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An experimental study was performed to develop a more fundamental understanding of the effects of secondary air injection (SAI) on exhaust gas emissions and catalyst light-off characteristics during cold start of a modern SI engine. The effects of engine operating parameters and various secondary air injection strategies such as spark retardation, fuel enrichment, secondary air injection location and air flow rate were investigated to understand the mixing, heat loss, and thermal and catalytic oxidation processes associated with SAI. Time-resolved HC, CO and CO₂ concentrations were tracked from the cylinder exit to the catalytic converter outlet and converted to time-resolved mass emissions by applying an instantaneous exhaust mass flow rate model. A phenomenological model of exhaust heat transfer combined with the gas composition analysis was also developed to define the thermal and chemical energy state of the exhaust gas with SAI.

Engine-out HC emissions from a PFI spark ignition engine were measured using a gas chromatograph and a flame ionization detector (FID). Two port fuel injectors were used respectively for ethanol and gasoline so that the delivered fuel was comprised of 0, 25, 50, 75 and 100% (by volume) of ethanol. Tests were run at 1.5, 3.8 and 7.5 bar NIMEP and two speeds (1500 and 2500 rpm). The main species identified with pure gasoline were partial reaction products (e.g. methane and ethyne) and aromatics, whereas with ethanol/gasoline mixtures, substantial amounts of ethanol and acetaldehyde were detected. Indeed, using pure ethanol, 74% of total HC moles were oxygenates. In addition, the molar ratio of ethanol to acetaldehyde was determined to be 5.5 to 1. The amount (as mole fraction of total HC moles) of exhaust aromatics decreased linearly with increasing ethanol in the fuel, while oxygenate species correspondingly increased.

Mechanisms of NH₃ generation using LNT-like catalysts have been studied in a bench reactor over a wide range of temperatures, flow rates, reformer catalyst types and synthetic exhaust-gas compositions. The experiments showed that the on board production of sufficient quantities of ammonia on board for SCR operation appeared feasible, and the results identified the range of conditions for the efficient generation of ammonia. In addition, the effects of reformer catalysts using the water-gas-shift reaction as an in-situ source of the required hydrogen for the reactions are also illustrated. Computations of the NH₃ and NOx kinetics have also been carried out and are presented. Design and impregnation of the SCR catalyst in proximity to the ammonia source is the next logical step. A heated synthetic-exhaust gas flow bench was used for the experiments under carefully controlled simulated exhaust compositions.

The effects of charge motion and laminar flame speeds on combustion and exhaust temperature have been studied by using an air jet in the intake flow to produce an adjustable swirl or tumble motion, and by replacing the nitrogen in the intake air by argon or CO₂, thereby increasing or decreasing the laminar flame speed. The objective is to examine the "Late Robust Combustion" concept: whether there are opportunities for producing a high exhaust temperature using retarded combustion to facilitate catalyst warm-up, while at the same time, keeping an acceptable cycle-to-cycle torque variation as measured by the coefficient of variation (COV) of the net indicated mean effective pressure (NIMEP). The operating condition of interest is at the fast idle period of a cold start with engine speed at 1400 RPM and NIMEP at 2.6 bar. A fast burn could be produced by appropriate charge motion. The combustion phasing is primarily a function of the spark timing.

The engine and its exhaust flow behaviors are investigated in a turbo-charged gasoline direct injection engine under simulated cold-fast-idle condition. The metrics of interest are the exhaust sensible and chemical enthalpy flows, and the exhaust temperature, all of which affect catalyst light off time. The exhaust sensible enthalpy flow is mainly a function of combustion phasing; the exhaust chemical enthalpy flow is mainly a function of equivalence ratio. High sensible and chemical enthalpy flow with acceptable engine stability could be obtained with retarded combustion and enrichment. When split injection is employed with one early and one later and smaller fuel pulse, combustion retards with early secondary injection in the compression stroke but advances with late secondary injection. Comparing gasoline to E85, the latter produces a lower exhaust temperature because of charge cooling effect and because of a faster combustion.

To meet future particle mass and particle number standards, gasoline vehicles may require particle control, either by way of an exhaust gas filter and/or engine modifications. Soot levels for gasoline engines are much lower than diesel engines; however, non-combustible material (ash) will be collected that can potentially cause increased backpressure, reduced power, and lower fuel economy. The purpose of this work was to examine the ash loading of gasoline particle filters (GPFs) during rapid aging cycles and at real time low mileages, and compare the filter performances to both fresh and very high mileage filters. Current rapid aging cycles for gasoline exhaust systems are designed to degrade the three-way catalyst washcoat both hydrothermally and chemically to represent full useful life catalysts. The ash generated during rapid aging was low in quantity although similar in quality to real time ash. Filters were also examined after a low mileage break-in of approximately 3000 km.

The engine out particular matter number (PN) distributions at engine coolant temperature (ECT) of 0° C to 40° C for ethanol/ gasoline blends (E0 to E85) have been measured for a direct-injection spark ignition engine under cold fast idle condition. For E10 to E85, PN increases modestly when the ECT is lowered. The distributions, however, are insensitive to the ethanol content of the fuel. The PN for E0 is substantially higher than the gasohol fuels at ECT below 20° C. The total PN values (obtained from integrating the PN distribution from 15 to 350 run) are approximately the same for all fuels (E0 to E85) when ECT is above 20° C. When ECT is decreased below 20° C, the total PN values for E10 to E85 increase modestly, and they are insensitive to the ethanol content. For E0, however, the total PN increases substantially. This sharp change in PN from E0 to E10 is confirmed by running the tests with E2.5 and E5. The midpoint of the transition occurs at approximately E5.

Selective catalytic reduction (SCR) of nitrogen oxides (NOx) is used in diesel-fueled mobile applications where urea is an added reducing agent. We show that the Ultera® dual-stage catalyst, with intercooling aftertreatment system, intrinsically performs the function of the SCR method in nominally stoichiometric gasoline vehicle engines without the need for an added reductant. We present that NOx is reduced during the low-temperature operation of the dual-stage system, benefiting from the typically periodic transient operation (acceleration and decelerations) with the associated swing in the air/fuel ratio (AFR) inherent in mobile applications, as commonly expected and observed in real driving. The primary objective of the dual-stage aftertreatment system is to remove non-methane organic gases (NMOG) and carbon monoxide (CO) slip from the vehicle’s three-way catalyst (TWC) by oxidizing these constituents in the second stage catalyst.

This paper reviews the relevant literature on the effects of sulfated ash, phosphorus, and sulfur on DPF, LNT, and SCR catalysts. Exhaust backpressure increase due to DPF ash accumulation, as well as the rate at which ash is consumed from the sump, were the most studied lubricant-derived DPF effects. Based on several studies, a doubling of backpressure can be estimated to occur within 270,000 to 490,000 km when using a 1.0% sulfated ash oil. Postmortem DPF analysis and exhaust gas measurements revealed that approximately 35% to 65% less ash was lost from the sump than was expected based on bulk oil consumption estimates. Despite significant effects from lubricant sulfur and phosphorus, loss of LNT NOX reduction efficiency is dominated by fuel sulfur effects. Phosphorus has been determined to have a mild poisoning effect on SCR catalysts. The extent of the effect that lubricant phosphorus and sulfur have on DOCs remains unclear, however, it appears to be minor.

A novel engine management strategy for achieving fast catalyst light-off without the use of an exhaust air pump in a port-fuel-injected, spark ignition engine was developed. A conventional 4-cylinder engine was operated with three cylinders running rich and the fourth one as an air pump to supply air to the exhaust manifold. Under steady-state cold coolant conditions, this strategy achieved near total oxidation of CO and HC with sufficiently retarded spark timing, resulting in a 400% increase in feedgas enthalpy flow and a 90% reduction in feedgas HC emissions compared to conventional operation. The strategy was also evaluated for crank starts. Using the existing engine hardware, implementing the strategy resulted in a reduction in catalyst light-off time from 28.0 seconds under conventional operation to 9.1 seconds.

Non-petroleum based liquid fuels are essential for reducing oil dependence and greenhouse gas generation. Increased substitution of alcohol fuel for petroleum based fuels could be achieved by 1) use in high efficiency spark ignition engines that are employed for heavy duty as well as light duty operation and 2) use of methanol as well as ethanol. Methanol is the liquid fuel that is most efficiently produced from thermo-chemical gasification of coal, natural gas, waste or biomass. Ethanol can also be produced by this process but at lower efficiency and higher cost. Coal derived methanol is in limited initial use as a transportation fuel in China. Methanol could potentially be produced from natural gas at an economically competitive fuel costs, and with essentially the same greenhouse gas impact as gasoline. Waste derived methanol could also be an affordable low carbon fuel.

Ethanol and acetaldehyde emissions from a direct ignition spark ignition were measured using mass spectrometry. Previous methods focused on eliminating or minimizing interference from exhaust species with identical atomic mass and fragment ions created in ionization process. This paper describes a new technique which exploits the fragment ions from ethanol and acetaldehyde. A survey of mass spectra of all major species of exhaust gas was conducted. It was found that ethanol contributes most ions in mass number 31 and that no other gas species produces ions at this mass number. Acetaldehyde detection suffers more interference. Nevertheless, it was estimated that detection at mass number 43 is possible with 10% error from 2-methylbutane. This new technique was validated in an engine experiment. By running the engine with pure gasoline and E85, the validity of the technique can be checked.

The fuel effects on HCCI operation in a spark assisted direct injection gasoline engine are assessed. The low load limit has been extended with a pilot fuel injection during the negative valve overlap (NVO) period. The fuel matrix consists of hydrocarbon fuels and various ethanol blends and a butanol blend, plus fuels with added ignition improvers. The hydrocarbon fuels and the butanol blend do not significantly alter the high or the low limits of operation. The HCCI operation appears to be controlled more by the thermal environment than by the fuel properties. For E85, the engine behavior depends on the extent that the heat release from the pilot injected fuel in the NVO period compensates for the evaporative cooling of the fuel.

Higher compression ratio and turbocharging, with engine downsizing can enable significant gains in fuel economy but require engine operating conditions that cause engine knock under high load. Engine knock can be avoided by supplying higher-octane fuel under such high load conditions. This study builds on previous MIT papers investigating Octane-On-Demand (OOD) to enable a higher efficiency, higher-boost higher compression-ratio engine. The high-octane fuel for OOD can be obtained through On-Board-Separation (OBS) of alcohol blended gasoline. Fuel from the primary fuel tank filled with commercially available gasoline that contains 10% by volume ethanol (E10) is separated by an organic membrane pervaporation process that produces a 30 to 90% ethanol fuel blend for use when high octane is needed. In addition to previous work, this paper combines modeling of the OBS system with passenger car and medium-duty truck fuel consumption and octane requirements for various driving cycles.

The autoignition characteristics of methanol, ethanol and MTBE (methyl tert-butyl ether) have been investigated in a rapid compression machine at pressures in the range 20-40 atm and temperatures within 750-1000 K. All three oxygenated fuels tested show higher autoignition temperatures than paraffins, a trend consistent with the high octane number of these fuels. The autoignition delay time for methanol was slightly lower than predicted values using reported reaction mechanisms. However, the experimental and measured values for the activation energy are in very good agreement around 44 kcal/mol. The measured activation energy for ethanol autoignition is in good agreement with previous shock tube results (31 kcal/mol), although ignition times predicted by the shock tube correlation are a factor of three lower than the measured values. The measured activation energy for MTBE, 41.4 kcal/mol, was significantly higher than the value previously observed in shock tubes (28.1 kcal/mol).

Recent evidence has linked vehicle catalysts to nitrous oxide emissions. As the population of catalyst-equipped vehicles increases, so does the need for a better understanding of this powerful greenhouse gas. Nitrous oxide measurements were made on fourteen vehicles over the FTP urban and highway cycles utilizing an FTIR analyzer. To quantify emissions from aged catalysts, emphasis was placed on testing in-use vehicles with oedometer readings between 30,000 and 120,000 kilometres. Tailpipe N2O emissions averaged 126 mg/mile for the nine aged catalyst vehicles and 74 mg/mile for the five new catalyst cars. These results are about two times greater than previous N2O studies using the FTP cycle. Also, twice as much N2O was produced during the urban driving cycle, than during the highway cycle. Based on our measurements, N2O emissions from light duty vehicles in Canada were estimated to range from 8 to 20 kilotonnes for 1992.

The use of hydrogen as a fuel supplement for lean-burn engines at higher compression ratios has been studied extensively in recent years, with good promise of performance and efficiency gains. With the advances in reformer technology, the use of a gaseous fuel stock, comprising of substantially higher fractions of hydrogen and other flammable reformate species, could provide additional improvements. This paper presents the performance and emission characteristics of a gas mixture of equal volumes of hydrogen, CO, and methane. It has recently been reported that this gas mixture can be produced by reforming of ethanol at comparatively low temperature, around 300C. Experiments were performed on a 1.8-liter passenger-car Nissan engine modified for single-cylinder operation. Special pistons were made so that compression ratios ranging from CR= 9.5 to 17 could be used. The lean limit was extended beyond twice stoichiometric (up to lambda=2.2).

Knock in gasoline engines at higher loads is a significant constraint on torque and efficiency. The anti-knock property of a fuel is closely related to its research octane number (RON). Ethanol has superior RON compared to gasoline and thus has been commonly used to blend with gasoline in commercial gasolines. However, as the RON of a fuel is constant, it has not been used as needed in a vehicle. To wisely use the RON, an On-Board Separation (OBS) unit that separates commercial gasoline with ethanol content into high-octane fuel with high ethanol fraction and a lower octane remainder has been developed. Then an onboard Octane-on-demand (OOD) concept uses both fuels in varying proportion to provide to the engine a fuel blend with just enough RON to meet the ever changing octane requirement that depends on driving pattern.

The Cu-zeolite (CuZ) SCR catalyst enables higher NOx conversion efficiency in part because it can store a significant amount of NH3. “NH3 storage control”, where diesel exhaust fluid (DEF) is dosed in accord with a target NH3 loading, is widely used with CuZ catalysts to achieve very high efficiency. The NH3 loading actually achieved on the catalyst is currently estimated through a stoichiometric calculation. With future high-capacity CuZ catalyst designs, it is likely that the accuracy of this NH3 loading estimate will become limiting for NOx conversion efficiency. Therefore, a direct measurement of NH3 loading is needed; RF sensing enables this. Relative to RF sensing of soot in a DPF (which is in commercial production), RF sensing of NH3 adsorbed on CuZ is more challenging. Therefore, more attention must be paid to the “microwave resonance cavity” created within the SCR assembly. The objective of this study was to develop design guidelines to enable and enhance RF sensing.

The focus of this study was the characterization and comparison of power-specific exhaust emission rates from a closed-loop small spark-ignited engine fuelled with ethanol and isobutanol gasoline blends. A 4-cycle Kohler ECH-630 engine certified to the Phase 3 emissions standards was operated over the G2 test cycle, a six-mode steady-state test cycle, in its original configuration. This engine was equipped with electronic ignition, electronic fuel injection and an oxygen sensor. Certification gasoline fuel was splash-blended by percent volume with ethanol and isobutanol to result in the test blend levels of E10, E15, iB16 and iB8-E10. Reductions in emission rates of carbon monoxide (up to 12.0% with the ethanol blends and up to 11.4% with the isobutanol blends) were achieved along with a reduction in total hydrocarbons (up to 10.9% with the ethanol blends and up to 8.2% with the isobutanol blends). Nitrogen oxide emissions were decreased by up to 9.8% with the ethanol blends.