| 1. |
- Anugwom, Ikenna, et al.
(författare)
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Switchable ionic liquids as delignification solvents for lignocellulosic materials
- 2014
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Ingår i: ChemSusChem. - : John Wiley & Sons. - 1864-5631 .- 1864-564X. ; 7:4, s. 1170-1176
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Tidskriftsartikel (refereegranskat)abstract
- 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).
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| 2. |
- Anugwom, Ikenna, et al.
(författare)
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Towards optimal selective fractionation for Nordic woody biomass using novel amine–organic superbase derived switchable ionic liquids (SILs)
- 2014
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Ingår i: Biomass and Bioenergy. - : Elsevier. - 0961-9534 .- 1873-2909. ; 70, s. 373-381
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Tidskriftsartikel (refereegranskat)abstract
- Abstract Improved fractionation process conditions for wood dissolution with switchable ionic liquids (SILs) were determined. The short time, high temperature (STHT) system was introduced as a selective and efficient way to extract components from lignocellulosic material. A SIL based on monoethanol amine (MEA) and 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) formed via coupling with SO2, was applied as a solvent in a 1:3 weight ratio with water. In essence, selective dissolution of mainly lignin was achieved by means of the aqueous SIL at 160 °C (∼6.1 bar corresponding to the vapor pressure of water) in 2 h and in a pressure vessel, for both hard- and soft-wood. About 95 wt-% of wood lignin was extracted. The dissolved components in the spent SIL were recovered by the addition of an anti-solvent whereupon over 70% of the dissolved components were recovered; the recovered fraction contained 19 wt-% hemicellulose while the rest of the material was in essence lignin. The non-dissolved, fluffy material contained ∼70 wt-% cellulose and ∼20 wt-% hemicellulose – a consistency resembling that of Kraft pulp.
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| 3. |
- Eta, Valerie, et al.
(författare)
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Catalysis for carbon dioxide activation
- 2013
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Ingår i: Catalysis in Finland. - Oulu : Finnish Catalysis Society. - 9789529330850 - 9789529330867
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Bokkapitel (övrigt vetenskapligt/konstnärligt)
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| 4. |
- Eta, Valerie, et al.
(författare)
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Deconstruction of Nordic hardwood in switchable ionic liquids and acylation of the dissolved cellulose
- 2016
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Ingår i: Carbohydrate Polymers. - : Elsevier. - 0144-8617 .- 1879-1344. ; 136, s. 459-465
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Tidskriftsartikel (refereegranskat)abstract
- Nordic hardwood (Betula pendula) was fractionated in a batch autoclave equipped with a custom-made SpinChem® rotating bed reactor, at 120°C using CO2 and CS2-based switchable ionic liquids systems. Analyses of the non-dissolved wood after treatment showed that 64 wt% of hemicelluloses and 70 wt% of lignin were removed from the native wood. Long processing periods or successive short-time treatments using fresh SILs further decreased the amount of hemicelluloses and lignin in the non-dissolved fraction to 12 and 15 wt%, respectively. The cellulose-rich fraction was partially dissolved in an organic superbase and an ionic liquid system for further derivatization. Homogeneous acylation of the dissolved cellulose in the presence or absence of catalyst resulted in cellulose acetates with variable degree of substitution (DS), depending on the treatment conditions. By varying the reaction conditions, the cellulose acetate with the desired DS could be obtained under mild conditions.
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| 5. |
- Eta, Valerie, et al.
(författare)
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Enhanced mass transfer upon switchable ionic liquid mediated wood fractionation
- 2014
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Ingår i: Industrial crops and products (Print). - : Elsevier. - 0926-6690 .- 1872-633X. ; 55, s. 109-115
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Tidskriftsartikel (refereegranskat)abstract
- The fractionation of lignocellulosic biomass to its major components is the primary step towards the conversion of biomass-based biopolymers to commodity chemicals in the integrated biorefinery process. Wood chips encased in a SpinChem® device and attached to the stirrer of a batch autoclave were used together with switchable ionic liquids (SILs) for the selective fractionation of hemicelluloses and lignin. Stirring of the wood chips in the SpinChem® device facilitated the diffusion of SIL into the chips through forced recirculation and at the same time avoiding mechanical fibrillation. The treatment of birch chips (Betula pendula) with SILs comprising 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), monoethanolamine (MEA) and CO2 at 120 °C in a SpinChem® device resulted in the fractionation of 82 wt.% hemicelluloses and 90 wt.% lignin, leaving the cellulose-rich non-dissolved material partially fibrillated and softened. The dissolved hemicelluloses and lignin were selectively precipitated using isopropanol and recovered from the spent SIL.
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| 6. |
- Eta, Valerie, et al.
(författare)
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Kinetics of dimethyl carbonate synthesis from methanol and carbon dioxide over ZrO2–MgO catalyst in the presence of butylene oxide as additive
- 2011
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Ingår i: Applied Catalysis A. - : Elsevier. - 0926-860X .- 1873-3875. ; 404:1-2, s. 39-46
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Tidskriftsartikel (refereegranskat)abstract
- A kinetic investigation of dimethyl carbonate (DMC) synthesis from methanol and CO2 over ZrO2–MgO was performed by using butylene oxide as a chemical trap for the water formed during the reaction. The effect of the catalyst amount, the stirring speed, the temperature, as well as the amount of butylene oxide on the reaction rate and the selectivity to DMC was studied. The analysis of the reaction pathway suggests that DMC and butylene glycol are formed via the reaction of adsorbed mono-methoxycarbonate intermediate and methoxybutanol or methanol. A kinetic model was developed based on the reaction mechanism and it was in agreement with the experimental data. The apparent activation energy for the formation of DMC was 62 kJ/mol.
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| 7. |
- Eta, Valerie, et al.
(författare)
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Loop vs. batch reactor setups in the fractionation of birch chips using switchable ionic liquids
- 2014
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Ingår i: Chemical Engineering Journal. - : Elsevier. - 1385-8947 .- 1873-3212. ; 238, s. 242-248
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Tidskriftsartikel (refereegranskat)abstract
- The fractionation of lignocellulosic feedstock into its major components with high purity represents an important commercialization milestone in the transformation of lignocellulosic forest derived products into fuels and commodity chemicals. A comparison between the traditionally used batch reactor and loop reactor systems demonstrates that improved dissolution of hemicelluloses and lignin are obtained using switchable ionic liquids in a loop reactor system which facilitates decreased heat and mass transfer restrictions. The treatment of birch chips using switchable ionic liquid (SIL) based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene, CO2 and diethanolamine at 120 °C for 30 h in a loop reactor resulted in 24% loss of original weight of wood corresponding to dissolution of 52 wt.% of hemicelluloses and 42 wt.% of lignin, respectively, as opposed to 20% weight loss corresponding to 43 wt.% dissolution of hemicelluloses and 38 wt.% of lignin in the batch system. The non-dissolved material obtained from both reactors was efficiently fibrillated and softened cellulose fibres. The flow of switchable ionic liquid through the loop reactor and agitation of the chips enhanced the dissolution of hemicelluloses and lignin. The dissolved fractions recovered from spent SIL after treatment contained both hemicelluloses and lignin.
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| 8. |
- Eta, Valerie, et al.
(författare)
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Synthesis of dimethyl carbonate from methanol and carbon dioxide : Circumventing thermodynamic limitations
- 2010
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Ingår i: Industrial & Engineering Chemistry Research. - : American Chemical Society. - 0888-5885 .- 1520-5045. ; 49:20, s. 9609-17
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis of dimethyl carbonate from methanol and CO2 catalyzed by ZrO2 doped with KCl was investigated using chemical traps for water to circumvent thermodynamic limitations. The reaction, promoted by magnesium, occurred via the formation of carbonated magnesium methoxide (CMM) which adsorbed on the surface of ZrO2. The surface migration of the oxygen atom of ZrO2 to the surface methoxy groups of CMM resulted in the formation of dimethyl carbonate. The resulting MgO then reacted with methanol forming water and regenerating magnesium methoxide. The water formed reacted with the dehydrating agent, thus shifting the equilibrium toward a higher yield of DMC. The yield of 7.2 mol % DMC and 13.6 mol % conversion of methanol was obtained when methanol reacted with CO2 at 150 °C and 9.5 MPa for 8 h. The plausible reaction pathway is described.
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| 9. |
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| 10. |
- Eta, Valerie, et al.
(författare)
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The Effect of Alkoxide Ionic Liquids on the Synthesis of Dimethyl Carbonate from CO2 and Methanol over ZrO2-MgO
- 2011
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Ingår i: Catalysis Letters. - : Springer Science and Business Media LLC. - 1011-372X .- 1572-879X. ; 141:9, s. 1254-1261
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Tidskriftsartikel (refereegranskat)abstract
- The use of carbon dioxide in the synthesis of chemicals, such as dimethyl carbonate (DMC), constitutes an environmentally attractive alternative to hazardous and toxic reagents. However, the direct synthesis of DMC from methanol and CO2 is characterized by low yields due to the reaction equilibrium and the thermodynamic limitations (Delta G(298K)(0) = + 26.3 kj/mol). Alkoxide ionic liquids possessing alkylimidazolium and benzalkonium cations were prepared, characterised and tested together with ZrO2-MgO catalyst for the synthesis of DMC from methanol and CO2. By using the novel ionic liquid as additives, ca. 12% conversion of methanol, and 90% selectivity to DMC was obtained at 120 A degrees C and 7.5 MPa. The water abstracting potential of the ionic liquids influenced the conversion of methanol and the selectivity to DMC. The alkoxide ionic liquids were recovered and reused in DMC synthesis without loss in activity and selectivity.
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