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Automotive Catalytic Converters: Current Status and Some Perspectives

OBJECTIVES
To illustrate the technology for abatement of exhaust emissions by analysing the current understanding of three-way-catalysts (TWCs). To study the specific role of the various components, the achievements and the limitations. To discuss about the challenges in the development of new automotive catalysts, which can meet future highly demanding pollution abatement requirements.

INTRODUCTION
Air pollution by mobile sources Increase of world vehicles fleet from 40 million vehicles to over 700 million in last 60 years. Non-perfect combustion cause exhaust contains significant amount of pollutants which need to transformed into harmless compound. Hence, the TWCs is important towards this matter.

Three Ways Catalysts (TWCs)


used in rich-burn or stoichiometric engines for simultaneous conversion of oxides of nitrogen (NOx), carbon monoxide (CO), hydrocarbons (HC), formaldehyde (CH2O) and Environmental Protection Agency (EPA) classified Hazardous Air Pollutants (HAPs). effective in a wide variety of engine applications and fuels, including natural gas, propane and gasoline.

A three-way catalytic converter has three simultaneous tasks: Reduction of nitrogen oxide to nitrogen and oxygen: 2NOx xO2 + N2 Oxidation of carbon monoxide to carbon dioxide: 2CO + O2 2CO2 Oxidation of unburnt hydrocarbons (HC) to carbon dioxide and water: CxH2x+2 + 2xO2 xCO2 + 2xH2O

Three Ways Catalysts

Design of TWCs

Basically, it is a stainless steel container which incorporates a honeycomb monolith made of cordierite (2MgO2Al2O35SiO2) or metal.

Traditionally, cordierite monoliths have been employed quite extensively, primarily due to their lower production cost. major advantages of the metal monoliths resides in; (i) their high thermal conductivity (ii) low heat capacity (iii) allow very fast heating of the CCCs during the phase-in of the engine (iv )minimising the light-off time.

The monolith is mounted in the container with a resilient matting material to ensure vibration resistance. The active catalysts is supported (washcoated) onto the monolith by dipping it into a slurry containing the catalyst precursors. common components, which represent the stateof-art of the washcoating composition: (i) Alumina, which is employed as a high surface area support. (ii) CeO2ZrO2 mixed oxides, principally added as oxygen storage promoters.

(iii) Noble metals (NM = Rh, Pt and Pd) as active phases. (iv) Barium and/or lanthana oxides as stabilisers of the alumina surface area

(i)

Al2O3 as carrier due to its high surface area and relatively good thermal stability under the hydrothermal conditions of the exhausts necessity of increasing the surface area of the honeycomb monolith which is typically below 24m2 l1 Suitable even for high temperature applications such as in close-coupled catalysts ( CCCs) stabilising agents are employed to improve the stability of the surface area. Not an important issue for next generation of TWCs.

(ii) CeO2ZrO2 mixed oxides

The beneficial effects of CeO2-containing formulations of the TWC performances has long been recognised Many different promotional effects have been attributed to this component, such as the ability to: promote the noble metal dispersion; increase the thermal stability of the Al2O3 support; promote the water gas shift (WGS) and steam reforming reactions; favour catalytic activity at the interfacial metal support sites; promote CO removal trough oxidation employing a lattice oxygen; store and release oxygen under, respectively, lean and rich conditions.

Thermal stability of CeO2ZrO2 mixed oxides Several ways to enhance the thermal stability of the CeO2-based materials i) design of microstructure / textural properties by adopting an appropriate synthesis methodology. ii) appropriate doping of CeO2. iii) dispersing of CeO2 on a carrier. i) Design of microstructure / texture properties - sinter ability of any material related to its textural properties and its pore structure - pore structure depends on the synthesis conditions

Example , co-precipitation is typically employed to prepare mixed oxide catalysts When the precipitated cake is treated at 80 C in the presence of surfactants, extensive mesoporous texture develops in the CeO2ZrO2 mixed oxides, leading to remarkably high surface areas compared to the traditional co-precipitation route .

Oxygen storage of CeO2ZrO2 mixed oxides Easily remove bulk oxygen species at moderate temperature even in highly sintered samples the ability of ZrO2 to modify the oxygen sublattice in the CeO2ZrO2 mixed oxides, generating defective structures and highly mobile oxygen atoms in the lattice which can be released even at moderate temperatures Efficiency of the OSC property can be achieved by using CeO2ZrO2 mixed oxides instead of CeO2

if the sample sinters under the high temperature reaction conditions, it should be more effective then CeO2 due to: - high oxygen mobility in the bulk - lattice oxygen species could effectively participate in redox processes even under fluctuating exhaust feed-stream conditions

Noble metals NMs represent the key component of the TWC, as the catalytic activity occurs at the noble metal centre Rh, Pd and Pt have long been employed in the TWCs there is a general agreement about the specificity of Rh to promote NO dissociation, thus enhancing the NO removal Pt and Pd are considered as metal of choice to promote the oxidation reaction, even though Rh also has a good oxidation activity.

Pd has extensively been added to TWC formulations starting from mid-1990s due to its ability to promote HC oxidation The increase of the use of Pd in the TWC technology adversely affected Pd market price, which is now comparable to that of Pt due to the straightforward way to increase the efficiency of the TWCs at low temperatures is that of increasing the NM loading and the cheapest NM among the three employed

Deactivation of TWCs
Sintering of NM, leading to decrease of active sites, is a major pathway for deactivation TWC. Poisoning of the catalyst may also attribute to their deactivation. There are other routes that contribute to deactivation; i) sintering of OSC promoter leading to loss of OSC ii) sintering of Al2O3 iii) deactivation of Rh due to the migration of Rh3+ into alumina lattice

Limitations of TWCs
TWCs represent quite a mature, highly effective technology for pollution abatement However, it has some inherent limitations which need further improvement and development These aspects are related to (i) Low activity at low temperatures (start-up of the engine) (ii) Use of stoichiometric A/F - large amounts of hydrocarbon are in fact emitted at rich A/F, which require and additional HC trap

Although catalytic converters are effective at removing hydrocarbons and other harmful emissions, most of exhaust gas leaving the engine through a catalytic converter is carbon dioxide (CO2) and nitrous oxide (N2O), ,one of the greenhouse gases indicated by the Intergovernmental Panel on Climate change (IPCC) to be a "most likely" cause of global warming. An alternative approach is that of developing new catalysts showing high conversion efficiency at low, nearly ambient, temperature

Alternative Catalysts
Lean DeNOx Capable of reducing NOx even in excess O2 Achieve significant fuel savings

Pt/Al2O3
Maximum of NO conversion at relatively low temperature Comparable starting temperatures for NO reduction and HC conversion Significant NO2 formation at high temperatures when all the HC is burned out. Strong sensitivity of the NO conversion Poor selectivity towards de-nitrogen formation of the Pt catalyst, N2O being the major product at low temperatures

Other alternative catalysts


Lean NOx traps Selective catalytic Nox reduction using urea

Particulate matter removal


Related to diesel engines Diesel particulate matter (DPM) is the most complex of diesel emissions Basic fractions of DPM are elemental carbon, heavy HCs and hydrated sulphuric acid DPM contains a large portion of the polynuclear aromatic hydrocarbons (PAH) found in diesel exhaust Non-gaseous diesel emissions are grouped into 3 categories : soluble organic fraction (SOF), sulpate and soot

Solutions
Removal of liquid fraction of PM generally achieved by an oxidation catalyst reduce HC, SOF content and CO Removal of soot achieved by means of filtration

Conclusion
Development of automotive converters has proceeded by a continuous improvement of the catalytic performances and durability of automotive catalysts. TWC is a complex and intergrated system that must be immediately effective and that its lifetime must be equivalent to that of the car.

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