Cellulose Activation and Dissolution

Heinze, Thomas; Seoud, Omar A. El; Koschella, Andreas

doi:10.1007/978-3-319-73168-1_3

Cited by 12 publications

(25 citation statements)

References 304 publications

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“…Below, we focus our discussion of these issues on ionic liquids (ILs), and two of their sub-classes: quaternary ammonium electrolytes (QAEs), and salts of super-bases. Additional discussion on aspects of dissolution of cellulose and other natural polymers in ILs and applications of the solutions obtained therefrom can be found elsewhere [7][8][9][10][11][12][13][14][15][16][17].…”

Section: Ionic Liquids Quaternary Ammonium Electrolytes and Salts Omentioning

confidence: 99%

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Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

et al. 2019

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This review is focused on assessment of solvents for cellulose dissolution and the mechanism of regeneration of the dissolved biopolymer. The solvents of interest are imidazole-based ionic liquids, quaternary ammonium electrolytes, salts of super-bases, and their binary mixtures with molecular solvents. We briefly discuss the mechanism of cellulose dissolution and address the strategies for assessing solvent efficiency, as inferred from its physico-chemical properties. In addition to the favorable effect of lower cellulose solution rheology, microscopic solvent/solution properties, including empirical polarity, Lewis acidity, Lewis basicity, and dipolarity/polarizability are determinants of cellulose dissolution. We discuss how these microscopic properties are calculated from the UV-Vis spectra of solvatochromic probes, and their use to explain the observed solvent efficiency order. We dwell briefly on use of other techniques, in particular NMR and theoretical calculations for the same purpose. Once dissolved, cellulose is either regenerated in different physical shapes, or derivatized under homogeneous conditions. We discuss the mechanism of, and the steps involved in cellulose regeneration, via formation of mini-sheets, association into "mini-crystals", and convergence into larger crystalline and amorphous regions. We discuss the use of different techniques, including FTIR, X-ray diffraction, and theoretical calculations to probe the forces involved in cellulose regeneration.

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Section: Ionic Liquids Quaternary Ammonium Electrolytes and Salts Omentioning

confidence: 99%

“…Colors of the solvatochromic polarity indicator 2,6-Dibromo-4-(E)-2-1(1methylpyridinium-4-yl)ethenyl]phenolate in different solvents; DCM refers to dichloromethane; reproduced from[17], with permission from Springer,2018.…”

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confidence: 99%

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

et al. 2019

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“…This may become a serious obstacle for large volume processes. While this potential hurdle is commonly overcome at a bench scale by ball-milling of cellulosic substrates [2,8], or other drastic methods [30], the problem of energy efficient pretreatment remains essentially unsolved. e Reaction conditions: substrate (20 g), ethanol solution of sulfuric acid, 200 °C [37].…”

Section: Resultsmentioning

confidence: 99%

Metal triflates are tunable acidic catalysts for high yielding conversion of cellulosic biomass into ethyl levulinate

Bodachivskyi

Kuzhiumparambil

Williams

2019

Fuel Processing Technology

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“…Binary mixtures (BMs) of ILs with molecular solvents are frequently used as cellulose solvents. In addition to a better mass/heat transfer due to the lower viscosity, many dissolve more Cel than their precursor ILs [ 6 , 7 ]. Because of its efficiency in Cel swelling [ 8 ] and high dipole moment and relative permittivity, dimethyl sulfoxide (DMSO) is most extensively employed as a co-solvent for ILs.…”

Section: Introductionmentioning

confidence: 99%

“…The usual procedure for optimizing the dissolution of Cel in a solvent is to change one experimental variable (or factor) at a time, e.g., temperature or composition of the BM. If needed, the first factor is fixed at its value that resulted in the maximum MCC-m%, and the other factor (e.g., BM composition) is then varied until a new maximum MCC-m% is reached [ 7 , 9 , 10 , 11 , 12 , 13 ]. Although useful, this approach does not guarantee a real MCC-m% maximum for both variables .…”

Section: Introductionmentioning

confidence: 99%

Cellulose Dissolution in Mixtures of Ionic Liquids and Dimethyl Sulfoxide: A Quantitative Assessment of the Relative Importance of Temperature and Composition of the Binary Solvent

et al. 2020

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We studied the dissolution of microcrystalline cellulose (MCC) in binary mixtures of dimethyl sulfoxide (DMSO) and the ionic liquids: allylbenzyldimethylammonium acetate; 1-(2-methoxyethyl)-3-methylimidazolium acetate; 1,8-diazabicyclo [5.4.0]undec-7-ene-8-ium acetate; tetramethylguanidinium acetate. Using chemometrics, we determined the dependence of the mass fraction (in %) of dissolved cellulose (MCC-m%) on the temperature, T = 40, 60, and 80 °C, and the mole fraction of DMSO, χDMSO = 0.4, 0.6, and 0.8. We derived equations that quantified the dependence of MCC-m% on T and χDMSO. Cellulose dissolution increased as a function of increasing both variables; the contribution of χDMSO was larger than that of T in some cases. Solvent empirical polarity was qualitatively employed to rationalize the cellulose dissolution efficiency of the solvent. Using the solvatochromic probe 2,6-dichloro-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (WB), we calculated the empirical polarity ET(WB) of cellobiose (a model for MCC) in ionic liquid (IL)–DMSO mixtures. The ET(WB) correlated perfectly with T (fixed χDMSO) and with χDMSO (fixed T). These results show that there is ground for using medium empirical polarity to assess cellulose dissolution efficiency. We calculated values of MCC-m% under conditions other than those employed to generate the statistical model and determined the corresponding MCC-m% experimentally. The excellent agreement between both values shows the robustness of the statistical model and the usefulness of our approach to predict cellulose dissolution, thus saving time, labor, and material.

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Cellulose Activation and Dissolution

Cited by 12 publications

References 304 publications

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Metal triflates are tunable acidic catalysts for high yielding conversion of cellulosic biomass into ethyl levulinate

Cellulose Dissolution in Mixtures of Ionic Liquids and Dimethyl Sulfoxide: A Quantitative Assessment of the Relative Importance of Temperature and Composition of the Binary Solvent

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