Profiling Alkyl Phosphates in Petroleum Samples by Comprehensive Two-dimensional Gas Chromatography with Nitrogen-phosphorus Detection GC×GC-NPD - Descarga este documento en PDF. Documentación en PDF para descargar gratis. Disponible también para leer online.

Alkyl Phosphates, GC×GC, Nitrogen-phosphorus detection, Backflush, Deans Switch, Petroleum

Nizio, Katie D

Supervisor and department: Harynuk, James Chemistry

Examining committee member and department: McDermott, Mark Chemistry Serpe, Michael Chemistry Reiner, Eric External Hall, Dennis Chemistry Harynuk, James Chemistry

Department: Department of Chemistry

Specialization:

Date accepted: 2014-07-09T13:28:10Z

Graduation date: 2014-11

Degree: Doctor of Philosophy

Degree level: Doctoral

Abstract: The profiling of alkyl phosphates in petroleum samples is of particular interest to refineries that process conventional crude oil derived from the Western Canadian Sedimentary Basin and other similar geologies. This is due to alkyl phosphate-based additives used during crude oil recovery processes and the subsequent contamination of the produced oil. Phosphate contamination causes numerous problems for refineries, including equipment fouling, the poisoning of catalysts, and potential impacts on downstream processes or consumers if these phosphates enter petroleum product streams. These issues have occurred at a number of facilities across Canada with the impacts measured in the tens of millions of dollars. In response, the Canadian Association of Petroleum Producers and the Canadian Crude Quality Technical Association have specified a limit of 0.5 μg-mL total distillable phosphorus in feedstock. This limit is monitored using inductively coupled plasma – optical emission spectroscopy ICP-OES, a technique plagued with poor precision and a high limit of detection 0.5 ± 1 µg phosphorus-mL, thus making the current specification difficult to enforce. Furthermore, this method cannot provide speciation information, which is critical for developing an understanding of the challenge of alkyl phosphates at a molecular level. This thesis approaches these challenges using comprehensive two-dimensional gas chromatography with post-column Deans switching to allow for effluent flow switching between a flame ionization detector and a nitrogen-phosphorus detector GC×GC-FID-NPD. Using trimethylsilyl derivatization, splitless injection, and concurrent backflushing, the GC×GC-FID-NPD method developed and optimized herein, represents the only analytical technique currently capable of: 1 separating the alkyl phosphates from each other and from the crude oil matrix; and 2 speciating and quantifying the phosphates reproducibly in petroleum samples at trace levels levels two to three orders of magnitude below those achievable by ICP-OES. Overall, this work presents a significant step towards a routine, robust method for profiling trace alkyl phosphates in industrial petroleum and process samples in a production environment. In addition, this thesis presents preliminary results from the first-ever detailed study of alkyl phosphate contamination in a refining environment. The final results of this study will hopefully provide the chemical information needed to contemplate future mitigation strategies for handling the -phosphate problem-. This will be important to refineries across Canada that struggle with issues of equipment fouling. A mitigation strategy would be, quite literally, a multimillion-dollar idea for the Canadian petroleum industry.

Language: English

DOI: doi:10.7939-R3V38P

Rights: Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.





Autor: Nizio, Katie D

Fuente: https://era.library.ualberta.ca/

Introducción

        Profiling  Alkyl  Phosphates  in  Petroleum  Samples  by  Comprehensive  Two-­‐ dimensional  Gas  Chromatography  with  Nitrogen-­‐phosphorus  Detection   (GC×GC-­‐NPD)     by     Katie  Diana  Nizio                 A  thesis  submitted  in  partial  fulfillment  of  the  requirements  for  the  degree  of       Doctor  of  Philosophy               Department  of  Chemistry   University  of  Alberta                         ©  Katie  Diana  Nizio,  2014            ABSTRACT   The  profiling  of  alkyl  phosphates  in  petroleum  samples  is  of  particular   interest   to   refineries   that   process   conventional   crude   oil   derived   from   the   Western  Canadian  Sedimentary  Basin  and  other  similar  geologies.  This  is  due   to  alkyl  phosphate-­‐based  additives  used  during  crude  oil  recovery  processes   and   the   subsequent   contamination   of   the   produced   oil.   Phosphate   contamination   causes   numerous   problems   for   refineries,   including   equipment   fouling,   the   poisoning   of   catalysts,   and   potential   impacts   on   downstream   processes   or   consumers   if   these   phosphates   enter   petroleum   product  streams.  These  issues  have  occurred  at  a  number  of  facilities  across   Canada   with   the   impacts   measured   in   the   tens   of   millions   of   dollars.   In   response, ...

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