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Study of Catalyst Deactivation in Three Different Industrial Processes
Växjö University, Faculty of Mathematics/Science/Technology, School of Technology and Design.ORCID iD: 0000-0002-5835-865X
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Deactivation of catalysts were investigated focusing on three industrial processes: 1) Selective Catalytic Reduction (SCR) for abatement of NOx from biomass combustion using V2O5-WO3 /TiO2 catalysts; 2) Catalytic oxidation of volatile organic compounds (VOC) from printing industries using a Pt/γ-Al2O3 catalyst; and 3) Ni and Pt/Rh catalysts used in steam reforming reaction of bio-syngas obtained from biomass gasification.

The aim has been to simulate industrial conditions in laboratory experiments in order to comprehend influence of compounds affecting catalysts performance. Typical catalyst lifetimes in industrial processes are several years, which are a challenge when accelerating deactivation in laboratory scale experiments where possible exposure times are few hours or days. Catalysts can be introduced to deactivating compounds through different routes. The first method examined was gaseous exposure, which was applied to deactivate VOC oxidation catalyst through exposure of gaseous hexamethyldisiloxane. The second method involved wet impregnation and was used for impregnation of SCR catalyst with salt solutions. The third method was based on exposure and deposition of size selected particles of deactivating substances on the catalyst. The latter device was developed during this work. It was applied to monolithic SCR catalysts as well as to pellet catalysts intended for steam reforming of biomass gasification syngas. Deactivated SCR catalyst samples by size selected exposure method were verified and compared with SCR catalysts used in a commercial biomass boiler for 6 500 h.

Evaluations of fresh and deactivated samples were investigated using BET surface area; chemisorption and temperature programmed desorption (TPD); surface morphology using Scanning Electron Microscopy (SEM) and poison penetration profile through SEM with an Electron Micro Probe Analyser (EMPA) also equipped with a energy dispersive spectrometer (EDS); chemical analysis of accumulation of exposed compounds by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES); and influence on catalyst performance. The size selected generated particles of deactivating substances were characterized with respect to mean diameter and number size distribution through Scanning Mobility Particle Sizer (SMPS) and mass size distribution applying an Electric Low Pressure Impactor (ELPI). Results from catalyst characterization methods were useful tools in evaluation of catalyst deactivation routes.

Understanding deactivation processes and impact on catalyst performance is vital for further optimization of catalysts with respect to performance and lifetime. Further research in this field can provide more resistant catalysts for application in industry leading to higher commercial benefits and further application of environmental catalysts in thermo-chemical conversion of biomass.

Place, publisher, year, edition, pages
Växjö: Växjö University Press , 2007.
Series
Acta Wexionensia, ISSN 1404-4307 ; 106/2007
Keywords [en]
deactivation, catalyst, SCR, VOC, steam reforming, aerosol particle, potassium, zinc, ash salts, biomass, organosilicon
National Category
Chemical Engineering
Research subject
Natural Science, Chemistry
Identifiers
URN: urn:nbn:se:vxu:diva-1058Libris ID: 10337438ISBN: 978-91-7636-533-5 (print)OAI: oai:DiVA.org:vxu-1058DiVA, id: diva2:204839
Public defence
2007-02-02, M1083, M, Växjö univsersitet, Växjö, 13:00
Opponent
Supervisors
Available from: 2007-02-01 Created: 2007-02-01 Last updated: 2017-02-24Bibliographically approved
List of papers
1. Deactivation of SCR Catalysts by Exposure to Aerosol Particles of Potassium and Zinc Salts
Open this publication in new window or tab >>Deactivation of SCR Catalysts by Exposure to Aerosol Particles of Potassium and Zinc Salts
2007 (English)In: Aerosol Science and Technology, ISSN 0278-6826, E-ISSN 1521-7388, Vol. 41, no 4, p. 369-379Article in journal (Refereed) Published
Abstract [en]

Generated aerosol particle deposition has been applied in laboratory scale to induce deactivation of commercial Selective Catalytic Reduction (SCR) catalysts Of V2O5-WO3/TiO2 monolithic type. The monolithic catalyst has been exposed to the generated submicrometer particle of inorganic salts, KCl, K2SO4, and ZnCl2 at 200 degrees C in a tubular reactor. The generated particles have been deposited on the catalytic surfaces by utilization of an electrostatic field. Physical characterization of the generated aerosol particles were conducted by Scanning Mobility Particle Sizer (SMPS) and Electric Low Pressure Impactor (ELPI) with and without catalyst in order to investigate the magnitude of the particle deposition. Particle charge distribution was also evaluated with a Tandem Differential Mobility Analyser (TDMA) set up.

SCR is the most common method to commercially reduce NOx emissions from combustion processes. Catalyst lifetime is important for process economics and extending catalyst life can allow future strengthened emission legislation and diminished NOx emissions.

Verification of particle deposition has been conducted through comparison with catalyst samples exposed to commercial biomass combustion condition.

The reactivity of both fresh and exposed catalyst samples as well as commercially used samples was examined in SCR reaction and the methods of deposition as well as the influence of the different salts on catalytic performance have been explored.

Catalyst samples have been evaluated with Scanning Electron Microscopy (SEM) with respect to surface morphology of the catalyst material. The laboratory deactivated catalyst samples showed resemblance with the commercially exposed catalyst sample with respect to salts concentration and deposition of the salts particles. The obtained influence on catalyst activity was comparable with commercially obtained catalyst activity reductions at comparable potassium concentration levels.

National Category
Energy Engineering
Research subject
Technology (byts ev till Engineering), Bioenergy Technology
Identifiers
urn:nbn:se:vxu:diva-4261 (URN)10.1080/02786820701203207 (DOI)
Available from: 2007-12-14 Created: 2007-12-14 Last updated: 2017-12-13Bibliographically approved
2. Targeting by Comparison with Laboratory Experiments the SCR Catalyst Deactivation Process by Potassium and Zinc Salts in a Large-Scale Biomass Combustion Boiler
Open this publication in new window or tab >>Targeting by Comparison with Laboratory Experiments the SCR Catalyst Deactivation Process by Potassium and Zinc Salts in a Large-Scale Biomass Combustion Boiler
2006 (English)In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 20, no 4, p. 1398-1405Article in journal (Refereed) Published
Abstract [en]

The deactivation of a commercial selective catalytic reduction (SCR) catalyst of type V2O5−WO3/TiO2 has been studied in this work through comparisons of results from a full-scale biomass combustion plant with those from laboratory experiments. In the latter, the catalyst was exposed to KCl, K2SO4, and ZnCl2 by both wet impregnation with diluted salt solutions and deposition of generated submicrometer aerosol particles by means of an electrostatic field. The reactivity of freshly prepared and deactivated catalyst samples was examined in the SCR reaction, for which the influence of the different salts and the method of exposure were explored. Chemical and physical characterizations of the catalyst samples were carried out focusing on surface area, pore volume, pore size, chemical composition, and the penetration profiles of potassium and zinc. Particle-deposition deactivation as well as commercially exposed catalyst samples were shown to impact surface area and catalyst activity similarly and to have penetration profiles with pronounced peaks. Salt impregnation influenced pore sizes and catalyst activity more strongly and showed flat penetration profiles. Deposition of submicrometer-sized particles on the monolithic SCR catalyst has been shown to induce deactivation of the catalyst with characteristics resembling those obtained in a commercial biomass combustion plant; the laboratory process can be used to further assess the deactivation mechanism by biomass combustion.

National Category
Chemical Engineering Energy Engineering
Research subject
Chemistry, Biotechnology
Identifiers
urn:nbn:se:vxu:diva-4244 (URN)10.1021/ef060077u (DOI)
Available from: 2007-03-01 Created: 2007-03-01 Last updated: 2025-02-18Bibliographically approved
3. Physical and chemical characterisation of potassium deactivation of a SCR catalyst for biomass combustion
Open this publication in new window or tab >>Physical and chemical characterisation of potassium deactivation of a SCR catalyst for biomass combustion
2007 (English)In: Topics in catalysis, ISSN 1022-5528, E-ISSN 1572-9028, Vol. 45, no 1-4, p. 149-152Article in journal (Refereed) Published
Abstract [en]

The deactivation of a commercial Selective Catalytic Reduction (SCR) catalyst, of V2O5-WO3/TiO2 type, has been studied through comparisons with results from a full-scale biomass combustion plant to that with laboratory experiments. In the latter, the catalyst was exposed to KCl and K2SO4 by both wet impregnation with diluted salt solutions and deposition of generated submicrometer aerosol particles by means of an electrostatic field. The reactivity of fresh and deactivated samples was examined in the SCR reaction. Chemical and physical characterizations were focusing on internal structures and chemical composition. Deposition of submicrometer sized particles on the monolithic SCR catalyst was shown to induce deactivation with characteristics resembling those obtained in a commercial biomass combustion plant.

Keywords
deactivation, poisoning, V2O5−WO3/TiO2 catalyst, SCR, aerosol particle, KCl, K2SO4, biomass combustion
National Category
Chemical Engineering
Research subject
Chemistry, Biotechnology
Identifiers
urn:nbn:se:vxu:diva-2767 (URN)10.1007/s11244-007-0256-1 (DOI)
Available from: 2007-12-14 Created: 2007-12-14 Last updated: 2025-02-18Bibliographically approved
4. Pilot-scale investigation of Pt/alumina catalysts deactivation by organosilicon in the total oxidation of hydrocarbons
Open this publication in new window or tab >>Pilot-scale investigation of Pt/alumina catalysts deactivation by organosilicon in the total oxidation of hydrocarbons
Show others...
2006 (English)In: Proceedings : 12th Nordic Symposium on Catalysis: May 28-30, Trondheim, Norway : Energy and Environmental Catalysis : Catalysis in Nordic Countries, 2006, p. 82-83Conference paper, Published paper (Other academic)
National Category
Chemical Engineering
Research subject
Natural Science, Chemistry
Identifiers
urn:nbn:se:vxu:diva-4263 (URN)82-995569-1-0 (ISBN)
Conference
12th Nordic Symposium on Catalysis : May 28-30, Trondheim, Norway
Available from: 2007-03-02 Created: 2007-03-02 Last updated: 2017-02-24Bibliographically approved
5. Investigation of reforming catalyst deactivation by exposure to fly ash from biomass gasification in laboratory scale
Open this publication in new window or tab >>Investigation of reforming catalyst deactivation by exposure to fly ash from biomass gasification in laboratory scale
Show others...
2007 (English)In: Energy & Fuels, ISSN 0887-0624, E-ISSN 1520-5029, Vol. 21, no 5, p. 2481-2488Article in journal (Refereed) Published
Abstract [en]

Production of synthesis gas by catalytic reforming of product gas from biomass gasification can lead to catalyst deactivation by the exposure to ash compounds present in the flue gas. The impact of fly ash from biomass gasification on reforming catalysts was studied at the laboratory scale. The investigated catalyst was Pt/Rh based, and it was exposed to generated K2SO4 aerosol particles and to aerosol particles produced from the water-soluble part of biomass fly ash, originating from a commercial biomass combustion plant. The noble metal catalyst was also compared with a commercial Ni-based catalyst, exposed to aerosol particles of the same fashion. To investigate the deactivation by aerosol particles, a flow containing submicrometer-size selected aerosol particles was led through the catalyst bed. The particle size of the poison was measured prior to the catalytic reactor system. Fresh and aerosol particle exposed catalysts were characterized using BET surface area, XRPD (X-ray powder diffraction), and H2 chemisorption. The Pt/Rh catalyst was also investigated for activity in the steam methane reforming reaction. It was found that the method to deposit generated aerosol particles on reforming catalysts could be a useful procedure to investigate the impact of different compounds possibly present in the product gas from the gasifier, acting as potential catalyst poisons. The catalytic deactivation procedure by exposure to aerosol particles is somehow similar to what happens in a real plant, when a catalyst bed is located subsequent to a biomass gasifier or a combustion boiler. Using different environments (oxidizing, reducing, steam present, etc.) in the aerosol generation adds further flexibility to the suggested aerosol deactivation method. It is essential to investigate the deactivating effect at the laboratory scale before a full-scale plant is taken into operation to avoid operational problems.

National Category
Energy Systems
Research subject
Chemistry, Biotechnology
Identifiers
urn:nbn:se:vxu:diva-2765 (URN)10.1021/ef060633k (DOI)
Available from: 2007-12-14 Created: 2007-12-14 Last updated: 2017-12-13Bibliographically approved

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Larsson, Ann-Charlotte

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