Systemanalys av kemikalieproduktion via integrerad medströmsförgasning av biomassa : Kvantifiering och förbättring av teknoekonomisk prestanda

Lignocellulosic biomass gasification is a promising production pathway for green chemicals, which can support the development towards a more sustainable society where fossil fuels are replaced. To be able to compete with fossil fuels, a highly efficient production of biomassbased products is required in order to maximize overall process economics and to minimizenegative environmental impact. Large production plants will likely be required to obtain favourable economy-of-scale effects and reasonable production cost. Entrained flow gasification (EFG) is a favourable technology due to its suitability for large-scale implementation and ability to produce a high quality syngas from various biomass feedstocks. In order to estimate overall energy efficiency and production costs for gasification-based biorefineries, it is important to be able to characterise the gasifiers’ performance. This in turnrequires reliable estimations of the gasification process. Integration of EFG-based biorefineries with existing pulp mills or other large-scale forestindustries can be achieved by integration of material and/or energy flows, as well as by coutilisation of process equipment. This could potentially induce both technical and economic added-values. At chemical pulp mills, an important feedstock for green chemical production may be the black liquor from the pulp production, since it provides an attractive combinationof advantages. The black liquor availability is, however, directly correlated to the pulp production (i.e. the mill size) and the potential green chemical production volume via pure black liquor gasification (BLG) is therefore limited.In this thesis, two systems are considered that expand on the BLG concept with the intent to increase the chemical production volume, since this could generate positive economy-of-scale effects and is a rather unexamined area. In addition to this, an EFG configuration entailing a lower availability related risk for the considered host pulp mill is also considered. The threeconsidered integrated systems are: (i) co-gasification of biomass-based pyrolysis oil blended with black liquor for methanol production, (ii) parallel operation of BLG and solid biomass EFG for methanol or ammonia production, and (iii) replacing the bark boiler with solid biomass EFG for methanol or ammonia production. These system solutions establish a combination of material, energy and equipment integration. The main aim of this thesis is to increase the knowledge of the characteristics of entrained flow biomass gasification systems and their opportunities for integration in existing industries for production of green chemicals (methanol and ammonia). An appropriate modelling framework that combines chemical modelling on a high level of detail with holistic industrial site modelling is designed and used to identify and quantify energetic and economic addedvalues for the integrated biorefineries. Mathematical process integration models based on Mixed Integer Linear Programming (MILP) of pulp mills are used to study integration of the biomass gasification systems with the mills. An iterative modelling approach is applied between the process integration model and the detailed biomass gasification models based on Aspen Plus or a Matlab-based thermodynamic equilibrium model. As a complement to themodelling framework, a multi-scale equivalent reactor network (ERN) solid biomass-based EFG model is developed to be able to identify and study influential parameters on the gasifiers’ performance in the Aspen Plus platform. This is approached by considering the effect of mass and heat transfer as well as chemical kinetics. The results show that replacing a recovery or a bark boiler with EFG for green chemicals production improves the overall energy system efficiency and the economic performance,compared to the original operation mode of the mill as well as compared to a stand-alone gasification plant. Significant economy-of-scale effects can be obtained from co-gasification of black liquor and pyrolysis oil. Co-gasification will add extra revenue per produced unit of methanol and reduces the production cost significantly compared to gasification of pure pyrolysis oil. In general, integrated EFG systems producing methanol sold to replace fossilgasoline are shown to constitute attractive investments if the product is exempted from taxes. Ammonia produced via EFG is per unit of produced chemical significantly more capital intense than the corresponding system producing methanol. The economic viability in the considered ammonia configurations is therefore found to be lower compared to methanol.The ERN model is shown to be able to estimate key performance indicators such as carbon conversion, cold gas efficiency, syngas composition, etc. for a real gasification process, showing good agreement with experimental results obtained from a pilot scale gasifier. This simulation tool can in future work be implemented in more global models to study and use to improve the techno-economic performance of EFG-based biorefineries, by quantifying theinfluence of important operational parameters. The main conclusion from this work is that production of green chemicals from biomass EFG integrated with a pulp mill is techno-economically advantageous compared to stand-alonealternatives. It is also concluded that the pulp mill size will be decisive for what integration route is the most favourable. Integration of an individual BLG plant with a pulp mill of maximum size would be the most economically beneficial alternative. However, the possibility to increase the green chemical production from a given black liquor volume improves the viability for integration in smaller mills. Increasing the production volume would therefore result in the highest efficiency and economic benefits given mill sizes up to300 kADt/y. From a resource perspective, this would however lead to an increased demand for biomass import to the mill, and this expansion could be limited by the overall availability of biomass resources.Keywords: Pulp mills, integration, biomass, gasification, green chemicals, methanol, ammonia.Godkänd; 2016; 20160115 (jimand); Nedanstående person kommer att disputera för avläggande av teknologie doktorsexamen. Namn: Jim Andersson Ämne: Energiteknik /Energy Engineering Avhandling: Systems Analysis of Chemicals Production via Integrated Entrained Flow Biomass Gasification Quantification and improvement of techno-economic performance Opponent: Senior Research Engineer, PhD Eric D Larson, Andlinger Center for Energy and the Environment, Princeton University, Princeton, USA. Ordförande: Professor Marcus Öhman, Avd för energivetenskap, Institutionen för teknikvetenskap och matematik, Luleå tekniska universitet, Luleå. Tid: Torsdag 17 mars, 2016 kl 10.00 Plats: E632, Luleå tekniska universite