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- Anugwom, I, et al.
(author)
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Selective Extraction of Hemicelluloses from Spruce using Switchable Ionic Liquids
- 2012
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In: Carbohydrate Polymers. - : Elsevier. - 0144-8617 .- 1879-1344. ; 87:3, s. 2005-2011
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Journal article (peer-reviewed)abstract
- Switchable Ionic Liquids (SILs) made from alcohols, either hexanol or butanol, and CO2 together with an amidine (1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU)) were investigated as dissolution/fractionation solvents for wood material. Both native spruce (Picea abies), and pre-extracted spruce were treated with either butanol SIL (SIL1) or hexanol SIL (SIL 2) for 5 days at 55 °C under normal pressure. The SILs were formed by bubbling CO2 through an equimolar mixture of either 1-hexanol or 1-butanol and DBU. The viscosity of the mixture increased from 7.1 mPas to 2980 mPas for SIL 2 and 5.1 to 1600 mPas for SIL 1. Melting points of the SILs 1 and 2 were at 8 and 14 °C, respectively. After the treatment time (5 days), the undissolved fraction contained 38 wt % less hemicelluloses compared to native spruce. There was an increase in the glucose content of the milled spruce treated with both SILs, since the milling step reduced the cellulose crystallinity of the wood and facilitated an easier SIL access into the wood. The solvents were very neutral in terms of lignin removal. Consequently, only about 2% of the lignin was removed from native wood. Moreover, a priori removal of the wood extractives did not influence the lignin removal. Highlights► Switchable Ionic Liquids made from, either hexanol or butanol, and CO2 together with an amidine (DBU) were studies as dissolution/fractionation solvents for spruce wood. ► After the treatment undissolved fraction contained 38 wt-% less hemicelluloses. ► We conclude that Switchable ionic liquids are effective solvent for fractionation of wood material, and they are easily recycled and can be reused.
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- Khokarale, Santosh G., et al.
(author)
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Switchable polarity liquids
- 2018
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In: Polymerized ionic liquids. - London : Royal Society of Chemistry. - 9781782629603 - 9781788010535 - 9781788012218 ; , s. 143-179
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Book chapter (other academic/artistic)abstract
- 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 switchable nature. The polarity 'switch' between a molecular liquid and ionic species in the case of SPSs is described on the basis of interactions occurring for various types of organic bases or silylamines with acid gases such as CO2 or SO2 and in the absence or presence of alcohols. The chapter consists of two principal parts where the synthesis of SPS systems is described as a result of interaction of one or two molecular components with acid gases. The molecular liquids in two-component SPSs comprise organic superbases such as 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) or 1,1,3,3-tetramethylguanindine (TMG or its derivatives) and lower to higher alcohols or water or glycerol. The one-component system involves the use of silylamines for SPS synthesis. The change in the composition and polarity of the reaction mixture during the synthesis, as well as the switchable nature of these SPSs, is demonstrated by gravimetric, spectroscopic and conductivity measurements. In the second part, various applications of SPS systems are described along with how the special characteristics of SPSs can be utilized.
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- Mäki-Arvela, P, et al.
(author)
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Dissolution of lignocellulosic materials and its constituents using ionic liquids - a review
- 2010
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In: Industrial crops and products (Print). - : Elseier B.V.. - 0926-6690 .- 1872-633X. ; 32:3, s. 175-201
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Journal article (peer-reviewed)abstract
- The state of art from the dissolution of cellulose, lignin and wood using ionic liquids is presented in this work. The emphasis is put on the relationship between the properties of ionic liquids and the dissolution capacity. The impact of the following solvation parameters, namely Hildebrand solubility parameter and hydrogen bond basicity are related to the dissolution of lignocellulosic material. Good solvents for cellulose are 1-butyl- and 1-allyl-3-methylimidazolium chlorides as well as 1-ethyl-3-methylimidazolium acetate, whereas for lignocellulosic material the best solvents are 1-ethyl-3-methylimidazolium acetate and 1-allyl-3-methylimidazolium chloride. In allyl group the ethylene functionality facilitates B-interactions with the aromatic lignin structure. Furthermore, small polarizable anions are also powerful when aiming at dissolution of cellulose. The properties of regenerated cellulose and reconstituted lignin are also given and compared with those of the native materials. Furthermore, the results from the regeneration and reuse of ionic liquids are presented here.
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7. |
- Anugwom, I, et al.
(author)
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Ionic liquid assisted extraction of nitrogen and sulphur-containing air pollutants from model oil and regeneration of the spent ionic liquid
- 2011
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In: Journal of Environmental Protection. - : Scientific Research Publishing. - 2152-2197 .- 2152-2219. ; 2:6, s. 796-802
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Journal article (peer-reviewed)abstract
- Removal of air pollutants, such as nitrogen and sulphur containing compounds from a model oil (dodecane) was studied. An ionic liquid (1-ethyl-3-methylimidazolium chloride [C2mim] [Cl]) was used as an extractant. Liquid-liquid extraction by using 1-ethyl-3-methylimidazolium chloride [C2mim] [Cl] was found to be a very promising method for the removal of N- and S-compounds. This was evaluated by using a model oil (dodecane) with indole as a neutral nitrogen compound and pyridine as a basic nitrogen compound. Dibenzothiophene (DBT) was used as a sulphur compound. An extraction capacity of up to 90 wt% was achieved for the model oil containing pyridine, while only 76 wt% of indole in the oil was extracted. The extraction capacity of a model sulphur compound DBT was found to be up to 99 wt%. Regeneration of the spent ionic liquid was carried out with toluene back-extraction. A 1:1 toluene-to-IL wt ratio was performed at room temperature. It was observed that, for the spent ionic liquid containing DBT as a model compound more than 85 wt% (corresponding 3852 mg/kg) could be removed from the oil. After the second regeneration cycle, 86 wt% of the DBT was recovered from the ionic liquid to toluene. In the case of indole as the nitrogen containing species, more than 99 wt%, (corresponding to 2993 mg/kg) of the original indole was transferred from the model oil to the ionic liquid. After the first-regeneration cycle of the spent ionic liquid, 54 wt% of the indole–in-IL was transferred to toluene. Thus, both extractions of nitrogen and sulphur model compounds were successfully carried out from model oil and the back-extraction of these compounds from the ionic liquids to toluene demonstrated the proved the concept of the regeneration point of view.
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- Eta, Valerie, et al.
(author)
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Enhanced mass transfer upon switchable ionic liquid mediated wood fractionation
- 2014
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In: Industrial crops and products (Print). - : Elsevier. - 0926-6690 .- 1872-633X. ; 55, s. 109-115
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Journal article (peer-reviewed)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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- Eta, Valerie, et al.
(author)
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Loop vs. batch reactor setups in the fractionation of birch chips using switchable ionic liquids
- 2014
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In: Chemical Engineering Journal. - : Elsevier. - 1385-8947 .- 1873-3212. ; 238, s. 242-248
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Journal article (peer-reviewed)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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- Kirilin, A, et al.
(author)
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Chemo-Bio Catalyzed Synthesis of R-1-Phenylethyl Acetate over Bimetallic PdZn Catalysts, Lipase, and Ru/Al2O3 : part II
- 2011
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In: Kinetics and catalysis. - : Maik Nauka/Interperiodica. - 0023-1584 .- 1608-3210. ; 52:1, s. 77-81
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Journal article (peer-reviewed)abstract
- One-pot synthesis of R-1-phenyethylacetate at 70 degrees C was investigated using three different catalysts simultaneously, namely a bimetallic PdZn/Al2O3 as a hydrogenation catalyst, an immobilized lipase as an acylation catalyst and Ru/Al2O3 as a racemization catalyst. The most active bimetallic catalyst was PdZn/Al2O3 calcined at 300 degrees C and reduced at 400 degrees C, whereas the most selective although less active catalyst was the one being calcined and reduced at 500 degrees C. The highest selectivity to R-1-phenylethyl acetate over this catalyst was 32 at 48% conversion. Ru/Al2O3 was confirmed to have a positive effect on the formation of the desired product, although it was not very active in the racemization during one-pot synthesis.
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