Engineering topics

Rabelo, Sarita C.

Publications and source records attributed to Rabelo, Sarita C..

3 records

DOE OSTI2021

Effect of Protic Ionic Liquids in Sugar Cane Bagasse Pretreatment for Lignin Valorization and Ethanol Production

Ionic liquids have been called designer solvents because it is possible to fine-tune their properties from a huge range of possible combinations of cations and anions. In this work, we evaluate the potential of protic ionic liquids (PILs) in the fractionation of sugar cane bagasse in a biorefinery context. Here, the PILs were designed to selectively solubilize lignin and leave a polysaccharides solid fraction. The carbohydrate fraction was further hydrolyzed to obtain pentose and hexose sugars, which were fermented using a pentose-consuming yeast. The results have shown that, differently from pretreatments that solubilize hemicelluloses, pentoses could be fermented together with hexoses without a prior detoxification step with high yield and productivity. The lignin recovered was characterized by 2D HSQC NMR, 31 P NMR, and GPC, showing that the design of the PIL influences lignin characteristics, but pretreatment temperature and time do not. The lignins obtained are sulfur-free, and the richness of their functional groups makes them attractive for conversion into a diversity of value-added products, which can make a biorefinery based on the proposed process viable.

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DOE OSTI2020

Influence of chain length in protic ionic liquids on physicochemical and structural features of lignins from sugarcane bagasse

We report the mechanisms behind lignin dissolution with protic ionic liquids (PILs) and their influence over lignin properties remain not fully explored. In this work, physicochemical and structural features of lignins extracted from sugarcane bagasse after pretreatment with a series of PILs (length of the cation chain combined with different anions) were assessed using analytical techniques. It was found that the lignin extracted with shorter chain length cations PILs showed the highest β-O-4 content. Opposite, the increase of the PILs cation chain length resulted in enhanced depolymerization. All lignins presented high polydispersity (>3.7), while the weight average molecular ranged from 1921 to 13,539 g/mol. The recovered [Eti][Mal] lignin presented the higher β-O-4 content and was possibly the most preserved lignin obtained. Opposite, lignin isolated from [Hex][Ac] and [Hex][For] treatments had less β-O-4 linkages attributed to the depolymerization of lignin via rupture of ether linkages generating intermediates that further repolymerized and/or depolymerized. These results suggest that the ionicity of the PIL is a crucial factor for lignin dissolution. Furthermore, these results illustrate that the proposed pretreatment using different PILs is useful to obtain high-quality lignins with distinct features and opens a new perspective for materials to match various applications.

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DOE OSTI2020

Structural characterization of sugarcane lignins extracted from different protic ionic liquid pretreatments

Previous studies based on protic ionic liquids have shown them to be effective for extracting lignins from biomass. Moreover, ILs synthesized with amine cations can promote the insertion of nitrogen into lignin, favoring its valorization for industrial applications. Here, lignins extracted from sugarcane bagasse by eight different PILs were analyzed. Several techniques of characterization were employed (2D HSQC NMR, 31P NMR, GPC, Py-GC/MS, TGA, FTIR, and elemental analysis), seeking a deeper understanding of lignin structure post-PILS treatment. In particular, lignin obtained with acetate and lactate anions with monoethanolamonium cations showed similar structural compositions. Lignins obtained from ethylenediamonium cation combined anions acetate and lactate exhibited relatively higher molecular weights compared to the other lignins studied. The elemental analysis of these lignins further revealed the presence of nitrogen in their structures, suggesting that amination occurred. In this work we used PILs not yet reported in the literature for this purpose, and consequently obtained lignins with specific structures. Overall, our results demonstrated that depending on the PILs used, lignins with distinct properties could be obtained which might be used for value-added applications. This work covered new advances in elucidation of lignin chemical structure and opened a new path for lignin valorization.

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