Direct Ethyl Levulinate Production from Raw Lignocellulosic Biomass Mediated by a Novel Taurine-Based Imidazolium Ionic Liquid

Author(s)

Gomes, Gustavo R. ; Scopel, Eupidio ; Rocha, Nicola L. ; Breitkreitz, Marcia C. ; Cormanich, Rodrigo A. ; Rezende, Camila A. ; Pastre, Julio C.

• Document type: Journal article
• Source: ACS SUSTAINABLE CHEMISTRY & ENGINEERING; v. N/A, p. 13-pg., 2022-11-21.

Abstract

In this work, a novel renewable taurine-based ionic liquid (IL), [TauIm][HSO4], was synthesized via the Debus- Radziszewski reaction. The synthesized IL was then used to produce ethyl levulinate (EL) from several lignocellulosic substrates under microwave irradiation. Experimental conditions (temperature, time, and IL quantity) for EL production from a model substrate (microcrystalline cellulose, MCC) were first investigated by design of experiment (DoE) using a central composite design (CCD). The highest EL yields (over 80%) in MCC were achieved at the upper limits of all factors (190 degrees C; 60 min; 10 equiv of IL). Computational studies revealed that the IL-cellobiose interaction is stronger than the IL itself at the reaction temperature (190 degrees C), indicating the efficiency of the IL in interacting with cellulose in the optimal reaction conditions. Moreover, the formation of the IL- cellobiose complex was mediated by the hydrogen sulfate anion, while the cation worked as a spacer. Optimized conditions from DoE were also applied to sugarcane bagasse and straw, elephant grass leaves and stems, rice husks and straw, and corn biomass. EL production yields from 12 to 59% were obtained from these biomasses using this novel imidazolium IL, with the highest EL yields obtained with raw sugarcane bagasse (SCB) without any pretreatments. The superior performance of SCB was associated with the higher content of hemicelluloses in its composition compared to that of the other biomasses. Together, these results presented herein open new possibilities for increasing biomass valorization using renewable and straightforward routes. (AU)

• FAPESP's process: 18/23769-1 - Preparation and applications of nanostructures from plant biomass
• Grantee: Camila Alves de Rezende
• Support Opportunities: Regular Research Grants
• FAPESP's process: 18/09861-2 - Synthesis of novel ionic liquids from renewable sources and application on biomass conversion
• Grantee: Gustavo Rodrigues Gomes
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 14/26378-2 - Development of methodologies and synthetic processes employing a new technological platform: micro and meso reactor assisted synthesis of natural products and derivatives with potential pharmacological activity
• Grantee: Júlio Cezar Pastre
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 18/03910-1 - Physicochemical studies of fluorinated organic compounds: experimental and theoretical approaches
• Grantee: Rodrigo Antonio Cormanich
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 21/06661-5 - Enabling technologies for the sustainable chemical synthesis of platform molecules, new chemicals and bioactive compounds
• Grantee: Júlio Cezar Pastre
• Support Opportunities: Program for Research on Bioenergy (BIOEN) - Young Investigators Grants - Phase 2
• FAPESP's process: 19/19360-3 - Plant cell wall-inspired nanocomposite hydrogels for biomedical applications
• Grantee: Eupídio Scopel
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 14/25770-6 - New frontiers in cross-coupling reactions promoted by palladium: combining enantioselective catalysis, C-H activations, new materials and in flux reactions aiming at high efficiency and sustainability in synthetic processes
• Grantee: Carlos Roque Duarte Correia
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 20/11578-7 - Enabling technologies allied to green chemistry: synthesis of high value-added compounds from biomass derivatives
• Grantee: Júlio Cezar Pastre
• Support Opportunities: Program for Research on Bioenergy (BIOEN) - Regular Program Grants