Pressurized Mixtures of Ionic Liquids as Process Solvents for Biomass
The present thesis investigates the application of pressurized mixtures of imidazolium-based ionic liquids with traditional organic solvents for the dissolution and extraction of lignocellulosic biomass, with bamboo as a specific example of renewable biomass. The approach has been unconventional in that the focus has been on solvent mixtures in which the ionic liquid is the minor component. The objective has been to combine the solvating power of the ionic liquid with a traditional solvent such as ethanol to modulate the outcomes of solubility and extractions by tuning the parameters of fluid composition, temperature, and pressure. Working with mixtures of ionic liquids in traditional solvents as process solvents lowers the viscosity of the medium and thus reduces the transport limitations that are often encountered when working with pure ionic liquids. Among other potential advantages are the reductions in overall process cost that are associated with ionic liquids, potentially easier recovery of post-extraction products, and the recycling of the ionic liquids. This thesis has also addressed another important question regarding the thermal stability of the ionic liquids as a processing medium at elevated temperatures and pressures over time, which may negatively impact their recovery and reuse, and may lead to environmentally unacceptable consequences. The dissolution experiments were carried out in a specially designed high-pressure view-cell equipped with sapphire windows for visual or optical observations. Evaluations were made employing standard characterization tools such as Thermogravimetric Analysis (TGA), Fourier Transform Infrared Spectroscopy (FTIR), UV-Vis Spectroscopy, and Scanning Electron Microscopy (SEM). Thermal stability studies were carried out using a combination of a view-cell and fiber optic UV-Vis capability at high pressures (up to 350 bar) and temperatures (up to 150 ℃).
The dissolution of bamboo was first explored using mixtures of 1-ethyl-3-methylimidazolium acetate ([EMIM]Ac) with ethanol at temperatures from 100 to 150 ℃ and pressures from 35 to 350 bar over 4 or 24 h extraction times. The fluid mixtures employed were in the range of 1 - 40 wt % ionic liquid, which is in contrast to relevant dissolution experiments reported in the literature which either use pure ionic liquids or have the ionic liquids as the majority component. The effects of changing the temperature, pressure, and solvent composition on the removal of different components of the bamboo were assessed. Temperature played the most significant role in the amount of material extracted from the bamboo, with higher temperatures resulting in the removal of more lignin than cellulose and greater conversion of crystalline cellulose to the less recalcitrant amorphous form of cellulose. The concentration of ionic liquid in solution was also important, with higher concentrations resulting in more dissolved biomass. Finally, increasing the pressure resulted in higher amounts of dissolved biomass.
The next series of studies focused on rigorously assessing the stability of 1-alkyl-3-methylimidazolium acetate and chloride ionic liquids with alkyl chain lengths from 2 to 10 under both isothermal and non-isothermal conditions via thermogravimetric analysis. Isothermal degradation experiments were conducted at temperatures ranging from 100 to 225 ℃ over time periods ranging from two hours to three weeks. Non-isothermal degradation experiments were conducted at heating rates of 5, 10, 15, and 20 ℃/min from room temperature to 650 ℃. The activation energies and pre-exponential factors were assessed with isoconversional integral methods; the activation energies () ranged from 115 to 157 kJ/mol, and the pre-exponential factors (()) ranged from 24-38. The degradation reactions could be described as 1st order, as they often are in the literature, but were best fit by the 3-dimensional reaction model. Ionic liquids with longer alkyl chains on their imidazolium rings decomposed more quickly and at lower temperatures.
The thermal stability of the most promising ionic liquids ([EMIM]Ac, [BMIM]Ac, [EMIM]Cl, and [BMIM]Cl) were then assessed more closely at the possible biomass processing conditions that were being considered. The primary interest was determining the effects of various cosolvents on the thermal stability of these ionic liquids at the process temperatures and pressures, from 100 to 150 ℃ and 35 to 350 bar. These evaluations were carried out in the same high-pressure view cell in which the extraction experiments were conducted. To assess the degradation of the ionic liquids, time-evolved UV spectra of the mixtures were generated. It was found that more protic solvents such as water attenuated the degradation of the ionic liquids, whereas aprotic solvents such as DMF significantly exacerbated their degradation. Among the ionic liquids evaluated, it was found that [BMIM]Cl had the greatest stability in ethanol at 150 ℃.
The bamboo extraction experiments were then continued with mixtures of [BMIM]Cl in ethanol. The results showed that higher temperatures are necessary to extract lignin and cellulose, with [BMIM]Cl's thermal stability at these temperatures giving it the advantage over [EMIM]Ac. In this system as well it was shown that higher concentrations of ionic liquid facilitated the extraction of more biomass. However, biomass constituents that dissolve into mixtures with lower concentrations of ionic liquid readily precipitate back out of solution when the mixture is returned to room conditions. Along with the results of the studies with [EMIM]Ac, the experiments conducted with [BMIM]Cl show that an increase in pressure results in greater amounts of dissolved biomass holding other conditions constant.
The thesis, in summary, presents for the first time (a) the use of ionic liquids as a minor component in organic solvents as a potential biomass processing media, (b) the thermal stability of ionic liquids in a cosolvents at high pressures and temperatures, and (c) experimental results showing that pressure can enhance the amount that can be extracted from biomass with mixtures of ionic liquids in a cosolvent like ethanol.