Many vehicles have a close-coupled converters unlimited located near the engine’s exhaust manifold. The converter heats up quickly, due to its exposure to the very hot exhaust gases, enabling it to reduce undesirable emissions during the engine warm-up period. This is achieved by burning off the excess hydrocarbons which result from the extra-rich mixture required for a cold start.
When converters unlimited were first introduced, most vehicles used carburetors that provided a relatively rich air-fuel ratio. Oxygen (O2) levels in the exhaust stream were therefore generally insufficient for the catalytic reaction to occur efficiently. Most designs of the time therefore included secondary air injection, which injected air into the exhaust stream. This increased the available oxygen, allowing the converters unlimited to function as intended.
Some three-way converters unlimited systems have air injection systems with the air injected between the first (NOx reduction) and second (HC and CO oxidation) stages of the converters unlimited. As in two-way converters, this injected air provides oxygen for the oxidation reactions. An upstream air injection point, ahead of the converters unlimited, is also sometimes present to provide additional oxygen only during the engine warm up period. This causes unburned fuel to ignite in the exhaust tract, thereby preventing it reaching the catalytic converter at all. This technique reduces the engine runtime needed for the converters unlimited to reach its “light-off” or operating temperature.
Most newer vehicles have electronic fuel injection systems, and do not require air injection systems in their exhausts. Instead, they provide a precisely controlled air-fuel mixture that quickly and continually cycles between lean and rich combustion. Oxygen sensors monitor the exhaust oxygen content before and after the converters unlimited, and the engine control unit uses this information to adjust the fuel injection so as to prevent the first (NOx reduction) catalyst from becoming oxygen-loaded, while simultaneously ensuring the second (HC and CO oxidation) converters unlimited is sufficiently oxygen-saturated.
Damage
Catalyst poisoning occurs when the converters unlimited is exposed to exhaust containing substances that coat the working surfaces, so that they cannot contact and react with the exhaust. The most notable contaminant is lead, so vehicles equipped with converters unlimited can run only on unleaded fuel. Other common converters unlimited poisons include sulfur, manganese (originating primarily from the gasoline additive MMT), and silicon, which can enter the exhaust stream if the engine has a leak that allows coolant into the combustion chamber. Phosphorus is another converters unlimited contaminant. Although phosphorus is no longer used in gasoline, it (and zinc, another low-level catalyst contaminant) was widely used in engine oil antiwear additives such as zinc dithiophosphate (ZDDP). Beginning in 2004, a limit of phosphorus concentration in engine oils was adopted in the API SM and ILSAC GF-4 specifications.
Depending on the contaminant, converters unlimited poisoning can sometimes be reversed by running the engine under a very heavy load for an extended period of time. The increased exhaust temperature can sometimes vaporize or sublimate the contaminant, removing it from the catalytic surface. However, removal of lead deposits in this manner is usually not possible because of lead’s high boiling point. [25]
Any condition that causes abnormally high levels of unburned hydrocarbons (raw or partially burnt fuel or oils) to reach the converter will tend to significantly elevate its temperature, bringing the risk of a meltdown of the substrate and resultant catalytic deactivation and severe exhaust restriction. These conditions include failure of the upstream components of the exhaust system (manifold/header assembly and associated clamps susceptible to rust/corrosion and/or fatigue e.g. the exhaust manifold splintering after repeated heat cycling), ignition system e.g. coil packs and/or primary ignition components (e.g. distributor cap, wires, ignition coil and spark plugs) and/or damaged fuel system components (fuel injectors, fuel pressure regulator, and associated sensors). Oil and/or coolant leaks, perhaps caused by a head gasket leak, can also cause high unburned hydrocarbons.