University of Oulu

Poisoning of automotive exhaust gas catalyst components : the role of phosphorus in the poisoning phenomena

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Author: Kröger, Virpi1,2
Organizations: 1University of Oulu, Faculty of Technology, Department of Process and Environmental Engineering
2University of Oulu, Faculty of Technology, Mass and Heat Transfer Process Laboratory
Format: ebook
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 4.1 MB)
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Language: English
Published: 2007
Publish Date: 2007-10-31
Thesis type: Doctoral Dissertation
Defence Note: Academic dissertation to be presented, with the assent of the Faculty of Technology of the University of Oulu, for public defence in Kuusamonsali (Auditorium YB210), Linnanmaa, on November 10th, 2007, at 12 noon
Reviewer: Professor Edd Anders Blekkan
Professor Jose Luis García Fierro


The aim of this thesis project was to gain new knowledge on the effect of phosphorus on the catalytic activity and characteristics of automotive exhaust gas catalyst components. The simultaneous roles of phosphorus and calcium were also studied.

The first test series of powdery catalyst samples contained Rh and oxide (Test series 1) and the second, Pt and oxide or ZSM-5 (Test series 2). The catalysts were analyzed when fresh and after two ageing and phosphorus poisoning procedures developed in this work. The procedures consisted of adding poison via impregnation in an aqueous solution (for Test series 1) and in the gaseous phase under hydrothermal conditions (for Test series 2). The poison compounds formed and the changes in the washcoat were studied by using physisorption analyses, SEM, TEM, XRD, and FTIR-ATR. The poison content of the samples was determined by ICP-OES and XRF. Laboratory-scale activity measurements were done to investigate the catalytic activity. Thermodynamic calculations were used to obtain information about ageing conditions and phosphorus compounds formed during ageing.

Phosphorus decreased the catalytic activity and the characteristic surface areas of the catalysts. Addition of calcium to a phosphorus-poisoned catalyst was found to have even a regenerating effect on the catalysts’ activity. The poisoning methods developed in this study resulted in the same phosphorus compounds as can be found in vehicle-aged catalysts. Phosphorus was identified as cerium, zirconium, aluminium, and titanium phosphates. Phosphorus was detected in zeolites, but phosphorus-containing compounds were not observed. Phosphorus poisoning takes place in the gas phase at high operating temperatures and with high oxygen and water contents. It was also shown that the role of phosphorus poisoning was more pronounced than the role of hydrothermal ageing alone. Phosphorus poisoning mainly affects the oxide components used in this study, not the noble metals.

The results can be utilized in the development of catalytic materials and catalyst compositions that can better tolerate phosphorus poisoning under hydrothermal conditions. The results can also be applied in evaluating the effects of phosphorus on different catalyst compositions and in estimating the age of commercial catalysts.

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Series: Acta Universitatis Ouluensis. C, Technica
ISSN-E: 1796-2226
ISBN: 978-951-42-8608-7
ISBN Print: 978-951-42-8607-0
Issue: 283
Copyright information: © University of Oulu, 2007. This publication is copyrighted. You may download, display and print it for your own personal use. Commercial use is prohibited.