OULU 2007

C 283

Virpi Kröger







C Te c h n i c a 2 8 3


The role of phosphorus in the poisoning phenomena

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

O U L U N Y L I O P I S TO, O U L U 2 0 0 7

Keiski Reviewed by Professor Edd Anders Blekkan Professor Jose Luis García Fierro ISBN 978-951-42-8607-0 (Paperback) ISBN 978-951-42-8608-7 (PDF) http://herkules. Oul.oulu.oulu.Copyright © 2007 Acta Univ.fi/isbn9789514286087/ ISSN 0355-3213 (Printed) ISSN 1796-2226 (Online) http://herkules. C 283. 2007 Supervised by Professor Riitta L.fi/issn03553213/ Cover design Raimo Ahonen OULU UNIVERSITY PRESS OULU 2007 .

P. Phosphorus poisoning takes place in the gas phase at high operating temperatures and with high oxygen and water contents. and FTIR-ATR. Phosphorus poisoning mainly affects the oxide components used in this study.Box 4300. Phosphorus decreased the catalytic activity and the characteristic surface areas of the catalysts. platinum. 2007 Oulu. Pt and oxide or ZSM-5 (Test series 2). University of Oulu. Poisoning of automotive exhaust gas catalyst components. It was also shown that the role of phosphorus poisoning was more pronounced than the role of hydrothermal ageing alone. Thermodynamic calculations were used to obtain information about ageing conditions and phosphorus compounds formed during ageing. aluminium. Department of Process and Environmental Engineering. Laboratory-scale activity measurements were done to investigate the catalytic activity. The poisoning methods developed in this study resulted in the same phosphorus compounds as can be found in vehicle-aged catalysts.Box 4000. P. TEM. Addition of calcium to a phosphorus-poisoned catalyst was found to have even a regenerating effect on the catalysts' activity. poisoning. 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). and titanium phosphates. Finland. XRD. Phosphorus was detected in zeolites. The poison content of the samples was determined by ICP-OES and XRF. Keywords: calcium. Oul. The simultaneous roles of phosphorus and calcium were also studied. zirconium. catalyst activity. diesel catalysts. University of Oulu. The results can be utilized in the development of catalytic materials and catalyst compositions that can better tolerate phosphorus poisoning under hydrothermal conditions. FI-90014 University of Oulu. phosphorus.O. Finland Acta Univ. The catalysts were analyzed when fresh and after two ageing and phosphorus poisoning procedures developed in this work. deactivation. Mass and Heat Transfer Process Laboratory. The results can also be applied in evaluating the effects of phosphorus on different catalyst compositions and in estimating the age of commercial catalysts. but phosphorus-containing compounds were not observed. three-way catalysts. not the noble metals. zeolite catalyst . Phosphorus was identified as cerium. The poison compounds formed and the changes in the washcoat were studied by using physisorption analyses. The first test series of powdery catalyst samples contained Rh and oxide (Test series 1) and the second. C 283. Virpi. The role of phosphorus in the poisoning phenomena Faculty of Technology.Kröger. SEM. FI-90014 University of Oulu. Finland Abstract 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. rhodium.O.


To my parents .

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Preface This study was carried out in the Department of Process and Environmental Engineering at the University of Oulu during the years 2003–2006. Aslak Suopanki. and the Institute of Materials Science at Tampere University of Technology. 7 . Part of the work was performed in the School of Chemical Engineering and Industrial Chemistry at the University of New South Wales. During this time the author was also a student in the Graduate School on Functional Surfaces. The study was carried out in co-operation with Ecocat Oy. Yun Lei for increasing my knowledge in the field of catalysis and for the unforgettable time I spent in Australia. Ulla Lassi. Prof. Riitta Raudaskoski for fruitful co-operation in both work and leisure activities. Katariina Rahkamaa-Tolonen. I warmly thank Dr. Keith Kosola is acknowledged for linguistic corrections. Jose Luis García Fierro. Dr. M. the work was a part of the ‘Catalytical Materials: Characterization and Control of the Surface Poisoning Phenomena’ (POISON) project funded by the Academy of Finland.Sc. the supervisor of this thesis project. Esa Turpeinen are acknowledged for their successful co-operation in the research work. In addition. Riitta Keiski. Katri Kynkäänniemi for her assistance in the laboratory work. Noel Cant.Sc. during a research visit in 2005. Special thanks are expressed to M. Hannele Nurminen for their invaluable help in developing the test procedures and in carrying out the experiments. Satu Ojala for the help and support they have given me during the past years. Marko Hietikko.Sc. Prof. My warm thanks are due to the advisor of the work. Mr.Sc. Dennys Angove. the Department of Chemistry at the University of Oulu. M. I also thank M.Tech. Risto Laitinen. I cordially thank Prof. I thank Mr. Dr. Minnamari Vippola. I present my gratitude to Prof. I also express my thanks to Prof. David Trimm. M. I also highly appreciate her expert knowledge on catalysis and the support she gave me during the work. and Dr. Edd Anders Blekkan and Prof. Dr. David French. Toivo Lepistö. whose help and encouragement were invaluable. and Dr. and M. for the opportunity to work in her research group in the Mass and Heat Transfer Process Laboratory. Dr. Lic. Thanks are also due to the other members of the Mass and Heat Transfer Process Laboratory staff. Dr. Prof. Australia. Prof. Mika Huuhtanen. who reviewed the manuscript of my thesis.Sc. Juha Ahola. Dr. Jorma Penttinen and Ms. Tanja Kolli. Kauko Kallinen. Tomi Kanerva.Sc.

and brother Vesa for their continuous care and support. I present loving thanks to my family.Finally. The work was funded by the Graduate School on Functional Surfaces and the Academy of Finland. and Finnish Catalysis Society. August 2007 Virpi Kröger 8 . The Regional Fund of Northern Ostrobothnia. Ecocat Oy is acknowledged for donating catalysts for the laboratory tests. sister Anne. father Heikki. I most cordially thank my mother Aira. Foundation of Technology. I thank my spouse Toni Kallio for bringing joy and a positive challenge into my life. who always encouraged me in my studies. Jenny and Antti Wihuri Foundation. The Finnish Cultural Foundation. Oulu University Scholarship Foundation. This thesis is dedicated to my parents. I also gratefully acknowledge the financial support given by the Faculty of Technology at the University of Oulu. Fortum Foundation. Finnish Konkordia Fund. Oulu.

List of abbreviations A/F ratio ATR BET BJH DOC EDS EDTA EGR EU FTIR HC ICP-OES OSC PGM PM SCR SEM SOF T50 TEM TPD TWC XRD XRF ZDDP Air-to-fuel ratio Attenuated Total Reflection Brunauer-Emmet-Teller theory Barrett-Joyner-Halenda theory Diesel Oxidation Catalyst Energy Dispersive X-ray Spectrometer Ethylene Diamine Tetraacetic Acid Exhaust Gas Recirculation European Union Fourier Transform Infrared Spectroscopy Hydrocarbon Induced Coupled Plasma Optical Emission Spectroscopy Oxygen Storage Capacity Platinum Group Metal Particulate Matter Selective Catalytic Reduction Scanning Electron Microscopy Soluble Organic Fraction The temperature of 50% conversion of the feed component Transmission Electron Microscopy Temperature Programmed Desorption Three-way Catalyst X-ray Diffraction X-ray Fluorescence Zinc Dialkyldithiophosphate 9 .

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III Kröger V. which are referred to in the text by their Roman numerals: I Kröger V. The manuscript was written in close collaboration with the first author. Topics in Catalysis 42–43: 409–413. Kanerva T. Lassi U. Topics in Catalysis 42–43: 433–436. Hietikko M. activity measurements. Vippola M. French D. Suopanki A & Keiski RL (2006) Methodology development for laboratory-scale exhaust gas catalyst studies on phosphorus poisoning. and surface area studies. Hietikko M. Topics in Catalysis 30/31: 469–473. The manuscripts for the publications (Papers I–V) were written by the author of this thesis. II Kröger V. Rahkamaa-Tolonen K. Laitinen R & Keiski RL (2004) Characterization of the effects of phosphorus and calcium on the activity of Rhcontaining catalyst powders.List of original papers This thesis is based on the following publications. V Kröger V. Angove D. Lassi U. Kröger V. Laitinen R & Keiski RL (2007) Effect of phosphorus poisoning on catalytic activity of diesel exhaust gas catalyst components containing oxide and Pt. Lepistö T & Keiski RL (2007) Phosphorus poisoning of ZSM-5 and Pt/ZSM-5 zeolite catalysts in diesel exhaust gas conditions. IV Kröger V. 11 . Rahkamaa-Tolonen K. Kallinen K. Kanerva T. Chemical Engineering Journal 120: 113–118. Topics in Catalysis 45: 153–157. Lepistö T & Keiski RL (2007) Structural changes in air aged and poisoned diesel catalysts. Lassi U. Topics in Catalysis 45: 137–142. the author was responsible for the chemical ageing procedure. Ahola J. Vippola M & Keiski RL (2007) Characterization of phosphorus poisoning on diesel exhaust gas catalyst components containing oxide and Pt. In Paper VI. Kynkäänniemi K. Suopanki A. Lassi U. Rahkamaa-Tolonen K. Lassi U. VI Kanerva T.

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... 37 4....2 NOx reduction......1 Poisoning by impregnation. 20 2........3 Thermal deactivation.1 Catalysts......................................................2 Three-way catalysis........................................................................ 42 4........................ 35 3.......................... 42 4..................3............ 22 2..1 General...................2.....................................2 Scanning Electron Microscopy.....................................3..3......................... 38 4........... 42 4.......... 39 4...................................5 X-ray diffraction............3...................2......................................................................................2 Poisoning by sulphur compounds.....................................2.......... 41 4.......................3................................................. 15 1......................4 Mechanical deactivation ........................................... 16 2 Automotive exhaust gas catalysis 19 2....2 Purpose of the work ........ 30 3..............................................................1 Overview................................................................Contents Abstract Preface 7 List of abbreviations 9 List of original papers 11 Contents 13 1 Introduction 15 1.................................... 33 3..................................................1 Background ......... 42 13 ...................................2 Gaseous phase poisoning...............................3 Diesel catalysis........................................... 34 3............................................3 Particulate filtration ................. 24 2...3 Poisoning by other compounds .1 Poisoning by phosphates ......................2......................................................................................................1 Physisorption analyses .................................. 19 2.................................................................... 34 3..............................1 Oxidation catalysis ...............3...............2 Phosphorus poisoning procedures......................2.......................................5 Catalyst regeneration................................................................3... 35 4 Experimental 37 4..........4 Chemical analyses ........................................ 27 3...... 29 3............................................................ 40 4................................................................................ 39 4....2 Chemical deactivation............................................................................................................................3 Transmission Electron Microscopy ................ 22 2....... 25 3 Catalyst deactivation 27 3.................3...3 Catalyst characterisation techniques ..................

...................... 71 6............... 51 5........... 69 6 Evaluation of the poisoning procedures 71 6............................................. 63 5........2 Evaluation and utilization of the results........................................................2 Effect of phosphorus and calcium ....................3 Suggestions for further research...3.....9 Thermodynamic calculations...8 Activity measurements ..................2 Phosphorus compounds .....7 X-ray Photoelectron Fluorescence........ 43 4.........3.......3.............................3...........2................. 43 4.......2 Accumulation of phosphorus ...... 51 5.......................................................................................4 Changes in the active metal particles and washcoat grain size . 72 6........6 Fourier Transform Infrared-Attenuated Total Reflection ........3................................... 73 7 Summary and conclusions 75 References 77 Original papers 85 14 .......................2...............1 Loss in catalytic surface area ............1 Phosphorus content.......................3 Loss of catalytic activity .....................................3.......................... 63 5..................... 68 5................................................................................................................... 47 5................... 55 5...............1 Integration of the results ....................................... 43 4............................................ 45 5 Poisoning-induced changes in the catalyst components 47 5..1 Effect of phosphorus.....4.......................

hydrocarbons (HCs). These pollutants include carbon monoxide (CO). Demand for a high performance catalyst and requirements for long catalyst life have increased the amount of research activity focused on automotive exhaust gas catalysis. 2004. Catalysis is one of the key technologies used in controlling air pollution. and particulate matter (PM) (Kalantar Neyestanaki et al. (Wallington et al. and it has been a success story in the development of environmental catalysts. Wallington et al. (Heck & Farrauto 1997. which originate from lubricating oils. calcium (Ca). Catalytic abatement of exhaust gas components has been used to reduce automobile emissions since the 1970s. and exhaust gas after-treatment. zinc (Zn). 2003.1 1. 2004). which increases the probability of their interaction with catalyst components such as aluminium oxide (Al2O3) and cerium oxide (CeO2) (Cabello Galisteo et al.1 Introduction Background Motor vehicles play a major role in urban air quality problems. are also needed. 2006). (Greening 2001. Kašpar et al. and phosphorus (P). 15 . Farrauto & Heck 2000. Twigg 2007) Catalytic materials used in future three-way catalyst (TWC) and diesel catalyst applications will have to be more effective in controlling emissions. but the mechanism of phosphorus poisoning is not yet completely known. Incomplete burning of petrol or diesel leads to formation of pollutants that have several harmful effects on the environment and human health. The increasing motor vehicle population and tightening emission standards create a major challenge for the development of more durable and effective automotive catalysts. fuel. and magnesium (Mg). nitrogen oxides (NOx). Thermal stability and good tolerance of poisons such as sulphur (S). Shelef & McCabe 2000. The role of phosphorus in the deactivation of automotive catalysts has been discussed in several studies. Robust research efforts are required to clarify the functioning of noble metals and washcoat components and to control deactivation phenomena. Lassi 2003) Many challenges remain before researchers and the catalyst industry can fulfil such demands. Further improvements are also needed in the efficiency and optimization of the entire system of engine. which originates from fuel. 2006) Phosphorus and sulphur are present in aged catalytic converters in higher concentrations than other poisons.

calculated according to energy content. 2003. this study was carried out with simplified model catalysts in order to obtain detailed knowledge on the poisoning phenomena of catalyst components. procedures for studying chemical ageing on the laboratory scale were developed in this study.Nowadays. interest in forms of energy that would replace traditional crude oil-based fuels is growing (Hamelinck & Faaij 2006. chemical deactivation of catalyst powders was studied. lubricating oils are normally a major source of phosphorus. The mechanism of phosphorus poisoning in automotive catalysts is not yet completely 16 .75% of energy.and engine-ageing methods provide realistic information about the overall deactivating effect caused by oil. 2004). Despite the increasing risk of phosphorus poisoning in automotive catalysis. Therefore. However. Sagar 1995). Xu et al. Uy et al. 5. the EU countries are supposed to replace the use of gasoline and diesel with a renewable form of energy to the extent that by the year 2010. 1. Vehicle. When using traditional fossil fuels. Therefore. engine-aged. Their disadvantages are that they are relatively expensive and time-consuming methods (Koltsakis & Stamatelos 1997). Research work in this area is essential in order to meet emission limits in the future. would come from renewable sources (EU 2003). production and use of biodiesel and other fuels derived from biomass is rapidly increasing (Mittelbach 1995). phosphorus as well as potassium (K) and other possible poison compounds may be present in various concentrations.2 Purpose of the work In the present work. It may also be difficult to determine the relevance of a single mechanism of deactivation to changes in catalytic activity and characteristics. Cabello Galisteo et al. over 95% of the world’s transportation fuel originates from fossil fuels (Wallington et al. In the case of biodiesel. 2006). due to the quest to reduce dependency on fossil fuels and to control climatic change.and fuel-derived contaminants and high operating temperatures. Research on deactivation of exhaust gas catalysts is widely carried out by studying vehicle-aged. According to EU directive 2003/30/EC. depending on the origin of the biomass (Grosser & Bowman 2006). and oven-aged catalysts on the laboratory scale (Koltsakis & Stamatelos 1997. Mittelbach 1995. 2004. Therefore. Romm 2006. This emphasizes the role of phosphorus in exhaust gas catalysis. the number of publications dealing with the effect of phosphorus on separate catalyst components is still very limited.

These calculations were also used as a tool for planning ageing conditions. In addition. safe. were studied using several characterization techniques. deactivation of automotive catalysts caused by phosphorus poisoning was studied by developing two different chemical ageing procedures on the laboratory scale. Chapter 2 describes the composition and function of three-way and diesel catalysts used in automotives. The mechanism of phosphorus poisoning is not completely known. In this research. the combined effect of phosphorus and calcium was also studied. Information about the formation and stability of poison compounds was gained by using thermodynamic calculations. phosphorus was chosen to be the poisoning compound in ageing. In addition.e. Another purpose of the work was to study the mechanism of phosphorus poisoning with different catalyst components used in present-day catalytic converters. However. Possible methods for regenerating 17 . differences between phosphorus poisoning of catalysts with and without a precious metal were investigated. caused by phosphorus poisoning and hydrothermal ageing. the studies were carried out with simplified model components. and therefore. The characteristics of aged samples containing different oxides were also compared. To understand poisoninginduced changes in the washcoat. The purpose of this thesis project was to examine the effect of phosphorus on the catalytic activity and characteristics of components widely used in automotive exhaust gas catalyst applications. chemical. alterations in the surface of powdered catalyst components. In Chapter 3 the causes leading to deactivation of automotive catalysts. are reviewed.known. The work also focused on obtaining information about the conditions in which poisoning takes place and finding out whether some components are more sensitive to phosphorus than others. As a special case. A further purpose of the work was to differentiate between the role of thermal ageing and the role of phosphorus poisoning in catalyst deactivation. To obtain detailed knowledge about the mechanism of poisoning. these methods are often relatively expensive and slow. and controlled way on the laboratory scale. This thesis is structured as follows. affordable. One objective of this study was to develop a methodology for accelerated chemical deactivation studies that can be carried out in a time-saving. studying the effects of a single deactivation mechanism on a decrease in catalytic activity may be complicated. thermal and mechanical deactivation. and therefore studies carried out with simplified model components are required. Vehicle-ageing and engine-ageing procedures are widely used in studying poisoning phenomena of exhaust gas catalysts. i.

Chapter 4 presents the experimental part of the work. The research results of the work are presented in Chapter 5 and further integrated and evaluated in Chapter 6. ageing procedures. 18 . and characterization techniques are described. the results are summarized and conclusions are drawn in Chapter 7. Chapter 6 also discusses suggestions for further studies. The catalyst samples.automotive catalysts are also discussed. Finally.

e. In order to maintain the high surface area with varying temperatures and gas compositions. for instance. The monolithic substrate is coated with a high-surface-area carrier material such as aluminium oxide (Al2O3). (Farrauto & Heck 1999. i. and NOx were dual-bed systems in which NOx was reduced in the first bed. 2006) 19 . A converter (Figure 1) typically consists of a metallic or ceramic monolithic substrate that provides a high geometric surface area with a low pressure drop. Seymor & O'Farrelly 2005) Rare earth metal oxides are used to stabilize the precious metals against sintering. The first automotive catalysts to convert HC. The stricter NOx standards in the 1980s led to development of three-way catalysts that simultaneously catalyze three types of reactions: oxidation of CO and HC and reduction of NOx. Precious metals. and releasing it when the engine’s operating conditions change to a low oxygen phase. platinum (Pt). enabling oxidation of HC and CO in the second bed. rhodium (Rh). barium (Ba) or silicon (Si) oxides. These early converters were used only to oxidize HC and CO emissions (Heck & Farrauto 2001). the carrier is stabilized with lanthanum (La). i. Secondary air was injected between the beds. Wallington et al. 2003) Modern automotive catalytic converters are very effective in reducing gaseous pollutants in exhaust gas to levels that meet emissions standards. (Gandhi et al. 2006. and palladium (Pd). (Heck & Farrauto 2001.e. an excess of oxygen. Different oxides like cerium (Ce) and zirconium (Zr) oxides are used to improve catalytic efficiency by storing oxygen in lean conditions.2 2. CO.1 Automotive exhaust gas catalysis General Automotive exhaust catalysts were introduced in the 1970s. are added to the catalyst in varying compositions to provide catalytic reduction and oxidation of pollutants to more harmless compounds. Wallington et al.

Fig. The oxygen content of the exhaust gas is measured by an oxygen or lambda sensor placed immediately before the catalyst in the exhaust manifold. nitrogen oxides (NOX) and hydrocarbons (HCs). whereas reduction of NOX takes place under rich conditions (Lox & Engler 1997).2 Three-way catalysis Automotive exhaust gases formed in gasoline engines normally contain carbon monoxide (CO). (Farrauto & Heck 1999) 2. An exhaust gas after-treatment system consists of a catalytic converter and an electronically controlled air-fuel management system. The typical composition of gasoline engine exhaust gases is presented in Table 1. 20 . 1. Air intake and fuel injection are controlled to provide an appropriate ratio between oxygen and fuel (air-to-fuel ratio. A/F). Typical structure of a metallic monolithic catalyst. A three-way catalyst is used to simultaneously remove these three major pollutants from a gasoline engine’s exhaust gases (Heck & Farrauto 2001). Under lean conditions the catalytic oxidation reactions of CO and hydrocarbons are favoured.

5 Balance N2 In ideal burning of gasoline.5 HC (ppm) 350 NOx (ppm) 900 H2 (vol-%) 0.Table 1. other significant reactions also take place in a TWC. 2003): CO + H 2 O → CO2 + H 2 HC + H 2 O → CO2 + H 2 (4) (8) 21 . Composition of gasoline engine exhaust gas (Heck & Farrauto 2001). leading to formation of a number of combustion products. the following simplified reaction takes place: gasoline + O2 (air ) → CO2 + H 2 O + heat (1) Combustion in a real engine is incomplete. An automotive catalyst promotes reactions between these compounds according the following equations (Heck & Farrauto 2001): Oxidation of HC: n n C y H n + ( y + )O2 → yCO2 + H 2 O 4 2 (2) Oxidation of CO: 1 CO + O2 → CO2 2 CO + H 2 O → CO2 + H 2 (3) (4) Reduction of NOx: 1 N 2 + CO2 2 1 NO / NO2 + H 2 → N 2 + H 2 O 2 n n n (2 + ) NO / NO2 + C y H n → (1 + ) N 2 + yCO2 + H 2 O 2 2 4 NO / NO2 + CO → (5) (6) (7) In addition to the oxidation and reduction reactions mentioned above. These reactions include water-gas shift and steam reforming reactions (Kašpar et al.17 H2O (vol-%) 10 CO2 (vol-%) 10 O2 (vol-%) 0. CO (vol-%) 0.

Composition of diesel engine exhaust gas (Neste Oil Oyj 2006. Solid emissions consist of dry carbon and soot. Twigg 2003). (Zelenka et al. and odorous compounds (Zelenka et al. vehicle application. as well as liquid sulphates. 1990.02 Bal. Zelenka et al. The temperature of diesel exhaust gas is relatively low. NOx control. Typical DOCs contain Pt in a highly 22 . Zelenka et al. Frost & Smedler 1995) Furthermore. SOF). 1996. 2005) Gaseous emissions contain CO and HC derived primarily from incompletely burned fuel. Therefore. 1998).3. a diesel engine employs a compression-ignited process in which the fuel is injected into a highly compressed charge of air.3 Diesel catalysis Unlike a spark-ignited engine. especially during low-speed driving. 1996). The liquid phase includes hydrocarbons derived from unburned fuel and engine lubricating oil (collectively Soluble Organic Fraction. CO (vol-%) 490 HC (ppm) 30 NOx (ppm) 1135 H2O (vol-%) 4-5 CO2 (vol-%) 7. The typical composition of diesel engine exhaust gas is presented in Table 2. NOx and sulphur (Zelenka et al. Table 2. Twigg 2006. (Zelenka et al. the requirements for diesel exhaust gas after-treatment are different from those of gasoline vehicles due to the unique demands of emissions standards. CO. The primary target in diesel emission control is reduction of particulates and NOx (Clerc 1996. aldehydes.1 O2 (vol-%) 10.1 Oxidation catalysis Diesel oxidation catalysts (DOC) are used to oxidate HC. and particulate filtration (Twigg 2006). oxygen is always in excess in a diesel engine.5 SO2 (ppm) 30 Particles (wt-%) <0.01 and 1 µm in diameter. N2 2. SOF. 1990.2. (Votsmeier et al. and high durability (Clerc 1996). Diesel emissions include all three phases of matter. 1996). This results in the challenge of achieving and maintaining sufficient catalytic performance at low temperatures. 1996) The size of a diesel exhaust gas particle is between 0. Especially the ultra(<100 nm) and micro-scale (<50 nm) particles are potentially hazardous to health because they are able to enter deep into the respiratory track and possibly even into cell membranes. There are three main after-treatment approaches to reducing harmful components in diesel exhaust gas: oxidation catalysis. Roduit et al.

1995).dispersed form. leading easily to a decrease in the operating temperature of a catalyst. At low catalyst temperatures (below 200°C). The temperature of diesel exhaust gas is normally relatively low. removal of gas phase HCs is attributed exclusively to zeolites. Zeolites have the ability to adsorb HCs. However. at higher temperatures (300°C and above). HC conversion depends on how the platinum is functioning in the catalyst. the exhaust gas contains a varying amount of sulphur oxides (SOx). addition of a HC adsorbent is needed. HC removal is effective over the entire exhaust temperature range with very low platinum loading. Sulphuric acid (H2SO4) is formed in the reaction between sulphur trioxide (SO3) and water. Therefore. Therefore. (Farrauto & Voss 1996) The desired main oxidation reactions in diesel exhaust catalysis are (Heck & Farrauto 2001): Oxidation of SOF: SOF + O2 → CO2 + H 2 O (9) Oxidation of HC: n n C y H n + (1 + )O2 → yCO2 + H 2 O 4 2 (2) Oxidation of CO: 1 CO + O2 → CO2 2 (3) Depending on the sulphur content of the fuel. thus preventing them from inhibiting active Pt sites. such as platinum-containing ZSM-5. (Twigg 2006) Some zeolite catalysts. have demonstrated their effectiveness in reducing NOx with hydrocarbons in diesel exhaust gas with a high oxygen content (Guo et al. Farrauto & Voss 1996) With zeolite-containing catalysts. oxidation of SO2 to SO3 should be minimized in the oxidation catalyst (Heck & Farrauto 2001): 1 SO2 + O2 → SO3 (10) 2 23 . Zeolites are used to adsorb HCs. which also improves NOx conversion with increasing temperature. (Shinjoh 2006.

1996). 2000. i. the fuel itself can be employed as a source of the reducing agent. thus preventing NO adsorption (Twigg 2006). 2000): 4 NH 3 + 4 NO + O2 → 4 N 2 + 6 H 2 O (16) 24 . Using HC as a reducing agent involves an advantage compared with other reductants because for instance. NOx reduction catalysis. under lean conditions the catalytically active metal surface becomes covered by strongly adsorbed oxygen. or NOx trapping is needed in exhaust gas after-treatment (Twigg 2006). 1996).3. Zelenka et al. High NOx conversion rates can be achieved by adding the reducing agent to the exhaust gas before the catalyst (Zelenka et al.e. ammonia (NH3) or urea ((NH2)2CO) is required (Lox & Engler 1997. Decomposition of NO to its elements is thermodynamically favoured between ambient and relatively high temperatures (Goralski & Schneider 2002): NO U 1 1 N 2 + O2 2 2 (11) However. The following reactions of NO with HC or alcohol are possible (Lox & Engler 1997): (6m + 2) NO + 2 Cm H 2 m + 2 U (3m + 1) N 2 + 2mCO2 + (2m + 2) H 2 O 6m NO + 2 Cm H 2 m +1OH U 3m N 2 + 2mCO2 + (2m + 2) H 2 O (13) (14) Besides HC and alcohol. 1996). a reducing agent such as alcohol. In SCR. (NH2)2CO is a compound that forms NH3 in the reaction with water (Koebel et al. 2000): ( NH 2 ) 2 CO + H 2 O → 2 NH 3 + CO2 (15) The main reaction of NO with NH3 and oxygen is (Koebel et al. Formation of NO2 becomes significant at moderate temperatures and with excess oxygen (Goralski & Schneider 2002): 1 NO + O2 U NO2 2 (12) In order to comply with emission standards under lean conditions. 2002).2 NOx reduction An improved combustion process and exhaust gas recirculation (EGR) are used to reduce NOx content in diesel exhaust gas (Zelenka et al. Madia et al. NH3 and (NH2)2CO can be used as reducing agents in SCR (Koebel et al.2. hydrocarbon. selective catalytic reduction (SCR).

(van Diepen et al. the reaction rate is faster than the rate of reaction (16) (Koebel et al. the residence time of soot in the catalyst is not long enough for oxidation. an undesired reaction in which NH3 is oxidized to NO may take place (Koebel et al. (Twigg 2006) Therefore. a wall-flow monolith. 25 . 2000): 4 NH 3 + 5O2 → 4 NO + 6 H 2 O (20) In the trapping method. Furthermore. 1999).With equimolar amounts of NO and NO2. Despite that. A very commonly used filter structure.3 Particulate filtration Soot is present in exhaust gas as an aerosol with a concentration that is too low to be burned in a catalytic converter. soot is collected in particulate filters from which it is finally removed (Koltsakis & Stamatelos 1997.3. the reaction with NH3 and NO2 (18) is slower than reactions (16) and (17) (Koebel et al. 2000): 7 4 NH 3 + 3 NO2 → N 2 + 6 H 2 O 2 (18) Formation of N2O is possible at temperatures above 400°C (Koebel et al. 2000): 4 NH 3 + 4 NO + 3 O2 → 4 N 2 O + 6 H 2 O (19) At very high temperatures. van Diepen et al. (Twigg 2006) 2. elimination of soot by filtration is still needed to prevent possible health effects of diesel PM. the stored NOx is released by changing the exhaust gas composition to be slightly reducing for a short period. Then. When the trapping material is saturated. 1999) Recent advances in the combustion processes of modern passenger car diesel engines have resulted in a reduction of PM emissions. NOx is reduced to N2 over a Rh-containing component. is presented in Figure 2. NOx is storaged as NO3 during the lean driving period. 2000): 4 NH 3 + 2 NO + 2 NO2 → 4 N 2 + 6 H 2 O (17) In contrast.

Fig. Passive regeneration methods include catalytic fuel additives and catalytic coating before or inside the trap. 1996. the filtering surface needs to be sequentially regenerated. In active regeneration the trap is cleaned with a fuel burner or an electrical heater. Regeneration methods can be divided into two categories: active and passive processes. A wall-flow monolith particulate filter (Bissett 1984). (Zelenka et al. To maintain engine efficiency. 2. Trapping material is based on ceramic or metallic substrates that allow up to 95% capture of dry soot. Stamatelos 1997) 26 .

Catalyst deactivation is a complicated phenomenon due to the several possible factors causing it. Moulijn et al. 2001). Richardson 1989) The types of deactivation phenomena can be divided into three categories: chemical. and fluctuating gas phase compositions and flow rates in a catalytic converter increase the possibility of deactivation (Forzatti & Lietti 1999. Thermally induced decrease in the catalytic surface. To give an example of different forms of deactivation. 27 . Loss of catalytic material due to abrasion of the internal surface area caused by mechanical crushing of the catalyst. Vaporization Vapour-solid and solid-solid reactions Thermal Thermal degradation Reaction of compounds with the catalyst phase to produce volatile compounds. Bartholomew 2001. Forzatti & Lietti 1999. Moulijn et al. Catalysts may loose their activity as a result of a number of unwanted chemical and physical changes. Mechanical Fouling Attrition/crushing Physical deposition of species from the gas phase onto the catalytic surface and pores.3 3. blocking of the active reaction sites. or promoter with the catalytic phase to produce an inactive phase. Table 3 shows one possible way to categorize these deactivation types and the related mechanisms of deactivation. Reaction of vapour. support. (Butt & Petersen 1988. and active phase-support reactions. 2001. Bartholomew 2004).1 Catalyst deactivation Overview Deactivation of automotive catalysts is a problem that has not been totally solved with current catalyst technology. Table 3. Bartholomew 2001. Types and mechanisms of catalyst deactivation and their descriptions (Bartholomew 2004). thermal and mechanical ageing (Bartholomew 2001. support surface area. Deactivation type Chemical Deactivation mechanism Poisoning Description of the mechanism Strong chemisorption of compounds on the catalytic surface. the presence of impurities. High temperatures and temperature gradients.

Deactivation of diesel catalysts in different temperature ranges (adopted and modified from Lox & Engler 1997). is also a relevant deactivation phenomenon (Koltsakis & Stamatelos 1997). while fouling and mechanical factors are more rarely the main reason for deactivation. the most viable method for prolonging the life of a catalyst is to prevent deactivation. 28 . Deactivation detected in present-day catalytic converters during normal vehicle operation is typically a result of chemical and thermal mechanisms. Deactivation can be induced by one cause or a combination of several deactivating factors. This can be done by decreasing the amount of poisons in fuel and lubricating oils to a more acceptable level. which takes place for instance in the form of physical breakage or crushing. Once an exhaust gas catalyst has become deactivated. Another approach is to develop catalyst components that are more resistant to poisoning and thermal ageing. (Forzatti & Lietti 1999) T (°C) 1000 Catalyst temperature range 800 Washcoat phase changes 600 Reaction of Zn and P with washcoat Exhaust gas temperature range Operation range 400 Formation and chemisorption of SO3 200 Adsorption of SO2 Adsorption of H2O and particulates 0 Fig. i. In any case. Mechanical deactivation. Taylor 1984) This thesis focuses on the mechanisms of chemical deactivation. However. the net effect is a reduction in catalytically active sites. Some methods for restoring its catalytic activity have been studied.Figure 3 presents deactivation of a diesel catalyst in different temperature ranges. regenerating it is a very difficult task. 3. (Koltsakis & Stamatelos 1997. poisoning.e.

In such a case. S. it still has an impact on the deactivation of TWCs (Fernándes Ruiz et al. lubricants and other impurities accumulate on the catalyst’s surface (Koltsakis & Stamatelos 1997). (Butt & Petersen 1988) Poisoning of an exhaust gas catalyst caused by accumulation of impurities on the active sites is typically a slow and irreversible phenomenon. The activity of an automotive catalyst declines gradually over the course of time as the harmful components of fuels.and fuel-derived contaminants found in used catalytic converters. Culley et al. The durability of the catalyst can also be improved by placing the active components 29 . depending on whether the poisoning is universal or takes place only at certain sites or crystal faces or affects only certain adsorbed species. 1984. Ca. 2003. 2001. Poisoning is defined as a loss of catalytic activity caused by chemisorption of impurities on the active sites of the catalyst. lead (Pb) was the major cause of poisoning (Williamson et al. Poisons accumulated on the catalyst surface block the access of reactants to the active sites. Angelidis & Sklavounos 1995. 1979b. However. 2005. These contaminants have been widely studied (Williamson et al. Poisoning by a certain compound can also be a reaction-specific phenomenon. (Butt & Petersen 1988.3. Developing and choosing catalyst materials appropriate for current applications is a feasible way to prevent thermal and chemical deactivation. Poisons are substances whose interaction with active sites is strong and often irreversible. 1985. Williamson et al. Deactivation by poisoning is often related to high operating temperatures and sudden temperature changes. Zn. Forzatti & Lietti 1999) Catalyst poisons can also be classified as selective or non-selective. Fernándes Ruiz et al. 1996. and Mg are typical oil. Williamson et al. P. 1979a. (Butt & Petersen 1988) Catalyst poisoning is possible even with a low level of impurities (Forzatti & Lietti 1999). but non-selective in another. 1992. Nowadays. the use of unleaded or low-lead gasoline has diminished the role of lead as a catalyst poison.2 Chemical deactivation Exposure to catalyst poisons aggravates the loss of activity in automotive exhaust gas catalysts. Uy et al. 2005). Monroe 1980). 2002). Poisons contaminate the washcoat and precious metals and reduce the catalytically active surface by blocking active sites (Butt & Petersen 1988. 2002. 2004. Inoue et al. Larese et al. Angelidis & Sklavounos 1995). Cabello Galisteo et al. In the first generation of catalytic converters. López Granados et al. Liu & Park 1993. Rokosz et al. the poison is selective in one reaction.

phosphorus and zinc (Kumar et al. precious metals used to control exhaust gas emissions have different levels of resistances against poisoning.15 wt-% (Bunting et al. (Laurikko 1994.2. 2004). (Dickey 2005) In automotive applications ZDDP is a common source of typical catalyst poisons. and then neutralizing the resultant acid with zinc oxide.08– 0. especially in moist conditions (van Kooten et al. a possible way to lengthen catalyst life is to use lubricants with a lower P content. As a result. 2004). ZDDP is an effective bearing corrosion inhibitor. 2000). (2004). The additive is also a secondary oxidation inhibitor that decomposes hydroperoxides in the branching step of hydrocarbon oxidation. 3. antioxidant. the individual and combined effects of poisons as well as the influence of simultaneous poisoning and thermal deactivation are still not sufficiently known. hydraulic oils.1 Poisoning by phosphates Zinc dialkyldithiophosphate (ZDDP) is an antiwear. Laurikko 1995) Furthermore. very strong wear-resistant lubricating films are formed.in separate washcoat layers. Lox & Engler 1997) Despite the numerous studies carried out with poisoned catalysts. Especially knowledge about effects related to deactivation of zeolites is still lacking. ZDDP is produced by first letting an alkyl or aryl alcohol react with phosphorous pentasulphide (P2S5). Caracciolo & Spearot (1976) have reported that catalytic activity decreases linearly as the amount of phosphorus detected in the catalyst increases. It is known that deactivation of zeolite-containing catalysts can occur at both low and high temperatures. and corrosioninhibiting additive that is used in engine lubricating oils. The phosphorus content of modern lubricating oils is typically 0. Table 4 shows typical characteristics of ZDDP. According to Kalantar Neyestanaki et al. and other lubricants. (Taylor 1993. it has been shown that Pt and Rh are less sensitive than Pd to poisoning by sulphur and lead. The frictional heat formed by two steel surfaces rubbing together in the engine causes ZDDP to react chemically with the surfaces. 30 . For instance. In addition.

Table 4. Typical characteristics of zinc dialkyldithiophosphate (Research Institute of Petroleum Industry 2002).
Characteristics Density (g/ml) at 15.5°C Viscosity (c.st) at 100°C Sulphur content (wt-%) Phosphorus content (wt-%) Zinc content (wt-%) pH Typical value 1.09 10.3 19 10 11 5–6

The chemical composition in which phosphorus can be found in catalytic converters depends on many factors, such as the chemical composition of oil and oil additives, the age of the oil used, and conditions in the motor (Xu et al. 2004). Phosphorus contamination can be observed on the surface of catalytic converters as several different compounds (Carduner et al. 1988, Xu et al. 2004). Firstly, as illustrated in Figure 4, phosphorus can form a phosphate-containing overlayer that is a mixture of Zn, Ca, and Mg phosphates on the washcoat (Liu & Park 1993, Rokosz et al. 2001). These compounds are very stable on the catalytic surface (Andersson et al. 2007). Low exhaust temperatures are favourable for the formation of zinc pyrophosphate (Zn2P2O7) (Williamson et al. 1985). According to Liu and Park (1993), formation of a glassy, amorphous phase of Pb, Zn, and Ca phosphates on the catalyst surface has been observed. Ca and Mg have also been reported to prevent phosphorus poisoning. Ueda et al. (1994) demonstrated that phosphorus poisoning of the catalyst and the oxygen sensor can be restrained by using Ca and Mg sulphonates as oil additives. Furthermore, Williamson et al. (1980) reported that fuel P (derived from cresyl diphenyl phosphate) can neutralize Pb deactivation by the formation of lead phosphates.


Fig. 4. Scanning electron microscope (SEM) image of a layer containing Zn, Ca, and Mg phosphates on a catalytic surface, magnified 5000 times (Rokosz et al. 2001).

Secondly, phosphate compounds can also be formed directly with washcoat components. In that case, the resulting compounds are, for instance, aluminium and cerium phosphates (Rokosz et al. 2001, Uy et al. 2003, Cabello Galisteo et al. 2004). In the case of aged diesel catalytic converters, the adsorbed phosphorus species have also been identified as phosphates (Beckmann et al. 1992, Bunting et al. 2005). For instance, the interaction between phosphorus and Al2O3, resulting in the formation of AlPO4, is expected to be partially responsible for deactivation observed in aged diesel catalysts (Cabello Galisteo et al. 2004). Furthermore, formation of CePO4 is also responsible for deterioration of the oxygen storage and release properties of cerium oxide (Battistoni et al. 1999, López Granados et al. 2006, Larese et al. 2003, Larese et al. 2004a, Larese et al. 2004b). Phosphorus is usually concentrated in the forward-most section of monolithic converters (Culley et al. 1996, Beck et al. 1997a, Beck et al. 1997b, Angove & Cant 2000, Webb et al. 2003). A decrease in catalytic activity and changes in characteristics, such as a loss of surface area, in the front section of a converter have been associated with extensive phosphorus deposition. (Beck et al. 1997, Angove & Cant 2000) Joy et al. (1985) have shown that as low an amount as 0.4 wt-% of phosphorus on the catalyst surface is enough to significantly reduce catalytic activity. In their study, no crystalline phosphorus compounds were detected. Instead, the presence of amorphous zinc phosphorus compounds was observed in SEM analyses.

3.2.2 Poisoning by sulphur compounds Sulphur poisoning is a complex phenomenon that can involve significant changes in the structural, morphological, and electronic properties of a catalyst (Rodriguez & Hrbek 1999). Gasoline and diesel contain sulphur in small amounts, but the cumulative effect of poisoning during the catalyst’s life can be substantial. In the case of TWCs, fast poisoning by sulphur can be to some extent reversible and the poisoned catalyst can be regenerated. (Yu & Shaw 1998) The role of sulphur poisoning is especially substantial in diesel catalysts due to the comparatively low operating temperatures involved. Despite the reduction in the sulphur content of fuel that has taken place during the past decades, sulphur is still present in diesel oil and gasoline in small amounts (Yu & Shaw 1998). Sulphur has a negative effect on the activity and oxygen storage capacity (OSC) of the catalyst (Boaro et al. 2001, Yu & Shaw 1998). The presence of sulphur can cause formation of new inactive compounds on the catalyst’s surface. Furthermore, morphological changes in the catalyst are also possible. (Yu & Shaw 1998) Depending on the temperature and partial pressure of oxygen, sulphur can be present in an exhaust gas catalyst in the form of sulphates, sulphides or oxysulphides (Karjalainen et al. 2005). In the fuel combustion process that takes place in the engine, sulphur oxidizes to SO2 and SO3, which are then adsorbed by the precious metal sites on the catalyst’s surface at temperatures below 300°C. In the reaction with aluminium oxides, aluminium sulphates are formed. These compounds deactivate the catalyst by reducing the active surface. Sulphur poisoning is a severe problem at low temperatures, whereas at temperatures above 1000°C adsorption of sulphur species is almost negligible. In addition, the effect of sulphur poisoning on TWCs has been observed to be more significant in oxidizing than in reducing conditions. (Butt & Petersen 1988, Heck & Farrauto 1996) Under reducing conditions sulphur forms H2S, which poisons metal surfaces and negatively affects oxidation of HCs (Rabinowitz et al. 2001). In the case of NOx storage, Fridell et al. (2001) have reported that sulphur deactivation is more severe when SO2 is added during a rich period than during the lean phase. Again, very stable sulphates, which are unattacked by reductants even at 1000°C, can be formed especially in the absence of water (Mahzoul et al. 2001).


3.2.3 Poisoning by other compounds Automotive catalysts can also be deactivated by compounds commonly used in the structure of an engine. For instance, iron (Fe) is a poison for platinum group metals (Kalantar Neyestanaki et al. 2004). Iron detected on the catalytic surface is often assumed to originate from the corrosion of metal components in the engine (Cabello Galisteo et al. 2004). Other similar impurities may be copper (Cu), nickel (Ni), and chromium (Cr). Chromium and nickel are added to the construction materials in order to improve the thermal stability of engines. Copper originates from engine bearings, for example. (Angelidis & Sklakovounos 1995) 3.3 Thermal deactivation

High temperatures and uncontrollable temperature changes cause sintering, formation of new compounds, phase changes in existing compounds, and volatilization of components, leading to a loss of active surface area of the catalytic materials and the washcoat (Richardson 1989, Mooney 2005). The operating temperature of light-duty diesel catalysts is normally relatively moderate (below 500°C), and therefore the contribution of thermal ageing to deactivation of these catalysts is of lesser importance compared with TWCs. Depending on the load, exhaust gas temperatures may vary from 100°C up to 700°C. Therefore, the influence of thermal ageing cannot be completely excluded. (Cabello Galisteo et al. 2004, Koltsakis & Stamatelos 1997) Sintering is a thermally activated process in which the surface area is decreased by structural modification of the catalyst. As a result of these modifications, active catalytic materials and also the washcoat can be affected. (Butt & Petersen 1988) Two different models have been proposed for the sintering of metal crystallites: the atomic migration model and the crystallite migration model. In atomic migration atoms migrate from one crystallite to another via the surface or the gas phase, causing an increase in crystallite size and thereby a decrease in surface area. In crystallite migration sintering occurs due to crystallite migration over the surface, resulting in collisions and coalescence of the crystallites. (Forzatti & Lietti 1999, Bartholomew 2001) Thermal degradation of washcoat materials also increases the risk of deactivation of the catalyst. Phase transformations and sintering of the washcoat decrease the catalytically active


surface area. In addition, changes in the catalyst structure can cause encapsulation of active metal particles. (Butt & Petersen 1988, Lassi 2003) 3.4 Mechanical deactivation

A catalytic converter can be damaged by a strong mechanical impact. In such a case, the monolith is crushed and as a result, the back pressure of the exhaust gas is increased. If the damage is not noticed in time, local overheating can cause thermal deactivation and finally melting of the honeycomb. Metallic catalysts can endure mechanical deactivation better than ceramic ones. (Laurikko 1995) Mechanical failure of the catalyst may also be a result of high temperatures. Two types of factors can cause high catalyst temperatures. The first one is engine operating conditions. Secondly, as the result of misfiring, non-combusted fuel-air mixtures undergo catalytic combustion, which can produce very strong exothermic reactions within the catalyst. At about 1200°C, the metallic foil starts to soften and probably shrink. If the catalyst temperature exceeds 1400°C, the foil will melt, after which it is destroyed. (Mooney 2005) 3.5 Catalyst regeneration

It is usually easier to prevent catalyst deactivation than to restore the original activity of the catalyst (Bartholomew 2001). However, some studies have been carried out to investigate the possibilities of regenerating activity that has decreased due to thermal ageing and poisoning. According to van Kooten et al. (2002), catalytic activity can be partially restored by heating the catalyst under oxygen-rich conditions, which removes some of the contaminant species (coke, HCs, nitrogen). However, van Kooten et al. (2002) reported that depositions of P, Zn, Ca, and S were very hard to remove with this method, and therefore they are associated with irreversible deactivation. Reactivation of sulphated oxidation catalysts has been performed by Cabello Galisteo et al. (2007), who decomposed aluminium sulphate in a deactivated catalyst with a reductive treatment. Furthermore, amorphous zinc pyrophosphate has been removed from the catalytic surface at high temperatures and in reducing conditions. The method is not viable from a practical point of view because as a result of sintering, the net activity of the catalyst is not restored. (Williamson et al. 1984)

Catalyst regeneration is also possible in the case of thermal deactivation. (2006). Birgersson et al. 2005a). it should be pointed out that the interactions between precious metals and washcoat materials differ from each other. in cases where regeneration of the catalyst is not possible. Cu. (2006) have shown that it is possible to efficiently remove phosphorus accumulated in the catalyst using oxalic acid. oxidation of Rh/Al2O3 at 800 °C caused diffusion of Rh into the aluminium oxide. (2000) have presented results that are congruent with those of Wong & McCabe. With this method. GonzalesVelasco et al. methods for recovering platinum group metals (PGMs) from spent TWCs have been developed (Angelidis 2001). Fe. could be removed. According to Christou et al. Therefore. and S. which was reported by Wong & McCabe (1989). Furthermore. 36 . For instance. Rokosz et al. (Wong & McCabe 1989) Finally. resulting in a decrease in CO oxidation activity. catalytic activity was restored. Fe.Washing a poisoned catalyst with organic acids has also been tested. P and S could be partially removed. depositions of Pb. who treated catalysts containing Ca. Washing a poisoned DOC with a dilute solution of citric acid has been demonstrated to remove a large amount of P and most of the S accumulated in the catalyst (Cabello Galisteo et al. Ca. Zn. and Zn compounds with acetic acid. but not P. P. The activity could be restored with a reductive treatment (H2 at 800°C) followed by reoxidation at 800°C (Wong & McCabe 1989). Ni. As a result. This oxychlorination treatment also seems to be a potential procedure for regenerating DOCs if thermal ageing and sintering are the main causes of deactivation (Cabello Galisteo et al. (2006) showed in their study that combined thermal and liquid chlorine treatments can increase the number of catalytically active noble metal sites on the washcoat surface. 2005b) In general. the catalytic material used significantly affects the possibility of regenerating the catalyst. Birgersson et al. catalytic activity was restored to a level corresponding to only thermal deactivation (Rokosz et al. which led to regaining of micropores. (2006) demonstrated that a TWC that has been deactivated in terms of activity and metal dispersion can be regenerated by adding chlorine to an oxygen stream. by washing a catalyst with EDTA (ethylene diamine tetraacetic acid). Mn. 2001). Similar results have been reported by Angelidis & Sklavounos (1995). S. Catalytic activity lost because of chemical interaction between catalytic materials can sometimes be restored by using suitable reaction conditions. (2004) and Anderson et al. (2001) and Christou et al. Pb.

The samples were studied when fresh and after the ageing and phosphorus poisoning procedures described in Chapter 4.4 4. The catalysts were donated by Ecocat Oy. The role of chemical deactivation 37 . The monoliths were divided into different test zones in the axial (front and rear) direction in order to evaluate the positiondependent role of poisons in catalytic activity.2. Figure 5 shows examples of the powdery components used in this study.1 Experimental Catalysts This work consists of two test series and two different sets of catalyst samples: powders containing Rh (2. In the latter test series washcoats without a precious metal were also studied.000 and 360.0 wt-%) or Pt (1. which represent components used in commercial exhaust gas catalysts.000 km in a petrol-driven vehicle) for Rh-loaded samples. In addition to the samples presented in Table 5. CeO2 Pt/ZrO2 Pt/CeO2 Al2O3 Pt/Al2O3 Fig. three vehicle-aged metallic catalyst monoliths were used as industrial reference catalysts for the poisoning: a Rh/Pd/Al2O3/La2O3/OSC catalyst (aged for 100. The samples are listed in Table 5. respectively) for Pt-loaded samples.5 wt-%). 5. and Pt/Al2O3/La2O3/OSC and Pt/Al2O3/OSC catalysts (aged for 80. Examples of powdery components used in automotive catalysts.000 km in a diesel-driven vehicle.

the test series consisted of Rh-loaded catalyst powders representing components used in TWC applications. calcium. were added via impregnation. 0.0 wt-% in the OSC material. 38 .85 wt-% Pt 1. Phosphorus was added to a sample under continuous air flow and at a high temperature with the purpose of simulating poisoning in hydrothermal ageing conditions.5 wt-% Pt 0.2 Phosphorus poisoning procedures Two different methods were utilized for phosphorus ageing.0 wt-% in Ce-stabilized Zr oxide Rh 2. the front zones of the commercial catalysts were used as reference material in this study. Catalyst sample Test series 1 Rh/Zr-CeO2 Rh/Ce-ZrO2 Rh/γ-Al2O3/OSC Test series 2 Al2O3 TiO2 CeO2 ZrO2 Zr-CeO2 Ce-ZrO2 ZSM-5 zeolite Pt/Al2O3 Pt/TiO2 Pt/ZSM-5 zeolite Pt/CeO2 Pt/ZrO2 Pt/Ce-ZrO2 Pt/Zr-CeO2 Zr-stabilized Ce oxide Ce-stabilized Zr oxide Si/Al2 29 Pt 1.5 wt-% in Zr-stabilized Ce oxide Rh 2.4 wt-% Pt 1. Gas phase poisoning was carried out with a test series consisting of Pt-loaded catalyst powders that represented components used in diesel catalyst applications. Phosphorus and as a special case.0 wt-% in Zr-stabilized Ce oxide Rh 2.is most significant in the forward-most section of monolithic converters.5 wt-% Pt 1. Therefore. the ageing procedure was further developed to better correspond to the extreme conditions in a catalytic converter during real driving (Papers II–VI). List and description of the powdery catalyst samples. (Papers I–II) In the other poison treatment. In the first stage of the methodology development.5 wt-% in the entire washcoat Description 4. Table 5.5 wt-% in Ce-stabilized Zr oxide Pt 1.5 wt-% Pt 1.

for one hour at 500°C. steel and ceramic reactor materials were tested. The quartz reactor was found to be resistant to corrosion even after several ageing treatments.1 Poisoning by impregnation The catalysts were pre-treated in a H2 flow at 900°C for 24 hours prior to poisoning. finally. The final concentrations of phosphorus and calcium in the catalyst powders were 1 wt-%. some of the catalysts were poisoned with the other poison (P+Ca or Ca+P) in order to study the combined effects of calcium and phosphorus. respectively. The phosphorus content detected in the front part of converters is normally less than 4 wt-% (Cant & Angove 1998). (Paper I) After poisoning with one poison.4. the catalyst powders were calcined in air for 30 minutes at 100°C. The sample was placed in the reactor between two pieces of inert quartz wool. The amount of phosphorus fed into a catalyst sample during ageing was set to correspond to the typical phosphorus content detected in aged catalysts.2. The aim was to develop an ageing procedure that is safe and easy to use. different equipment constructions and materials were tested during the development process. Aqueous salt solutions of (NH4)2HPO4 and Ca(NO3)2·4H2O were used as sources of phosphorus and calcium. 39 . the horizontal reactor position was chosen.2 Gaseous phase poisoning The ageing temperature of 700°C was chosen to correspond to the peak temperature in diesel catalytic converters (Koltsakis & Stamatelos 1997). (Paper II) A schematic illustration of the gaseous phase poisoning equipment is presented in Figure 6.2. The steel and ceramic reactors were severely corroded by the repeated exposure to hydrothermal conditions and phosphorus addition. which was performed with an incipient wetness impregnation method. A thermoelement was also installed inside the reactor for temperature indication. followed by another 30 minutes at 200°C and. Vertical and horizontal reactor positions were tested in the construction. Tubular quartz. Subsequently. (Paper I) 4. Due to plugging caused by moisture in the sample in the vertical position. For XRD analysis the poison concentration was increased to 5 wt-% to obtain better detectability. Therefore. The phosphorus content detected in vehicle-aged diesel catalysts varies depending on the literature source and the method used for the detection.

the final phosphorus content in the samples varied depending on the catalyst.1 ml/min) were set to correspond to a 6 wt-% target content of phosphorus in the sample.Mass flow controller Air 250ml/min Quartz reactor Temperature indicator Peristaltic pump Sample 1.01ml/min 700°C / 4 hours Fig. To ensure sufficient poisoning. In addition.5g Furnace Moisture collector Aqueous salt solution of (NH4)2HPO4 0. several techniques were used to obtain information about the characteristics of the catalysts. One aim of the studies for which this ageing procedure was developed was to compare the effects of phosphorus poisoning on samples containing different oxides. The poisoning-induced changes in the washcoat 40 .13 mol/l) and feeding rate of the solution (0. The air stream was controlled by a mass flow controller (Brooks 5850TR). an aqueous salt solution of (NH4)2HPO4 was fed into the quartz reactor with a peristaltic pump. After four hours of ageing the (NH4)2HPO4 feed was turned off and the sample was dried in the air stream at 500°C for one hour. Therefore. 4. Schematic illustration of the equipment used for gaseous phase poisoning studies. 6.3 Catalyst characterisation techniques In this study. It was demonstrated that less than 70% of the phosphorus adhered to the sample. Air (250 ml/min) was used as a carrier gas for the (NH4)2HPO4 feed. In order to simulate phosphorus poisoning in lean hydrothermal conditions. the ageing time (4 hours) as well as the (NH4)2HPO4 content (0. ageing was carried out with all the samples according to the same procedure without changing the ageing time or the amount of phosphorus in the feed.

Thermodynamic calculations were used to obtain information about ageing conditions and phosphorus compounds formed during ageing. for instance. The BJH theory was used to evaluate the total pore volume (ml/g) and average pore size (nm) of the samples. TEM. Laboratory-scale activity measurements were applied to study catalytic activity. they may also be interconnected with one another. 7. The poison content of the samples was determined by chemical analyses (ICP-OES) and XRF.3. (Webb & Orr 1997) Fig. for the calculations of the numerical values. SEM. certain approximations were made concerning pore shape. The internal surface areas were determined using the t-test method. 41 . Micromeritics ASAP 2020 apparatus used for physisorption measurements. and FTIR-ATR. However.1 Physisorption analyses To characterize the catalysts before and after ageing. Specific surface areas (m2/g) were calculated according to the BET theory. XRD. physisorption measurements were carried out with a Micromeritics ASAP 2020 unit (Figure 7) and a Coulter Omnisorp 360CX unit. It should be mentioned that. Furthermore. the pores may have different structures. 4. The calculations were carried out by using N2 adsorption isotherms at –196°C and assuming that the pores had a cylindrical shape.and the poison compounds formed were studied using physisorption analyses.

4. H2SO4. Samples containing cerium were digested by heating them in a solution of (NH4)2SO4 solid salt.3. The TEM studies were carried out at Tampere University of Technology. and HF and digested by using microwaves. After digestion.3.020° intervals in the range of 12° ≤ 2θ ≤ 75° with 1 s count accumulation per step. and HCl. The measurements were carried out with an analytical transmission electron microscope.2 Scanning Electron Microscopy SEM-EDS was used to detect contaminant levels in the poisoned catalysts. 4.4 Chemical analyses The phosphorus content of the samples was determined with ICP-OES. The other samples were mixed with a solution of HNO3. In order to avoid a systematic error in the results. The TEM samples were prepared from the powder samples by crushing the samples between glass slides. 40 kV.3. The X-ray diffraction diagrams were recorded from the catalyst powders on a plastic sample holder with a Siemens D5000 or Philips X’PERT diffractometer employing nickel-filtered Cu Kα radiation (λ = 1. 4. the ICP-OES backgrounds of the above-mentioned solutions were measured. JEM 2010 from Jeol.5 X-ray diffraction X-ray diffraction (XRD) was used to identify phosphorus compounds in the aged catalyst samples. 30 mA) at 0.3 Transmission Electron Microscopy Transmission electron microscopy (TEM) was used to characterize the composition and microstructure of the samples and to determine changes in the washcoat and Pt particle sizes after the ageing treatments. Possible spatial differences in poison accumulation were also studied. The crushed powder was then dispersed onto a perforated carbon-covered Cu grid with ethanol. The samples were cast in epoxy resin and polished and coated with carbon. Diffraction patterns were assigned using a PDF database 42 . HCl.3. operated at 200 kV and equipped with a Noran Vantage energydispersive spectrometer. the samples were diluted with water and analyzed with a GBC Integra XMP ICP-OES analyzer.5406 Å.4. The equipment used for the SEM studies was Jeol JSM-6400.

4. The test gas mixtures are shown in Table 6.6 Fourier Transform Infrared-Attenuated Total Reflection FTIR-ATR studies were carried out to identify phosphorus compounds and to detect possible ageing-induced changes in the catalyst structure.3. The XRF measurements were carried out with a Philips MagiX apparatus containing Super Q Analytical software.3. The gas mixture for Test series 1 (samples containing oxide and Rh) was used to simulate lean gasoline exhaust gas conditions. The measurements were carried out with a Perkin Elmer Spectrum One FTIR-ATR. Table 6. Composition of the test gas mixtures for the activity measurements.3. Gas component Test series 1 CO NO Test series 2 C3H6 NO O2 1000 ppm 1000 ppm 10 vol-% 800 ppm 1000 ppm Concentration 43 . 4.supplied by International Centre for Diffraction Data (PDF-2 Powder Diffraction File Database). 4. Catalytic activities were determined in lean reaction conditions by using model reactions.8 Activity measurements Activity measurements were carried out by using laboratory-scale light-off experiments to study poisoning-induced changes between fresh and aged catalyst powder samples. The gas mixture for Test series 2 (samples containing oxide and Pt and ZSM-5) simulated diesel exhaust gas conditions.7 X-ray Photoelectron Fluorescence X-ray photoelectron fluorescence was used to determine the phosphorus content of the poisoned catalyst samples. Both gas mixtures were balanced with N2.

Figure 8 illustrates the experimental setup.25 g for oxides and 0.10 g for zeolites. The pre-treatments and measurements were carried out at atmospheric pressure in a tubular furnace using a quartz reactor. The temperature of the catalyst was increased from room temperature up to 500°C. followed by 15 minutes at 550°C. The samples were placed in the reactor tube with a support of quartz wool. 8. Quartz reactor 5. Mass flow controllers 2. The concentrations of the feed and product gases were measured as a function of temperature every 5 seconds with a FTIR gas analyzer (GasmetTM CR2000). Tubular furnace 4. equipped with a GASMET Analyzer. FT-IR Gasmet™ Analyzer 1 3 2 4 5 6 Fig. The samples were mixed with quartz sand to prevent agglomeration of the catalyst. Temperature controller 6. The weight of a powder sample was 0. and the total gas flow during the experiments was 1 l/min. Gas flow was controlled by mass flow controllers (Brooks 5850TR). and therefore. with a linear heating rate of 10–15°C/min. TM Gas 44 . Thermocouple 3. 1. The samples in Test series 2 were oxidized in a 50 ml/min air flow for 20 minutes at 500°C. to prevent diffusional effects in the catalyst bed.Before the measurements the samples in Test series 1 were reduced in a 500 ml/min hydrogen flow for 10 minutes at 500°C. Experimental setup for activity measurements.

The software can be used as a tool for calculating chemical equilibriums between pure components in ideal solutions and.11 software includes a thermochemical database that contains enthalpy. either as a function of temperature or in isothermal conditions.11 software. Phase stability diagrams present the stability areas of condensed phases in ternary systems. Equilibrium compositions are calculated with a solver that uses the Gibbs energy minimization method.9 Thermodynamic calculations Thermodynamic equilibrium calculations were carried out using commercial HSC Chemistry® 5. 45 . Thermodynamic modelling does not provide any information on reaction kinetics. but physically possible phenomena can be estimated by using thermochemical calculations. The HSC Chemistry® 5.3.4. entropy and heat capacity values. These diagrams are useful for a quick estimation of the prevailing phases. in some cases. in non-ideal solutions.

46 .

hydrothermally aged (H2O). and changes in the active metal particles and washcoat grain size. Figures 9 and 10 present the specific surface areas of the catalysts in Test series 2 (samples containing oxide and Pt and ZSM-5). The BET surface areas of all the phosphoruspoisoned catalyst powders were significantly diminished compared with the fresh samples.1 Loss in catalytic surface area As a result of poisoning and ageing. 5. Specific surface areas of fresh. The sections are: loss in catalytic surface area. alterations in the specific surface areas of the catalyst samples were detected. and phosphoruspoisoned (P+H2O) catalyst samples with Pt. Surface area (m2/g) 400 Fresh H2O P+H2O 288 346 323 263 300 203 200 156 100 101 67 25 15 0 Pt/Al2O3 Pt/TiO2 188 93 61 6 2 Pt/CeO2 Pt/ZrO2 Pt/Zr-CeO2 Pt/Ce-ZrO2 Pt/ZSM-5 62 38 58 4128 Fig. 9. loss of catalytic activity. 47 .5 Poisoning-induced changes in the catalyst components The research results and the changes caused by poisoning and hydrothermal ageing detected in the catalyst components are classified in this chapter into four sections. accumulation of phosphorus.

The poisoning-induced changes in the 48 .e. (Paper IV) In the case of zeolites. i. The respective values for Rh/Zr-CeO2 were 41 m2/g and 55 m2/g (Papers II and IV). CeO2. for the samples in Test Series 1 (samples containing oxide and Rh). the specific surface area of the poisoned Pt/Zr-CeO2 was one fifth of the surface area of the fresh sample. the BET results showed that the fresh ZSM-5 and Pt/ZSM-5 samples had rather high specific surface areas (Figures 9 and 10). 10. Pt/CeO2. Zr-CeO2.Surface area (m2/g) 400 Fresh H2O P+H2O 401 330 294 260 217 200 166 145 79 68 2421 0 Al2O3 TiO2 CeO2 46 6 ZrO2 Zr-CeO2 Ce-ZrO2 ZSM-5 60 42 61 40 33 201 300 100 Fig. The higher specific surface area of the fresh ZSM-5 may explain the larger phosphorus content (Figure 15 and 16) measured in this sample compared with the sample containing platinum. Furthermore. For instance. the surface area of the phosphorus-poisoned Pt/ZrO2 sample as well as the hydrothermally aged and phosphorus-poisoned ZrO2 samples could not be determined. and Pt/Zr-CeO2 (Figures 9 and 10). hydrothermally aged (H2O). The specific surface areas of Pt/ZrO2 and ZrO2 (Figures 9 and 10) were also strongly affected by ageing. (Paper V) The effects of ageing were detected as changes in the average pore sizes and total pore volumes of the samples. Specific surface areas of fresh. and Rh/Zr-CeO2 (not shown). the surface area of the phosphorus-treated Rh/Zr-CeO2 was less than one tenth (12 m2/g) of the surface area of the fresh sample (191 m2/g). The effect of the ageing treatments was most significant for the surface areas of the ceria-based samples. As a result. and phosphoruspoisoned (P+H2O) catalyst samples without Pt.

49 0.01 Pt/ZrO2 Pt/Zr-CeO2 Pt/Ce-ZrO2 Pt/ZSM-5 0.12 0.17 0.0 Al2O3 TiO2 CeO2 ZrO2 Zr-CeO2 Ce-ZrO2 ZSM-5 0.13 0.6 0.5 0.25 0.10 0.17 0.49 0. Total pore volumes of fresh.13 Fig.01 0.4 0.08 0. hydrothermally aged (H2O).19 0.4 0.25 0.5 0.19 0.41 0.50 0.22 0.10 0.2 0. Figures 11–12 illustrate the total pore volumes and Figures 13–14 the average pore sizes of the catalysts in Test series 2 (samples containing oxide and Pt and ZSM-5).2 0.14 0. 11. and phosphoruspoisoned (P+H2O) catalyst samples with Pt. 49 .6 0.49 0.13 Fig.01 0.observed specific surface areas of the samples could be explained by decreases in the pore volumes and increases in the pore sizes detected in these samples.21 Fresh H2O P+H2O 0. 12. Total pore volumes of fresh.19 0.0 Pt/Al2O3 Pt/TiO2 Pt/CeO2 0.27 0. Total pore volume (ml/g) 0.19 Fresh H2O P+H2O 0.33 0.1 0. hydrothermally aged (H2O).19 0.17 0.25 0. and phosphoruspoisoned (P+H2O) catalyst samples without Pt.3 0.29 0.11 0.13 0. Total pore volume (ml/g) 0.18 0.25 0.14 0.3 0.1 0.19 0.20 0.

Average pore sizes of fresh. The average pore size of the hydrothermally aged Ce-ZrO2 was higher than the value of the poisoned sample (Figure 14). and only a few exceptions to this were observed. The 50 . hydrothermally aged (H2O). and phosphoruspoisoned (P+H2O) catalyst samples without Pt.Average pore size (nm) 30 Fresh H2 O P+H2O 20 16 13 10 10 14 20 21 19 20 14 9 7 8 3 8 4 3 3 3 11 13 0 Pt/Al2O3 Pt/TiO2 Pt/CeO2 Pt/ZrO2 Pt/Zr-CeO2 Pt/Ce-ZrO2 Pt/ZSM-5 Fig. and phosphoruspoisoned (P+H2O) catalyst samples with Pt. 14. hydrothermally aged (H2O). Average pore size (nm) 30 Fresh H2O P+H2O 19 19 20 15 12 12 10 9 10 11 7 3 1 0 Al2O3 TiO2 CeO2 ZrO2 Zr-CeO2 11 13 15 20 18 3 3 3 Ce-ZrO2 ZSM-5 Fig. It can be seen from Figures 11–14 that the effect of phosphorus was more significant than the effect of hydrothermal treatment alone. 13. Average pore sizes of fresh.

1 Phosphorus content The XRF analyses showed that phosphorus was adsorbed almost quantitatively on the powdery samples during the incipient wetness impregnation method. as can be seen in Figures 11 and 12. (Paper V) 5. After phosphorus poisoning.2. which was in agreement with the specific surface area determined for the Ce-ZrO2 samples. a decrease in the pore volumes of these samples was detected. The effect of phosphorus was clearly observed in the pore volumes of the Al2O3 and Pt/Al2O3 samples. (Paper IV) For ZSM-5 and Pt/ZSM-5 the total pore volumes of the fresh samples were not affected by hydrothermal ageing. thermodynamic calculations were used to support these methods. which did not decrease as a result of hydrothermal ageing.smallest pore volume was. In the case of Al2O3 and TiO2. The semi-quantitative amount of phosphorus measured by XRF for Test Series 1 (the Rh-loaded powder samples) was 1 wt-%. which was congruent with the results from the BET analyses and activity measurements. Any further explanation of the changes in the specific surface areas or activity could not be found in the pore size distributions. (Paper I) The amount of phosphorus adsorbed in the powdered catalyst samples during gas phase ageing varied depending on the catalyst composition. however. SEM-EDS and elemental analyses were used to detect phosphorus accumulation in the aged catalyst powders. The difference between the amounts of phosphorus detected in the samples can be explained by the dissimilar 51 . giving the same average pore width for all six samples (3 nm) (Figures 13 and 14). 5. In addition. which was the target phosphorus content in this procedure. calculated for the poisoned sample. phosphorus poisoning caused a decrease in the pore volumes of both samples. the average pore sizes of the hydrothermally aged and poisoned samples were equal. Phosphorus compounds formed in the samples were identified with XRD and FTIR-ATR. Figures 15 and 16 present the phosphorus contents of the samples treated with the gaseous phase poisoning method.2 Accumulation of phosphorus XRF. determined by ICP-OES. This phenomenon was not observed in the specific surfaces or average pore sizes of the Al2O3-based samples. In contrast.

0 3.tendencies of different materials to accumulate impurities.8 3. The very low specific surface areas of the fresh ZrO2 and Pt/ZrO2 are probably the reason for the small phosphorus content measured in these samples. Phosphorus contents of the samples with Pt. 15.9 4. However. 52 .0 Pt/Al2O3 Pt/TiO2 Pt/CeO2 Pt/ZrO2 Pt/Zr-CeO2 Pt/Ce-ZrO2 Pt/ZSM-5 Fig.1 2.0 2.0 0.6 1.0 2.4 0.0 4. (Paper IV) Phosphorus content (wt-%) 5. treated with the gaseous phase poisoning method.3 2. Further studies are needed to explore the possible attributes that give a correlation between certain characteristics and the catalyst’s tendency to adsorb poisoning compounds.4 3. no correlation between the characteristics of the fresh samples and the phosphorus content detected in the samples after ageing was observed in this study.

However. Furthermore. According to the XRF analyses. As can be seen in Figure 17. penetration of phosphorus and calcium into the upper areas of the washcoat was observed.000 km in a petrol-driven vehicle). Therefore.4 2.3 1.0 4. mainly Ca3(PO4)2.5 wt-% of phosphorus. The first 2 cm from the inlet of the catalyst comprised the most severely poisoned zone. the reference catalyst was poisoned by phosphorus. sulphur was not detected. In contrast.0 1.Phosphorus content (wt-%) 5. The elemental analyses (XRF) showed that the catalyst contained 3. the final phosphorus content of the sample is equal to the amount of phosphorus impregnated into the sample.0 2. the gas phase ageing procedure can be used as a tool for studying possible distinctions in the behaviour of different catalyst components in chemical ageing conditions.0 0. (Paper II) Poisoning can be considered a relevant deactivation mechanism for the TWC reference catalysts (Rh/Pd/Al2O3/La2O3/OSC catalyst aged for 100.0 Al2O3 TiO2 CeO2 ZrO2 Zr-CeO2 Ce-ZrO2 ZSM-5 3.0 2. the contaminated layer contained phosphates. the poisons were accumulated on the top overlayer of the vehicle-aged catalyst. including a back-scattered electron image and selected elemental distribution maps (X-ray maps) obtained by EDS.5 3.9 2.0 3. 16. in the impregnation ageing procedure.4 Fig. calcium and zinc. (Paper II) 53 . According to the chemical analyses. treated with the gaseous phase poisoning method.2 0. Figure 17 presents the elemental analysis data from the inlet region of the TWC. Phosphorus contents of the samples without Pt.

EDS elemental maps of B) Al. and contaminant overlayer. Due to the overlapping peaks of phosphorus and zirconium. zirconium was detected throughout the catalyst. No contaminated overlayer was observed in the SEM-EDS studies (Figure 18). Unlike phosphorus. XRF analyses showed that the phosphorus content of the diesel reference catalyst (Pt/Al2O3/La2O3/OSC aged for 80. Elemental analyses (X-ray maps) taken at the inlet of the vehicle-aged TWC catalyst. (Paper II) 54 . washcoat.000 km in a diesel-driven vehicle) was 0. C) P. sulphur had penetrated evenly throughout the entire depth of the washcoat.4 wt-%. phosphorus had accumulated in the top overlayer of the catalyst. The catalyst was mainly poisoned by sulphur. Instead. A) backscattered electron image showing the metal foil. 17. Small concentrations of calcium and zinc were also detected. quantitative EDS analyses were used to indicate that phosphorus was located only on the upper layers of the catalyst.A) B) C) D) Fig. In contrast. and D) Ca (Paper II).

C) P. poisoning contributes to approximately 20% of the total deactivation. 18. A) backscattered electron image showing the metal foil and contaminated washcoat. Elemental analyses (X-ray maps) taken at the inlet of the vehicle-aged diesel catalyst.2 Phosphorus compounds XRD studies Phosphorus compounds formed with OSC components could be detected with XRD after both chemical ageing procedures. EDS elemental maps of B) Al. and D) S (Paper II). 5. with phosphorus being the major contaminant. CePO4 was present in Rh/Zr-CeO2.2. based on the activity measurements carried out with the vehicle-aged TWC reference (Lassi 2003). 55 . However.A) B) C) D) Fig. It should be pointed out that the deactivation of the reference catalysts is the result of a combination of several ageing phenomena and not phosphorus poisoning alone.

zirconium phosphates were not detected in the samples containing pure zirconium oxide (ZrO2 and Pt/ZrO2). c = ZrO2 (monoclinic). Pt/Zr-CeO2) as CePO4 (monazite-Ce). its presence could not be confirmed (Paper I). (Paper III) The presence of aluminium phosphate (AlPO4) was expected in Rh/γAl2O3/OSC. (ii) P-poisoned Rh/ZrCeO2. phosphorus had adhered to the ceria-based samples (CeO2. and (iii) P+Ca-poisoned Rh/Zr-CeO2.000 km in a petrol-driven vehicle) (Figure 19). Formation of CeAlO3 was also observed in the TWC reference due to the reactions of Al2O3 with the pure CeO2 in the catalyst's washcoat. 19. In the case of Pt/Al2O3. and Rh = rhodium (Paper I).Rh/Ce-ZrO2 and the TWC reference samples (Rh/Pd/Al2O3/La2O3/OSC catalyst aged for 100.u. CePO4 was also found in Ce-ZrO2 but not in Pt/Ce-ZrO2. (Paper III) d 300 d d d (iii d Intensity (a. Pt/CeO2.Scale Fig. a = Ce(PO4). XRD diffractograms of (i) P-poisoned Rh/Al2O3/OSC. Zr-CeO2. d = Ce-rich CeXZr1-XO2 mixed oxide. This may be due to the fact that the phosphorus content of these two samples was low and therefore could not be detected by XRD. 56 . The Zr-rich mixed oxides (Ce-ZrO2 and Pt/Ce-ZrO2) contained zirconium phosphate (Zr(P2O7)). (Paper I) According to the XRD studies.) a 200 a a a a a c (ii b 100 c b&c b&c c a c b&c Rh a b&c (i 0 13 20 30 40 50 60 7 2-Theta . However. b = Zr-rich CeXZr1-XO2 mixed oxide. but due to the small peak intensities and the overlapping peaks of CePO4.

XRD diffractograms of (i) fresh Pt/Al2O3. By contrast. b = AlPO4. a = Al2O3. (iii) fresh Pt/CeO2. it could not be verified due to the small intensities and overlapping peaks of CePO4.u. and Pt = platinum. 20. c = CeO2.Scale Fig. The presence of calcium phosphate Ca3(PO4)2 in the Test series 1 samples (the Rh-loaded powders) treated with both phosphorus and calcium (Ca+P or P+Ca) was also considered.000 km) as phosphorous oxide (P4O6) and elemental phosphorus. (Paper I) The diffraction peaks of the ZSM-5 structure and Pt were identified according to JCPDS File Cards nos. However. no AlPO4 or any other phosphorus-containing compounds could be observed in the Al2O3 sample. Phosphorus was detected in both TiO2 and Pt/TiO2 as titanium pyrophosphate (TiP2O7). and (iv) P-poisoned Pt/CeO2. No indication of phosphorus or phosphate formation was found in the patterns of the poisoned samples. One explanation for this could be that the reference 57 . as illustrated in Figure 20. (Paper V) Phosphorus was detected in the diesel reference catalyst (360. (Paper III) c 600 c 500 d d d c d c c iv) Intensity (a. no presence of phosphates was observed. d = CePO4. respectively. However. (ii) P-poisoned Pt/Al2O3.) 400 iii) 300 Pt a a Pt a 200 b b a ii) 100 i) 0 10 20 30 40 50 60 70 2-Theta .phosphorus appeared as aluminium phosphate AlPO4. 44–0003 and 04–0802.

which may have covered phosphorus on the surface of the catalysts. since phosphate bands were identified at 1066 cm-1.2 wt-%). Pt/Zr-CeO2). Phosphates that could not be detected with XRD were detected with IR in the ZrO2 and Pt/ZrO2 samples. (Paper III) 58 . a difference between the spectra of fresh and poisoned samples was clearly observed. In the same way with XRD. Pt/CeO2. although phosphorus compounds could not be detected with XRD in the latter sample. The presence of AlPO4 was detected in both the Pt/Al2O3 (Figure 21) and Al2O3 samples. Phosphate bands can be detected at 1100−1000 cm-1 in the IR spectra. phosphates were observed in the ceria-based samples (CeO2. Zr-CeO2.sample contained a substantial amount of sulphur (3. It is also possible that the catalyst used in this study did not reach temperatures high enough to convert phosphorus oxide to phosphates with the washcoat components. In the case of TiO2 and Pt/TiO2 (Figure 21). (Paper III) FTIR-ATR studies FTIR-ATR studies were carried out in addition to XRD to produce supplementary information about the poison compounds.

c) fresh Pt/TiO2. FTIR-ATR spectra of a) fresh Pt/Al2O3. 21. this does not completely exclude the possibility of the presence of phosphates in the poisoned ZSM-5 and Pt/ZSM-5 samples. The presence of phosphorus compounds was expected on the basis of the elemental analyses and XRD studies. in which phosphorus was detected as phosphates after the same poisoning procedure.u. (Paper III) Thermodynamic studies Thermodynamic equilibrium calculations were used to explore the reactions between phosphorus compounds and catalyst components and to find new 59 Absorbance (a. This is an interesting result that may differentiate the phosphorus poisoning mechanism of these zeolites from other catalyst components.120 a) b) 1394 110 100 90 1066 c) d) e) 80 1078 70 60 3600 3100 2600 cm -1 2100 1600 1100 600 Fig. No phosphorus or any ageing-induced structural changes could be detected in the ZSM-5 and Pt/ZSM-5 samples with FTIR-ATR. but could not be confirmed due to the overlapping bands of the metal oxides and sulphates. d) P-poisoned Pt/TiO2 and e) vehicle-aged reference catalyst (Paper III). such as Zr-CeO2 mixed oxides.000 km). phosphorus could not be detected with certainty with IR.) 3666 2988 . (Paper V) In the case of the diesel reference catalyst (360. b) P-poisoned Pt/Al2O3. Still. The latter phases show an IR adsorption band at around 1078 cm-1.

information about the stability of the phosphorus compounds. were carried out with commercial HSC Chemistry® 5. Cerium and aluminium oxides were also studied with phase stability diagrams. The calculations with CeO2 and Al2O3 in the presence of a (NH4)2HPO4-H2O-air mixture. 2007) Equilibrium compositions and phase stability diagrams were calculated as a function of temperature and partial pressures of phosphorus and oxygen.405 ml (NH4)2HPO4 (in the liquid phase). 13. which are 0. 46. The following mixture was used to simulate the feed gas: 0. (Kröger et al. which all were considered bulk materials. the relative amount of CePO4 formed at the chosen ageing temperature (700°C) is higher than the amount of AlPO4 at the same temperature.11 software. 23. At temperatures above 100°C.595 ml H2O (in the liquid phase). According to the calculations. respectively.2 l O2. the gas phase is composed almost exclusively of gaseous water and air (N2 and O2) and only very small mole fractions of NH3 and H2 are present. formation of AlPO4 and CePO4 starts at approximately 70°C and the levels of these compounds are balanced at temperatures above 300°C. O2 and N2 are presented in Figs.23. The oxidizing conditions were chosen to simulate the conditions of the feed gas mixture in the laboratory-scale chemical ageing procedure developed in this work (Paper II). (Kröger et al.8 l N2. changing the partial pressures of oxygen and phosphorus at different temperatures. respectively. The solid input included 1. In the thermodynamic calculations the input corresponded to the total amount of solid oxide. The influence of reaction conditions on the poisoning phenomena was also studied. 2007) 60 . The results from the thermodynamic equilibrium calculations were given as figures that present the mole fractions of the compounds as a function of temperature within a range of 0°C to 1000°C. This can be seen by comparing the molar proportions of CePO4 with CeO2 and AlPO4 with Al2O3. aqueous salt solution of (NH4)2HPO4 and air fed into the system during the four hours of ageing. (Kröger et al.5 g cerium oxide or aluminium oxide. As can be seen in the figures. 22 and 23. H2O.54 and 0. 2007) Mole fractions of phosphorus-containing compounds as a function of temperature in the presence of Al2O3 or CeO2 and the feed gas mixture containing (NH4)2HPO4.

Fig. O2 and N2 (Kröger et al. H2O. 2007). 2007). It can also be seen that with the same partial pressure of phosphorus. 23. H2O. O2 and N2 (Kröger et al. Mole fractions of phosphorus-containing compounds as a function of temperature in the presence of CeO2 and the feed gas mixture containing (NH4)2HPO4. formation of 61 . Fig. Phase stability diagrams of the Al-O-P and Ce-O-P systems at 700°C as a function of partial pressures of phosphorus and oxygen are presented in Figures 24 and 25. Mole fractions of phosphorus-containing compounds as a function of temperature in the presence of Al2O3 and the feed gas mixture containing (NH4)2HPO4. The figures show that both AlPO4 and CePO4 are formed in oxidizing conditions. 22.

Phase stability diagrams of the Al-O-P system at 700°C as a function of phosphorus and oxygen partial pressure (Kröger et al. (Kröger et al. 2007). 2007). 24. 2007) Fig.CePO4 starts already at a lower partial pressure of oxygen than does formation of AlPO4. 25. Fig. Phase stability diagrams of the Ce-O-P system at 700°C as a function of phosphorus and oxygen partial pressure (Kröger et al. 62 .

According to the calculations. Figures 26 and 27 illustrate that the C3H6 light-off temperatures of all the phosphorus-treated samples were significantly higher than those of the fresh catalysts in Test series 2 (samples containing oxide and Pt and ZSM-5). which was chosen to be the temperature used in the ageing procedure developed and evaluated in this work.3. formation of phosphates with the washcoat components is thermodynamically favourable in the oxidizing conditions and with the oxide samples and phosphorus source used in this study.1 Effect of phosphorus In activity measurements. Phosphorus poisoning has a significant deactivating effect on the activities of most of the samples. Some of the aged samples were strongly deactivated and their exact light-off temperatures could not be determined due to the vicinity of the autoignition temperature of the feed gas. it was observed that already a low phosphorus content had a considerable deactivating impact on the activity of the catalysts even though the poison was evenly distributed in the catalyst powders and not only on the surface. In addition. 2007) 5. (Kröger et al. the light-off temperatures (T50) of the fresh and aged catalyst components were compared with each other. T50 is defined as the temperature of 50% conversion of the feed component. In addition. (Papers III and V) 63 .3 Loss of catalytic activity 5. it was shown that aluminium and cerium phosphates can be formed at the peak temperature of diesel exhaust gas catalytic converters.

hydrothermally aged. C3H6 light-off temperatures of the fresh. and poisoned samples without Pt. hydrothermally aged. T50 (°C) 500 Fresh H2O P+H2O 383 350 362 364 388 369 346 370 367 400 300 228 200 100 0 Al2O3 TiO2 CeO2 ZrO2 Zr-CeO2 Ce-ZrO2 ZSM-5 Fig. 26. C3H6 light-off temperatures of the fresh. 64 . and poisoned samples with Pt. 27.T50 (°C) 500 Fresh H2O P+H2O 269 243 228 227 240 179 185 292 400 309 261 214 290 300 297 259 304 262 247 199 302 231 325 200 100 0 Pt/Al2O3 Pt/TiO2 Pt/CeO2 Pt/ZrO2 Pt/Zr-CeO2 Pt/Ce-ZrO2 Pt/ZSM-5 Fig.

(Paper II) The activities in the propene oxidation reaction (Test series 2. 26) samples. it can be seen that the increase in the light-off temperatures for the cerium-rich Rh/Zr-CeO2 and Pt/Zr-CeO2 (see Fig. were higher. Most of the samples without Pt were strongly deactivated. but in both cases they were less than the autoignition temperature of 65 . and the exact propene light-off temperatures of these samples could not be determined due to the vicinity of the autoignition temperature of propene (460°C). 26) samples after phosphorus poisoning was smaller compared with the results with the zirconium-rich Rh/Ce-ZrO2 and Pt/Ce-ZrO2 (see Fig. light-off temperature of CO for Rh/Zr-CeO2 was 186°C when fresh and 232°C when poisoned and for Rh/Ce-ZrO2 173°C and 229°C. Pt/ZrO2 and Pt/Ce-ZrO2. including those containing Pt. had low propene light-off temperatures. ZrO2. could not be determined) had increased by over 170°C compared with the fresh sample. When comparing the results from Test series 1 and 2. where the propene light-off temperature (>400°C. After phosphorus treatment the parent samples were strongly deactivated and the light-off temperatures of all the samples without the precious metal were above 400°C. In addition. respectively. The most substantial effect was detected in the case of Al2O3. it can be concluded that the cerium-rich mixed oxides studied in this work can better sustain the deactivating impact of phosphorus than can the zirconium-rich mixed oxides in terms of catalytic activity. Figures 26 and 27) were significantly higher in the case of samples containing platinum than were the activities of the same catalyst components without the precious metal. The CO light-off temperatures of the Rh/Ce-ZrO2 and Rh/Zr-CeO2 samples were approximately the same after phosphorus impregnation. the platinum-containing samples were also substantially deactivated as a result of hydrothermal ageing. Therefore. The propene light-off temperatures of the samples without Pt were expectedly high even with the fresh samples.In the case of Test series 1 (samples containing oxide and Rh). CeO2. The light-off temperatures of the ceria-based samples. (Paper III) The Al2O3-based sample showed the highest activity of all the samples. the only exception being Al2O3. their light-off temperatures increased after hydrothermal ageing and poisoning. but the relative decrease in the activities of the phosphorus-treated Rh/Zr-CeO2 and Pt/Zr-CeO2 was almost equal. The light-off temperatures of the fresh TiO2. Similar to the samples without a precious metal. Pt/TiO2 as well as the zirconia-based samples. Figure 28 shows an example of C3H6 conversion curves for the Pt/ZrO2 samples. Pt/CeO2 and Pt/Zr-CeO2. Notably. Hydrothermal ageing considerably decreased the activities of the samples. and Ce-ZrO2 samples were all between 350 and 370°C. Zr-CeO2.

the propene conversion curve of fresh ZSM-5 was not as steep. 28. and a steep rise in the propene conversion curve could be observed. T50 = 262°C Fig. T50 = 290°C 20 0 0 100 200 T (°C) 300 400 500 C3H6 conversion (%) Fresh. the increase in the light-off temperature was highest for Pt/ZrO2 and lowest for Pt/CeO2 compared with the fresh samples. In the hydrothermally aged case. In contrast. C3H6 conversion as a function of temperature and light-off temperatures (T50) of the fresh. At temperatures higher than that. T50 = 214°C H2O. and phosphorus-poisoned Pt/ZrO2 samples (Paper III). the most substantial effect of phosphorus poisoning also occurred in the Pt/ZrO2 sample. the activities in propene oxidation were higher in the Pt/ZSM-5 samples than were the activities of the samples without the precious metal. (Paper V) 66 . hydrothermally aged. The presence of a precious metal did not affect the amount of HC adsorbed. but unlike in the comparison with fresh samples. (Paper III) 100 80 60 40 P+H2O. resulting in a considerably higher light-off temperature compared with the sample containing Pt. the smallest increase in the light-off temperature occurred with the Pt/Zr-CeO2 sample. Propene desorbed in the temperature range of 80–190°C. After phosphorus ageing. The fresh zeolite samples showed the ability to adsorb propene at low temperatures.propene (460°C). platinum started to affect propene conversion. With zeolites. as shown in Figure 29. As a result. The propene light-off temperature of fresh Pt/ZSM-5 was significantly lower than that of fresh ZSM-5 (Figure 26 and 27). the light-off temperature of the fresh Pt/ZSM-5 sample was relatively low.

was almost completely lost. C3H6 conversion as a function of temperature and light-off temperatures (T50) of the fresh. the maximum conversions of NO and NOx decreased and the temperatures of the maximum conversions increased compared with the fresh samples. T50 = 302°C Fig. resulting in very low NO and NOx conversions. After hydrothermal ageing and phosphorus poisoning. and phosphorus-poisoned Pt/ZSM-5 samples (Paper V).100 80 C 3H 6 conversion (%) 60 40 P+H2O. The reasons behind the low NO and NOx conversions were the lean gas mixture and the relatively high gas flow in the activity tests. T50 = 231°C H2O. (Paper V) 67 . After both hydrothermal and phosphorus ageing the adsorption behaviour of the Pt/ZSM-5 and ZSM-5 samples for propene. 29. hydrothermally aged. The ageing treatments also affected the hydrocarbon adsorption capacity of the zeolites. (Paper V) NO and NOx (combined NO and NO2) conversions remained low with the test gas mixture and diesel catalyst samples used in this work. Hydrothermal ageing increased the light-off temperature of Pt/ZSM-5 and the effect of phosphorus ageing was even more substantial. The ageing treatments had a deactivating effect on the catalytic activity of the zeolite samples. T50 = 325°C 20 0 0 -20 100 200 300 T (°C) 400 500 Fresh. The hydrothermally aged and phosphorus-poisoned samples were deactivated. observed with the fresh samples. After hydrothermal and phosphorus ageing. the ZSM-5 samples were heavily deactivated and the exact propene light-off temperatures of these samples could not be determined due to the vicinity of the autoignition temperature of propene (460°C).

are presented in Figure 30. measured in lean reaction conditions.In summary. CO light-off temperatures of the fresh. The CO light-off temperatures (T50) of the fresh. and Ca+P-treated Rh/ZrCeO2 and Rh/Al2O3/OSC samples. no deactivation was observed. whereas in the case of powder Rh/Al2O3/OSC. P+Ca. P.2 Effect of phosphorus and calcium The role of calcium as a catalyst poison has been of a lesser interest in the literature compared with. 5.3. (Paper I) T50 (°C) 300 232 216 200 186 196 196 179 163 158 157 186 100 Fresh P P+Ca Ca Ca+P 0 Rh/Zr-CeO2 Rh/λ-Al2O3/OSC Fig. Ueda et al. (1994) have 68 . and Ca+P-treated Rh/ZrCeO2 and Rh/γ-Al2O3/OSC samples. In all the samples the deactivating effect of calcium was clearly smaller than that caused by P poisoning. 30. Calcium treatment after phosphorus poisoning (P+Ca poisoning) had a regenerating effect on the light-off temperatures (Paper I). Deactivation appears to be associated with phosphorus compounds formed with the washcoat components. Ca. However. P. calcium has a deactivating effect on some Rh-containing catalyst powders. the phosphorus treatment deactivated the catalyst samples more than the hydrothermal treatment alone. phosphorus and sulphur. P+Ca. Calcium poisoning carried out with the impregnation method deactivated Rh/Ce-ZrO2 and Rh/Zr-CeO2 to a small extent. Ca. for instance. as described next.

calcium can decrease the catalytic activity of components used in automotive catalysts. The platinum particles had grown in both treatments. Therefore. Platinum particles appear in black in the images. Once again. 5. (Paper VI) Figure 31 presents TEM images of the fresh. Clustering of large Pt crystallites was observed in the phosphoruspoisoned Pt/ZSM-5. (Paper I) As demonstrated in this study. Poisoning treatments carried out in a reversed order (Ca+P poisoning) showed that phosphorus treatment also had a regenerating effect on Ca-poisoned Rh/Ce-ZrO2 and Rh/Zr-CeO2. The grain size of the Pt/Al2O3 washcoat had not increased and no transition from the γ-phase to the αphase had occurred.also reported congruent results according to which the addition of calcium was observed to reduce the poisoning effect of phosphorus by forming calcium phosphates that prevent accumulation of phosphorus on the surfaces of the catalysts. Detection of platinum was very difficult. this was not the case with Rh/Al2O3/OSC. However. and no clear indications of Pt particle growth were observed in the treated catalysts. and further studies of poisoning mechanisms are needed. thus only a few large Pt particles were observed in the treated catalysts. hydrothermally aged. The Pt particles have grown larger in the poisoned Pt/ZSM-5 69 . According to the analysis. Detection of platinum was very difficult also in these two samples. The grain size of both the Pt/CeO2 and Pt/Zr-CeO2 washcoats had increased from under 10 nm to 10–20 nm. and only occasionally were large Pt particles observed in the aged catalysts.4 Changes in the active metal particles and washcoat grain size The TEM analysis indicated considerable structural changes in the catalyst washcoat and Pt particles after both ageing treatments. the role of calcium in catalyst deactivation should be considered more profoundly. It is possible that the more complex composition and the presence of Al2O3 in Rh/Al2O3/OSC affect the reaction between calcium and phosphorus. the washcoat of the zirconia-based Pt/ZrO2 and Pt/Ce-ZrO2 samples had gone through only minor changes due to the treatments. platinum particles were very hard to detect. The grain size of the Pt/TiO2 washcoat had grown from about 10–15 nm to 30–40 nm after the treatments. and phosphorus-poisoned Pt/ZSM-5 catalysts. Some large particles (>100 nm) were also detected. and phosphorus treatment of calcium-poisoned Rh/Al2O3/OSC reduced catalytic activity.

31. (Paper V) Fig.than in the hydrothermally aged Pt/ZSM-5. The accumulation of phosphorus. The number of small Pt particles (diameter of 0–25 nm) is higher in the fresh Pt/ZSM5 than in the treated samples. Both atomic migration and crystallite migration are possible mechanisms of Pt cluster formation. However. the increase in the washcoat grain size and the growth of Pt crystallites cause a loss of active surface area needed for catalytic reactions to take place. (Paper VI) 70 . The changes in the characteristics observed in the physisorption studies are consistent with the microstructural changes detected by TEM in the Pt-containing samples after ageing. The hydrothermal ageing and phosphorus poisoning treatments did not cause any clear changes in the microstructures of the ZSM-5 and Pt/ZSM-5 zeolite washcoats. TEM images of the Pt/ZSM-5 catalyst when (a) fresh. the platinum particle size distribution measurements of the Pt/ZSM-5 zeolite showed an increase in Pt particle size after both hydrothermal ageing and poisoning. Clusters of large Pt crystallites were observed in the phosphorus-poisoned Pt/ZSM-5. and (c) phosphorus-poisoned (Paper V). The growth of the Pt particles in the hydrothermally aged Pt/ZSM-5 occurred at the expense of small Pt particles. Phosphorus ageing affected the characteristics of the samples more than did hydrothermal ageing alone. (b) hydrothermally aged.

An increase in Pt particle size and washcoat grain size was also detected after phosphorus poisoning. the effect of pure phosphorus poisoning could be differentiated from the effect of hydrothermal ageing conditions by comparing the results from the activity tests carried out with the samples poisoned in hydrothermal conditions and with the hydrothermally aged samples. Phosphorus poisoning also had a deactivating effect on the activity of catalyst components in Test series 2 (Pt and oxides and ZSM-5). Pore plugging was also observed by Joy et al. In this study. Phosphorus added to the ageing treatments decreased the characteristic surface areas of all the powder catalyst samples and reduced their catalytic activity.6 6. It was shown that the role of phosphorus poisoning is relevant in the deactivation of automotive catalyst components. (1985). adding calcium to a phosphorus-poisoned catalyst was found to have even a regenerating effect on its activity. 2003. 71 . Uy et al. Furthermore.1 Evaluation of the poisoning procedures Integration of the results This work was carried out in order to study the mechanisms of phosphorus poisoning on different automotive catalyst components. Hietikko et al. 2004. Furthermore. the samples’ ability to adsorb propene was lost after the phosphorus treatment. The changes were associated with formation of compounds between phosphorus and the catalyst components or plugging of pores on the catalytic surfaces. two procedures for studying chemical ageing on the laboratory scale were developed. The aim was to obtain information about the poisoning conditions that catalyst components should be able to withstand during motor operation. phosphorus had a deactivating impact on the activity of the catalyst powders. In addition. Rokosz et al. the results from the surface characterizations of the powder samples contaminated by phosphorus compounds formed during the ageing procedures are congruent with the results observed with the reference catalysts used in this work as well as with the results from earlier studies (Lassi 2003. who suggested that it accounts for some of the deactivation. the order in which calcium and phosphorus were added significantly affected the properties of the catalyst powders. 2001. Cabello Galisteo et al. In the case of zeolites. 2004. Xu et al. In the case of Test series 1 (Rh-loaded powder samples). In contrast. 2004) carried out with aged catalysts. The deactivating effect of calcium was not as pronounced as that of phosphorus.

The method also produced new information about changes in washcoat and Pt particle sizes. Physisorption analyses were carried out to characterize the poisoning and ageing-induced changes in the specific surface area (BET theory) of the samples. but to a lesser extent than did phosphorus ageing.According to the results. Laboratory scale light-off experiments were conducted to study the poisoning-induced changes between the fresh and aged catalyst powder samples. XRD was used to identify phosphorus compounds in the aged catalyst samples. A significant decrease in catalytic activity was detected when comparing the activities of the fresh and poisoned samples. hydrothermal ageing conditions alone deactivated the samples. Phosphorus was observed to accumulate in the top overlayer of the catalysts. the TEM studies did not provide any information about accumulation of phosphorus in the samples. We evaluated the changes in total pore volume and average pore size by using the BJH theory. An increase in washcoat grain size and growth of Pt crystallites were detected. TEM studies were used to characterize the composition and microstructure of the samples. 6. it was shown that there were spatial differences in the accumulation of poisons in the reference catalysts. The method was applicable for studying poison compounds in both powdery and metallic catalyst samples. In addition. The calculations showed that formation of phosphates is thermodynamically possible at both the temperatures 72 . The information about poison compounds obtained with XRD was supplemented by carrying out FTIR-ATR studies. whereas sulphur was observed also in the inner layers of the catalyst.2 Evaluation and utilization of the results Several characterization techniques were used in this thesis to gain information about phosphorus poisoning of automotive catalyst components. ICP-OES was shown to be a feasible and accurate method for determining the phosphorus content of the powdery samples. Useful information about the contaminant levels in the poisoned samples was gathered with SEM-EDS. With this method we demonstrated that the specific surface area of most of the samples was significantly affected by phosphorus poisoning. XRF was a good tool for quick determination of the phosphorus content of the poisoned catalyst samples. However. The procedure was shown to be a viable method for laboratory-scale catalyst studies. New information about the formation and stability of phosphorus compounds was obtained by using thermodynamic calculations.

calcium or magnesium could be used to simulate the accumulation of other lubricating oil-derived impurities on exhaust gas catalysts. 6. However. In the future.3 Suggestions for further research To prevent poisoning and to prolong the life of automotive catalysts. For instance. zinc. calcium can decrease the catalytic activity of catalyst components.of normal diesel catalyst operation (below 500°C) and the peak temperature used in this study (700°C). produces the same poison compounds found in vehicle-aged catalysts. Furthermore. gaseous phase ageing can be carried out by using different poison sources to determine their separate and simultaneous effect on the behaviour of a catalyst. namely incipient wetness impregnation with an aqueous salt solution of (NH4)2HPO4 and addition of an aqueous salt solution of (NH4)2HPO4 into a gaseous phase. Furthermore. affordable. Therefore. further studies are needed. the methods are considered to be potential ageing procedures when studying accelerated chemical poisoning of powdery automotive exhaust catalyst components on the laboratory scale. it would also be possible to vary the gas composition and flow rate as well as the ageing time and temperature. It was shown that accumulation of phosphorus combined with hydrothermal ageing conditions caused a decrease in the catalytic activity of zeolites. According to the results. Therefore. The results demonstrated that poisoning by both methods used in this work. and safe way with both of these methods. especially to obtain more information about the poisoning mechanisms of zeolites. calcium also has a regenerating effect on catalysts poisoned by phosphorus. Phosphorus can be added to samples in a repeatable. the role of calcium in catalyst deactivation and in preventing the deactivating effects of other poison compounds should be studied in more detail. time-saving. 73 . the form in which the poison adhered to the sample could not be identified with the characterization techniques used in this work. depending on the real driving conditions that are to be simulated.

74 .

The results indicate that phosphorus poisoning mainly affects the oxide components used in this study instead of affecting the noble metals. but no phosphoruscontaining compounds were observed. During the gaseous phase phosphorus ageing procedure. The regenerating effect that calcium had on some catalyst components is also a very interesting phenomenon that merits an in-depth study. the effect of phosphorus poisoning was detected in the catalytic activity and characteristics of the catalyst. calcium can decrease the catalytic activity of components used in automotive catalysts. the phosphorus content varied between the catalyst samples. activity measurements. Al and Ti. XRF. As a result of poisoning. these samples maintained some of their activity in the ageing procedures.7 Summary and conclusions Both poisoning methods used in this study produced the same phosphorus compounds that can be found in vehicle-aged catalysts. According to the results. most of the samples that did not contain any noble metal suffered from a very significant decrease in catalytic activity. It was also shown that the role of phosphorus poisoning was more pronounced than the role of hydrothermal ageing alone. FTIR-ATR. Furthermore. it was difficult to find correlations between the amount of phosphorus attached to the sample and the characteristics of the sample observed in this study. Regardless of whether the component contained a noble metal or not. However. ICP-OES. The role of laboratory-scale activity measurements. The methods used in the deactivation studies (i. Phosphorus was detected in the poisoned samples as phosphates of Ce.e. and thermodynamic calculations) of this thesis project are relevant and timely methods for gathering information about deactivation phenomena and for catalyst characterization in catalyst deactivation studies. The role of calcium in catalyst deactivation should be studied further. Despite the decrease in the activity of the catalysts containing a noble metal. In the case of zirconium oxides. Zr. By contrast. the very low specific surface area of the fresh ZrO2 and Pt/ZrO2 must have been the reason for the small phosphorus content measured in these samples. According to the results. and XRD combined with FTIR75 . less than 70% of the phosphorus fed into the reactor accumulated on the samples. SEM. phosphorus poisoning takes place at high operating temperatures and with high oxygen and water content in the gas phase. in zeolites phosphorus was detected with elemental analysis. XRD. physisorption studies. TEM. physisorption analyses.

the presence of impurities and temperature windows. more precisely. To obtain more accurate information about the causes of deactivation and their influence on catalyst activity and selectivity. Other areas where the results can be applied include evaluation of the effects of phosphorus poisoning on different catalyst compositions and prediction of the age of commercial catalysts. The results of this work can be utilized in the development of catalytic materials and catalyst compositions that can withstand phosphorus poisoning at high temperatures and in moist ageing conditions better than existing ones do. e. These methods are recommended to be used as tools in the engineering approach to analysis of deactivation of exhaust gas catalysts. a deeper analysis of catalyst activity versus catalyst characteristics should be done to be able to design catalysts from the point of view of materials and to specify their operating conditions.ATR is most relevant.g. 76 .

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277. Janne P. Jari (2007) Intensified use of process measurements in hydrometallurgical zinc production processes Turtinen. Box 8200. 271. Markus (2007) Learning and recognizing texture characteristics using local binary patterns Sarpola. 279.) (2007) The 1st Nordic Innovation Research Conference—Finnkampen Pikka. 280. FI-90014 University of Oulu. 281. Annukka (2007) Strategiakeskeinen kyvykkyyden johtaminen organisaation strateginen valmius. 273. Box 7500. 278. Arja (2007) The hydrolysis of aluminium. 274. Kahden johtamismallin testaus ja Jokinen. Eva Wiklund. its concepts. Tapio (2007) Optical method for liquid sorption measurements in paper Miao. 269. Finland Distributed by OULU UNIVERSITY LIBRARY P. Esa (2007) A multiscale framework for affine invariant pattern recognition and registration Book orders: OULU UNIVERSITY PRESS P. Hanna (2007) Screening and cleaning of pulp—a study to the parameters affecting separation Sarja. a mass spectrometric study Keski-Säntti. (2007) Frequency domain model fitting and Volterra analysis implemented on top of harmonic balance simulation Oiva. mechanical properties and corrosion behaviour of high-Mn TWIP steels Rahtu. Jarmo (2007) Neural networks in the production optimization of a kraft pulp bleach plant Hamada. Géza (2007) Computer modeling supported fabrication processes for electronics applications Näsi. Maarit Hiltunen ja Esa Vesmanen (2007) Yksilölliset toiveet asuntotuotannossa Fabritius. 272.O. Vesa (2007) A Business Enabling Network.ACTA UNIVERSITATIS OULUENSIS SERIES C TECHNICA 266. elements and actors Noora Ervasti. Lingyun (2007) The key activities of partnership development in China—a study of Sino-Finnish partnerships Aikio. 276. Atef Saad (2007) Manufacturing. 270. 267. Tiina (2007) Measurement. 275. FI-90014 University of Oulu. 268. A case study of a high-tech network. Honglei (2007) Channel estimation and positioning for multiple antenna systems Wang. Elina Pietikäinen. 282. Finland .O. Harri Haapasalo & Päivi Iskanius (Eds. nature and removal of stickies in deinked pulp Tóth.

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