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Atmospheric modelers and development engineers need accurate measures of NO2 emissions from motor vehicles. Due to the oxidative reaction of oxygen with NO, these measurements (typically taken from a bag sample) can be inaccurate if care is not taken to minimize the sample residence time in the bags. This reaction occurs slowly at low NO concentrations, however, at higher NO concentrations the reaction can rapidly speed up (for example, 50 ppm NO will experience a 10% concentration reduction in 6.5 minutes). This report explores the factors contributing to this artifact for emissions test cells. Estimates of the error in NO2 emission rate measurements for several scenarios are presented. Additionally, kinetic expressions of the reaction rate are shown to be fairly accurate for our test conditions, but should not be used in general without verification of the non-existence of competing, hindering or accelerating species within the sample bag.

The use of Selective Catalytic Reduction (SCR) for NOx emissions control has resulted in a new challenge for the emissions measurement community. Most SCR systems require injection of urea or ammonia into the exhaust stream. Residual ammonia present in vehicle exhaust can have deleterious effects on NOx analyzers using chemiluminescent detectors (CLD). Ammonia can poison converter catalysts in CLD NOx analyzers and may react with NO2 across the converter. Both of these issues lead to erroneous NOx measurements, as well as increased maintenance costs and downtime. This paper will describe the development and use of a low-cost, simple ammonia scrubber that can easily be integrated into sampling systems and requires little change in test cell maintenance procedures. Validation results show the scrubber to have capacity sufficient to last for a full day of testing of typical vehicles.

Measurements of particulate matter (PM) from spark ignition (SI) engine exhaust using dilution tunnels will become more prevalent as emission standards are tightened. Hence, a study of the dilution process was undertaken in order to understand how various dilution related parameters affect the accuracy with which PM sizes and concentrations can be determined. A SI and a compression ignition (CI) engine were separately used to examine parameters of the dilution process; the present work discusses the results in the context of SI exhaust dilution. A Scanning Mobility Particle Sizer (SMPS) was used to measure the size distribution, number density, and volume fraction of PM. Temperature measurements in the exhaust pipe and dilution tunnel reveal the degree of mixing between exhaust and dilution air, the effect of flowrate on heat transfer from undiluted and diluted exhaust to the environment, and the minimum permissible dilution ratio for a maximum sample temperature of 52°C.

In order to understand how unburned hydrocarbons emerge from SI engines and, in particular, how non-fuel hydrocarbons are formed and oxidized, a new gas sampling technique has been developed. A sampling unit, based on a combination of techniques used in the Fast Flame Ionization Detector (FFID) and wall-mounted sampling valves, was designed and built to capture a sample of exhaust gas during a specific period of the exhaust process and from a specific location within the exhaust port. The sampling unit consists of a transfer tube with one end in the exhaust port and the other connected to a three-way valve that leads, on one side, to a FFID and, on the other, to a vacuum chamber with a high-speed solenoid valve. Exhaust gas, drawn by the pressure drop into the vacuum chamber, impinges on the face of the solenoid valve and flows radially outward.

Previous research into Particulate Matter (PM) emissions from a spark-ignition engine has shown that the main factor determining the how PM emissions respond to transient engine operating conditions is the effect of those conditions on intake port processes such as fuel evaporation. The current research extends the PM emissions data base by examining the effect of transient load and speed operating conditions, as well as engine start-up and shut-down. In addition, PM emissions are examined during “real-world” driving conditions - specifically, the Federal Test Procedure. Unlike the previous work, which was performed on an engine test stand with no exhaust gas recirculation and with a non-production engine controller, the current tests are performed on a fully-functional, production vehicle operated on a chassis dynamometer to better examine real world emissions.

In order to understand why emissions of Particulate Matter (PM) from Spark-Ignition (SI) automobiles peak during periods of transient operation such as rapid accelerations, a study of controlled, repeatable transients was performed. Time-resolved engine-out PM emissions from a modern four-cylinder engine during transient load and air/fuel ratio operation were examined, and the results could be fit in most cases to a first order time response. The time constants for the transient response are similar to those measured for changes in intake valve temperature, reflecting the strong dependence of PM emissions on the amount of liquid fuel in the combustion chamber. In only one unrepeatable case did the time response differ from a first order function: showing an overshoot in PM emissions during transition from the initial to the final steady state PM emission level.