling innovation, the manufacturability, the implementation cost, and the technology’s competitive advantage, such as functionality improvement(s) over the routine process or existing products. Future-minded thinking outside the accepted margins and innovative execution are involved in creating new markets. The majority of this chapter is dedicated to our experiences in pursuing the transition of ionic liquids (ILs)-based technology from academia to industry for the extraction of chitin ((C8H13O5N)n), the second most abundant biopolymer on the planet, directly from shrimp shells. While the dissolution and extraction of chitin was demonstrated as early as 2010, the necessity of using an IL presented hurdles for scaling the technology to a commercial level. The resultant chitin polymer could be extracted while maintaining its high-molecular weight and providing materials with high strength and unique control of the final form. In 2012, a Laboratory Demonstration Pilot Unit (LDPU) was built and tested, followed by further scale-up to a mini-pilot plant in 2014–2015 with funding from the U.S. Department of Energy. Currently, this mini-pilot plant provides the groundwork for the construction of a larger plant for a scaled-up chitin extraction by Mari Signum, Mid-Atlantic. This will allow the generation of sufficient supplies of chitin and create new markets for this polymer. The high quality of the polymer and the ability to produce high-value products from it will give Mari Signum, Mid-Atlantic a competitive advantage not only to enter multiple focused profitable markets but also to create new markets. Once the polymer becomes available on a large-scale not only will the price decrease, but it will become available for the invention of additional products. When large-scale supply is available, it will provide confidence to investors due to known and manageable marketing and supply costs. The tremendous potential of chitin will soon be exploited for a number of industrial applications utilizing the full potential of this IL-based platform.


Biomass Biopolymers Chitin Commercialization Ionic liquid Process development Product development Renewable polymers 



The authors would like to thank 525 Solutions, Inc., U.S. Department of Energy Small Business Innovation Research Program (DOE-SBIR Grant No. DE-SC0010152, Phase I/II), and DOE Office of Nuclear Energy, Nuclear Energy University Programs (DOE NEUP Grant No. DE-NE0000672) for financial support. We would also like to express our sincere gratitude to Dr. Eric Schneider (University of Texas at Austin, Mechanical Engineering in Cockrell School of Engineering) for the help with technology economic assessment, and Mr. Jonathan Bonner (Poly Engineering, Tuscaloosa, AL) for the help with scaling up the equipment to the production scale.


  1. 1.
    Plastics market analysis by product (PE, PP, PVC, PET, polystyrene, engineering thermoplastics), by application (film & sheet, injection molding, textiles, packaging, transportation, construction) and segment forecasts to 2020. Grand View Research, Inc., 2015. Available at: Last accessed 04-02-18
  2. 2.
    University of Georgia (2017) More than 8.3 billion tons of plastics made: most has now been discarded. Science Daily, 19 July 2017. Available at: Last accessed 12-10-19
  3. 3.
    Geyer R, Jambeck JR, Law KL (2017) Production, use, and fate of all plastics ever made. Sci Adv 3:e1700782. Scholar
  4. 4.
    Ellen MacArthur Foundation 2016 Report. Rethinking the future of plastics: Last accessed 07-28-19
  5. 5.
    Tunnicliffe H (2017) Turning ocean trash into cash. TCE: the chemical engineer 913/914:36–38. Available at: Last accessed 07-16-19
  6. 6.
    North EJ, Halden RU (2013) Plastics and environmental health: the road ahead. Rev Environ Health 28:1–8. Scholar
  7. 7.
    Popa V (2018) Biomass for fuels and biomaterials. In: Popa VI, Volf I (eds) Biomass as renewable raw material to obtain bioproducts of high-tech value, Elsevier, pp 1–37.
  8. 8.
    Intro to plantbottle packaging. Available at: Last accessed 04-19-18
  9. 9.
    Edge M, Hayes M, Mohammadian M, Allen NS, Jewitt TS, Brems K, Jones K (1991) Aspects of poly(ethylene terephthalate) degradation for archival life and environmental degradation. Polym Degrad Stab 32:131–153. Scholar
  10. 10.
    Allen NS, Edge M, Mohammadian M, Jones K (1994) Physicochemical aspects of the environmental degradation of poly(ethylene terephthalate). Polym Degrad Stab 43:229–237. Scholar
  11. 11.
    Rogers RD (2015) Eliminating the need for chemistry. C&EN 93(48):42–43.
  12. 12.
    Gao X, Chen X, Zhang J, Guo W, Jin F, Yan N (2016) Transformation of chitin and waste shrimp shells into acetic acid and pyrrole. ACS Sustain Chem Eng 4:3912–3920. Scholar
  13. 13.
    Prudden JF, Migel P, Hanson P, Friedrich L, Balassa L (1970) The discovery of a potent pure chemical wound-healing accelerator. Am J Surg 119:560–564. Scholar
  14. 14.
    Jayakumar R, Prabaharan M, Kumar PTS, Sudheesh Kumar PT, Nair SV, Furnike T, Tamura H (2011) Novel chitin and chitosan materials in wound dressing. In: Laskovski AN (ed) Biomedical engineering trends in materials science, InTech 3–24.
  15. 15.
    Vázquez JA, Rodríguez-Amado I, Montemayor MI, Fraguas J, González M del P, Murado MA (2013) Chondroitin sulfate, hyaluronic acid and chitin/chitosan production using marine waste sources: characteristics, applications and eco-friendly processes: a review. Mar Drugs 11:747–774.
  16. 16.
    Mori T, Okumura M, Matsuura M, Ueno K, Tokura S, Okamoto Y, Minami S, Fujinaga T (1997) Effects of chitin and its derivatives on the proliferation and cytokine production of fibroblasts in vitro. Biomaterials 18:947–951. Scholar
  17. 17.
    Hirano S, Nakahira T, Nakagawa M, Kim SK (1999) The preparation and application of functional fibres from crab shell chitin. J Biotechnol 70:373–377. Scholar
  18. 18.
    Wan ACA, Tai BCU (2013) Chitin—a promising biomaterial for tissue engineering and stem cell technologies. Biotech Adv 31:1776–1785. Scholar
  19. 19.
    Barber PS, Kelley SP, Griggs CS, Wallace S, Rogers RD (2014) Surface modification of ionic liquid-spun chitin fibers for the extraction of uranium from seawater: seeking the strength of chitin and the chemical functionality of chitosan. Green Chem 16:1828–1836.
  20. 20.
    Muzarelli RAA, Boudrant J, Meyer D, Manno N, DeMarchis M, Paoletti MG (2012) Current views on fungal chitin/chitosan, human chitinases, food preservation, glucans, pectins and inulin: a tribute to Henri Braconnot, precursor of the carbohydrate polymers science, on the chitin bicentennial. Carbohydr Polym 87:995–1012. Scholar
  21. 21.
    Dutta PK, Dutta J, Tripathi VS (2004) Chitin and chitosan: chemistry, properties and applications. J Sci Ind Res 63:20–31.CrossRefGoogle Scholar
  22. 22.
    Domard A (2011) A perspective on 30 years research on chitin and chitosan. Carbohydr Polym 84:696–703. Scholar
  23. 23.
    Tharanathan RN, Kittur FS (2003) Chitin—the undisputed biomolecule of great potential. Critical Rev Food Sci Nutr 43:61–87. Scholar
  24. 24.
    Synowiecki J, Al-Khateeb NA (2003) Production, properties, and some new applications of chitin and its derivatives. Critical Rev Food Sci Nutr 2:145–171. Scholar
  25. 25.
    Ravi Kumar MNV (2000) A review of chitin and chitosan applications. React Funct Polym 46:1–27. Scholar
  26. 26.
    Chitin market: agrochemical end use industry segment inclined towards high growth—moderate value during the forecast period: global industry analysis (2012–2016) and opportunity assessment (2017–2027). Last accessed 04-02-18
  27. 27.
    Yang T-L (2011) Chitin-based materials in tissue engineering: applications in soft tissue and epithelial organ. Int J Mol Sci 12:1936–1963. Scholar
  28. 28.
    Khor E, Lim LY (2003) Implantable applications of chitin and chitosan. Biomaterials 24:2339–2349. Scholar
  29. 29.
    Mi F-L, Shyu S-S, Lin Y-M, Wu Y-B, Peng C-K, Tsai Y-H (2003) Chitin/PLGA blend microspheres as a biodegradable drug delivery system: a new delivery system for protein. Biomaterials 24:5023–5036. Scholar
  30. 30.
    Rejinold NS, Chennazhi KP, Tamura H, Nair SV, Jayakumar R (2011) Multifunctional chitin nanogels for simultaneous drug delivery, bioimaging, and biosensing. ACS Appl Mater Interfaces 3:3654–3665; 11.13832. Scholar
  31. 31.
    Ding F, Deng H, Du Y, Shi X, Wang Q (2014) Emerging chitin and chitosan nanofibrous materials for biomedical applications. Nanoscale 6(16):9477–9493. Scholar
  32. 32.
    Singh R, Shitiz K, Singh A (2017) Chitin and chitosan: biopolymers for wound management. Int Wound J 14:1276–1289. Scholar
  33. 33.
    Jayakumar R, Prabaharan M, Sudheesh Kumar PT, Nair SV, Tamura H (2011) Biomaterials based on chitin and chitosan in wound dressing applications. Biotech Adv 29:322–337. Scholar
  34. 34.
    Shigemasa Y, Minami S (1996) Applications of chitin and chitosan for biomaterials. Biotech Genetic Eng Rev 13:383–420. Scholar
  35. 35.
    Trutnau M, Bley T, Ondruschka J (2011) Chapter 1: Chitosan from fungi. In: Davis SP (ed) Chitosan: manufacture, properties, and usage, Nova Science Publishers, Inc., New York, NY, pp. 1–70.Google Scholar
  36. 36.
    Tidal Vision, USA. Last accessed 04-03-18
  37. 37.
    CarboMer. Last accessed 04-03-18
  38. 38.
    Shiau S-Y, Yu Y-P (1998) Chitin but not chitosan supplementation enhances growth of grass shrimp, Penaeus monodon. J Nutr 128:908–912. Scholar
  39. 39.
    Sharp RG (2013) A review of the applications of chitin and its derivatives in agriculture to modify plant-microbial interactions and improve crop yields. Agronomy 3:757–793. Scholar
  40. 40.
    Bhatnagar A, Sillanpää M (2009) Applications of chitin- and chitosan-derivatives for the detoxification of water and wastewater—a short review. Adv Colloid Interface Sci 152:26–38. Scholar
  41. 41.
    Araki J, Yamanaka Y, Ohkawa K (2012) Chitin-chitosan nanocomposite gels: reinforcement of chitosan hydrogels with rod-like chitin nanowhiskers. Polymer J 44:713–717. Scholar
  42. 42.
    Unitika history creates its next history. Last accessed 04-04-18
  43. 43.
    Eisai Co., last accessed 04-04-18
  44. 44.
    Minami S, Okamoto Y, Miyatake A, Matsuhashi A, Kitamura Y, Tanigawa T, Tanaka Y, Shigemasa Y (1996) Chitin induces type IV collagen and elastic fiber in implanted non-woven fabric of polyester. Carbohydrate Polym 29:295–299. Scholar
  45. 45.
    SyvekExcel. Last accessed 04-04-18
  46. 46.
    Technical Information: ExcelArrest® XT. Last accessed 04-04-18
  47. 47.
    Poeloengasih CD, Hernawan, Angwar M (2008) Isolation and characterization of chitin and chitosan prepared under various processing times. Indo J Chem 8:189–192.
  48. 48.
    Beaney P, Lizardi-Mendoza J, Healy M (2005) Comparison of chitins produced by chemical and bioprocessing methods. J Chem Tech Biotech 80:145–150. Scholar
  49. 49.
    Rinaudo M (2006) Chitin and chitosan: properties and applications. Prog Polym Sci 31:603–632. Scholar
  50. 50.
    Khoushab F, Yamabhai M (2010) Chitin research revisited. Mar Drugs 8:1988–2012. Scholar
  51. 51.
    Shamshina JL, Barber PS, Gurau G, Griggs CS, Rogers RD (2017) Pulping of crustacean waste using ionic liquids: to extract or not to extract. ACS Sust Chem Eng 4:6072–6081. Scholar
  52. 52.
    Younes I, Rinaudo M (2015) Chitin and chitosan preparation from marine sources. Structure, properties and applications. Mar Drugs 13:1133–1174. Scholar
  53. 53.
    Silva SS, Mano JF, Reis RL (2017) Ionic liquids in the processing and chemical modification of chitin and chitosan for biomedical applications. Green Chem 19:1208–1220. Scholar
  54. 54.
    King C, Shamshina JL, Gurau G, Berton P, Khan NFAF, Rogers RD (2017) A platform for more sustainable chitin films from an ionic liquid process. Green Chem 19:117–126. Scholar
  55. 55.
    Shen X, Shamshina JL, Berton P, Bandomir J, Wang H, Gurau G, Rogers RD (2016) Comparison of hydrogels prepared with ionic-liquid-isolated vs commercial chitin and cellulose. ACS Sustainable Chem Eng 4:471–480. Scholar
  56. 56.
    Kadokawa J (2016) Dissolution, gelation, functionalization, and material preparation of chitin using ionic liquids. Pure Appl Chem 88:621–629. Scholar
  57. 57.
    Shamshina JL, Zavgorodnya O, Bonner JR, Gurau G, Di Nardo T, Rogers RD (2017) “Practical” electrospinning of biopolymers in ionic liquids. ChemSusChem 10:106–111. Scholar
  58. 58.
    Zavgorodnya O, Shamshina JL, Bonner JR, Rogers RD (2017) Electrospinning biopolymers from ionic liquids requires control of different solution properties than volatile organic solvents. ACS Sustain Chem Eng 5:5512–5519. Scholar
  59. 59.
    Turner MB, Spear SK, Holbrey JD, Rogers RD (2004) Production of bioactive cellulose films reconstituted from ionic liquids. Biomacromol 5:1379–1384. Scholar
  60. 60.
    Turner MB, Spear SK, Holbrey JD, Daly DT, Rogers RD (2005) Ionic liquid-reconstituted cellulose composites as solid support matrices for biocatalyst immobilization. Biomacromol 6:2497–2502. Scholar
  61. 61.
    Sun N, Swatloski RP, Maxim ML, Rahman M, Harland AG, Haque A, Spear SK, Daly DT, Rogers RD (2008) Magnetite-embedded cellulose fibers prepared from ionic liquid. J Mater Chem 18:283–290. Scholar
  62. 62.
    Bagheri M, Rodríguez H, Swatloski RP, Spear SK, Daly DT, Rogers RD (2008) Ionic liquid-based preparation of cellulose–dendrimer films as solid supports for enzyme immobilization. Biomacromol 9:381–387. Scholar
  63. 63.
    Shamshina JL, Gurau G, Block LE, Hansen LK, Dingee C, Walters A, Rogers RD (2014) Chitin–calcium alginate composite fibers for wound care dressings spun from ionic liquid solution. J Mater Chem B 2:3924–3936. Scholar
  64. 64.
    Maxim ML, White JF, Block LE, Gurau G, Rogers RD (2012) Advanced biopolymer composite materials from ionic liquid solutions in ionic liquids: science and applications. In: Visser AE, Bridges NJ, Rogers RD (eds) Ionic liquids: science and applications, ACS Symp Ser 1117:167–187.
  65. 65.
    Takegawa A, Murakami M, Kaneko Y, Kadokawa J (2010) Preparation of chitin/cellulose composite gels and films with ionic liquids. Carbohydr Polym 79:85–90. Scholar
  66. 66.
    Singh N, Koziol KKK, Chen J, Patil AJ, Gilman JW, Trulove PC, Kafienah W, Rahatekar SS (2013) Ionic liquids-based processing of electrically conducting chitin nanocomposite scaffolds for stem cell growth. Green Chem 15:1192–1202. Scholar
  67. 67.
    Mundsinger K, Müller A, Beyer R, Hermanutz F, Buchmeiser MR (2015) Multifilament cellulose/chitin blend yarn spun from ionic liquids. Carbohydr Polym 131:34–40. Scholar
  68. 68.
    Sun N, Li W, Stoner B, Jiang X, Lu X, Rogers RD (2011) Composite fibers spun directly from solutions of raw lignocellulosic biomass dissolved in ionic liquids. Green Chem 13:1158–1161. Scholar
  69. 69.
    Shamshina JL, Berton P, Rogers RD (2019) Advances in functional chitin materials: a review. ACS Sustain Chem Eng 7:6444–6457. Scholar
  70. 70.
    Qin Y, Lu X, Sun N, Rogers RD (2010) Dissolution or extraction of crustacean shells using ionic liquids to obtain high molecular weight purified chitin and direct production of chitin films and fibers. Green Chem 12:968–971. Scholar
  71. 71.
    Wang H, Gurau G, Rogers RD (2014) Dissolution of biomass using ionic liquids. In: Zhang S, Wang J, Lu X, Zhou Q (eds) Structures and interactions of ionic liquids 151. Springer, Berlin, Heidelberg, pp 79–105.
  72. 72.
    Shamshina JL, Zavgorodnya O, Rogers RD (2018) Advances in processing chitin as promising biomaterial from ionic liquids. In: Itoh T, Koo Y-M (eds) Application of ionic liquids in biotechnology. Advances in biochemical engineering/biotechnology. Springer, Cham, pp. 177–198.
  73. 73.
    Alabama Innovation Fund (AIF): Alabama EPSCOR. Last accessed 4-03-18
  74. 74.
    Gulf Coast Agricultural and Seafood COOP. Last accessed 07-28-19
  75. 75.
    Zavgorodnya O, Shamshina JL, Berton P, Rogers RD (2017) Translational research from academia to industry: following the pathway of George Washington Carver. In: Shiflett MB, Scurto AM (eds) Ionic liquids: current state and future directions, ACS Symp Ser 1250:17–33.
  76. 76.
    Barber PS, Griggs CS, Bonner JR, Rogers RD (2013) Electrospinning of chitin nanofibers directly from an ionic liquid extract of shrimp shells. Green Chem 15:601–607. Scholar
  77. 77.
    Mari Signum, Mid-Atlantic. Last Accessed 04-19-18

Copyright information

© Springer Nature Switzerland AG 2020

Authors and Affiliations

  1. 1.Mari Signum, Mid Atlantic, LLCRichmondUSA
  2. 2.525 Solutions, Inc.TuscaloosaUSA

Personalised recommendations