Date of Award

2006

Degree Type

Thesis

Degree Name

Doctor of Philosophy

Program

Electrical and Computer Engineering

Supervisor

Dr. Zdenek Kucerovsky

Abstract

The project is focused on the determination of Raman spectra of hydrocarbon fuel samples using a spectrometer employing a silicon linear array detector which has a spectral range of 400 nm to 1.1 um. The spectra are processed using chemometric techniques in order to determine the concentrations of the tracked blend components and analytical values that are used to ensure that desired specifications are achieved. The verification is based on the American Standard Testing Methods procedures for the determination of the motor, research, and road octane numbers, simulated distillation and Reid vapour pressure. Blending is one of the most important steps in the final production of hydrocarbon fuels; as many as ten complex components are mixed to achieve the desired properties of the final product. Traditionally, blending relies on well-established analytical methods such as gas chromatography for component and simulated distillation analysis, knock engines and near infrared spectroscopy for octane analysis. All of these methods are reliable and accurate, but their results are not available in real time but rather with a substantial delay, since it is in the nature of the methods that the sample must be transported from a test site to the site where the instrument is located. Additional time is required for performing the analytical procedure; e.g. the results of a gas chromatography analysis are only available from minutes to hours after the sample has been introduced into the instrument. Consequently, the results, although accurate, become only available after the process of blending has been completed. The thesis describes an implementation of a Raman spectroscopic method, which is novel in the given context, since it allows monitoring and control of the blending process online, in real time. A Raman spectrometer was designed, using a solid state laser for excitation (785 nm, 800 mW), a blazed grating for the diffraction (600 lines-per-millimeter, 750 nm blaze, 635 nm spectral range). The spectrometer was integrated with a silicon, linear array detector, cooled with a Peltier effect stack. In order to make the optical system of the spectrometer suitable for industrial use, the instrument comprised optical fiber conduits that have alleviated the alignment difficulties, eliminated the sample transport delay, and allowed the sample collection via an optical probe. The spectrometer has been tested in an industrial environment and the results obtained compared with the data yielded by the traditional analytical method of gas chromatography, and the contemporary near infrared spectroscopy. For benzene, which was used as a standard, the noise-limited detection limit of the spectrometer was 1600 ppmv for the Raman spectrometer, which compares to the detection limit of 5000 ppmv of the near infrared spectrometer, and the typical value of 10 ppm yielded by a gas chromatograph. The time interval between the sampling and availability of results was from 10 to 30 seconds for the near infrared the Raman instruments, which compared favourably with the approximately 5 to 120 minute interval required in gas chromatography.

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