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Experimental and Modeling Studies on the Release and Condensation of Inorganics in a Pressurized Biomass Fluidized Bed Gasification Process
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Chemical Engineering, Process Technology.
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

A major challenge facing society today is the emissions of fossil CO2(g) that strongly contributes to global warming. It is therefore crucial to find ways to reduce these emissions. Biomass is only stored energy, deriving from direct or indirect photosynthesis in plants, and is therefore considered a carbon-neutral fuel. An attractive technology to utilize this stored energy is thermochemical conversion by means of gasification.

During biomass gasification, impurities, such as alkalis, particulates, tars, HCl(g), H2S(g), COS(g), NH3(g), and HCN(g), are released into the gas phase. To find strategies to deal with these impurities in a gasification-based process, the release and condensation of inorganics and tars under different conditions should be investigated.

In this thesis work, a process model of steam/oxygen blown fluid bed gasification, predicting the release and condensation of minor elements (i.e., Al, Ca, Fe, K, Mg, Mn, Na, P, Si, Ti, and Zn), was developed using SimuSage software. Results of experiments performed in a pilot-scale steam/oxygen blown fluidized bed gasification facility, were used to validate the developed process model and customized thermodynamic database. The process model and customized thermodynamic database were used to study the speciation of inorganics in the condensed phase during gas cooling. The model was improved by combining a model in Aspen Plus with SimuSage, to predict the release of major elements (i.e., C, H, O, N, S, and Cl), using a semi-empirical model. This combined model was also used to investigate the effects of various operating parameters, including gasification temperature, biomass composition, pressure of syngas in downstream processes, and using CO2(g) as a gasification agent, on the fate of inorganics during gasification and downstream processes.

Abstract [sv]

En av samhällets stora utmaningar av idag är utsläppen av fossilt CO2(g), som starkt bidrar till den globala uppvärmningen. Det är därför enormt viktigt att hitta sätt att minska dessa utsläpp. Biomassa är den enda lagrade energin, som direkt eller indirekt härrör från fotosyntes i växter, och därför kan anses vara ett s.k. kolneutralt bränsle. En attraktiv teknik för att utnyttja denna lagrade energi är termokemisk omvandling genom förgasning.

Vid förgasning av biomassa bildas föroreningar, till exempel alkalier, partiklar, tjäror, HCl(g), H2S(g), COS(g), NH3(g) och HCN(g), som frisläpps med den producerade gasen. För att identifiera strategier för att kunna hantera dessa föroreningar i en förgasningsprocess är det viktigt att undersöka hur dessa organiska föroreningar frisläpps och kondenserar under olika förhållanden.

I detta doktorandarbete utvecklades en processmodell med hjälp av programvaran SimuSage för ång- och syrgasblåst fluidbäddförgasning, som förutsäger frisättning och kondensation av mindre element (Al, Ca, Fe, K, Mg, Mn, Na, P, Si, Ti och Zn). Experimentella resultat från försök i pilotskala i en ång- och syrgasblåst fluidiserad bäddförgasningsanläggning användes för att validera den utvecklade modellen och den skräddasydda termodynamiska databasen. Processmodellen och den termodynamisk databas användes för att studerade bildningen av oorganiska ämnen i kondenserad fastillstånd under gaskylning. Modellen förbättrades ytterligare genom att kombinera en Aspen Plus-modell med SimuSage, för att förutsäga frisättningen av huvudelementen (C, H, O, N, S och Cl) med hjälp av en semi-empirisk modell. Denna kombinerade modell användes för att för att undersöka effekterna av olika driftsparametrar, som till exempel förgasningstemperatur, biomassa-sammansättning, effekt av och användning av CO2(g) som oxidant, på utvecklingen av oorganiska ämnen under förgasningen och i processer nedströms förgasaren.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2025. , p. 72
Series
TRITA-CBH-FOU ; 2024:62
Keywords [en]
Biomass, Gasification, Inorganics, Alkalis, Release, Condensation
Keywords [sv]
Biomassa, förgasning, oorganiska ämnen, alkalier, frisläppande, kondensering
National Category
Other Chemical Engineering
Research subject
Chemical Engineering
Identifiers
URN: urn:nbn:se:kth:diva-358736ISBN: 978-91-8106-161-1 (print)OAI: oai:DiVA.org:kth-358736DiVA, id: diva2:1929557
Public defence
2025-02-13, LOGOS, Teknikringen 42, https://kth-se.zoom.us/j/67663594947?pwd=DmNtjCqfqRxvyR7WUhulilb8peim8E.1, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20250121

Available from: 2025-01-21 Created: 2025-01-20 Last updated: 2025-12-16Bibliographically approved
List of papers
1. Experimental and modelling studies on condensation of inorganic species during cooling of product gas from pressurized biomass fluidized bed gasification
Open this publication in new window or tab >>Experimental and modelling studies on condensation of inorganic species during cooling of product gas from pressurized biomass fluidized bed gasification
2018 (English)In: Energy, ISSN 0360-5442, E-ISSN 1873-6785, Vol. 153, p. 35-44Article in journal (Refereed) Published
Abstract [en]

In a biomass gasification process, condensation of inorganic species can cause problems such as corrosion and deposition on the downstream equipment. In this work, in order to investigate the condensation of inorganics during the gas cooling step of the biomass gasification system, both experimental and modelling studies were conducted. Experiments were performed on a pilot-scale steam/oxygen blown fluidized bed gasification facility. A CO2 cooled probe was located at the head of a filter to condense inorganic species. Five thermocouples were used to monitor the probe temperature profile. Deposits on the probe were characterized using scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) to analyze the elemental composition of deposits. A process model based on the local chemical and phase equilibriums was developed using software SimuSage to predict both release and condensation of inorganics. A customized thermodynamic database extracted from the FactSage 7.1 was used during model calculations. Two cases including with and without addition of bed material were calculated. Results show that the identified elemental compositions of deposit under different gas cooling temperatures reasonably agree with the elemental compositions predicted by model calculations. This demonstrates that the established model and the customized thermodynamic data are valid. A large amount of carbon is identified in the deposit of low temperature probe sections, which may come from the condensed tar. Additionally, a temperature window is found, where melts are formed during gas cooling.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Biomass, Inorganics, Condensation, Gasification
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-234209 (URN)10.1016/j.energy.2018.04.031 (DOI)000436651100005 ()2-s2.0-85046675283 (Scopus ID)
Note

QC 20180905

Available from: 2018-09-05 Created: 2018-09-05 Last updated: 2025-01-20Bibliographically approved
2. Novel Model for the Release and Condensation of Inorganics for a Pressurized Fluidized-Bed Gasification Process: Effects of Gasification Temperature
Open this publication in new window or tab >>Novel Model for the Release and Condensation of Inorganics for a Pressurized Fluidized-Bed Gasification Process: Effects of Gasification Temperature
2018 (English)In: ACS Omega, E-ISSN 2470-1343, Vol. 3, no 6, p. 6321-6329Article in journal (Refereed) Published
Abstract [en]

A model is established to investigate the release and condensation of inorganics for a wood steam/oxygen-blown fluidized-bed gasification process. In the established model, fates of major elements (C, H, O, N, S, and Cl) and minor elements (Al, Ca, Fe, K, Mg, Mn, Na, P, Si, Ti, and Zn) are modeled separately. The composition of gaseous species involving major elements is predicted using Aspen Plus based on a semiempirical model. The release of minor elements and the condensation of inorganics are predicted using software SimuSage. The combination of Aspen Plus with SimuSage is achieved by manually inputting the stream parameters calculated from Aspen Plus into SimuSage. On the basis of this developed model, effects of gasification temperature on the condensation of Na-, K-, and Cl-containing species during gas cooling are studied. Results show that the process model established by combining Aspen Plus and SimuSage is valid and can be used to investigate the release of inorganics during gasification and condensation of inorganics during gas cooling. Under the investigated gasification conditions, regardless of the bed material, there are two temperature ranges within which no salt melt is formed during gas cooling. As the gasification temperature increases, the high-temperature range without salt melt formation becomes successively wider.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC, 2018
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-232415 (URN)10.1021/acsomega.8b00019 (DOI)000436340500045 ()31458814 (PubMedID)2-s2.0-85046646445 (Scopus ID)
Funder
Swedish Energy Agency
Note

QC 20180726

Available from: 2018-07-26 Created: 2018-07-26 Last updated: 2025-02-18Bibliographically approved
3. Model investigation of condensation behaviors of alkalis during syngas treatment of pressurized biomass gasification
Open this publication in new window or tab >>Model investigation of condensation behaviors of alkalis during syngas treatment of pressurized biomass gasification
2018 (English)In: Chemical Engineering and Processing, ISSN 0255-2701, E-ISSN 1873-3204, Vol. 129, p. 28-36Article in journal (Refereed) Published
Abstract [en]

In order to eliminate problems such as corrosion and ash deposition caused by alkalis, effects of the biomass composition and the pressure of syngas in the downstream process on condensation of alkalis in a wood steam/oxygen blown fluidized bed gasification process are investigated based on a model. This model is established by combining Aspen Plus with SimuSage. Aspen Plus is applied to predict the composition of major gas species formed by C, H, O, N, S and Cl, using empirical correlations to predict the yields of non-equilibrium substances. SimuSage is used to study the release and condensation of inorganics associated with the minor elements (Al, Ca, Fe, K, Mg, Na, P, Si and Ti) based on a customized thermodynamic database. Results show that carbonation reactions between alkalis and CO/CO2 can be occurred during gas cooling, leading to form alkali carbonates in the condensed phase. The temperature window forming melts varies with the change of the downstream pressure of syngas and the elemental composition of biomass. As the syngas pressure in the downstream process decreases, the initial temperature of forming melts during gas cooling is reduced. For biomass lower in K/Cl ratio, the condensate with the largest mass formed during gas cooling is potassium chloride. The condensation rate of Cl increases with the decrease of the K/Cl ratio in biomass.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Alkali metal, Biomass, Condensation, Gasification
National Category
Metallurgy and Metallic Materials
Identifiers
urn:nbn:se:kth:diva-228721 (URN)10.1016/j.cep.2018.05.001 (DOI)000435059000004 ()2-s2.0-85046685389 (Scopus ID)
Funder
Swedish Energy Agency
Note

QC 20180530

Available from: 2018-05-30 Created: 2018-05-30 Last updated: 2025-01-20Bibliographically approved
4. Effects of Adding Carbon Dioxide on the Release of K, Na and S during Biomass Steam/Oxygen Blown Fluidized Bed Gasification: A Model Study
Open this publication in new window or tab >>Effects of Adding Carbon Dioxide on the Release of K, Na and S during Biomass Steam/Oxygen Blown Fluidized Bed Gasification: A Model Study
(English)Manuscript (preprint) (Other academic)
National Category
Other Chemical Engineering Energy Engineering
Identifiers
urn:nbn:se:kth:diva-358809 (URN)
Note

QC 20250122

Available from: 2025-01-21 Created: 2025-01-21 Last updated: 2025-01-22Bibliographically approved

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