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Journal ArticleDOI

Correlation of static aging effects on automotive catalysts

01 Sep 2014-Canadian Journal of Chemical Engineering (Wiley-Liss Inc.)-Vol. 92, Iss: 9, pp 1526-1530
TL;DR: In this article, the effect of aging time and temperature on CO light-off activity of three-way catalyst samples, aged in a static air (oxidizing) atmosphere, was analyzed.
Abstract: This study identifies and analyzes the effect that aging time and temperature have on the CO light-off activity of three-way catalyst samples, aged in a static air (oxidizing) atmosphere. The bench aging time (BAT) equation proposed by the Environmental Protection Agency (EPA), which describes aging as dependent upon time at temperature, was used to calculate a range of oven aging times and temperatures based on a RAT-A engine bench aging cycle. CO light-off tests carried out on cores aged between 800 and 900 °C have shown that it is the aging temperature that has the greatest effect on catalyst deterioration for static aging testing, with aging time having little effect. These results were in contradiction to the BAT equation, an industry norm for the aging of catalysts. This demonstrates that static aging, whilst showing how temperature affects aging, gives little or no time effects. The results have shown that static aging is not representative of actual aging on a vehicle. Progressive aging conducted at a temperature of 1000 °C was shown to cause a decrease in catalyst activity as the aging time increased. However, even in these extreme conditions, static aging gave a slower rate of aging with time when compared to engine aging as defined by the BAT equation. Overall, static aging in air has been shown to produce a greater increase in aging due to temperature than predicted by the BAT equation, but less aging due to aging time.

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Citations
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Journal ArticleDOI
TL;DR: In this paper, a specific washcoat extraction method was developed, and the separated washcoat was analyzed using XRD, TEM microscopy, Raman Spectroscopy and BET.
Abstract: The main system to reduce engine emissions of gasoline-fueled vehicles is represented by the three-way catalyst (TWC). The main catalyst of this system usually works in extreme conditions which induce a phenomenon called thermal ageing, the major way of catalyst deactivation. Increasingly stringent emissions standards require not only high efficiency in emissions abatement, but also maintaining the performances at high vehicle mileage. Automotive manufacturers need to accelerate testing methods and that should be representative of the ageing on vehicle, at the minimum expense in terms or time and cost. In order to develop and validate such methods, a deep understanding of all the microscopic processes associated with ageing is necessary. In this work we discuss a methodology for the study of the static thermal ageing of a commercial TWC. A specific washcoat extraction method was developed, and the separated washcoat was analyzed using XRD, TEM microscopy, Raman Spectroscopy and BET. These techniques allow to follow the main morphological and chemical changes in the sample: the loss of porosity, the evolution of crystalline phases and metal particles sintering and oxidation. The potential of Raman spectroscopy for the spatially resolved analysis of ageing is also highlighted. The results allowed to understand the process that involve the washcoat at high temperature.

11 citations

Journal ArticleDOI
TL;DR: In this article, a series of identical catalysts aged in different conditions are characterized in order to understand the correlation between the real and accelerated ageing protocols, and a complete morphological characterization is performed and interlaced with functional testing.
Abstract: The increasingly stringent emission limits require high performances also at high mileage, increasing the need for reliable catalysts characterization during their whole useful life. Thermal ageing is the main problem: high temperatures, variable environment and the presence of water lead to a progressive deactivation of the components. Due to the cost of ageing a converter on-road or on an engine bench, much more rapid laboratory aging methods are now becoming very interesting, rising the problem of the correlation between real and accelerated ageing conditions. In this work a series of identical catalysts aged in different conditions are characterized in order to understand the correlation between the real and accelerated ageing protocols. Applying a wide spectrum of techniques (XRD, SEM, TEM, BET) a complete morphological characterization is performed and interlaced with functional testing, in order to understand the link between the catalysts modification due to thermal effects and their deactivation, and to allow the design of more realistic laboratory ageing protocols. The correlation between real samples, coming from an ageing on an engine, and laboratory ageing is good for the medium-high mileage sample, which results very similar in terms of performance and morphology with the sample aged at hydro-thermal condition. Some differences remain due to the chemical ageing, which was not possible to replicate on the laboratory scale.

4 citations

Journal ArticleDOI
TL;DR: In this article , an in-depth review of smelting technologies for recovering platinum-group metals (PGMs) from spent automotive catalysts (SAC) has been provided.
Abstract: The necessity, economics, and sustainability of recycling platinum-group metals (PGMs) from spent automotive catalysts (SAC) have stimulated the emergence of many relevant treatment technologies. Considering the industrial feasibility and recovery efficiency of smelting, this study provided an in-depth review of smelting technologies for recovering PGMs from SAC. Based on the understanding of the characteristics and deactivation mechanisms of automotive catalysts, the effects of various factors on the performance of slagging, collection and separation of PGMs and the features of main smelting processes involving using lead, iron, copper, matte, and wastes as collectors of the metals were reviewed and discussed. The measures for improving the recovery efficiency of PGMs by smelting were proposed from the perspectives of selection of additives and collectors, regulation of slag properties, and optimization of smelting conditions, introduction of microwave field, etc. In addition, the solutions for reducing the dependence of catalysts on PGMs were offered to further resolve the conflict between supply and demand of PGMs.

4 citations

Journal ArticleDOI
TL;DR: In this paper , the authors proposed a supply management-recycling (SMR) chain for the explication of the ownership of PGMs in the service life of the product, with the intensification of the links between producers, users, and recyclers of PGM, the increase of their recovery, and the minimization of their loss during the mining-use-deactivation deactivationrecycling processes.
Abstract: The global demand for platinum-group metals (PGMs), including Pt, Pd, and Rh, far exceeds the supply of natural resources. Scarce and inhomogeneous distribution of resources, high production costs, and serious environmental risks stimulate the recycling of PGMs from spent automotive catalysts (SAC). From this point, the global current and future accessibility and sustainability of PGMs were first evaluated by analyzing their demand, supply, consumption, and recycling both globally and in several large PGMs-consuming regions. It is predicted that 195-307 t or 52-478 t of PGMs can be recovered from SAC annually according to the consumption of PGMs in automotive catalysts or the recoverable PGMs amount in the new sales/registrations of vehicles, respectively. Based on the above analysis, the reasons for the insufficient recovery of PGMs were discussed and roughly classified into the recovery technology and social factors, including the difference in recovery progress and initiative in different regions, the changeable ownership, untimely tracking of PGMs, and the absence of responsible parties for PGMs throughout product lifecycle. It was followed by proposing the establishment and improvement of a supply-management-recycling (SMR) chain for the explication of the ownership of PGMs in the service life of the product, with the intensification of the links between producers, users, and recyclers of PGMs, the increase of their recovery, and the minimization of their loss during the mining-use-deactivation-recycling processes. Finally, some suggestions were provided to reduce the dependence of catalysts on PGMs to balance the contradiction between production and consumption, pursuing the sustainable utilization of PGMs.
References
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Journal ArticleDOI
TL;DR: The literature treating mechanisms of catalyst deactivation is reviewed in this paper, which can be classified into six distinct types: (i) poisoning, (ii) fouling, (iii) thermal degradation, (iv) vapor compound formation accompanied by transport, (v) vapor solid and/or solid solid reactions, and (vi) attrition/crushing.
Abstract: The literature treating mechanisms of catalyst deactivation is reviewed. Intrinsic mechanisms of catalyst deactivation are many; nevertheless, they can be classified into six distinct types: (i) poisoning, (ii) fouling, (iii) thermal degradation, (iv) vapor compound formation accompanied by transport, (v) vapor-solid and/or solid-solid reactions, and (vi) attrition/crushing. As (i), (iv), and (v) are chemical in nature and (ii) and (v) are mechanical, the causes of deactivation are basically three-fold: chemical, mechanical and thermal. Each of these six mechanisms is defined and its features are illustrated by data and examples from the literature. The status of knowledge and needs for further work are also summarized for each type of deactivation mechanism. The development during the past two decades of more sophisticated surface spectroscopies and powerful computer technologies provides opportunities for obtaining substantially better understanding of deactivation mechanisms and building this understanding into comprehensive mathematical models that will enable more effective design and optimization of processes involving deactivating catalysts. © 2001 Elsevier Science B.V. All rights reserved.

2,526 citations

Journal ArticleDOI
TL;DR: In this paper, the causes of deactivation and the influence on reaction rate are discussed and methods for minimising catalyst deactivation, by tailoring catalyst properties and/or process operations, are presented.
Abstract: Catalyst deactivation is usually inevitable, although the rate at which it occurs varies greatly. This article discusses the causes of deactivation and the influence on reaction rate. Methods for minimising catalyst deactivation, by tailoring catalyst properties and/or process operations, are presented, as well as reactor configurations suitable for the regeneration of deactivated catalysts. Alkane dehydrogenation is used as an example to demonstrate the variety of engineering solutions possible.

639 citations

Journal ArticleDOI
TL;DR: In this paper, the influence of a reducing atmosphere on the thermal stability of CeO2 was studied on a high surface area ceria sample (115 m2 g−1) treated 2 h under hydrogen or carbon monoxide at various temperatures between 673 and 1123 K.
Abstract: The influence of a reducing atmosphere on the thermal stability of CeO2 was studied on a high surface area ceria sample (115 m2 g−1) treated 2 h under hydrogen or carbon monoxide at various temperatures between 673 and 1123 K. Comparative experiments were done under air or vacuum, and also in presence of water or carbon dioxide in order to estimate the relative importance of the reduction products. An important decrease of the specific surface area was observed between 850 and 1000 K under air, vacuum, carbon monoxide or water pressure, the residual BET area being below 10 m2 g−1 at 1100 K. Under hydrogen, the same loss of surface was obtained at ca. 150 K lower temperatures. In all cases, the first step was the elimination of the microporosity followed by the growth of the crystallites. The peculiar influence of hydrogen was related to the high concentration of lattice oxygen vacancies created during the reduction of the bulk. In the case of carbon monoxide atmosphere which also reduces the sample, the carbonate species formed during the reduction are eliminated from the bulk at higher temperatures, which explain the better resistance to sintering compared to hydrogen. This was confirmed by a treatment under carbon dioxide atmosphere which was found to preserve the specific surface area better because of the stabilization of the carbonate species on the ceria.

139 citations

Journal ArticleDOI
TL;DR: In this article, both fresh and accelerated aging of TWC catalysts were tested for activity as TWC, both fresh [G.C. Koltsakis, and A.M. Stamatelos, Progr. Energy Combust. Sci. 23 (1997) 1] and after accelerated aging.

95 citations

Journal ArticleDOI
TL;DR: In this paper, the authors make the link between sintering of a 1.6% Pt/Al2O3 catalyst and its activity for CO oxidation reaction and its performance for CO degradation.
Abstract: The goal of this paper was to make the link between sintering of a 1.6% Pt/Al2O3 catalyst and its activity for CO oxidation reaction. Thermal aging of this catalyst for different durations ranging from 15 min to 16 h, at 600 and 700 °C, under 7% O2, led to a shift of the platinum particle size distributions towards larger diameters, due to sintering. These distributions were studied by transmission electron microscopy. The number and the surface average diameters of platinum particles increase from 1.3 to 8.9 nm and 2.1 to 12.8 nm, respectively, after 16 h aging at 600 °C. The catalytic activity for CO oxidation under different CO and O2 inlet concentrations decreases after aging the catalyst. The light-off temperature increased by 48 °C when the catalyst was aged for 16 h at 600 °C. The CO oxidation reaction is structure sensitive with a catalytic activity increasing with the platinum particle size. To account for this size effect, two intrinsic kinetic constants, related either to platinum atoms on planar faces or atoms on edges and corners were defined. A platinum site located on a planar face was found to be 2.5 more active than a platinum site on edges or corners, whatever the temperature. The global kinetic law {r (mol m−2 s−1) = 103 × exp(−64,500/RT)[O2]0.74[CO]−0.5)} related to a reaction occurring on a platinum atom located on planar faces allows a simulation of the CO conversion curves during a temperature ramp. Modeling of the catalytic CO conversion during a temperature ramp, using the different aged catalysts, allows prediction of the CO conversion curves over a wide range of experimental conditions.

64 citations

Frequently Asked Questions (15)
Q1. What contributions have the authors mentioned in the paper "Correlation of static ageing effects on automotive catalysts" ?

Blades et al. this paper used the QUB global catalyst simulation model to simulate the light-off behavior of catalyst samples for tests conducted on two different laboratory catalyst test rigs. 

Further work on dynamic ageing must be conducted in order to see if any correlation exists between static ageing and dynamic ageing under laboratory conditions. 

The three-way catalytic converter is the most common method of reducing these emissions and uses precious metals such as Pt, Pd or Rh, as the catalytic material. 

Due to the increasing complexity of modern automotive aftertreatment systems, and the slow and expensive nature of testing and ageing catalyst samples on-road or on an engine test bench, much more rapid laboratory testing and ageing methods, as well as computer simulation models are now becoming a critical part of the automotive catalyst design phase. 

It is predicted that the light-off variation between samples is due to a variation in precious metal particles from one core to the next, which is also indicated by the initial baseline light-off test results. 

Static ageing in air has been shown to cause increased ageing due to temperature than predicted by the BAT equation, but less due to time. 

After the baseline light-off tests had been carried out on all of the de-greened cored samples, static ageing was conducted in a furnace oven, in air, for ageing temperatures and times calculated using the BAT equation. 

by using the BAT equation, with the activation energy for CO oxidation of approximately 100 kJ/mol,[17] it is estimated that the performance after 23.6 hours should only be 5% of the initial performance. 

After the initial 1.18 hours of ageing, it can be seen that most ageing occurs in the first 11.8 hours (100 hours equivalent on a RAT-A cycle), with a light-off shift of 11 ᵒC being observed. 

The Horiba SIGU 2000 Series Gas Generator and Catalyst Test System generates a simulated exhaust gas, and temperature profile, to allow testing and evaluation of catalyst samples. 

Light-off tests conducted by Fernandes et al.[8] showed shifts in light-off to higher temperatures as the ageing time was increased at ageing temperatures of 900 ᵒC and 1200 ᵒC. Yang[13] showed the effect that ageing time had for a dynamically aged catalyst. 

From the BAT equation it would be expected that as the ageing time increases the catalyst activity decreases, with a corresponding increase in light-off temperature. 

Regulations for automotive exhaust emissions are becoming more stringent, requiring the development of more effective catalytic control systems. 

even though static ageing at 1000 ᵒC has shown a decrease in catalytic activity with respect to ageing time, it is occurring at a much slower rate than when compared to engine ageing as defined by the BAT equation. 

The EPA recommends an R factor for the standard bench cycle of between 17500 and 18500, depending on the vehicle type, however if a different ageing cycle is used the R value is expected to be different.