Ikenna Anugwom

Switchable Ionic liquids (SILs) based on glycerol and acid gases

New types of switchable ionic liquids (SILs), containing 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), glycerol and an acid gas (CO2, SO2), were synthesized and characterized in this study. [DBU][Carbonate] or [sulfonate] were easily synthesized from a non-ionic mixture of molecular organic polyol and amidine base upon bubbling of an acid gas (CO2, SO2). Moreover, they were switched back to the original molecular solvents by flushing out the acid gas (CO2, SO2) by heating and/or bubbling an inert gas such as N2 through it. The structures of the SILs were confirmed by NMR and FTIR. The change from low polarity (molecular solvent) to high polarity (Switchable Ionic Liquid, SIL) was also indicated by the changes in properties, such as viscosity and miscibility with different organic solvents. The decomposition temperatures of the SILs were determined by means of Thermo Gravimetric Analysis (TGA) and gave values in the range of 50 °C and 120 °C for DBU-glycerol-CO2 (SIL1) and DBU-glycerol-SO2 (SIL2), respectively. Due to the reasonable decomposition temperatures, these novel SILs can be employed in multiple applications.

Switchable Ionic Liquids as Delignification Solvents for Lignocellulosic Materials

The transformation of lignocellulosic materials into potentially valuable resources is compromised by their complicated structure. Consequently, new economical and feasible conversion/fractionation techniques that render value-added products are intensely investigated. Herein an unorthodox and feasible fractionation method of birch chips (B. pendula) using a switchable ionic liquid (SIL) derived from an alkanol amine (monoethanol amine, MEA) and an organic super base (1,8-diazabicyclo-[5.4.0]-undec-7-ene, DBU) with two different trigger acid gases (CO2 and SO2 ) is studied. After SIL treatment, the dissolved fractions were selectively separated by a step-wise method using an antisolvent to induce precipitation. The SIL was recycled after concentration and evaporation of anti-solvent. The composition of undissolved wood after MEA-SO2 -SIL treatment resulted in 80 wt % cellulose, 10 wt % hemicelluloses, and 3 wt % lignin, whereas MEA-CO2 -SIL treatment resulted in 66 wt % cellulose, 12 wt % hemicelluloses and 11 wt % lignin. Thus, the MEA-SO2 -SIL proved more efficient than the MEA-CO2 -SIL, and a better solvent for lignin removal. All fractions were analyzed by gas chromatography (GC), Fourier transform infrared spectroscopy (FT-IR), (13) C nuclear magnetic resonance spectroscopy (NMR) and Gel permeation chromatography (GPC).

Treating birch wood with a switchable 1,8-diazabicyclo-[5.4.0]-undec-7-ene-glycerol carbonate ionic liquid

Abstract The suitability of a new switchable ionic liquid (SIL) has been investigated as a solvent for fractionation of lignocellulosic materials. SIL was prepared from inexpensive chemicals, e.g., glycerol, CO2, and 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU). Fresh Nordic birch wood (B. pendula) was treated with the SIL for a time period of 1–5 days at 100°C and under atmospheric pressure. Upon SIL treatment, at best, 57% of the hemicelluloses were dissolved and 50% of lignins were dissolved from the native birch. The slightly fibrillated SIL treated chips contained about 55% cellulose. Up to 76% of the recovered species removed from the spent SIL liquor was originating from hemicelluloses, mainly from xylan. The spent SILs were reused for fresh wood dissolution in four consecutive cycles and each time the wood dissolution efficiency was similar. SILs could offer affordable (easy-to-synthesize) solvent systems for partial elimination of hemicelluloses and lignin from wood. SILs can also be prepared in-situ and on-site.

Realtime (31)P NMR Investigation on the Catalytic Behavior of the Enzyme Adenylate kinase in the Matrix of a Switchable Ionic Liquid.

The integration of highly efficient enzymatic catalysis with the solvation properties of ionic liquids for an environmentally friendly and efficient use of raw materials such as wood requires fundamental knowledge about the influence of relevant ionic liquids on enzymes. Switchable ionic liquids (SIL) are promising candidates for implementation of enzymatic treatments of raw materials. One industrially interesting SIL is constituted by monoethanol amine (MEA) and 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) formed with sulfur dioxide (SO2) as the coupling media (DBU-SO2-MEASIL). It has the ability to solubilize the matrix of lignocellulosic biomass while leaving the cellulose backbone intact. Using a novel (31)P NMR-based real-time assay we show that this SIL is compatible with enzymatic catalysis because a model enzyme, adenylate kinase, retains its activity in up to at least 25 wt % of DBU-SO2-MEASIL. Thus this SIL appears suitable for, for example, enzymatic degradation of hemicellulose.

The effect of switchable ionic liquid (SIL) treatment on the composition and crystallinity of birch chips (Betula pendula) using a novel alkanol amine-organic superbase-derived SIL

Abstract Two-step treatment of birch chips (Betula pendula) was tested using diethanolamine (DEA)-1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU)-CO2-switchable ionic liquid (SIL), resulting in a 23% weight reduction in 24 h. The weight of the chips was reduced to 32% of their initial weight upon the second treatment with fresh SIL. SIL to wood ratio of 5:1, at 100°C for 24 h, without stirring, was applied in both steps. The relative amount of wood lignin reduced from 24% to 14% after two treatment cycles. The relative amount of cellulose of the undissolved fraction after SIL treatment increased from 43% (native birch wood) to 68% after the second cycle. Also, the undissolved material was efficiently fibrillated. The dissolved materials recovered from spent SIL, after treatment, contained high xylan content, about 90% of the total hemicelluloses, which was 85% of the recovered material. The powder X-ray diffraction (XRD) results revealed that the crystallinity of the undissolved material increased slightly, indicating dissolution of the amorphous material. Moreover, transformation of cellulose form I to form II in the remaining undissolved chips was not observed.

CHAPTER 5:Switchable Polarity Liquids

In this chapter, the synthesis and characterization, as well as applications, of various types of switchable polarity solvents (SPSs) are summarized in order to unravel their composition and switch ...