Note: Descriptions are shown in the official language in which they were submitted.
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TITLE OF THE INVENTION
METHOD AND SYSTEM FOR CHEMICAL AND PHYSICAL
CHARACTERIZATION OF COMPLEX SAMPLES
BACKGROUND OF THE INVENTION
Field of the Invention
[0002) The present
invention relates to a method and system for rapid
determination of composition, of crude oils and fractions thereof, as well as
other
substances and obtaining the information necessary to assess the yield of
commercially valuable fuel and lube oil fractions, for example, in a single
process.
In particular, the present invention is directed to a method and system for
determining yields and compositions in terms of a simultaneous boiling point
distributions and hydrocarbon types breakdown, across the boiling range of
interest, and determining the changes in chemical composition and yields in
upgrading and/or conversion processes, compiling a preliminary evaluation of a
variety of geochemical parameters or biomarIcers for the correlation to
fingerprint
identification, maturity, origins, etc., and compiling experimental data to
chemical
and physical properties.
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Backoround of the Technology
[0003] Gas Chromatography is a chemical analysis instrument for
separating chemicals in a complex sample. A gas chromatograph uses a narrow
tube, known as a column, through which different chemical constituents of a
sample pass in a gas stream. The gas stream is also called the carrier gas or
mobile phase. Gas Liquid Chromatography (GLC), or simply pas Chromatography
(GC) is a type of chromatography in which the mobile phase is a gas. The
chemical constituents within the sample pass through the column at different
rates,
depending on their various chemical and physical properties and their
interaction
with a specific column phase . This column phase is called the stationary
phase
and is a microscopic layer of liquid on an inert solid support in the column.
If the
phase is bonded directly to the tubing it is called a capillary column The
column is
often flexible so that a very long column can be wound into a small coil.
[0004] The column(s) in a GC are contained in an oven, the temperature of
which is precisely controlled (e.g., electronically). The rate at which a
sample
passes through the column is directly proportional to the temperature of the
column. The higher the column temperature, the faster the sample moves through
the column. However, when a sample moves quickly through the column, it
interacts less with the stationary phase, and the analytes are less separated.
(0005) As the chemical constituents exit the end of the column, they are
detected and identified electronically by a detector.. The stationary phase
separates the different components, causing each one to exit the column at a
different time, which is called the retention time. Other parameters can also
be
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used to alter the order or time of the retention, such as the carrier gas flow
rate and
the temperature as well as the chemical nature of the phase..
100061 However,
conventional GC may require high resolution techniques in
order to provide a satisfactory analysis of the chemical constituents of a
complex
sample.
SUMMARY OF THE INVENTION
100071 There is
a need in the art, therefore, for methods and systems for
analyzing complex samples using gas chromatography that do not require high
resolution techniques. The present invention solves the above-identified
needs, as
well as others by providing methods and systems for rapid determination of
composition of crude oils and fractions thereof, as well as other substances,
and in
a single process obtaining the information necessary to assess the yield of
commercially valuable petroleum fuel and lube oil fractions using Gas
Chromatography ¨ FID/Mass Spectrometry. Variations of the present invention
also include auto sampler features, a wall coated capillary column, a
temperature
programmable injector and data processing features for compiling and
processing
experimental data. Embodiments of the present invention further include a
computer system with application software and a communication network. The
present invention, in one embodiment, provides a graphical user interface for
the
entry of data, and for displaying information, such as in a graphical manner,
to
show the relationship of various determined outputs and results.
100081 Among
other things, the present invention enables
multidimensionality with simple hardware, wherein a low resolution column is
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sufficient for analyses and additional highly resolving techniques are not
required.
In addition, the present invention provides hydrocarbon type analysis and
Simulated Distillation ("SimDis") data, including providing such analysis and
data in
a single process.
100091
Additional advantages and novel features of the invention will be set
forth in part in the description that follows, and in part will become more
apparent
to those skilled in the art upon examination of the following or upon learning
by
practice of the invention.
BRIEF DESCRIPTION OF THE FIGURES
1000101 For a
more complete understanding of the present invention,
the needs satisfied thereby, and the objects, features, and advantages
thereof,
reference is now made to the following description taken in connection with
the
accompanying drawings.
1000111 Figure 1
shows a diagram of an exemplary Gas Chromatography¨
FID/Mass Spectrometry apparatus (GC-FID/MS) according to an embodiment of
the present invention.
1000121 Figure 2
illustrates a block diagram of various exemplary computer
system components for use in accordance with one embodiment of the present
invention
[00013] Figure 3
shows an exemplary communication system of the present
invention for use with the computer system 1 of Figure 2.
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[00014] Figure 3B shows a flow chart of an exemplary method according to
an embodiment of the present invention.
[00015) Figure 4 shows the results of a sample analyzed in accordance with
a method and system of an embodiment of the present invention.
[00016) Figure 5 shows results for three injections of a similar material
analyzed according to a method and system of an embodiment of the present
invention.
1000171 Figure 6 shows results for three injections of a similar material
analyzed according to a method and system of an embodiment of the present
invention.
1000181 Figure 7 shows a retention time standard for ASTM D 7169-2005.
[00019] Figure 8 shows a crude oil boiling point calibration curve.
[00020] Figure 9 shows the measured results of a reference material.
1000211 Figure 10 shows the measured results for a crude oil sample.
1000241 Figure 11 shows a retention time calibration standard useable in
accordance with embodiments of the present invention.
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100025) Figure 12 shows a whole crude oil analysis useable in accordance
with embodiments of the present invention.
[00026] Figure 13 shows experimental results of a measured fraction
analyzed in accordance with methods and systems of embodiments of the present
invention.
1000271 Figure 14 shows the signal overlapping from fractions, along with
crude oil, produced using analysis in accordance with methods and systems of
embodiments of the present invention.
(00028) Figure 15 shows an analysis of Fraction #1. as analyzed according
to
a method and system of an embodiment of the present invention.
1000291 Figure 16 shows an analysis of Fraction #1 cut in whole crude, as
analyzed according to a method and system of an embodiment of the present
invention.
[00030] Figure 17 shows the results of a sample of paraffinic light crude
oil,
as analyzed according to a method and system of an embodiment of the present
invention.
[00031] Figure 18 shows the results of a sample of paraffinic crude oil, as
analyzed according to a method and system of an embodiment of the present
invention.
[00032] Figure 19 shows the results for samples of lube oil fractions, as
analyzed according to a method and system of an embodiment of the present
invention.
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1000314 Figures 20-42
contain various ciete and other infcrmation produced
using systiwns and methods of tie present invention.
DETAILED DESCRIPTION
1000371 Referring now to
Figure I. therein shown Is the general architecture
of an exemplary Gas Chronutography¨FIO/Mass Spectrometry apparatus (GC-
F1D/MS). as used in accordanai with a method and system of the present
invention.
MOM) The GC-FIDAiR3 of
Figure 1 includes a gas chromabgraph (100),
which indudes an injector (200), a oolurnn (300), and an oven (400); a mass
spectrometer (MS) (SOO); a flame ion detector (FE)) (500); a divkler (700) end
a
data processing system for acquiring and processing the dots. One variation
provides a graphical user literface for the entry of data and for dimpleying
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information, such as in a graphical manner, to show the relationship of
various
determined outputs and results.
[00039] In
certain embodiments, the GC-FID/MS may also include an
automatic liquid sampler (ALS). In addition, the column may be a wall coated
capillary column, and the inlet may be a temperature programmable injector.
[00040] In
operation, the gas chromatograph (100) utilizes the difference in
chemical properties between different chemical constituents in a sample to
separate the chemical constituents. As the different chemical constituents
exit the
gas chromatograph at different times, the mass spectrometer, which is located
downstream in the gas flow, evaluates the chemical constituents separately and
is
able to identify the constituents.
[00041] The
mass spectrometer (600) identifies the various chemical
constituents that pass through it at a flow D2 by breaking each constituent
into
ionized fragments and detecting these fragments using the mass to charge ratio
of
the fragments.
[00042] The FID
(500) is, for example, an ion detector that uses an air-
hydrogen flame to produce ions. As the chemical constituents in the sample
exit
the gas chromatograph at a flow D1, they pass through the flame and are
burned,
producing ions. The ions then produce an electric current, which is used to
provide
the signal output of the FID. The FID of some embodiments can only detect
components that can be burned, and the FID destroys the components during
detection. Thus, no further detection is made after the FID completes
processing.
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1000431 However, it should be noted that the nature and amount of
constituents that flow through the mass spectrometer 600 and through the FID
500
may be similar in order to combine the results obtained by the MS 600 and by
the
FID 500. For this reason, the apparatus of this embodiment of the present
invention also includes a divider (700) that divides the exiting chemical
constituent
between the FID and the MS, so that portions of the exiting chemical
constituent
are analyzable by both the FID and MS simultaneously. The divider 700 should
be
able to prevent molecule discrimination in the constituents and distribute the
constituents equally between the flow D1 and the flow 02, which is achieved by
heating the constituents at a temperature necessary to ensure that no
molecular
discrimination occurs. Furthermore, pneumatic control module (PCM) may be part
of the GC-FID/MS, that controls the pressure of the sample as it passes
through
the divider in order to preserve an equal ratio of constituents flowing
through D1,
and another PCM that controls the pressure of the sample as it passes through
the
divider in order to preserve an equal ratioof constituents flowing through D2,
so
that the amount of constituents that pass through D1 is about equal to the
amount
of constituents that pass through D2. In one embodiment, the divider may be or
include a micro influx divider. In one embodiment, the division between the
portion
of the exiting chemical constituent that is sent to the MS (02) and the
portion of the
exiting chemical constituent that is sent to the FID (Dl) are approximately
equal,
so that approximately D2/D1 = I. The influx of chemical constituents are
precisely
divided in a controlled manner without compromising the sample integrity. The
controlled division of the elution of the column towards the two detectors is
prevented from being discriminatory, either of light components or of heavy
components, for the samples under analysis.
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1000441 An exemplary embodiment, of the present invention uses a
megabore capillary high throughput column and a temperature programmable
injector. In one embodiment, the column includes a capillary column element
that
is about 5 m by 0.53 mm i.d. by about 0.1 pm; the FID detector is an FID 440
Celsius; the carrier gas is Helium at a constant flux rate of about 12 mUmin;
the
oven is programmed to start at about 40 Celsius, to raise about 100
Celsius/min
until about 430 Celsius is reached, to maintain the temperature for about 12
minutes, with an equilibrium time of about two minutes; the injection volume
is
about 0.2 pL; and the dilution is about 2% in CS2. It should be noted that
hydrogen could be used instead of helium as the carrier gas.
1000451 In one embodiment of the present invention, the GC-FID/MS may be
used to analyze the physical and chemical characterization of petroleum
fractions.
Using the GC-FID/MS, a rapid determination may be made of the composition of
crude oils, for example. This apparatus and method may also be applied to
fractions of crude oil, or other substance. Information necessary to access
the
yield of commercially available valuable fuel and lube oil fractions can also
be
obtained in a single process. Using quantitative software or other processing,
the
mass spectral data may be converted to weight and volume percent chemical
composition. The system and method provide the boiling point distribution and
chemical composition of the analyzed substance based on saturate and aromatic
group types.
[00046] Crude oil, for example, may contain a mixture of chemical
compounds from a family of several hundred chemical compounds. Some
chemicals that may be found in crude oil include hexane, jet fuels fraction,
diesel
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fractions, benzene, toluene, xylenes, naphthalene, and fluorine, in addition
to other
petroleum products such as heavy diesel, atmospheric residues, vacuum residues
and gasoline naphtha to be used in gasolines. The characterization of complex
fractions and versatility are improved by combining the signals of the FID
detector
and the mass spectrometer detector in a single processing apparatus. In an
exemplary embodiment, the signal from the FID detector is in the simulated
distillation mode and the MD detector is in a single environment of
synergistic
mode. The MD detector provides ion fragmentation at continuous time intervals
during the elution of the sample though the column.
1000471 The present
invention thus is able to provide a powerful analytical
tool allowing the simultaneous physical and chemical characterization of whole
crude oil samples and their fractions, without the need to perform the
physical
separation of the hydrocarbon fractions.
(00048) In an exemplary
embodiment, the FID detector is in a simulated
distillation mode. Simulated
distillation (SimDis) is a gas chromatography
technique that separates individual hydrocarbon components in their order of
boiling points and is used to simulate the time-consuming laboratory-scale
physical
distillation procedure referred to as true boiling point distillation. Using a
gas
chromatograph equipped with an oven and inlet that can be temperature
programmed, an FID is used for detection and measurement of the hydrocarbon
analytes. The result of SimDis analysis provides a distillation curve which is
a
quantitative percent mass yield as a function of boiling point of the
hydrocarbon
components of the sample.
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[00049] In some
embodiments, the present invention conforms with the
ASTM (American Society for Testing and Materials) standards for stimulated
distillation: D-2887, D-6352, and 0-7169. Simulated distillation is a proven
and
accepted technique for the physiochemical characterization of crude and
fractions
of oil. Recently, ASTM D2 accepted a new method for the analysis of fractions
with a final boiling point of 615 Celsius (C5 to C60). See ASTM D 7213-05.
[00050] The
quantitative methods of mass spectrometry can also serve as
helpful tools in the chemical characterization of products with a vast range
of
boiling points. Mass spectrometry reports a composition in the basis of five
principal groups: paraffin, napthalene, aromatic, sulfur, and non-identified.
All of
the ASTM methods, with the exception of those applying to napthalenes, require
a
chromatographic separation of the saturated and aromatics. Such separation
requires high resolution methods. High resolution requires complex and costly
equipment. New multidimensional analytical mechanisms, such as GC x GC and
GC-MS-TOF, also require complex instruments and procedures, even for the
gasoline range.
[00051] The
present invention enables spectrometric analysis within fractions
at a low resolution. Thus, it allows simple and quick analysis.
[00052] Figure 2
illustrates a block diagram of various computer system
components useable with an exemplary implementation of a physical and chemical
characterization of petroleum fractions by GC/SIMDIS/MS, in accordance with
embodiments of the present invention.
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[000531 As shown
in Figure 2, the controller of the present invention may be
implemented using hardware, software or a combination thereof and may be
implemented in one or more computer systems or other processing systems. In
one embodiment, the invention is directed toward one or more computer systems
capable of carrying out the functionality described herein.
[00054] Figure 2
shows a computer system 1 that includes one or more
processors, such as processor 4. The processor 4 is connected to a
communication infrastructure 6 (e.g., a communications bus, cross-over bar, or
network). Various software embodiments are described in terms of this
exemplary
computer system. After reading this description, it will become apparent to a
person skilled in the relevant art(s) how to implement the invention using
other
computer systems and/or architectures.
[000551 Computer
system 1 can include a display interface 2 that forwards
graphics, text, and other data from the communication infrastructure 6 (or
from a
frame buffer not shown) for display on the display unit 30. Computer system 1
also
includes a main memory 8, preferably random access memory (RAM), and may
also include a secondary memory 10. The secondary memory 10 may include, for
example, a hard disk drive 12 and/or a removable storage drive 14,
representing a
floppy disk drive, a magnetic tape drive, an optical disk drive, etc. The
removable
storage drive 14 reads from and/or writes to a removable storage unit 18 in a
well
known manner. Removable storage unit 18, represents a floppy disk, magnetic
tape, optical disk, etc., which is read by and written to removable storage
drive 14.
As will be appreciated, the removable storage unit 18 includes a computer
usable
storage medium having stored therein computer software and/or data.
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[000561 In alternative embodiments, secondary memory 10 may include other
similar devices for allowing computer programs or other instructions to be
loaded
into computer system 1. Such devices may include, for example, a removable
storage unit 22 and an interface 20. Examples of such may include a program
cartridge and cartridge interface (such as that found in video game devices),
a
removable memory chip (such as an erasable programmable read only memory
(EPROM), or programmable read only memory (PROM)) and associated socket,
and other removable storage units 22 and interfaces 20, which allow software
and
data to be transferred from the removable storage unit 22 to computer system
1.
1000571 Computer system 1 may also include a communications interface 24.
Communications interface 24 allows software and data to be transferred between
computer system 1 and external devices. Examples of communications interface
24 may include a modem, a network interface (such as an Ethernet card), a
communications port, a Personal Computer Memory Card International Association
(PCMCIA) slot and card, etc. Software and data transferred via communications
interface 24 are in the form of signals 28, which may be electronic,
electromagnetic, optical or other signals capable of being received by
communications interface 24. These signals 28 are provided to communications
interface 24 via a communications path (e.g., channel) 26. This path 26
carries
signals 28 and may be implemented using wire or cable, fiber optics, a
telephone
line, a cellular link, a radio frequency (RF) link and/or other communications
channels. In this document, the terms "computer program medium" and "computer
usable medium" are used to refer generally to media such as a removable
storage
drive 14, a hard disk installed in hard disk drive 12, and signals 28. These
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computer program products provide software to the computer system 1. The
invention is directed to such computer program products.
[00058] Computer
programs (also referred to as computer control logic) are
stored in main memory 8 and/or secondary memory 10. Computer programs may
also be received via communications interface 24. Such computer programs,
when executed, enable the computer system 1 to perform the features of the
present invention, as discussed herein. In particular, the computer programs,
when executed, enable the processor 4 to perform the features of the present
invention. Accordingly, such computer programs represent controllers of the
computer system 1.
[00059] In an
embodiment where the invention is implemented using
software, the software may be stored in a computer program product and loaded
into computer system 1 using removable storage drive 14, hard drive 12, or
communications interface 24. The control logic (software), when executed by
the
processor 4, causes the processor 4 to perform the functions of the invention
as
described herein. In another embodiment, the invention is implemented
primarily
in hardware using, for example, hardware components, such as application
specific integrated circuits (ASICs). Implementation of the hardware state
machine
so as to perform the functions described herein will be apparent to persons
skilled
in the relevant art(s).
[00060] In yet
another embodiment, the invention is implemented using a
combination of both hardware and software.
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1000611 Figure 3
shows a communication system 30 of the present invention
for use with the computer system 1 of Figure 2. The communication system 30
includes an accessor 31 (also referred to interchangeably herein as a "user)
and a
terminal 32. In one embodiment, data for use in the computer system 1 is, for
example, input and/or accessed by the accessor 31 via the terminal 32, such as
a
personal computer (PC), minicomputer, mainframe computer, microcomputer,
telephonic device, or wireless device, such as a hand-held wireless device
coupled
to a server 33, such as a PC, minicomputer, mainframe computer, microcomputer,
or other device having a processor and a repository for data and/or connection
to a
processor and/or repository for data, via, for example, a network 34, such as
the
Internet or an intranet, and couplings 35, 36. The couplings 35, 36 include,
for
example, wired, wireless, or fiberoptic links. In another embodiment, the
method
and system of the present invention operate in a stand-alone environment, such
as
on a single terminal.
1000621 Figure
3B shows a flow chart according to a method in accordance
with an embodiment of the present invention. In step S1, a sample to be
analyzed
is injected into a column of a gas chromatograph along with a flowing gas via
an
injector. In step S2, the constituents of the sample are separated within the
column of the gas chromatograph. In step S3, the constituents are moved
through
and out of the column with the flowing gas. In step S4, the constituents of
the
sample are divided as the constituents exit the column. The divided
constituents
are supplied to a flame ion detector and a mass spectrometer. According to
various exemplary embodiments, the sample is divided via a divider, and the
constituents are heated at a temperature necessary to ensure that there is no
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molecule discrimination between the supply of constituents to the mass
spectrometer and the supply of constituents to the flame ion detector. Thus,
the
portion of the constituents that is sent to the mass spectrometer and the
portion of
the constituents that is sent to the flame ion detector are approximately
equal, and
the integrity of the constituents is preserved. In step S5, the
characteristics of the
constituents of the sample are detected via the flame ion detector. In step
S6, the
characteristics of the constituents of the sample are detected via the mass
spectrometer. It should be noted that although steps S5 and S6 describe the
detection via the mass spectrometer occurring before the detection via the
flame
ion detector, the order could be reversed, or the detection via both the mass
spectrometer and the flame ion detector can take place at the same time. After
the
characteristics are detected, the data may be acquired and processed by a data
processing system. The accumulated data from both detectors obtained from
continuous equal time slice analysis is stored for subsequent processing.
[00063] Yields
and compositions, in terms of the boiling point distributions
and hydrocarbon type breakdowns across the boiling range of interest, may be
determined. In addition, changes in chemical compositions and yields in
upgrading
and/or conversion processes may be analyzed and studied.
[00064] Among
other things, the present invention may be used to establish a
preliminary evaluation of a variety of geochemical parameters or biomarkers
for the
correlation to fingerprint identification, maturity, origins, etc., of crude
oil or fraction
thereof that is analyzed. Experimental data may be correlated to chemical and
physical properties. This enables refining strategies to be planned to
maximize
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yields of required products without affecting their quality. Feedstocks can be
rapidly tested by correlating the composition of products to quality.
1000651 In
addition, the distribution and type of sulphur compounds in
distillates may be determined. The profile and quantities of heterocompounds
in
distillates may be studied by coupling specific detectors to the apparatus.
1000661
Exemplary results produced using application of the present
invention to crude oil is shown in Figure 4. Figure 4 shows the
multidimensionality
of the information that may be gathered. Figure 4 also shows the results
detected
by the MS, the results detected by the FID, and the combined information.
1000671 The
present invention is fast, with high repeatability, as shown in
Figures 5 and 6. Figure 5 shows the results for 3 injections, with one axis
showing
the signal intensity and the other showing time. The three results nearly
overlap
each other. The actual values for the three injections are shown in the
boiling point
table. Figure 6 shows another set of results for three injections of
paraffinic crude
oil, produced using a method and system in accordance with an embodiment of
the
present invention. Thus, the present invention can serve as an excellent
screening
technique to study the efficiency of physical distillations and refining
processes and
can rapidly establish the main compositional characteristics of crude oils, so
that
their quality for decision making purposes can be quickly established.
Further, the
present invention can serve as part of a quick exploration tool to establish
the
principle characteristics of crude oil quality allowing for decisions on
refinement
planning and commercialization.
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[00068] Figure 7 shows
a retention time standard for ASTM D 7169-2005.
Figure 8 shows a crude oil boiling point calibration curve. Figure 9 shows the
measured results of a reference material. Figure 10 shows the measured results
for a crude oil sample. Table 1 shows
algorithms used for analyzing for each
time slice the contributions of each ion characteristic of the hydrocarbon
group of
aromatics and saturates. Although Table 1 references algorithms disclosed in
Robinson (Analytical Chemistry, Vo. 43, 11, 1971), these algorithms are
exemplary
only and other, more refined algorithms and multiple variant equations may be
used to extract the various compositions of the various constituents of the
sample
being tested. These algorithms allow the superimposition of masses at various
time intervals to extract the composition of each constituent. Table 2 shows a
group type analysis of compounds that may be found within crude oil. Figure 11
shows a retention time calibration standard, useable according to a method and
system of an embodiment of the present invention. Figure 12 shows a whole
crude oil analysis, produced according to a method and system of an embodiment
of the present invention. Figure 13 shows experimental results of a measured
fraction. Figure 14 shows the signal overlapping from fractions, along with
crude
oil. Figure 15 shows an analysis of Fraction #1. Figure 16 shows an analysis
of
fraction #1 cut in whole crude. Figure 17 shows the results of a sample of
paraffinic light crude oil. Figure 18 shows the results of a sample of
paraffinic
crude oil. Figure 19 shows the results for samples of lube oil fractions.
Tables 3
and 4 show a hydrocarbon type analysis from a whole crude sample. Table 5
shows a comparative study of middle hydrocarbon samples.
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WON Figures 20-42 and Tables 6.7,8 and 9 contain various data and other
information produced using systems and methods of the present invention.
Waal Example antmllments of
the present inverehon hem now been
desalbed in acconlance ibalth Ihe above advents:9es. It we be appreciated that
the exerrades are merely
Illustrative of the Invention. Many verb:done end
medications I be appose* lb boom skilled In the art.
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The Algorithm:
AROMATICS
SATURATES
/43 - paraffins
E104+...117 ...-Clase II 155
cycloparaffins
N.) E 81
- dicycloparaffins ED
E130+...129+...-Clase III
0-
cr)
/ 93 - tricycloparaffins
/128 ...141 ...-Clase IV
/1541-...167+...-Clase V
E166+...179+...-Clase VI
/1784-...191+...-Clase VII
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Table 2
Group Type Analysis
Compound Class Type
. Series Group
Alkyl benzenes I 0 -6 Monoaromatics
Benzothiophenes I 1 -10S Thiophenoaromatics
Naphthenephenantrenes I 2 -20 Tri aromatics
Naphthenebenzenes II 0 -8 Monoaromatics
Pyrenes II 1 -22 Tetraaromatics
Unidentified II 2 Unidentified
Dinaphthenebenzenes III 0 -10 Monoaromatics
Chrysenes III 1 -24 Tetraaromatics
Unidenitifed III 2 Unidentified
Naphtalenes IV 0 -12 Diaromatics
Dibenzothiophenes IV 1 -16S Thiophenoaromatics
Unidentified IV 2 Unidentified
Acenaphthenes+ V 0 -14-160 Diaromatics
Dibenzofurans
Perylenes V 1 -28 Pentaaromatics
Unidentified V 2 Unidentified
Fluorenes VI 0 -16 Diaromatics
Dibenzanthracenes VI 1 -30 Pentaaromatics
Unidentified VI 2 Unidentified
Ph enanthrenes VII 0 -18 Triaromatics
Naphthobenzothiophenes VII 1 -22S Thiophenoaromatics
Unidentified VII 2 Unidentified
- 22 -
CA 02659402 2013-11-07
WO 2008/005335 PC17US2007/015131
Table 3
Hydrocarbon Type Analysis (From the Whole Crude)
SP 0 LMO MMO
Time Time Time
interval interval interval
21 - 33 min. 24 - 42 28 - 56 min
min.
= Total Saturates, %p
76.0 (75.3) I 69.2 (693) 54.2 (53.6)
Paraffins 42,7 (39,7) 1 33.5 (27.2)
20.2 (17.4)
Monocycloparaffins 14.3 (13.1) 1 13.8 (14.2)
12.2 (13.4)
Dicycloparaffins 10.4 (7.2) I 10,9 (12.6) 9.4
(10.3)
Tricycloparaffins+ 8.6 (15.4) 11,0(15.4) 12.3(12.6)
- Total Aromatics, %p 24.0 (24.7) 30.8 (30.5)
45.8 (46.4)
Monoaromatics 10.8 (10.5) 11,9 (12.9) 20.7
(21.0)
Benzenes 3.8 (3.3) 3.8 (4.0) 7.1 (7.0)
Naphthenebenzenes 3.2 (3.4) 3.7 (4.0) 6.3 (6.5)
Dinaphthenebenzenes 3.9 (3.7) 1 4.4 (4.9) 7.2 (7.4)
- Diaromatics I 4.0 (5.2) I 5.4 (3.5) 7.6 (6.9)
Naphthalenes I 0.0 (0.0) 0.0 (0,0) 0.0 (0.0)
Acenaphthenes, 1.4 (2.5) 1.9 (0.8) 1,8 (2.0)
Dibenzofurans
Fluorenes 2.6 (2.7) 3.5 (2.7) 5.7 (4.9)
- Triaromatics 2.7 (1.9) 3.8 (2.2) 1.7 (3.0)
Phenanthrenes 2.0 (1.1) 2.4 (1.0) , 1.2 (1.6)
Naphthenophenanthrenes 0.7 (0.9) 1,4 (1.2) 0.6 (1.4)
- Tetraaromatics 1.7 (2.1) 3.1 (4.3) 4.7 (3.4)
Pyrenes 1.4 (1.60 2.2 (2.7) 2.7 (1.8)
Chrysenes 0.3 (0.5) 1.0 (1.6) 1.9 (1.6)
- Pentaaromatics 0.0 (0.6) 0.3 (0.5) 0.9 (1.3)
Perylenes 0.0 (0.6) 0.2 (0.4) 0.5 (1.1)
Dibenzanthracenes 0.0 (0.0) 0.1 (0.1) 0.3 (0.2)
- Thiophenes 4.7 (4.2) 6.2 (6.8) 7.3 (6.8)
Benzothiophenes 2.4 (2.1) 2.5 (2.3) 2.6 (2.4)
Dibenzathiophenes 2.1 (2,1) 3.2 (2.9) 3.6 (3.2)
Naphthobenzothlophenes 0.2 (0.0) 0.5 (1.6) 1.1 (1,2)
Unidentified Aromatics 0.0 (0.0) 0.1 (0.3) 3.1 (4.1)
Class II 0.0 (0.0) 0.1 (0.0) 0.3 (1.1)
Class III 0.0 (0,0) 0.0 (0.0) 0.3 (0.4)
IClass IV I 0.0 (0.0) I 0.0 (0.3) 2.3 (2.2)
Class V 1 0.0 (0.0) 1 0.0 (0.0) 0.0 (0.0) 1
- 23 -
CA 02 659402 2013-11-07
WO 2008/005335 PCT/US2007/015131
Table 4
Hydrocarbon Type Analysis (From the Whole Crude)
SPO MMO LMO
Time Time Time
interval interval interval
21-33 mins. 24-42 28-56 mins.
min.
Unidentified Aromatics 0.0 (0.0) 0.1 (0.3) 3.1 (4.1)
Class II 0.0 (0.0) 0.1 (0.0) 0.3 (1.1)
Class III 0.0 (0.0) 0.0 (0.0) 0.3 (0.4)
Class IV 0.0 (0.0) 0.0 (0.3) 2.3 (2.2)
Class V 0.0 (0.0) 0.0 (0.0) 0.0 (0.0)
Class VI 0.0 (0.0) 0.0 (0.0) 0.0 (0.1)
Class VII 0.0 (0.0) 0.0 (0.0) 0.1 (0.3)
- 24 -
(s]
01
C=J
u,
COMPARATIVE STUDY OF MIDDLE HYDROCARBON SAMPLES
0
0,
TOTAL AROMATICS CONTENT %w
0
ty=
SAMPLE SEC
MS 0
(xi
01
ASTM D 5186
Group Type
Mono
Mono 0
Low Sulphur Diesel 23.8
27.27
Jet Fuel 14.57
12.19
Light Catalytic Gas Oil 30.51
33.74
*- Poliolefins matrix interference
c)
(A
r74;
0
a
Quantitative Analysis for groups
g
Lii
,,,
AROMATIC
SATURATED
78+...91+... - mono 43
- paraffins (,
104+...117+... -Clase II 55
- cycloparaffins 2
¨1 `11'
co ,.
,
IQ 81
- dicycloparaffins F-D- 2
a) 130-F...129+...- Case III
,
,0)
',.7;
araffins
clop
i
128+...141+... -Clase IV 93
- tricy ,-
,-
,
0
,
154+..A67+... -Clase V
166+...179+... -Clase VI
no
n
zi
178+...191+... -Clase VII
4
8
z.I
d
C.J. Robinson. Analytical Chemistry, vol. 43, 11,1971
.-
,,-
..,
CA 02 659402 2013-11-07
WO 2008/005335 PCT/US2007/015131
Table 7
- Total Aromatics Top 124.0 (24.7) Typical Report
Monoaromatics 110.8 (10.5)
benzenes I 3.8 (3.3)
naphthenebenzenes - 3.2 (3.4) -Total Saturated
76.0 (75.3)
Dinaphthenebenzenes 3.9 (3.7) %p
Diaromatics 4.0 (5.2) Paraffins 42.7
(39.7)
Naphthalenes 0.0 (0.0)
Acenaohthenes, 1.4 (2.6) Monoparaffins
14.3 (13.1)
Dibenzothiophenes
Fluorenes 2.6 (2.7) dicycloparaffins
10.4 (7.2)
Triaromatics 2.7 (1.9)
Phenanthrenes 2.0 (1.1)
Tricycloparaffins+ 8.6 (15.4)
naphthenephenantrenes 0.7 (0.9)
tetraaromatics 1.7 (2.1)
pyrenes 1.4 (1.60)
chrysenes 0.3 (0.5)
pentaaromatics 0.0 (0.6)
preylenes 0.0 (0.6)
dibenzofurans 0.0 (0.0)
-thiophenoaromatics I 4.7 (4.2)
benzothiophenes 2,4 (2.1)
dibenzothiophenes I 2.1 (2.1)
naphthobenzothioph 0.2 (0.0)
Unidentified Aromatics 0.0 (0.0)
- 27 -
0
t.)
=
=
GC
a
!A
C.4
La
CA
COMPARATIVE STUDY OF MEDIUM DISTILLATIONS
0
.
i.,
H
(3,
0,
a)
ko
c:)-
0.
r.) Total Aromatics %w
a) 0
1.)
co
L
0
1-.
w
i
1-.
1-.
i
0
Mono Total
Mono Total ..,
Diesel 23.18 33.23
27.27 36.64
Jet Fuel 14.57 18.38
12.19 16.90
Gas Oil 30.51 75.25
33.74 87.26*
v
en
.-3
-e-
up
IQ
o
0
-a
,...
4
e..)
1-,
CA 02659402 2014-02-05
WO 2wwestu33 PCINS2111117/1115131
Table 9
Fraction Yield
I field %
Fraction Medium Heavy Integrated
Crude Crude Product
Medium
Distillation 22.05 16.91 17.77
420 F ¨
755 F
Lubricants
650 F ¨ 24.84 22.30 34.28
1000 F
