Note: Descriptions are shown in the official language in which they were submitted.
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Rapid Thermal Processing of Heavy Hydrocarbon Feedstocks
The present invention relates to the rapid thermal processing of viscous oil
feedstocks. More specifically, this invention relates to the use of pyrolysis
in order to
upgrade and reduce the viscosity of these oils.
BACKGROUND OF THE INVENTION
Heavy oil and bitumen resources are supplementing the decline in the
production of conventional light and medium crude oil, and production form
these
resources is expected to dramatically increase. Pipeline expansion is expected
to handle
the increase in heavy oil production, however, the heavy oil must be treated
in order
to permit its transport by pipeline. Presently heavy oil and bitumen crudes
are either
made transportable by the addition of diluents or they are upgraded to
synthetic crude.
However, diluted crudes or upgraded synthetic crudes are significantly
different from
conventional crude oils. As a result, bitumen blends or synthetic crudes are
not easily
processed in conventional fluid catalytic cracking refineries. Therefore, in
either case
the refiner must be configured to handle either diluted or upgraded
feedstocks.
Many heavy hydrocarbon feedstocks are also characterized as comprising
significant amounts of BS&W (bottom sediment and water). Such feedstocks are
not
suitable for transportable by pipeline, or upgrading due to the sand, water
and
corrosive properties of the feedstock. Typically, feedstocks characterized as
having
less than 0.5 wt. % BS&W are transportable by pipeline, and those comprising
greater
amount of BS&W require some degree of processing and treatment to reduce the
BS&W content prior to transport. Such processing may include storage to let
the water
and particulates settle, followed by heat treatment to drive of water and
other
components. However, these manipulations are expensive and time consuming.
There
is therefore a need within the art for an efficient method for upgrading
feedstock
comprising a significant BS&W content prior to transport or further processing
of the
feedstock.
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Heavy oils and bitumens can be upgraded using a range of rapid processes
including thermal (e.g. US 4,490,234; US 4,294,686; US 4,161,442),
hydrocracking
(US 4,252,634) visbreaking (US 4,427,539; US 4,569,753; US 5,413,702) or
catalytic
cracking (US 5,723,040; US 5,662,868; US 5,296,131; US 4,985,136; US
4,772,378;
US 4,668,378, US 4,578,183) procedures. Several of these processes, such as
visbreaking or catalytic cracking, utilize either inert or catalytic
particulate contact
materials within upflow or downflow reactors. Catalytic contact materials are
for the
most part zeolite based (see for example US 5,723,040; US 5,662,868; US
5,296,131;
US 4,985,136; US 4,772,378; US 4,668,378, US 4,578,183; US 4,435,272; US
4,263,128), while visbreaking typically utilizes inert contact material (e.g.
US
4,427,539; US 4,569,753), carbonaceous solids (e.g. US 5,413,702), or inert
kaolin
solids (e.g. US 4,569,753).
The use of fluid catalytic cracking (FCC), or other, units for the direct
processing of bitumen feedstocks is known in the art. However, many compounds
present within the crude feedstocks interfere with these process by depositing
on the
contact material itself. These feedstock contaminants include metals such as
vanadium
and nickel, coke precursors such as Conradson carbon and asphaltenes, and
sulfur, and
the deposit of these materials results in the requirement for extensive
regeneration of
the contact material. This is especially true for contact material employed
with FCC
processes as efficient cracking and proper temperature control of the process
requires
contact materials comprising little or no combustible deposit materials or
metals that
interfere with the catalytic process.
To reduce contamination of the catalytic material within catalytic cracking
units,
pretreatment of the feedstock via visbreaking (US 5,413,702; US 4,569,753; US
4,427,539), thermal (US 4,252,634; US 4,161,442) or other processes, typically
using
FCC-like reactors, operating at temperatures below that required for cracking
the
feedstock (e.g US 4,980,045; US 4,818,373 and US 4,263,128;) have been
suggested.
These systems operate in series with FCC units and function as pre-treaters
for FCC.
These pretreatment processes are designed to remove contaminant materials from
the
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feedstock, and operate under conditions that mitigate any cracking. This
ensures that
any upgrading and controlled cracking of the feedstock takes place within the
FCC
reactor under optimal conditions.
Several of these processes (e.g. US 4,818,373; US 4,427,539; US 4,311,580;
US 4,232,514; US 4,263,128;) have been specifically adapted to process
"resids" (i.e.
feedstocks produced from the fractional distillation of a whole crude oil) and
bottom
fractions, in order to optimize recovery from the initial feedstock supply.
The disclosed
processes for the recovery of resids, or bottom fractions, are physical and
involve
selective vaporization or fractional distillation of the feedstock with
minimal or no
chemical change of the feedstock. These process are also combined with metals
removal and provide feedstocks suitable for FCC processing. The selective
vaporization of the resid takes place under non-cracking conditions, without
any
reduction in the viscosity of the feedstock components, and ensures that
cracking
occurs within an FCC reactor under controlled conditions. None of these
approaches
disclose the upgrading of feedstock within this pretreatment (i.e. metals and
coke
removal) process. Other processes for the thermal treatment of feedstocks
involve
hydrogen addition (hydrotreating) which results in some chemical change in the
feedstock.
US 4,294,686 discloses a steam distillation process in the presence of
hydrogen
for the pretreatment of feedstock for FCC processing. This document also
indicates
that this process may also be used to reduce the viscosity of the feedstock
such that the
feedstock may be suitable for transport within a pipeline. However, the use of
short
residence time reactors to produce a transportable feedstock is not disclosed.
There is a need within the art for a rapid and effective upgrading process of
a
heavy oil or bitumen feedstock that involves a partial chemical upgrade or
mild
cracking of the feedstock in order to obtain a product characterized in having
a reduced
viscosity over the starting material. Ideally this process would be able to
accommodate
feedstocks comprising significant amounts of BS&W. This product would be
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transportable for further processing and upgrading. Such a process would not
involve
any catalytic-cracking activity due to the known contamination of catalyst
contact
materials with components present in heavy oil or bitumen feedstocks. The
rapid and
effective upgrading process would produce a product characterized in having
reduced
viscosity, reduced metal content, increased API, and an optimal product yield.
The present invention is directed to the upgrading of heavy hydrocarbon
feedstocks, for example but not limited to heavy oil or bitumen feedstocks,
that utilizes
a short residence pyrolytic reactor operating under conditions that cracks and
chemically upgrades the feedstock. The feedstock used within this process may
comprise significant levels of BS&W and still be effectively processed,
thereby
increasing the efficiency of feedstock handling. The process of the present
invention
provides for the preparation of a partially upgraded feedstock exhibiting
reduced
viscosity and increased API gravity. The process described herein selectively
removes
metals, salts, water and nitrogen from the feedstock, while at the same time
maximizes
the liquid yield, and minimizing coke and gas production. Furthermore, this
process
reduces the viscosity of the feedstock to an extent which can permit pipeline
transport
of the feedstock without addition of diluents. The partially upgraded product
optionally permits transport of the feedstock offsite, to locations better
equipped to
handle refining. Such facilities are typically located at a distance from the
point where
the crude feedstock is obtained.
SUM1\'IARY OF THE INVENTION
The present invention relates to the rapid thermal processing of viscous oil
feedstocks. More specifically, this invention relates to the use of pyrolysis
in order to
upgrade and reduce the viscosity of these oils.
According to the present invention there is provided a method for upgrading a
heavy hydrocarbon feedstock comprising:
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i) introducing a particulate heat carrier into an upflow reactor;
ii) introducing the heavy hydrocarbon feedstock into the upflow reactor at
at least one location above that of the particulate heat carrier so that a
loading ratio of the particulate heat carrier to feedstock is from about
10:1 to about 200:1;
iii) allowing the heavy hydrocarbon feedstock to interact with the heat"
carrier with a residence time of less than about 5 seconds, to produce a
product stream;
iv) separating the product stream from the particulate heat carrier;
v) regenerating the particulate heat carrier; and
vi) collecting a gaseous and liquid product from the product stream,
wherein the liquid product exhibits an increased API gravity, a reduced pour
point, reduced viscosity and a reduced level of contaminants over that of said
feedstock.
Preferably, the loading ratio of the method as outlined above is from about 20
:1 to
about 30:1.
This invention also includes the method as outlined above wherein the heavy
hydrocarbon feedstock is either heavy oil or bitumen. Furthermore, the
feedstock is
pre-heated prior to its introduction into the upflow reactor.
The present invention also relates to the method as defined above, wherein the
temperature of the upflow reactor is less than 750'C, wherein the residence
time is
from about 0.5 to about 2 seconds, and wherein the particulate heat carrier is
silica
sand.
This invention is also directed to the above method wherein the contaminants,
including Conradson carbon (coke), BS&W, nickel and vanadium are removed from
the feedstock or deposited onto the heat carrier
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The present invention also includes the method as defined above, wherein said
product stream of a first pyrolysis run is separated into a lighter fraction
and a heavier
fraction, collecting the lighter fraction from the product stream, and
recycling the
heavier fraction back into the upflow reactor for further processing within a
second
pyrolysis run to produce a second product stream. Preferably, the further
processing
includes mixing the heavier fraction with the particulate heat carrier,
wherein the
temperature of the particulate heat carrier of the second pyrolysis run is at
about, or
above, that used in the processing of the feedstock within the first pyrolysis
run. For
example, the temperature of the upflow reactor within the first pyrolysis run
is from about 300"C to
about 590 C, and the temperature of the upflow reactor in the second pyrolysis
run is from about
530 C to about 700 C. The residence time of the second pyrolysis run is-the
same as,
or longer than, the residence time of the first pyrolysis run. Furthermore,
the heavier
fraction may be added to unprocessed feedstock prior to being introduced into
the
upflow reactor for the second pyrolysis run.
The present invention is also directed to an upgraded heavy oil characterized
by the following properties:
i) an API gravity from about 13 to about 23;
ii) a density from about 0.92 to about 0.98;
iii) a viscosity at 40 C (cSt) from about 15 to about 300; and
iv) a reduced Vanadium content of about 60 to about 100 ppm; and
v) a reduced Nickel content of about 10 to about 50 ppm.
This invention also embraces an upgraded bitumen characterized by the
following properties.
i) an API gravity from about 10 to about 21;
ii) a density from about 0.93 to about 1.0;
iii) a viscosity at 40 C (cSt) from about 15 to about 300; and
iv) a reduced Vanadium content of about 60 to about 100 ppm; and
v) a reduced Nickel content of about 10 to about 50 ppm.
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The present invention also pertains to a liquid product characterized in
having
at least one of the following properties:
i) less than 50% of the components evolving at temperatures above 538 C
during simulated distillation;
ii) from about 60 % to about 95 % of the product evolving below 538
during simulated distillation;
iii) from about 1.0% to about 10% of the liquid product evolving below
193 C during simulated distillation;
iv) from about 2% to about 6 % of the liquid product evolving between 193-
232 C during simulated distillation;
v) from about 10% to about 25 % of the liquid product evolving between
232-327 C during simulated distillation;
vi) from about 6 % to about 15 % of the liquid product evolving between
327-360 C during simulated distillation; and
vii) from about 34.5 % to about 60% of the liquid product evolving between
360-538 C during simulated distillation.
This invention also includes an upflow pyrolysis reactor for heavy hydrocarbon
feedstock upgrading comprising:
i) a means for pre-heating the heavy hydrocarbon feedstock;
ii) 'at least one injection means at at least one of a plurality of locations
along the upflow reactor, the at least one injection means for
introducing the heavy hydrocarbon feedstock into the upflow reactor;
iii) an inlet for introducing a particulate heat carrier, the inlet located
below
25. the at least one injection means, the particulate heat carrier present at
a loading ratio of at least 10:1;
iv) a conversion section within the upflow reactor;
v) a separation means at an outlet of the upflow reactor to separate the
gaseous and liquid products from the particulate heat carrier;
vi) a particulate heat carrier regeneration means;
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vii) a particulate heat carrier recirculation line from the regeneration means
to the inlet for supplying the particulate heat carrier to said mixing
section;
viii) a condensing means for cooling and condensing the liquid products;
The present invention also relates to the upflow reactor as defined above,
wherein the plurality of locations, includes locations distributed along the
length of said
reactor. Furthermore, the upflow reactor may comprise a hot condenser means
prior
to the condensing means. Preferably, the particulate heat carrier is silica
sand, and the
loading ratio is from about 20:1 to about 30:1. The upflow reactor as defined
above
may also comprise a heavy fraction product recirculation means from the hot
condensing means to the injection means of the upflow reactor.
The present invention also pertains to a method for upgrading a heavy
hydrocarbon feedstock comprising:
i) introducing a particulate heat carrier into an upflow reactor;
ii) introducing a feedstock into the upflow reactor at at least one location
above that of the particulate heat carrier so that a loading ratio of the
particulate heat carrier to the heavy hydrocarbon feedstock is from
about 10:1 to about 200:1;
iii) allowing the feedstock to interact with the heat carrier with a residence
time of less than about 1 second, to produce a product stream;
iv) separating the product stream from the particulate heat carrier;
v) regenerating the particulate heat carrier; and
vi) collecting a gaseous and liquid product from the product stream,
wherein the feedstock is obtained from the direct contact between the product
stream and a heavy hydrocarbon feedstock, within a condenser.
The present invention addresses the need within the art for a rapid upgrading
process of a heavy oil or bitumen feedstock involving a partial chemical
upgrade or
mild cracking of the feedstock. This product may, if desired, be transportable
for
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further processing and upgrading. The process as described herein also reduces
the
levels of contaminants within feedstocks, thereby mitigating contamination of
catalytic
contact materials with components present in heavy oil or bitumen feedstocks.
Furthermore, a range of heavy hydrocarbon feedstocks may be processed by
the methods as described herein, including feedstocks comprising significant
amounts
of BS&W. Feedstocks comprising significant BS&W content are non-transportable
due
to their corrosive properties. Current practices for the treatment of
feedstocks to
decrease their BS&W content are time consuming and costly, and still require
further
processing or partial upgrading prior to transport. The methods described
herein
permit the use of feedstocks having a substantial BS&W component, and produce
a
liquid product that is partially upgraded and suitable for pipeline or other
methods, of
transport. The present invention therefore provides for earlier processing of
feedstocks
and reduces associated costs and processing times.
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BRIEF DESCRIPTION OF THE DRAWINGS
These and other features of the invention will become more apparent from the
following description in which reference is made to the appended drawings
wherein:
FIGURE 1 is a schematic drawing of an embodiment of the present invention
relating
to a system for the pyrolytic processing of feedstocks.
FIGURE 2 is a schematic drawing of an embodiment of the present invention
relating
to the feed system for introducing the feedstock to the system for the
pyrolytic
processing of feedstocks.
FIGURE 3 is a schematic drawing of an embodiment of the present invention
relating
to the feed system for introducing feedstock into the second stage of a two
stage process using the system for the pyrolytic processing of feedstocks as
described herein.
FIGURE 4 is a schematic drawing of an embodiment of the present invention
relating
to the recovery system for obtaining feedstock to be either collected from a
primary condenser, or recycled to the second stage of a two stage process
using the system for the pyrolytic processing of feedstocks as described
herein.
FIGURE 5 is a schematic drawing of an embodiment of the present invention
relating
to a multi stage system for the pyrolytic processing of feedstocks.
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DESCRIPTION OF PREFERRED EMBODIMENT
The present invention relates to the rapid thermal processing of viscous crude
oil feedstocks. More specifically, this invention relates to the use of
pyrolysis in order
to upgrade and reduce the viscosity of these oils.
The following description is of a preferred embodiment by way of example only
and without limitation to the combination of features necessary for carrying
the
invention into effect.
By "feedstock" it is generally meant a heavy hydrocarbon feedstock comprising,
but not limited to, heavy oil or bitumens. However, the term "feedstock" may
also
include other hydrocarbon compounds such as petroleum crude oil, atmospheric
tar
bottom products, vacuum tar bottoms, coal oils, residual oils, tar sands,
shale oil and
asphaltic fractions. Furthermore, the feedstock may comprise significant
amounts of
BS&W (Bottom Sediment and Water), for example, but not limited to, a BS&W
content of greater than 0.5 % (wt%). Feedstock may also include pre-treated
(pre-
processed) feedstocks as defined below, however, heavy oil and bitumen are the
preferred feedstock. These heavy oil and bitumen feedstocks are typically
viscous and
difficult to transport. Bitumens typically comprise a large proportion of
complex
polynuclear hydrocarbons (asphaltenes) that add to the viscosity of this
feedstock and
some form of pretreatment of this feedstock is required for transport. Such
pretreatment typically includes dilution in solvents prior to transport.
Typically tar-sand derived feedstocks (see Example 1 for an analysis of
examples, which are not to be considered limiting, of such feedstocks) are pre-
processed prior to upgrading, as described herein, in order to concentrate
bitumen.
However, pre-processing may also involve methods known within the art,
including
hot or cold water treatments, or solvent extraction that produces a bitumen-
gas oil
solution. These pre-processing treatments typically reduce the sand content of
bitumen.
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For example one such water pre-processing treatment involves the formation of
a tar--
sand containing bitumen- hot water/NaOH slurry, from which the sand is
permitted to
settle, and more hot water is added to the floating bitumen to dilute out the
base and
ensure the removal of sand. Cold water processing involves crushing tar-sand
in water
and floating the bitumen containing tar-sands in fuel oil, then diluting the
bitumen with
solvent and separating the bitumen from the sand-water residue. A more
complete:
description of the cold water process is disclosed in US 4,818,373.
Such pre-processed or pre-treated feedstocks may also be
used for further processing as described herein.
Bitumens may be upgraded using the process of this invention, or other
processes such as FCC, visbraking, hydrocracking etc. Pre-treatment of tar
sand
feedstocks may also include hot or cold water treatments, for example, to
partially
remove the sand component prior to upgrading the feedstock using the process
as
described herein, or other upgrading processes including FCC, hydrocracking,
coking,
visbreaking etc. Therefore, it is to be understood that the term "feedstock"
also
includes pre-treated feedstocks, including, but not limited to those prepared
as
described above.
It is to be understood that lighter feedstocks may also be processed following
the method of the invention as described herein. For example, and as described
in
more detail below, liquid products obtained from a first pyrolytic treatment
as
described herein, may be further processed by the method of this invention
(for
example composite recycle and multi stage processing; see Figure 5 and
Examples 3
and 4) to obtain a liquid product characterized as having reduced viscosity, a
reduced
metal (especially nickel, vanadium) and water content, and a greater API.
Furthermore, liquid products obtained from other processes as known in the
art, for
example, but not limited to US 5,662,868; US 4,980,045; US 4,818,373; US
4,569,753; US 4,435,272; US 4,427,538; US 4,427,539; US 4,328,091; US
4,311,580; US 4,243,514; US 4,294,686, may also be used as feedstocks for the
process described herein. Therefore, the present invention also contemplates
the use
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of lighter feedstocks including gas oils, vacuum gas oils, topped crudes or
pre-
processed liquid products, obtained from heavy oils or bitumens. These lighter
feedstocks may be treated using the process of the present invention in order
to
upgrade these feedstocks for further processing using, for example, but not
limited to,
FCC, visbreaking, or hydrocracking etc, or for transport and further
processing.
The liquid product arising from the process as described herein may be
suitable
for transport within a pipeline to permit further processing of the feedstock
elsewhere.
Typically, further processing occurs at a site distant from where the
feedstock is
obtained. However, it is considered within the scope of the present invention
that the
liquid product produced using the present method may also be directly input
into a unit
capable of further upgrading the feedstock, such as, but not limited to, FCC,
coking:,
visbreaking, hydrocraking, or pyrolysis etc. In this capacity, the pyrolytic
reactor of
the present invention partially upgrades the feedstock while at the same time
acts as a
pre-treater of the feedstock for further processing, as disclosed in, for
example, but not
limited to US 5,662,868; US 4,980,045; US 4,818,373; US 4,569,753; ,US
4,435,272;
US 4,427,538; US 4,427,539; US 4,328,091; US 4,311,580; US 4,243,514; US
4,294,686.
The feedstocks of the present invention are processed using a fast pyrolysis
reactor, such as that disclosed in US 5,792,340 (WO 91/11499; EP 513,051)
involving
contact times between the heat carrier and feedstock from about 0.01 to about
2 sec.
Other known riser reactors with short residence times may also be employed,
for
example, but not limited to US 4,427,539, 4,569,753,.4,818,373, 4,243,514.
It is preferred that the heat carrier used within the pyrolysis reactor
exhibits low
catalytic activity. Such a heat carrier may be an inert particulate solid,
preferably
sand, for example silica sand. By silica sand it is meant a sand comprising
greater than
about 80 % silica, preferably greater than about 95 % silica, and more
preferably
greater than about 99% silica. Other components of the silica sand may
include, but
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are not limited to, from about 0.01 % (about 100 ppm) to about 0.04 % (400
ppm) iron
oxide, preferably about 0.035% (358 ppm); about 0.00037% (3.78 ppm) potassium
oxide; about 0.00688% (68.88 ppm) aluminum oxide; about 0.0027 (27.25)
magnesium oxide; and about 0.0051 % (51.14 ppm) calcium oxide. It is to be
understood that the above composition is an example of a silica sand that can
be used
as a heat carrier as described herein, however, variations within the
proportions of
these ingredients within other silica sands may exist and still be suitable
for use as a
heat carrier. Other known inert particulate heat carriers or contact
materials, for
example kaolin clays, rutile, low surface area alumina, oxides of magnesium
aluminum and calcium as described in US 4,818,373 or US 4,243,514, may also be
used.
Processing of feedstocks using fast pyrolysis results in the production of
product vapours and solid byproducts associated with the heat carrier. After
removal
of the heat carrier from the product stream, the product vapours are condensed
to
obtain a liquid product and gaseous by-products. For example, which is not to
be
considered limiting, the liquid product produced from the processing of heavy
oil, as
described herein, is characterized in having the following properties:
= a boiling point of less than about about 600 C, preferably less than about
525 C, and more preferably less than about 500 C;
= an API gravity of at least about 12', and preferably greater than about 17
(where API gravity = [141.5/specific gravity]-131.5; the higher the API
gravity,
the lighter the compound);
= greatly reduced metals content, including V and Ni.
= greatly reduced viscosity levels (more than 25 fold lower than that of the
feedstock, for example, as determined @ 40 C), and
= yields of liquid product of at least 60 vol%, preferably the yields are
greater
than about 70 vol %, and more preferably they are greater than about 80 %.
Following the methods as described herein, a liquid product obtained from
processing
bitumen feedstock, which is not to be considered limiting, is characterized as
having:
= an API gravity from about 10 to about 21;
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= a density @ 15 C from about 0.93 to about 1.0;
= greatly reduced metals content, including V and Ni.
= a greatly reduced viscosity of more than 20 fold lower than the feedstock
(for
example as determined at 40 C), and
= yields of liquid product of at least 60 vol%, preferably the yields are
greater
than about 75 vol % .
The high yields and reduced viscosity of the liquid product produced according
to this invention may permit the liquid product to be transported by pipeline
to
refineries for further processing with the addition of little or no diluents.
Furthermore,
the liquid products exhibit reduced levels of contaminants (e.g. metals and
water), with
the content of sulphur and nitrogen slightly reduced. Therefore, the liquid
product
may also be used as a feedstock, either directly, or following transport, for
further
processing using, for example, FCC, hydrocracking etc.
Furthermore, the liquid products of the present invention may be characterised
using Simulated Distillation (SimDist) analysis, as is commonly known in the
art, for
example but not limited to ASTM D 5307-97 or HT 750 (NCUT). SimDist analaysis,
indicates that liquid products obtained following processing of heavy oil or
bitumen can
be characterized by any one of, or a combination of, the following properties
(see
Examples 1, 2 and 5):
= having less than 50% of their components evolving at temperatures
above 538 C (vacuum resid fraction);
= comprising from about 60 % to about 95 % of the product evolving
below 538'. Preferably, from about 62% to about 85% of the product
evolves during SimDist below 538 C (i.e. before the vacuum resid.
fraction);
= having from about 1.0% to about 10% of the liquid product evolve
below 193 C. Preferably from about 1.2% to about 6.5% evolves
below 193 C (i.e. before the naphtha/kerosene fraction);
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= having from about 2 % to about 6 % of the liquid product evolve
between 193-232 C. Preferably from about 2.5 % to about 5 % evolves
between 193-232'C (kerosene fraction);
= having from about 10% to about 25% of the liquid product evolve
between 232-327 C. Preferably, from aboutl3 to about 24% evolves
between 232-327 C (diesel fraction);
= having from about 6 % to about 15 % of the liquid product evolve
between 327-360 C. Preferably, from about 6.5 to about 11 % evolves
between 327-360 C (light VGO fraction);
having from about 34.5 % to about 60 % of the liquid product evolve
between 360-538 C. Preferably, from about 35 to about 55% evolves
between 360-538 C (Heavy VGO fraction);
A first method for upgrading a feedstock to obtain liquid products with
desired.
properties involves a one stage process. With reference to Figure 1, briefly,
the fast.
pyrolysis system includes a feed system generally indicated as (10; also see
Figures 2
and 3), that injects the feedstock into a reactor (20), a heat carrier
separation system
that separates the heat carrier from the product vapour (e.g .100 and 180) and
recycles
the heat carrier to the reheating/regenerating system (30), a particulate
inorganic heat
carrier reheating system (30; see also Figure 5) that reheats and regenerates
the heat carrier, and primary
(40) and secondary (50) condensers that collect the product. The pre-heated
feedstock
enters the reactor just below the mixing zone (170) and is contacted by the
upward
flowing stream of hot inert carrier within a transport fluid, typically a
recycle gas
supplied by a recycle gas line (210; see also Figure 5). A through and rapid
mixing and conductive heat
transfer from the heat carrier to the feedstock takes place in the short
residence time
conversion section of the reactor. The feedstock may enter the reactor through
at least
one of several locations along the length of the reactor. The different entry
points
indicated- in Figures 1 and 2 are non-limiting examples of such entry
locations. By
providing several entry points along the length of the reactor, the length of
the
residence time within the reactor may be varied. For example, for longer
residence
times, the feedstock enters the reactor at a location lower down the reactor,
while, for
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shorter residence times, the feedstock enters the reactor at a location higher
up the
reactor. In all of these cases, the introduced feedstock mixes with the
upflowing heat
carrier within a mixing zone (170) of the reactor. The product vapours
produced
during pyrolysis are cooled and collected using a suitable condenser means
(40, 50) in
order to obtain a liquid product.
It is to be understood that other fast pyrolysis systems, comprising
differences.
in reactor design, that utilize alternative heat carriers, heat carrier
separators, differenc
numbers or size of condensers, or different condensing means, may be used for
the:
preparation of the upgraded product of this invention. For example, which is
not to
be considered limiting, reactors disclosed in US 4,427,539, 4,569,753,
4,818,373õ
4,243,514 may be modified to operate
under the conditions as outlined herein for the production of a chemically
upgraded
product with an increased API and reduced viscosity.
-
Following pyrolysis of the feedstock in the presence of the inert heat
carrier,
some contaminants present within the feedstock are deposited onto the inert
heat:
carrier. These contaminants include metals (especially nickel and vanadium),
coke,
and to some extent nitrogen and sulphur. The inert heat carrier therefore
requires
regeneration (30) before re-introduction into the reaction stream. The heat
carrier may
be regenerated via combustion within a fluidized bed at a temperature of about
600 to
about 900 C. Furthermore, as required, deposits may also be removed from the
heat
carrier by an acid treatment, for example as disclosed in US 4,818,373
The heated, regenerated, heat-carrier is then re-introduced
to the reactor (20) and acts as heat carrier for fast pyrolysis.
The feed system (10; Figure 1) provides a preheated feedstock to the reactor
(20). An
example of a feed system which is not to be considered limiting in any manner,
is
shown in Figure 2, however, other embodiments of the feed system are within
the
scope of the present invention, for example but not limited to a feed pre-
heater unit as
shown in Figure 5 (discussed below) and may be optionally used in conjunction
with
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a feed system (10; Figure 5). The feed system (generally shown as 10, Figures
1 and
2) is designed to provide a regulated flow of pre-heated feedstock to the
reactor unit
(20). The feed system shown in Figure 2 includes a feedstock pre-heating surge
tank:
(110; see also Figure 3), heated using external band heaters (130) to 80 C,
and is associated
with a recirculation/transfer pump (120; see also Figure 3). The feedstock is
constantly
heated and mixed in this tank at 80 C. The hot feedstock is pumped from the
surge tank to
a primary feed tank (140; see also Figure 3), also heated using external band
heaters (130;
see also Figure 3), as required. However, it is to be understood that
variations on the feed
system may also be employed, in order to provide a heated feedstock to the
reactor. The
primary feed tank (140) may also be fitted with a recirculation/delivery pump
(150; see also
.10 Figures 1 and 3). Heat traced transfer lines (160; see also Figures 1 and
3) are maintained
at about 150 C and pre-heat the feedstock prior to entry into the reactor via
an injection
nozzle (70; see also Figure 5). Atomization at the injection nozzle (70)
positioned near the
mixing zone (170) within reactor (20) may be accomplished by any suitable
means.
The nozzle arrangement should provide for a homogeneous dispersed flow of
material
into the reactor. For example, which is not considered limiting in any manner,
mechanical pressure using single-phase flow atomization, or a two-phase flow
atomization nozzle may be used. With a two phase flow atomization nozzle, pre-
heated
air, nitrogen or recycled by-product gas may be used as a carrier.
Instrumentation is
also dispersed throughout this system for precise feedback control (e.g.
pressure
transmitters, temperature sensors, DC controllers, 3-way valves gas flow
metres etc.)
of the system.
Conversion of the feedstock is initiated in the mixing zone (170; e.g. Figure
1)
under moderate temperatures (typically less than 750'C) and continues through
the
conversion section within the reactor unit (20) and connections (e.g. piping,
duct work)
up until the primary separation system (e.g. 100) where the bulk of the heat
carrier is
removed from the product vapour stream. The solid heat carrier and solid coke
by-
product are removed from the product'vapour stream in a primary separation
unit.
Preferably, the product vapour stream is separated from the heat carrier as
quickly as
possible after exiting from the reactor (20), so that the residence time of
the product:
vapour stream in the presence of the heat carrier is as short as possible.
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The primary separation unit may be any suitable solids separation device, for
example but not limited to a cyclone separator, a U-Beam separator, or Rams
Horn
separator as are known within the art. A cyclone separator is shown
diagrammatically
in Figures 1, 3 and 4. The solids separator, for example a primary cyclone
(100), is
preferably fitted with a high-abrasion resistant liner. Any solids that avoid
collection
in the primary collection system are carried downstream and recovered in a
secondary
collection system (180). The secondary separation unit may be the same as the
primary
separation unit, or it may comprise an alternate solids separation device, for
example
but not limited to a cyclone separator, a 1/4 turn separator, for example a
Rams Horn
separator, or an impingement separator, as are known within the art. A
secondary
cyclone separator (180) is graphically represented in Figures 1 and 4,
however, other
separators may be used as a secondary separator unit.
The solids that have been removed in the primary and secondary collection
systems are transferred to a vessel for regeneration of the heat carrier, for
example,
but not limited to a direct contact reheater system (30). In a direct contact
reheater
system (30), the coke and by-product gasses are oxidized to provide processes
thermal
energy which is directly carried to the solid heat carrier, as well as
regenerating the
heat carrier. The temperature of the direct contact reheater is maintained
independent
of the feedstock conversion (reactor) system. However, as indicated above,
other
methods for the regeneration of the heat carrier may be employed, for example
but not
limited to, acid treatment.
The hot product stream from the secondary separation unit is quenched in a
primary collection column (or primary condenser, 40; Figure 1). The vapour
stream
is rapidly cooled from the conversion temperature to less than about 400 C.
Preferably the vapour stream is cooled to about 300 C. Product is drawn from
the
primary column and pumped (220) into product storage tanks. A secondary
condenser
(50) can be used to collect any material that evades the primary condenser
(40).
Product drawn from the secondary condenser (50) is also pumped (230) into
product
storage tanks. The remaining non-condensible gas is compressed in a blower
(190) and
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a portion is returned to the heat carrier regeneration system (30) via line
(200; see also Figure 5), and the
remaining gas is returned to the reactor (20) by line (210) and acts as a heat
carrier,
and transport, medium.
It is preferred that the reactor used with the process of the present
invention is
capable of producing high yields of liquid product for example at least
greater than 60
vol %, preferably the yield is greater than 70 vol %, and more preferably the
yield is
greater than 80 %, with minimal byproduct production such as coke and gas.
Without
wishing to limit the scope of the invention in any manner, an example for the
suitable
conditions for a the pyrolytic treatment of feedstock, and the production of a
liquid
product is described in US 5,792,340, This
process utilizes sand (silica sand) as the heat carrier, and a reactor
temperature ranging
from about 480 to about 620 C, loading ratios of heat carrier to feedstock
from about
10:1 to about 200:1, and residence times from about 0.3 5 to about 0.7 sec.
Preferably the;
reactor temperature ranges from about 500 to about 550 C. The preferred
loading
ratio is from about 15:1 to about 50:1, with a more preferred ratio from about
20:1 to
about 30:1. Furthermore, it is to be understood that longer residence times
within the
reactor, for example up to about 5 sec, may be obtained if desired by
introducing the:
feedstock within the reactor at a position towards the base of the reactor, by
increasing
the length of the reactor itself, by reducing the velocity of the heat carrier
through the
reactor (provided that there is sufficient velocity for the product vapour and
heal:
carrier to exit the reactor), or a combination thereof. The preferred
residence time is
from about 0.5 to about 2sec.
Without wishing to be bound by theory, it is thought that the chemical
upgrading of the feedstock that takes place within the reactor system as
described
above is in part due to the high loading ratios of feedstock to heat carrier
that are used.
within the method of the present invention. Prior art loading ratios typically
ranged.
from 5:1 to about 12.5:1. However, the loading ratios as described herein, of
from
about 15:1 to about 200:1, result in a very rapid, ablative and consistent
transfer of
heat from the heat carrier to the feedstock. The high volume and density of
heat carrier
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within the mixing and conversion zones, ensures that a rapid and even
processing
temperature is achieved and maintained. In this way the temperatures required
for
cracking process described herein are easily controlled. This also allows for
the use of
relatively low temperatures to minimize over cracking, while ensuring that
mild
cracking of the feedstock is still achieved. Furthermore, with an increased
density of
heat carrier within the reactor, contaminants and undesired components present
in the
feedstock and reaction by-products, including metals (e.g. nickel and
vanadium), coke,
and to some extent nitrogen and sulphur, are readily adsorbed due to the large
surface
area of heat carrier present. This ensures efficient and optimal removal of
contaminants
from the feedstock, during the pyrolytic processing of the feedstock. As a
larger
surface area of heat carrier is employed, the heat carrier itself is not
unduly
contaminated, and any adsorbed metal or coke and the like is readily stripped
during
regeneration of the heat carrier. With this system the residence times can be
carefully
regulated in order to optimize the processing of the feedstock and liquid
product yields.
The liquid product arising from the processing of heavy oil as described
herein
has significant conversion of the resid fraction when compared to heavy oil or
bitumen
feedstock. As a result the liquid product of the present invention, produced
from the
processing of heavy oil is characterized, for example, but which is not to be
considered
limiting, as having an API gravity of at least about 13 , and more preferably
of at least
about 17 . However, as indicated above, higher API gravities may be achieved
with
a reduction in volume. For example, one liquid product obtained from the
processing
of heavy oil using the method of the present invention is characterized as
having from
about 10 to about 15 % by volume bottoms, from about 10 to about 15 % by
volume
light ends, with the remainder as middle distillates.
The viscosity of the liquid product produced from heavy oil is substantially
reduced from initial feedstock levels, of from 250 cSt @ 80 C, to product
levels of 4.5
to about 10 cSt @ 80 C, or from about 6343 cSt @ 40 C, in the feedstock, to
about
15 to about 35 cSt @40 C in the liquid product. Following a single stage
process,
liquid yields of greater than 80 vol% and API gravities of about 17, with
viscosity
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reductions of at least about 25 times that of the feedstock are obtained
(@40'Q.
These viscosity levels are suitable for pipeline transport of the liquid
product. Results
from Simulated Distillation (SimDist; e.g. ASTM D 5307-97, HT 750, (NCUT))
analysis further reveals substantially different properties between the
feedstock and
liquid product as produced herein. For heavy oil feedstock, approx. 1 % (wt%)
of the
feedstock is distilled off below about 232 C (Kerosene fraction), approx. 8.7%
from
about 232 to about 327 C (Diesel fraction), and 51.5 % evolved above 538 C
(Vacuum resid fraction; see Example 1 for complete analysis). SimDist analysis
of the
liquid product produced as described above may be characterized as having, but
is not
limited to having, the following properties: approx. 4% (wt%) evolving below
about
232'C (Kerosene fraction), approx. 14.2% from about 232 to about 327'C
(Diesel
fraction), and 37.9% within the vacuum resid fraction (above 538 C). It is to
be
understood that modifications to these values may arise depending upon the
composition of the feedstock used. These results demonstrate that there is a
significant
alteration in many of the components within the liquid product when compared
with
the heavy oil feedstock, with a general trend to lower molecular weight
components
that evolve earlier during SimDist analysis following rapid thermal
processing.
Therefore, the present invention is directed to a liquid product obtained from
single stage processing of heavy oil may that may be characterised by at least
one of
the following properties:
= having less than 50% of their components evolving at temperatures
above 538 C (vacuum resid fraction);
= comprising from about 60 % to about 95 % of the product evolving
below 538'. Preferably, from about 60% to about 80% evolves during
Simulated Distillation below 538 C (i.e. before the vacuum resid.
fraction);
= having from about 1.0 % to about 6 % of the liquid product evolve below
193 C. Preferably from about 1.2 % to about 5 % evolves below 193'C
(i.e. before the naphtha/kerosene fraction);
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= having from about 2 % to about 6 % of the liquid product evolve
between 193-232'C. Preferably from about 2.8 % to about 5 % evolves
between 193-232 C (diesel fraction);
= having from about 12 % to about 25 % of the liquid product evolve
between 232-327 C. Preferably, from aboutl3 to about 18% evolves
between 232-327'C (diesel fraction);
= having from about 5 % to about 10 % of the liquid product evolve
between 327-360 C. Preferably, from about 6.0 to about 8.0% evolves
between 327-360 C (light VGO fraction);
having from about 40% to about 60% of the liquid product evolve
between 360-538 C. Preferably, from about 30 to about 45% evolves
between 360-538 C (Heavy VGO fraction);
Similarly following the methods as described herein, a liquid product obtained
from processing bitumen feedstock following a single stage process, is
characterized
as having, and which is not to be considered as limiting, an increase in API
gravity of
at least about 10 (feedstock API is typically about 8.6). Again, higher API
gravities
may be achieved with a reduction in volume. The product obtained from bitumen
is
also characterised as having a density from about 0.93 to about 1.0 and a
greatly
reduced viscosity of at least about 20 fold lower than the feedstock (i.e.
from about 15
g/ml to about 60 g/ml at 40 C in the product, v. the feedstock comprising
about 1500
g/ml). Yields of liquid product obtained from bitumen are at least 60% by vol,
and
preferably greater than about 75% by vol. SimDist analysis also demonstrates
significantly different properties between the bitumen feedstock and liquid
product as
produced herein. Highlights from SimDist analysis indicates that for a bitumen
feedstock, approx. 1 % (wt%) of the feedstock was distilled off below about
232 C
(Kerosene fraction), approx. 8.6% from about 232 to about 327 C (Diesel
fraction),
and 51.2 % evolved above 538 C (Vacuum resid fraction; see Example 2 for
complete
analysis). SimDist analysis of the liquid product produced from bitumen as
described
above may be characterized, but is not limited to the following properties:
approx.
5.7% (wt%) is evolved below about 232 C (Kerosene fraction), approx. 14.8%
from
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about 2320 to about 327 C (Diesel fraction), and 29.9% within the vacuum resid
fraction (above 538 C). Again, these results may differ depending upon the
feedstock
used, however, they demonstrate the significant alteration in many of the
components
within the liquid product when compared with the bitumen feedstock, and the
general
trend to lower molecular weight components that evolve earlier during SimDist
analysis in the liquid product produced from rapid thermal processing.
Therefore, the present invention is also directed to a liquid product obtained
from single stage processing of bitumen which is characterised by having at
least one
of the following properties:
= having less than 50% of their components evolving at temperatures
above 538 C (vacuum resid fraction);
= comprising from about 60 % to about 95 % of the product evolving
below 538'. Preferably, from about 60% to about 80% evolves during
Simulated Distillation below 538 C (i.e. before the vacuum resid.
fraction);
= having from about 1.0 % to about 6 % of the liquid product evolve below
1930C. Preferably from about 1.2% to about 5% evolves below 193'C
(i.e. before the naphtha/kerosene fraction);
having from about 2% to about 6% of the liquid product evolve
between 193-232 C. Preferably from about 2.0% to about 5% evolves
between 193-232 C (diesel fraction);
= having from about 12 % to about 25 % of the liquid product evolve
between 232-327 C. Preferably, from aboutl3 to about 18% evolves
between 232-327 C (diesel fraction);
= having from about 5 % to about 10 % of the liquid product evolve
between 327-360 C. Preferably, from about 6.0 to about 8.0% evolves
between 327-360 C (light VGO fraction);
= having from about 40 % to about 60 % of the liquid product evolve
between 360-538 C. Preferably, from about 30 to about 50% evolves
between 360-538 C (Heavy VGO fraction);
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The liquid product produced as described herein also exhibits a high degree of
stability. Analysis of the liquid product over a 30 day period indicates
negligible
change in SimDist profile, viscosity, API and density for liquid products
produced
from either heavy oil or bitumen feedstocks (see Example 1 and 2).
Because the crack is not as severe, and the residence time short, unwanted
reactions that can generate excessive amounts of undesirable aromatics and
olefins.
Furthermore, it has been found that contaminants such as metals and water are
significantly reduced. There is no concentration of contaminants in the liquid
product.
Also as disclosed herein, further processing of the liquid product obtained
from
the process of heavy oil or bitumen feedstock may take place following the
method of
this invention. Such further processing may utilize conditions that are very
similar to
the initial fast pyrolysis treatment of the feedstock, or the conditions may
be modified
to enhance removal of lighter products (a single-stage process with a mild
crack)
followed by more severe cracking of the recycled fraction (i.e. a two stage
process).
In the first instance, that of further processing under similar conditions the
liquid product from a first pyrolytic treatment is recycled back into the
pyrolysis
reactor in order to further upgrade the properties of the final product to
produce a
lighter product. In this arrangement the liquid product from the first round
of
pyrolysis is used as a feedstock for a second round of pyrolysis after the
lighter
fraction of the product has been removed from the product stream. Furthermore,
a
composite recycle may also be carried out where the heavy fraction of the
product
stream of the first process is fed back (recycled) into the reactor along with
the addition
of fresh feedstock (e.g. Figure 3, described in more detail below).
The second method for upgrading a feedstock to obtain liquid products with
desired properties involves a two-stage pyrolytic process (see Figures 2 and
3). This
two stage processes comprises a first stage where the feedstock is exposed to
conditions
that mildly cracks the hydrocarbon components in order to avoid overcracking
and
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excess gas and coke production. An example of these conditions includes, but
is not
limited to, injecting the feedstock at about 150 C into a hot gas stream
comprising the
heat carrier at the inlet of the reactor. The feedstock is processed with a
residence time
less than about one second within the reactor at less than 500 C, for example
300 C.
The product, comprising lighter materials (low boilers) is separated (100, and
180,
Figure 3), and removed following the first stage in the condensing system
(40). The
heavier materials (240), separated out at the bottom of the condenser (40) are
collected
subjected to a more severe crack within the reactor (20) in order to render a
liquid
product of reduced viscosity and high yield. The conditions utilized in the
second
stage include, but are not limited to, a processing temperature of about 530
to about
590 C. Product from the second stage is processed and collected as outlined in
Figure
1 using a primary and secondary cyclone (100, 180, respectively) and primary
and
secondary condensers (40 and 50, respectively).
Following such a two stage process, an example of the product, which is not
to be considered limiting, of the first stage (light boilers) is characterized
with a yield
of about 30 vol%, an API of about 19, and a several fold reduction in
viscosity over
the initial feedstock. The product of the high boiler fraction, produced
following the
processing of the recycle fraction in the second stage, is typically
characterized with
a yield greater than about 75 vol%, and an API gravity of about 12, and a
reduced
viscosity over the feedstock recycled fraction. SimDist analysis for liquid
product
produced from heavy oil feedstock is characterized with approx. 7.4 % (wt %)
of the
feedstock was distilled off below about 232 C (Kerosene fraction v. 1.1 % for
the
feedstock), approx. 18.9% from about 232 to about 327 C (Diesel fraction v.
8.7%
for the feedstock), and 21.7 % evolved above 538 C (Vacuum resid fraction v.
51.5 %
for the feedstock; see Example 1 for complete analysis). SimDist analysis for
liquid
product produced from bitumen feedstock is characterized with approx. 10.6%
(wt%)
of the feedstock was distilled off below about 232 C (Kerosene fraction v.
1.0% for
the feedstock), approx. 19.7% from about 232 to about 327 C (Diesel fraction
v.
8.6% for the feedstock), and 19.5 % evolved above 538 C (Vacuum resid fraction
v.
51.2% for the feedstock; see Example 2 for complete analysis).
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Alternate conditions of a two stage process may include a first stage run
where
the feedstock is preheated to 150 C and injected into the reactor and
processed at about
530 to about 620 C, and with a residence time less than one second within the
reactor
(see Figure 2). The product is collected using a primary cyclone (100; Figures
2 and 4) and a
secondary cyclone (180; Figure 4), and the remaining product is transferred to
a hot condenser
(250; Figure 4). The condensing system (Figure 4) is engineered to selectively
recover the heavy ashphaltene components using a hot condenser (250) placed
before
the primary condenser (40). The heavy alsphaltenes are collected and returned
to the
reactor (20) for further processing (i.e. the second stage). The second stage.
utilizes
reactor conditions operating at higher temperatures, or longer residence
times, or at
higher temperatures and longer residence times (e.g. injection at a lower
point in the
reactor), than that used in the first stage to optimize the liquid product.
Furthermore,
a portion of the product stream may be recycled to extinction following this
method.
Yet another modification of the composite and two stage processing systems,
termed "multi-stage" processing, comprises introducing the primary feedstock
(raw
feed) into the primary condenser (see figure 5) via line 280, and using the
primary
feedstock to rapidly cool the product vapours within the primary condenser.
Product
drawn from the primary condenser,'is then recycled to the reactor via line 270
for
combined "first stage'" and "second stage" processing (i.e. recycled
processing). The
recycled feedstock is exposed to conditions that mildly crack the hydrocarbon
components in order to avoid overcracking and excess gas and coke production.
An
example of these conditions includes, but is not limited to, injecting the
feedstock at
about 150 C into a hot gas stream comprise the heat carrier at the inlet of
the reactor.
The feedstock is processed with a residence time of less than about two
seconds within
the reactor at a temperature of between about 500 C to about 600 C.
Preferably, the
residence time is from about 0.8 to about 1.3 sec., and the reactor
temperature is from
about 520 to about 580 C The product, comprising lighter materials (low
boilers) is
separated (100, and 180, Figure 5), and removed in the condensing system (40).
The
heavier materials (240), separated out at the bottom of the condenser (40)
are. collected
and reintroduced into the reactor (20) via line 270. Product gasses that exit
the primary
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condenser (40) enter the secondary condenser (50) where a liquid product of
reduced
viscosity and high yield (300) is collected (see Example % for run analysis
using this
method). With multi-stage processing, the feedstock is recycled through the
reactor
in order to produce a product that can be collected from the second condenser,
thereby
upgrading and optimizing the properties of the liquid product.
Alternate feeds systems may also be used as required for one, two, composite
or multi stage processing. For example, in the system outlined Figure 5, the
feedstock
(primary feedstock or raw feed) is obtained from the feed system (10), and is
transported within line (280; which may be heated as previously described) to
a
primary condenser (40). The primary product obtained from the primary
condenser
may also be recycled back to the reactor (20) within a primary product recycle
line
(270). The primary product recycle line may be heated if required, and may
also
comprise a pre-heater unit (290) as shown in Figure 5, to re-heat the recycled
feedstock
to desired temperature for introduction within the reactor (20).
Following the recycle process as outlined above and graphically represented in
Figure 5, product with yields of greater than 60, and preferably above 75 %
(wt %), and
with the following characteristics, which are not to be considered limiting in
any
manner, may be produced from either bitumen or heavy oil feedstocks: an API
from
about 14 to about 19; viscosity of from about 20 to about 100 (cSt @40 C); and
a low
metals content (see Example 5).
From SimDist analaysis, liquid products obtained following multi-stage
processing of heavy oil can be characterized by comprising at least one of the
following
properties:
= having less than 50% of their components evolving at temperatures
above 538 C (vacuum resid fraction);
comprising from about 60 % to about 95 % of the product evolving
below 538'. Preferably, from about 70% to about 90%, and more
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preferably from about 75 to about 87% of the product evolves during
Simulated Distillation below 538 C (i.e. before the vacuum resid.
fraction);
= having from about 1.0 % to about 6 % of the liquid product evolve below
193'C. Preferably from about 1.2 % to about 5 %, and more preferably
from about 1.3 % to about 4.8 % evolves below 193 C (i.e. before the
naphtha/kerosene fraction);
= having from about 2% to about 6% of the liquid product evolve
between 193-232 C. Preferably from about 2.8% to about 5% evolves
between 193-232 C (diesel fraction);
= having from about 15 % to about 25 % of the liquid product evolve
between 232-327 C. Preferably, from aboutl8.9 to about 23.1%
evolves between 232-327 C (diesel fraction);
= having from about 8 % to about 15 % of the liquid product evolve
between 327-360'C. Preferably, from about 8.8 to about 10.8 % evolves
between 327-360 C (light VGO fraction);
= having from about 40% to about 60% of the liquid product evolve
between 360-538'C. Preferably, from about 42 to about 55% evolves
between 360-538 C (Heavy VGO fraction);
The liquid product obtained from multi-stage processing of bitumen may be
charachterized as having at least one of the following properties:
= having less than 50% of their components evolving at temperatures
above 538 C (vacuum resid fraction);
comprising from about 60 % to about 95 % of the product evolving
below 538'. Preferably, from about 60 % to about 85 % evolves during
Simulated Distillation below 538 C (i.e. before the vacuum resid.
fraction);
= having from about 1.0 % to about 8 % of the liquid product evolve below
193 C. Preferably from about 1.5 % to about 7 % evolves below 193 C
(i.e. before the naphtha/kerosene fraction);
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= having from about 2 % to about 6 % of the liquid product evolve
between 193-232'C. Preferably from about 2.5 % to about 5 % evolves
between 193-232 C (diesel fraction);
= having from about 12 % to about 25 % of the liquid product evolve
between 232-327 C. Preferably, from aboutl5 to about 20% evolves
between 232-327 C (diesel fraction);
= having from about 5 % to about 12 % of the liquid product evolve
between 327-360 C. Preferably, from about 6.0 to about 10.0 % evolves
between 327-360 C (light VGO fraction);
having from about 40% to about 60% of the liquid product evolve
between 360-538 C. Preferably, from about 35 to about 50% evolves
between 360-538 C (Heavy VGO fraction);
Collectively these results show that a substantial proportion of the
components with
low volatility in either of the feedstocks have been converted to components
of higher
volatitly (light naphtha, kerosene and diesel) in the liquid product. These
results
demonstrate that the liquid product are substantially upgraded, and exhibits
properties
suitable for transport.
The above description is not intended to limit the claimed invention in any
manner, furthermore, the discussed combination of features might not be
absolutely
necessary for the inventive solution.
The present invention will be further illustrated in the following examples.
However it is to be understood that these examples are for illustrative
purposes only,
and should not be used to limit the scope of the present invention in any
manner.
Example 1: Heavy Oil (Single Stage)
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Pyrolytic processing of Saskatchewan Heavy Oil and Athabasca Bitumen (see
Table 1) were carried out over a range of temperatures using a pyrolysis
reactor as
described in US 5,792,340.
Table 1: Characteristics of heavy oil and bitumen feedstocks
Compound Heavy Oily Bitumen2)
Carbon (wt%) 84.27 83.31
Hydrogen (wt%) 10.51 10.31
Nitrogen (wt%) <0.5 <0.5
Sulphur (st%) 3.6 4.8
Ash (wt%) 0.02 0.02
Vanadium (ppm) 127 204
Nickel (ppm) nd 82
Water content (wt%) 0.8 0.19
Gravity API 11.0 8.6
Viscosity @ 40 C (cSt) 6343 30380
Viscosity @ 60 C (cSt) 892.8 1268.0
Viscosity @ 80 C (cSt) 243.4 593.0
Aromaticity (C13 NMR) 0.31 0.35
1) Saskatchewan Heavy Oil
2) Athabasca Bitumen (neat)
Briefly the conditions of processing include a reactor temperature from about
500 to about 620 C. Loading ratios for particulate heat carrier (silica sand)
to
feedstock of from about 20:1 to about 30:1 and residence times from about 0.35
to
about 0.7 sec. These conditions are outlined in more detail below (Table 2).
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Table 2: Single stage processing of Saskatchewan Heavy Oil
Crack Temp Viscosity @ Yield wt% Density @ API Yield Vol%
C 40 C (cSt) 15 g/ml
620 4.61) 71.5 0.977 13.3 72.7
592 15.21) 74.5 0.970 14.4 76.2
590 20.2 70.8 0.975 13.6 72.1
590 31.6 75.8 0.977 13.3 77.1
560 10.01) 79.92) 0.963 15.4 82.32)
560 10.01) 83.03) 0.963 16.23) 86.33)
550 20.8 78.5 0.973 14.0 80.3
5504) 15.7 59.82) 0.956 16.5 61.52)
5504) 15.7 62.03) 0.956 18.323 65.13)
530 32.2 80.92) 0.962 15.7 82.82)
530 32.2 83.83) 0.962 16.63) 87.13)
1) Viscosity @ 80 C
2) Yields do not include overhead condensing
3) Estimated yields and API with overhead condensing
4) Not all of the liquids were captured in this trial.
The liquid products of the runs at 620 C, 592 C and 560 C were analysed for
metals, water and sulphur content. These results are shown in Table 3. Nickel,
Vanadium and water levels were reduced 72, 69 and 87 %, respectively, while
sulphur
and nitrogen remained the same or were marginally reduced. No metals were
concentrated in the liquid product.
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Table 3: Metal Analysis of Liquid Products (ppm)1)
Component Saskatchewan Run cQ 620 C Run @ 592 C Run a 560 C
Heavy Oil
Aluminum <1 <1 11 <1
Iron < 1 2 4 < 1
Nickel 44 10 12 9
Zinc 2 < 1 2 1
Calcium 4 2 3 1
Magnesium 3 1 2 < 1
Boron 21 42 27 < 1
Sodium 6 5 5 4
Silicon 1 10 140 4
Vanadium 127 39 43 39
Potassium 7 7 < 1 4
Water(wt%) 0.78 0.19 0.06 .10
Sulphur (wt%) 3.6 3.5 3.9 3.5
1) Copper, tin, chromium, lead, cadmium, titanium, molybdenum, barium and
manganese all showed
less than 1 ppm in feedstock and liquid products.
The gas yields for two runs are presented in Table 4.
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Table 4: Gas analysis of Pyrolysis runs
Gas (wt%) Run @620'C Run @ 560'C
Total Gas Yield 11.8 7.2
Ethylene 27.0 16.6
Ethane 8.2 16.4
Propylene 30.0 15.4
Methane 24.0 21.0
The pour point of the feedstock improved and was reduced from 32 F to about
-54'F. The Conradson carbon reduced from 12. wt % to about 6.6 wt % .
Based on the analysis of these runs, higher API values and product yields were
obtained for crack temperatures of about 530 to about 560 C. At these
temperatures,
API gravities of 14 to 18.3, product yields of from about 80 to about 87 vol%,
and
viscosities of from about 15 to about 35 cSt (@40 C) or about 10 cST (@80 C)
were
obtained (the yields from the 550 C run are not included in this range as the
liquid
yield capture was not optimized during this run). These liquid products
reflect a
significant degree of upgrading, and exhibit qualities suitable for pipeline
transport.
Simulated distillation (SimDist) analysis of feedstock and liquid product
obtained from several separate runs is present in Table 5. SimDist analysis
followed
the protocol outlined in ASTM D 5307-97, which reports the residue as anything
with
a boiling point higher than 538 C. Other mthods for SimDist may also be used,
for
example HT 750 (NCUT; which includes boiling point distribution through to 750
C).
These results indicate that over 50% of the components within the feedstock
evolve at
temperatures above 538 C. These are high molecular weight components with low
volatility. Conversely, in the liquid product, the majority of the components,
approx
62.1 % of the product are more volatile and evolve below 538 C.
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Table 5: SimDist anlaysis of feedstock and liquid product after single stage
processing (Reactor temp 538 C)
Fraction Temp ( C) Feedstock R245
Light Naphtha < 71 0.0 0.5
Light/med Naphtha 71-100 0.0 0.3
Med Naphtha 100-166 0.0 1.4
Naphtha/Kerosene 166-193 0.1 1.0
Kerosene 193-232 1.0 2.8
Diesel 232-327 8.7 14.2
Light VGO 327-360 5.2 6.5
Heavy VGO 360-538 33.5 35.2
Vacuum Resid. > 538 51.5 37.9
The feedstock can be further characterized with approx. 0.1 % of its
components
evolving below 193'C (naphtha/kerosene fraction), v. approx. 6% for the liquid
product. The diesel fraction also demonstrates significant differences between
the
feedstock and liquid product with 8.7 % and 14.2 % evolving at this
temperature range
(232-327 C), respectively. Collectively these results show that a substantial
proportion
of the components with low volatility in the feedstock have been converted to
components of higher volatitly (light naphtha, kerosene and diesel) in the
liquid
product.
Stability of the liquid product was also determined over a 30 day period
(Table
6). No significant change in the viscosity, API or density of the liquid
product was
observed of a 30 day period.
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Table 6: Stabilty of liquid products after single stage processing
Fraction Time = 0 7 days 14 days 30days
Density @ 15.6 C (g/cm3) 0.9592 0.9590 0.9597 0.9597
API (deg. API) 15.9 15.9 15.8 15.8
Viscosity @40 C (cSt) 79.7 81.2 81.2 83.2
Example 2 Bitumen (single stage)
Several runs using Athabaska Bitumen were conducted using the pyrolysis
reactor described in US 5,792,340. The conditions of processing included a
reactor
temperature from 520 to about 590'C. Loading ratios for particulate heat
carrier to
feedstock of from about 20:1 to about 30:1, and residence times from about
0.35 to
about 1.2 sec. These conditions, and the resulting liquid products are
outlined in more
detail below (Table 7).
Table 7: Single Stage Processing with Undiluted Athabasca Bitumen
Crack Viscosity @ Yield wt% Density @ Metals V Metals Ni API
Temp 40 C (cSt) 15 C (PPm)* (PPm)**
519 C 205 81.0 nd nd nd 13.0
525 C 201 74.4 0.979 88 24 12.9
528 C 278 82.7 nd nd nd 12.6
545 C 151 77.4 0.987 74 27 11.8
590 C 25.6 74.6 0.983 nd nd 12.4
* feedstock V 209 ppm
** feedstock Ni 86 ppm
These results indicates that undiluted bitumen may be processed according to
the method of this invention to produce a liquid product with reduced
viscosity from
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greater than 1300 cSt (@40'C) to about 25.6 - 200 cSt (@40'C (depending on the
run
conditions; see also Tables 8 and 9), with yields of over 75 % to about 85 %,
and an
improvement in the product API from 8.6 to about 12 - 13. Again, as per
Example 1,
the liquid product exhibits substantial upgrading of the feedstock. SimDist
analysis,and
other properties of the liquid product are presented in Table 8, and stability
studies in
Table 9.
Table 8: Properties and SimDist anlaysis of feedstock and liquid product after
single stage processing (Reactor temp. 545 C).
Fraction Temp ( C) Feedstock 8239
14 days 30 days
Density @15.5'C -- 0.9871 0.9876
API - 11.7 11.6
Viscosity @40 C -- 162.3 169.4
Light Naphtha < 71 0.0 0.2 0.1
Light/med Naphtha 71-100 0.0 0.2 0.2
Med Naphtha 100-166 0.0 1.5 1.4
Naphtha/Kerosne 166-193 0.1 1.0 1.0
Kerosene 193-232 0.9 3.1 3.0
Diesel 232-327 8.6 15.8 14.8
Light VGO 327-360 5.2 7.9 7.6
Heavy VGO 360-538 34.0 43.9 42.0
Vacuum Resid. > 538 51.2 26.4 29.9
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Table 9: Stabilty of liquid products after single stage processing (reactor
temperature 525'C)
R232
Fraction Temp Feedstock day 0 7 days 14 days 30days
( C)
Density @ 15.6 C* - 1.0095 0.979 0.980 0.981 0.981
API - 8.5 12.9 12.7 12.6 12.6
Viscosity @40 C** - 30380 201.1 213.9 214.0 218.5
Light Naphtha < 71 0.0 0.1 0.1 0.1 0.1
Light/med Naphtha 71-100 0.0 0.1 0.1 0.1 0.1
Med Naphtha 100-166 0.0 1.5 1.5 1.5 1.4
Naphtha/Kerosne 166-193 0.1 1.0 1.0 1.0 1.1
Kerosene 193-232 1.0 2.6 2.6 2.6 2.7
Diesel 232-327 8.7 14.1 14.1 14.3 14.3
Light VGO 327-360 5.2 7.3 7.3 7.4 7.4
Heavy VGO 360-538 33.5 41.3 41.3 41.7 42.1
Vacuum Resid. > 538 51.5 32.0 32.0 31.2 30.8
*g./cm3
**cSt
The slight variations in the values presented in the stability studies (Table
9 and
other stability studies disclosed herein) are within the error of the test
methods
employed, and are acceptable within the art. These results demonstrate that
the liquid
products are stable.
These results indicate that over 50% of the components within the feedstock
evolve at temperatures above 538 C (vacuum resid fraction). This fraction is
characterized by high molecular weight components with low volatility.
Conversely,
over several runs, the liquid product is characterized as comprising approx 68
to 74 %
of the product that are more volatile and evolve below 538 C. The feedstock
can be
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further characterized with approx. 0.1 % of its components evolving below 193
'C (naphtha/kerosene fraction), v. approx. 2.7 to 2.9 % for the liquid
product. The diesel
fraction also demonstrates significant differences between the feedstock and
liquid
product with 8.7 % (feedstock) and 14.1 to 15.8 % (liquid product) evolving at
this
temperature range (232-327 C). Collectively these results show that a
substantial
proportion of the components with low volatility in the feedstock have been
converted
to components of higher volatitly (light naphtha, kerosene and diesel) in the
liquid
product. These results demonstrate that the liquid product is substantially
upgraded,
and exhibits properties suitable for transport.
Example 3: Composite/recycle of feedstock
The pyrolysis reactor as described in US 5,792,340 may be configured so that
the recovery condensers direct the liquid products into the feed line to the
reactor (see
Figures 3 and 4). -
The conditions of processing included a reactor temperature ranging from about
530 to about 590 C. Loading ratios for particulate heat carrier to feedstock
for the
initial and recycle run of about 30:1, and residence times from about 0.35 to
about 0.7 sec
were used. These conditions are outlined in more detail below (Table 10).
Following
pyrolysis of the feedstock, the lighter fraction was removed and collected
using a hot
condenser placed before the primary condenser (see Figure 4), while the
heavier
fraction of the liquid product was recycled back to the reactor for further
processing
(also see Figure 3). In this arrangement, the recycle stream (260; Figure 3)
comprising heavy fractions
was mixed with new feedstock (270; Figure 3) resulting in a composite
feedstock (240; Figure 3)
which was then processed using the same conditions as with the initial run
within the
pyrolysis reactor.
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Table 10: Composite/Recycle operation using Saskatchewan Heavy Crude Oil
and Undiluted Athabasca Bitumen
Feedstock Crack Yield Vol % AP1 Recycle" Recycle"
Temp C Yield vol% AP1
Heavy Oil 590 77.11) 13.3 68.6 17.1
560 86.32) 16.2 78.1 21.1
550 50.11 14.0 71.6 17.8
550 65.12,31 18.3 56.4 22.9
530 87.12) 16.6 78.9 21.0
Bitumen 590 75.22) 12.4 67.0 16.0
1) Yield and API gravity include overhead condensing (actual)
2) Yield and API gravity include overhead condensing (estimated)
3) Not all of the liquid was recovered in this run
4) These values represent the total recovery of product following the recycle
run, and presume the
removal of approximately 10% heavy fraction which is recycled to extinction.
This is therefore a
conservative estimate of yield as some of the heavy fraction will produce
lighter components that enter
the product stream, since not all of the heavy fraction will end up as coke.
The API gravity increased from 11.0 in the heavy oil feedstock to about 13 to
about 18.5 after the first treatment cycle, and further increases to about 17
to about 23
after a second recycle treatment. A similar increase in API is observed for
bitumen
having a API of about 8.6 in the feedstock, which increase to about 12.4 after
the first
run and to 16 following the recycle run. With the increase in API, there is an
associated increase in yield from about 77 to about 87 % after the first run,
to about 67
to about 79 % following the recycle run. Therefore associated with the
production of
a lighter product, there is a decrease in liquid yield. However, an upgraded
lighter
product may be desired for transport, and recycling of liquid product achieves
such a
product.
Example 4: Two-Stage treatment of Heavy Oil
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Heavy oil or bitumen feedstock may also be processed using a two-stage
pyrolytic process which comprises a first stage where the feedstock is exposed
to
conditions that mildly crack the hydrocarbon components in order to avoid
overcracking and excess gas and coke production. Lighter materials are removed
following the processing in the first stage, and the remaining heavier
materials are
subjected to a more severe crack at a higher temperature. The conditions of
processing
within the first stage include a reactor temperature ranging from about 510 to
about
530 C (data for 515 C given below), while in the second stage, a temperature
from
about 590 to about 800 C (data for 590 C presented in table 11) was employed.
The
loading ratios for particulate heat carrier to feedstock range of about 30:1,
and residence
times from about 0.35 to about 0.7 sec for both stages. These conditions are
outlined
in more detail below (Table 11).
Table 11: Two-Stage Runs of Saskatchewan Heavy Oil
Crack Viscosity a Yield wt% Density @ AP1 Yield Vol%"
Temp. C 80 C (cSt) 15 C g/ml
515 5.3 29.8 0.943 18.6 31.4
590 52.6 78.9 0.990 11.4 78.1
515 &590 nd nd nd 13.9 86.6
"nd" means not determined
1)Light condensible materials were not captured. Therefore these values are
conservative estimates.
These results indicate that a mild initial crack which avoids overcracking
light
materials to gas and coke, followed by a more severe crack of the heavier
materials
produces a liquid product characterized with an increased API, while still
exhibiting
good product yields.
Other runs using a two stage processes, involved injecting the feedstock at
about 150 C into a hot gas stream maintained at about 515 C and entering the
reactor
at about 300 C (processing temperature). The product, comprising lighter
materials
(low boilers) was separated and removed following the first stage in the
condensing
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system. The heavier materials, separated out at the bottom of the cyclone were
collected subjected to a more severe crack within the reactor in order to
render a liquid
product of reduced viscosity and high yield. The conditions utilized in the
second stage
were a processing temperature of between about 5300 to about 590 C. Product
from
the second stage was processed and collected.
Following such a two stage process the product of the first stage (light
boilers)
is characterized with a yield of about 30 vol %, an API of about 19, and a
several fold
reduction in viscosity over the initial feedstock. The product of the high
boiling point
fraction, produced following the processing of the recycle fraction in the
second stage,
is typically characterized with a yield greater than about 75 vol %, and an
API gravity
of about 12, and a reduced viscosity over the feedstock recycled fraction.
Example 5: "Multi-Stage" treatment of Heavy Oil and Bitumen, using Feedstock
for Quenching within Primary Condenser.
Heavy oil or bitumen feedstock may also be processed using a "Multi-stage"
pyrolytic process as outlined in Figure 5. In this system, the pyrolysis
reactor
described in US 5,792,340 is configured so that the primary recovery condenser
directs
the liquid product into the feed line back to the reactor, and feedstock is
introduced
into the system at the primary condenser where it quenches the product vapours
produced during pyrolysis.
The conditions of processing included a reactor temperature ranging from
about 530 to about 590 C. Loading ratios for particulate heat carrier to
feedstock for
the initial and recycle run of from about 20:1 to about 30:1, and residence
times from
about 0.35 to about 1.2 sec were used. These conditions are outlined in more
detail
below (Table 12). Following pyrolysis of the feedstock, the lighter fraction
is
forwarded to the secondary condenser while the heavier fraction of the liquid
product
obtained from the primary condenser is recycled back to the reactor for
further
processing (Figure 5).
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Table 12: Charaterization of the liquid product obtained following Multi-Stage
processing of Saskatchewan Heavy Oil and Bitumen
Crack Temp. C Viscosity @ Yield wt% Density @ AP1 Yield Vol%"
40 C (cSt) 15.6 C g/ml
Heavy Oil
543 80 62.6 0.9592 15.9 64.9
557 24 58.9 0.9446 18.2 62.1
561 53 70.9 0.9568 16.8 74.0
Bitumen
538 40 61.4 0.9718 14.0 71.1
The liquid products produced from multi-stage processing of feedstock exhibit
properties suitable for transport with greatly reduced viscosity down from
6343 cSt
(@40 C) for heavy oil and 30380 cSt (@40 C) for bitumen. Similarly, the API
increased from 11 (heavy oil) to from 15.9 to 18.2, and from 8.6 (bitumen) to
14.7.
Furthermore, yeilds for heavy oil under these reaction conditions are from 59
to 68 %
for heavy oil, and 82 % for bitumen.
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Table 13: Properties and SimDist of liquid products prepared from Heavy Oil
using the multi- stage Process (for feedstock properties see Tables 1 and 5).
R241* R242** R244***
Fraction Temp ( C) Day 0 Day 30 Day 30
Density @ 15.6 C - 0.9592 0.9597 0.9465 0.9591
API - 15.9 15.8 17.8 15.9
Viscosity @40 C - 79.7 83.2 25.0 49.1
Light Naphtha < 71 0.0 0.2 0.3 0.3
Light/med Naphtha 71-100 0.0 0.1 :'= 0.2 0.3
Med Naphtha 100-166 0.1 0.4 2.5 1.8
Naphtha/Kerosne 166-193 0.6 0.6 1.8 1.5
Kerosene 193-232 2.8 2.5 5.0 3.5
Diesel 232-327 21.8 21.0 23.1 18.9
Light VGO 327-360 10.8 10.2 9.9 8.8
Heavy VGO 360-538 51.1 45.0 44.9 43.2
Vacuum Resid. > 538 12.7 20.0 12.3 21.7
* reactor temp. 543 C
** reactor temp. 557 C
*** reactor temp.561 C
Under these run conditions the API increased from 11 to about 15.9 to 17.8.
Product yields of 62.6 (wt%; R241), 58.9 (wt%; R242) and 70.9 (wt%; P.244)
were
achieved along with greatly reduced viscosity levels. These liquid products
have been
substantially upgraded over the feedstock and exhibit properties suitable for
pipeline
transport.
SimDist results indicate that over 50% of the components within the feedstock
evolve at temperatures above 538 C (vacuum resid fraction), while the liquid
product
is characterized as comprising approx 78 to 87 % of the product that are more
volatile
and evolve below 538 C. The feedstock can be further characterized with
approx. 0.1
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% of its components evolving below 193 C (naphtha/kerosene fraction), v.
approx. 1.3
to 4.8 % for the liquid product. The kerosene and diesel fractions also
demonstrates
significant differences between the feedstock and liquid product with 1 % of
the
feedstock fraction evolving between 193-232'C v. 2.8 to 5 % for the liquid
product,
and with 8.7% (feedstock) and 18.9 to 23.1 % (liquid product) evolving at this
temperature range (232-327 C; diesel). Collectively these results show that a
substantial proportion of the components with low volatility in the feedstock
have been
converted to components of higher volatitly (light naphtha, kerosene and
diesel) in the
liquid product. These results demonstrate that the liquid product is
substantially
upgraded, and exhibits properties suitable for transport.
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Table 14: Properties and SimDist of liquid products prepared from
Bitumen following "Two Stage" processing (reactor temp. 538'C; for feedstock
properties see Tables 1, 8 and 9).
Fraction Temp ('Q R243
Density @ 15.6 C - 0.9737
API - 13.7
Viscosity @40 C - 45.4
Light Naphtha <71 0.3
Light/med Naphtha 71-100 0.4
Med Naphtha 100-166 3.6
Naphtha/Kerosne 166-193 1.9
Kerosene 193-232 4.4
Diesel 232-327 19.7
Light VGO 327-360 9.1
Heavy VGO 360-538 41.1
Vacuum Resid. > 538 19.5
Under these run conditions the API increased from 8.6 to about 14. A product
yield of 68.4 (wt%) was obtained along with greatly reduced viscosity levels
(from
30380 cSt @40 C in the feedstock, to approx. 45 cSt in the liquid product).
Simulated distillation analysis demonstrates that over 50% of the components
within the feedstock evolve at temperatures above 538 C (vacuum resid
fraction) while
80.5% of the liquid product evolves below 538 C. The feedstock can be further
characterized with approx. 0.1 % of its components evolving below 193 C
(naphtha/kerosene fraction), v. 6.2 % for the liquid product. The diesel
fraction also
demonstrates significant differences between the feedstock and liquid product
with
8.7 % (feedstock) and 19.7 % (liquid product) evolving at this temperature
range (232-
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327'C). Collectively these results show that a substantial proportion of the
components with low volatility in the feedstock have been converted to
components of
higher volatitly (light naphtha, kerosene, and diesel) in the liquid product.
These
results demonstrate that the liquid product is substantially upgraded, and
exhibits
properties suitable for transport.
The present invention has been described with regard to preferred
embodiments. However, it will be obvious to persons skilled in the art that a
number
of variations and modifications can be made without departing from the scope
of the
invention as described herein.
