Industrial scale chromatographic separation of valuable compounds from biomass hydrolysates and side streams

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Kemian tekniikan korkeakoulu | Doctoral thesis (article-based)
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Aalto University publication series DOCTORAL DISSERTATIONS , 42/2011
Carbohydrates are composed of a number of various monosaccharides, glucose being the most abundant. Some of the monosaccharides are valuable compounds used in the food and pharmaceutical industries. They can be separated from biomass hydrolysates e.g. by chromatographic methods. In this thesis, chromatographic separation of valuable compounds using ion exchange resins was studied on an industrial scale. Of special interest were rare monosaccharides in biomass hydrolysates. A novel chromatographic separation process was developed for fucose, starting from pre-processed spent sulfite liquor. The core of the process consists of three chromatographic separations with different types of ion exchange resins. Chromatographic separation of galactose was tested with three biomass hydrolysates; lactose, gum arabic and hemicellulose hydrolysates. It was demonstrated that also galactose can be separated from complex carbohydrate mixtures. A recovery process for arabinose from citrus pectin liquid residual and for mannose from wood pulp hydrolysate were also developed and experimentally verified. In addition to monosaccharides, chromatographic separation of glycinebetaine from vinasse was examined with a hydrogen form weak acid cation exchange resin. The separation involves untypical peak formation depending, for example, on the pH and the cation composition. The retention mechanism was found to be hydrogen bonding between glycinebetaine and the resin. In the experimental part, all four resin types - strong acid cation, strong base anion, weak acid cation and weak base anion exchange resins - were used. In addition, adsorption equilibria data of seven monosaccharides and sucrose were measured with the resins in sodium and sulfate forms because such data have been lacking. It was found out that the isotherms of all sugars were linear under industrial conditions. A systematic method for conceptual process design and sequencing of chromatographic separation steps were developed. Heuristics were drawn from the current industrial practices also for the selection of a suitable ion exchange resin for the separation of a sugar from a biomass hydrolysate.
Supervising professor
Hurme, Markku, Prof.
Thesis advisor
Hurme, Markku, Prof.
chromatography, fucose, galactose, arabinose, mannose, glycinebetaine, conceptual process design, ion exchange resin, adsorption isotherm
Other note
  • [Publication 1]: Saari, P., Häkkä, K., Heikkilä, H., Jumppanen, J., Hurme, M. A Novel Chromatographic Production Scale Separation Process for L-Fucose, J. Liq. Chromatogr. Related Technol. 32 (2009) 2050-2064.
  • [Publication 2]: Saari, P., Häkkä, K., Jumppanen, J., Heikkilä, H., Hurme, M. Study on Industrial Scale Chromatographic Separation Methods of Galactose from Biomass Hydrolysates, Chem. Eng. Technol. 33 (2010) 137-144.
  • [Publication 3]: Saari, P., Paananen, H., Hurme, M., Study on the Retention of Glycinebetaine on a Weak Acid Cation Exchange Resin, J. Liq. Chromatogr. Related Technol. 34 (2011) 622-633.
  • [Publication 4]: Saari, P., Heikkilä, H., Hurme, M., Adsorption Equilibria of Arabinose, Fructose, Galactose, Glucose, Mannose, Rhamnose, Sucrose, and Xylose on Ion-Exchange Resins, J. Chem. Eng. Data 55 (9) (2010) 3462-3467.
  • [Publication 5]: Saari, P., Hurme, M., Process Synthesis Principles in the Chromatographic Separation of Sugars from Biomass Hydrolysates, Chem. Eng. Technol. 34 (2011) 282-288.