Phenomena-Based Modeling of Alkaline Pulping Processes

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School of Chemical Technology | Doctoral thesis (article-based) | Defence date: 2021-03-23

Date

2021

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Mcode

Degree programme

Language

en

Pages

78 + app. 36

Series

Aalto University publication series DOCTORAL DISSERTATIONS, 20/2021

Abstract

This doctoral thesis focuses on developing a phenomena-based molecular-level model for kraft and other alkaline pulping processes by utilizing fundamental knowledge on reaction kinetics, thermodynamics and mass transfer. A major benefit from the fundamental approach applied is that the model is, in principle, valid regardless of the reaction environment. Modelling of the pulping process at molecular level provides a new way to examine the relative importance of various phenomena, the validity of theories and provide a platform for developing and testing new ideas. In comparison with experimental research, simulation can be a more cost-efficient way to study and rethink processes, to make them more efficient and environmentally friendly and to improve the quality products with minimal cost. The objective of this thesis work was to create a comprehensive pulping chemistry model, including carbohydrate degradation and delignification in kraft and other alkaline pulping processes. The work was divided into parts and problems were solved in turns. First, literature was reviewed with a target to find the necessary data on the reaction mechanisms and the kinetic parameters of the reactions involved. Secondly, the missing knowledge on the reaction kinetics of strong nucleophiles with non-phenolic lignin with α-carbonyl functionality was obtained experimentally through applying the dimeric model compound adlerone. Further, lignin and carbohydrates were modelled as monomeric pseudo-compounds with experimentally determined chemical characteristics. The macromolecular aspect of lignin was considered in lignin dissolution. The pulping model developed is formed of an extensive library of the reactions of hydroxyl and hydrogen sulfide ions with pseudo-lignin and carbohydrate structures. When simulating the pulping under given conditions, the outcome consists of time-dependent concentrations of the pseudo-structures and real chemical compounds. Additionally, some engineering parameters, such as kappa number, intrinsic viscosity and brightness, were included in the model that derives them from the chemical composition. Consequently, the model could be validated by analytical data as well as by engineering parameters values. The model prediction was compared against experimental results and demonstrated generally a good correlation. The Donnan effect included in the model was important for predicting the content of hexenuronic acid in the system correctly. Inclusion of thermodynamic and stereochemical aspect of lignin could possibly improve the model prediction further.

Description

Defense is held on 23.3.2021 12:00 – 15:00 https://aalto.zoom.us/j/63585702463

Supervising professor

Vuorinen, Tapani, Prof., Aalto University, Department of Bioproducts and Biosystems, Finland

Thesis advisor

Ruuttunen, Kyösti, Dr., Aalto University, Finland

Keywords

alkaline pulping, modeling, reaction kinetics, reaction mechanism

Other note

Parts

  • [Publication 1]: Olesya Fearon; Susanna Kuitunen; Tapani Vuorinen (2016) Reaction kinetics of strong nucleophiles with a dimetric non-phenolic lignin model compound with α-carbonyl functionality (adlerone) in aqueous alkali solution. Holzforschung, volume 70, issue 9, pages 811-818. DOI 10.1515/hf-2015-0236
  • [Publication 2]: Olesya Fearon; Susanna Kuitunen; Kyösti Ruuttunen; Ville Alopaeus; Tapani Vuorinen (2020) Detailed Modeling of Kraft Pulping Chemistry. Delignification. Industrial&Engineering Chemistry Research, volume 59, issue29, pages 12977-12985.
    Full text in Acris/Aaltodoc: http://urn.fi/URN:NBN:fi:aalto-202010165895
    DOI: 10.1021/acs.iecr.0c02110 View at publisher
  • [Publication 3]: Olesya Fearon; Vesa Nykänen; Susanna Kuitunen; Kyösti Ruuttunen; Raimo Alén; Ville Alopaeus; Tapani Vuorinen (2020) Detailed modeling of the kraft pulping chemistry: carbohydrate reactions. AIChE Journal, volume 66, issue 8, pages 1-9.
    Full text in Acris/Aaltodoc: http://urn.fi/URN:NBN:fi:aalto-202101251557
    DOI: 10.1002/aic.16252 View at publisher

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