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Formic and Levulinic Acid from Cellulose via Heterogeneous Catalysis
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Myr- och levulinsyra ur cellulosa via heterogen catalys (Swedish)
Abstract [en]

The chemical industry of today is under increased pressure to develop novel green materials, bio-fuels as well as sustainable chemicals for the chemical industry. Indeed, the endeavour is to move towards more eco-friendly cost efficient production processes and technologies and chemical transformation of renewables has a central role considering the future sustainable supply of chemicals and energy needed for societies. In the Nordic countries, the importance of pulping and paper industry has been particularly pronounced and the declining European demand on these products as a result of our digitalizing world has forced the industry to look at alternative sources of revenue and profitability. In this thesis, the production of levulinic and formic acid from biomass and macromolecules has been studied. Further, the optimum reaction conditions as well as the influence of the catalyst and biomass type were also discussed.

Nordic sulphite and sulphate (Kraft) cellulose originating from two Nordic pulp mills were used as raw materials in the catalytic synthesis of green platform chemicals, levulinic and formic acids, respectively. The catalyst of choice used in this study was a macro-porous, cationic ion-exchange resin, Amberlyst 70, for which the optimal reaction conditions leading to best yields were determined. Cellulose from Nordic pulp mills were used as raw materials in the catalytic one-pot synthesis of ‘green’ levulinic and formic acid. The kinetic experiments were performed in a temperature range of 150–200 °C and an initial substrate concentration regime ranging from 0.7 to 6.0 wt %. It was concluded that the most important parameters in the one-pot hydrolysis of biomass were the reaction temperature, initial reactant concentration, acid type as well as the raw material applied. The reaction route includes dehydration of glucose to hydroxymethylfurfural as well as its further rehydration to formic and levulinic acids. The theoretical maximum yield can hardly be obtained due to formation of humins. For this system, maximum yields of 59 mol % and 68 mol % were obtained for formic and levulinic acid, respectively. The maximum yields were separately obtained in a straight-forward conversion system only containing cellulose, water and the heterogeneous catalyst. These yields were achieved at a reaction temperature of 180 °C and an initial cellulose intake of 0.7 wt % and belong to the upper range for solid catalysts so far presented in the literature.

The reaction network of the various chemical species involved was investigated and a simple mechanistic approach involving first order reaction kinetics was developed. The concept introduces a one-pot procedure providing a feasible route to green platform chemicals obtained via conversion of coniferous soft wood pulp to levulinic and formic acids, respectively. The model was able to describe the behaviour of the system in a satisfactory manner (degree of explanation 97.8 %). Since the solid catalyst proved to exhibit good mechanical strength under the experimental conditions applied here and a one-pot procedure providing a route to green platform chemicals was developed. A simplified reaction network of the various chemical species involved was investigated and a mechanistic approach involving first order reaction kinetics was developed.

Place, publisher, year, edition, pages
Umeå: Umeå universitet , 2014. , 57 p.
Keyword [en]
Levulinic acid, formic acid, Amberlyst 70
National Category
Other Chemistry Topics
Identifiers
URN: urn:nbn:se:umu:diva-85216ISBN: 978-91-7459-798-1 (print)OAI: oai:DiVA.org:umu-85216DiVA: diva2:692192
Public defence
2014-02-14, Naturvetarhuset, N320, Umeå universitet, Umeå, 13:00 (English)
Opponent
Supervisors
Available from: 2014-01-31 Created: 2014-01-30 Last updated: 2014-01-31Bibliographically approved
List of papers
1. One-pot catalytic conversion of Nordic pulp media into green platform chemicals
Open this publication in new window or tab >>One-pot catalytic conversion of Nordic pulp media into green platform chemicals
2013 (English)In: Applied Catalysis A: General, ISSN 0926-860X, E-ISSN 1873-3875, Vol. 454, 21-29 p.Article in journal (Refereed) Published
Abstract [en]

In this paper, both sulphite and sulphate (Kraft) cellulose from Nordic pulp mills were used as raw materials in the catalytic one-pot synthesis of green platform chemicals, levulinic and formic acids, respectively. The catalyst of choice was a macro-porous, cationic ion-exchange resin, Amberlyst 70. The optimal reaction conditions were determined and the influence of various gas atmospheres was investigated. The maximum yields of 53% formic acid and 57% of levulinic acid were separately obtained in a straight-forward conversion system only containing cellulose, water and the heterogeneous catalyst. The concept introduces a one-pot procedure providing a feasible route to green platform chemicals obtained via conversion of coniferous soft wood pulp to levulinic and formic acids, respectively.

Keyword
Wood pulp, Solid acid catalysis, Amberlyst 70, Levulinic acid, Formic acid
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-64221 (URN)10.1016/j.apcata.2013.01.004 (DOI)
Available from: 2013-01-21 Created: 2013-01-21 Last updated: 2017-12-06Bibliographically approved
2. Reaction Network upon One-pot Catalytic Conversion of Pulp
Open this publication in new window or tab >>Reaction Network upon One-pot Catalytic Conversion of Pulp
Show others...
2013 (English)In: / [ed] Sauro Pierucci, Jiří J. Klemeš, AIDIC - associazione italiana di ingegneria chimica, 2013, Vol. 32, 649-654 p.Conference paper, Published paper (Refereed)
Abstract [en]

Nordic sulphite and sulphate (Kraft) cellulose originating from Nordic pulp mills were used as raw materials in the catalytic synthesis of green platform chemicals, levulinic and formic acids, respectively. The catalyst of choice used in this study was a macro-porous, cationic ion-exchange resin Amberlyst 70 for which the optimal reaction conditions leading to best yields were determined. For this system, maximum yields of 53 mol-% and 57 mol-% were obtained for formic and levulinic acid, respectively. The reaction network of the various chemical species involved was investigated and a simple mechanistic approach involving first order reaction kinetics was developed. The prototype model was able to describe the behaviour of the system in a satisfactory manner.

Place, publisher, year, edition, pages
AIDIC - associazione italiana di ingegneria chimica, 2013
Series
Chemical Engineering Transactions, ISSN 1974-9791 ; 32
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-72681 (URN)10.3303/CET1332109 (DOI)000335952100109 ()978-88-95608-23-5 (ISBN)
Conference
11th International Conference on Chemical and Process Engineering (ICheaP),Milan, ITALY, JUN 02-05, 2013
Available from: 2013-06-10 Created: 2013-06-10 Last updated: 2014-07-10Bibliographically approved
3. Macro-molecules as a source of levulinic acid
Open this publication in new window or tab >>Macro-molecules as a source of levulinic acid
2014 (English)In: International Review of Chemical Engineering, ISSN 2035-1755, Vol. 16, no 1, 44-58 p.Article in journal (Refereed) Published
Abstract [en]

The production of levulinic acid from biomass and macromolecules has been reviewed. It was concluded that the most important parameters in the one-pot hydrolysis of biomass, also including dehydration of glucose to hydroxymethylfurfural as well as its further rehydration to formic and levulinic acids, respectively, are the reaction temperature, initial reactant concentration, acid type as well as the raw material applied. The theoretical maximum yield can hardly be obtained due to formation of humins. Further, the optimum reaction conditions as well as the influence of the catalyst and biomass type are also discussed.

Place, publisher, year, edition, pages
Praise Worthy Prize, 2014
Keyword
Biomass, acid catalysts, levulinic acid
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-84661 (URN)
Available from: 2014-01-14 Created: 2014-01-14 Last updated: 2017-04-03Bibliographically approved
4. Experimental and Kinetic Modelling Studies upon Conversion of Nordic Pulp into Levulinic Acid
Open this publication in new window or tab >>Experimental and Kinetic Modelling Studies upon Conversion of Nordic Pulp into Levulinic Acid
(English)Manuscript (preprint) (Other academic)
Abstract [en]

In this paper, sulphite cellulose from a Swedish pulp mill was applied as the raw material upon catalytic, one-pot synthesis of green platform chemicals – levulinic and formic acids. Cationic ion-exchange resin, Amberlyst 70, was the catalyst of choice and the optimal reaction conditions leading to best yields were determined. The kinetic experiments were performed in a temperature range of 180–200 °C and an initial substrate concentration regime ranging from 0.7 to 6.0 wt %. For this system, maximum theoretical yields of around 59 mol % and 68 mol % were obtained for formic and levulinic acid, respectively. These yields were achieved at a reaction temperature of 180 °C and an initial cellulose intake of 0.7 wt %. A simplified reaction network of the various chemical species involved was investigated and a mechanistic approach involving first order reaction kinetics was developed. The model was able to describe the behaviour of the system in a satisfactory manner (degree of explanation 97.8 %). Since the solid catalyst proved to exhibit good mechanical strength under the experimental conditions applied here, the concept introduces a one-pot procedure providing a route to green platform chemicals from coniferous soft wood pulp to produce levulinic and formic acids, respectively.

National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-84662 (URN)
Available from: 2014-01-14 Created: 2014-01-14 Last updated: 2014-01-30Bibliographically approved

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