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Ionic liquids in bio-refining: synthesis and applications
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Fossil fuel resources are not limitless so alternative renewable recourses are needed to fill the void that inevitably will be created once the supplies of this resource start do dwindle. Biomass has the potential to fill this void. Today only a small part of the world annual production of biomass is utilized by humankind, while the rest is allowed to decay naturally. To utilize this renewable resource in the production of fuel and chemicals, the so called bio-refineries specialized in fractionation and making use of all component of the biomass are needed. Ionic liquids could aid in this task.

Ionic liquids (ILs) have shown great potential in the field of biomass processing in general and in the pretreatment of (ligno)-cellulose in particular. However, a few things need to be addressed before any large-scale processing can be considered: Finding new routes for IL synthesis that make "on-site" production possible; Investigation into the challenges facing IL pretreatment of (ligno)-cellulose such as possible depolymerization of cellulosic material during the pretreatment and investigating what influence different ILs have on the pretreatment of cellulosic material by methods like enzymatic hydrolysis.

This work aims to address these issues and will present a route for IL synthesis making use of alcohols and carboxylic acids both commonly found in a biorefinery. Some of these ILs have also been tested for their ability of dissolve cellulose. Furthermore, this work will address the possibilities but also challenges upon IL-mediated (ligno)-cellulose processing. This includes investigating several ILs and their efficiency as a pretreatment solvent for enzymatic hydrolysis; these studies involve a large variety of different cellulosic materials. This work demonstrated that depolymerization during the IL pretreatment is a possibility and that this can complicate the recovery processes. Furthermore, this work gives guidance into what type of ILs might be suited as pretreatment solvents for different cellulosic materials, including amorphous and crystalline cellulose, processed and native lignocellulose, different types of wood samples and hemicellulose.

Place, publisher, year, edition, pages
Umeå: Umeå universitet , 2013. , 104 p.
Keyword [en]
Ionic liquid
Keyword [sv]
Joniska vätskor
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:umu:diva-69125ISBN: 978-91-7459-655-7 (print)OAI: oai:DiVA.org:umu-69125DiVA: diva2:619365
Public defence
2013-05-30, KBC-huset, KB3B1, Umeå universitet, Umeå, 10:00 (English)
Opponent
Supervisors
Available from: 2013-05-07 Created: 2013-05-03 Last updated: 2013-05-03Bibliographically approved
List of papers
1. Halogen-free ionic liquids and their utilization as cellulose solvents
Open this publication in new window or tab >>Halogen-free ionic liquids and their utilization as cellulose solvents
2012 (English)In: Journal of Molecular Structure, ISSN 0022-2860, E-ISSN 1872-8014, Vol. 1028, 156-163 p.Article in journal (Refereed) Published
Abstract [en]

This work demonstrates a novel synthesis route to halogen-free ionic liquids. A one-pot synthetic reaction route avoiding the use of toxic and high-energetic alkyl halides was developed to reduce the environmental impact of the synthesis process of ionic liquids. However, the elimination of halogens and alkyl halides in the preparation of ionic liquids is not just an environmental issue: the aforementioned species are also among the most common and persistent contaminants in today’s Ionic Liquids (ILs). Thus, this paper introduces a range of quaternized nitrogen based ionic liquids, including both aromatic and non-aromatic components, all prepared without alkyl halides in any step of the process. Moreover, bio-renewable precursors such as (bio-)alcohols and carboxylic acids were employed as anion sources and alkylation media, thus avoiding halogen contamination or halogen-containing anions. The IL’s prepared were designed to dissolve cellulose, some of which was included in a cellulose dissolution study using a sulphite cellulose from the company Domsjö.

Place, publisher, year, edition, pages
Elsevier, 2012
Keyword
Cellulose, Ionic liquid, Bio-refinery
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-58469 (URN)10.1016/j.molstruc.2012.06.044 (DOI)
Available from: 2012-08-30 Created: 2012-08-30 Last updated: 2017-12-07Bibliographically approved
2. Challenges and perspectives of ionic liquids vs. traditional solvents for cellulose processing
Open this publication in new window or tab >>Challenges and perspectives of ionic liquids vs. traditional solvents for cellulose processing
2012 (English)In: Handbook of ionic liquids: properties, applications & hazards / [ed] Jihoon Mun, Haeun Sim, New York: Nova Science Publishers, Inc., 2012, 1-34 p.Chapter in book (Refereed)
Abstract [en]

It is commonly accepted that world-wide production of oil, coal and natural gas will eventually come to a halt, although we still heavily depend on these non-renewable feed stocks and their associated chemical derivatives. Therefore, new, sustainable resources for the production of industrially important chemicals are required. Biomaterials offer much promise in this regard, since they generally contain a lot of cellulose which can be transformed and potentially provide a great source of industrially important chemicals. Presently, only a small part of the annual biomass growth in the world is utilized by industry, while the rest is decaying along natural pathways. In order to effectively process cellulose, it needs to be dissolved in some liquid medium. Present state-of-the-art commercial technologies employ very toxic and hazardous processing with volatile organic solvents like CS2. However, this need not be the case. Ionic liquids (ILs) have shown great potential for the dissolution of cellulose. Some ILs also have attractive physical properties such as: low vapor pressure, high thermal stability and reusability. Thus, they are potentially viable and more environmentally friendly alternatives. Hereby, we present and discuss some of the challenges and perspectives for ILs in terms of their potential for cellulose processing. We briefly review the historical processes and current methods for cellulose processing, and look at alternative processes taking advantage of ILs.

Place, publisher, year, edition, pages
New York: Nova Science Publishers, Inc., 2012
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-48337 (URN)9781621003496 (ISBN)1621003493 (ISBN)
Available from: 2011-10-17 Created: 2011-10-17 Last updated: 2013-05-03Bibliographically approved
3. Ionic liquid fractionation of woody biomass for fermentable monosaccharides
Open this publication in new window or tab >>Ionic liquid fractionation of woody biomass for fermentable monosaccharides
Show others...
2011 (English)In: Cellulose Chemistry and Technology, ISSN 0576-9787, Vol. 45, no 7-8, 483-486 p.Article in journal (Refereed) Published
Abstract [en]

The goal of the present study, devoted to wood fractionation, was to obtain monosaccharides, hexoses and pentoses by means of an ionic liquid (IL) based pre-treatment procedure. Softwood sawdust (maximum particle size of 2 mm) of Scots pine (Pinus sylvestris) and Norway spruce (Picea abies) were exposed to ionic liquids – 1-ethyl-3-methylimidazolium acetate (C2mimAce) and 1-ethyl-3-methylimidazolium chloride (C2mimCl) – and thermal treatment (80-150 °C), for various time intervals (0-72 h). Furthermore, cellulose of various origins (plants, wood pulps) was dissolved in C2mimAce and 1-butyl-3-methylimidazolium chloride (C4 mimCl) for the study of the dissolved fractions, stress being laid on monosaccharides and possible by-products, 5-hydroxymethylfurfural and furfural. Knowing the challenges in analysis techniques when ILs and sugars are involved, the present work focuses on the development of suitable analysis methods. To this end, a Hewlett Packard 1100 series HPLC equipped with a refractive index (RI), detector model HP1047 A and a diode array UV detector (DAD) fitted with a carbohydrate column HPX-87K was utilized. Challenges and improvements are discussed.

 

Place, publisher, year, edition, pages
Cellulose Chemistry and Technology, 2011
Keyword
ionic liquid fractionation, cellulose, softwood, fermentable monosaccharides, biomass
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-48267 (URN)000299143700007 ()
Available from: 2011-10-13 Created: 2011-10-13 Last updated: 2017-12-08Bibliographically approved

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