Profiling Alkyl Phosphates in Petroleum Samples by Comprehensive Two-dimensional Gas Chromatography with Nitrogen-phosphorus Detection GC×GC-NPD

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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, ...