Note: Descriptions are shown in the official language in which they were submitted.
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Description
Title of Invention
Method of partially upgrading heavy oil at well-site
Field of the invention
This invention relates to partial upgrader set at
well-site which yields lighter fraction by thermal cracking of
heavy oil having an API gravity of 20 or less, and
substantially produce fuel source to generate assist steam to
recover heavy oil by injecting steam into a reservoir.
Background of the invention
SAGD (Steam Assisted Gravity Drainage) and CSS
(Cyclic Steam Stimulation), in which assist steam is used, are
adopted for in-situ recovery of heavy oils. Assist steam is
generated at boilers by firing natural gas, whose cost will
occupy more than half of the total operating cost for heavy oil
recovering. Therefore, it is necessary to find alternatives
other than natural gas from the view points of natural gas
availability and the reduction of cost related to fuel for
steam generation.
The recovered heavy oil will not meet pipelineable
specifications because of low API gravity and poor fluidity due
to high viscosity at ambient temperature. Therefore heavy oil
being diluted with naphtha or condensate is pipelined as so
called DilBit in Canada directly to the market or a refinery,
where the diluent is recovered then returned to the well-site
via. diluent pipeline. In the former case, the vol% of diluent
is about 30 to the total volume of DilBit whose cost is
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substantially affected by diluent price and the availability of
diluent will be another issue. In the latter case, the pipeline
shall be so designed as to accommodate the increased massive
volume of heavy oil by dilution and two pipelines are
necessary, one for shipment and the other for diluent return
between the well-site and the refinery.
Heavy oils are transacted in the market at lower
price than conventional crudes for their high contents of
impurities such as sulfur, nitrogen and heavy metals like
nickel and vanadium and they are more discounted when they are
high-TAN (Total Acid Number).
From above situation, it is necessary to optimize the
processing of heavy oils at well-site to upgrade properties and
to improve transportability.
Such processes as thermal cracking, solvent
deasphalting (SDA) and hydrocraking, which are commonly used to
process atmospheric or vacuum residue at conventional refinery
configuration, are not suitable for the upgrading of heavy oils
at well-site from the following reasons.
Among the thermal cracking processes, coker is not
fit to well-site because of a large amount of by-product coke,
which requires rather complicated handling works and related
facilities. Visbreaker has less upgrading margin from its
conversion limitation by the stability of cracked oil.
SDA is an extraction process to separate asphaltene-
containing fraction and DA0 (de-asphalted oil) in heavy oil
feedstock by certain solvent and operating conditions without
any reaction to crack or modify the original molecules in the
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feedstock.
As described in US-B 6,357,526, the SCO (synthetic
crude oil), composed of pre-separated gas oil fraction from
bitumen and DAO of the residue by SDA, has an only 4-5 degree
improvement of API gravity. This eventually means that API
gravity of the obtained SCO from the bitumen supposing API 8 is
only 12-13, which is less upgrading effect than the present
invention.
The catalyst used in hydrocracking process is
subjected to activity degradation due to contamination by
nitrogen and heavy metals like nickel and vanadium highly
contained in heavy oils. The hydracracking process requires
high pressure equipment, and hydrogen production unit and
source of hydrogen. Thus hydrocracking process may be less
applicable to well-site upgrading from its operability and
economic disadvantage.
It is pronounced to generate steam by gasification of
residue, SDA asphaltene and coke. However gasification process
is not appropriate for well-site upgrading for its scale and
complexity.
JP-A 6-88079 discloses thermally cracking a heavy oil
and treating the cracking product with stripping steam, that
is, HSC (High conversion Soaker Cracking) process.
Hydrocarbon Processing, Sept., 1989, p. 69 shows a
conventional visbreaker and a conventional HSC.
Above cited HSC is technically and economically
effective for upgrading of heavy oil at well-site replacing
natural gas with the thermal cracked residue, by-product of the
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HSC, for SAGD and CSS from the view points of natural gas
availability and the reduction of cost related to fuel for
assist-steam generation.
Summary of Invention
The invention provides a method of partially
upgrading heavy oil, having an API gravity of 20 or less,
fractions having boiling points of 500deg C or lower in an
amount of 45 wt% or smaller, residual carbon (MCR) in an amount
of 10 wt% or larger, a total acid number (TAN) of 1.0 or larger
and a kinematic viscosity at 50deg C of 1,000 mm2/s or larger,
the method comprising thermal cracking heavy oil at well-site,
wherein the thermal cracked residue is used as the fuel to
produce the assist steam for recovering heavy oil from
reservoir.
The invention provides a method of transporting, in
pipeline, the thermal cracked oil product. Further the
invention provides a method of transporting, in pipeline, a
mixture of the thermal cracked oil product with heavy oil
recovered from resevoir for pipeline transportation.
In some embodiments, there is provided a method of
partially upgrading heavy oil, having an API gravity of 20 or
less, fractions having boiling points of 500 C or lower in an
amount of 45 wt% or smaller, residual carbon (MCR) in an amount
of 10 wt% or larger, a total acid number (TAN) of 1.0 or larger
and a kinematic viscosity at 50 C of 1,000 mm2/s or larger,
the method comprising thermal cracking heavy oil at well-site,
using a thermal cracked residue as a fuel to produce steam for
recovering heavy oil from reservoir, further comprising thermal
cracking of the heavy oil at a pressure of 0 to 0.1 MPaG at a
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temperature of 370 to 440 C for 15 to 150 minutes in a soaking
drum (R1) and at the same time injecting stripping steam into
the soaking drum to separate a thermal cracked oil, generated
in a liquid phase of the soaking drum, as a gaseous thermal
cracked oil, from a thermal cracked residue, to obtain a
thermal cracked oil product, wherein the liquid phase of the
soaking drum is maintained to have an S-value of 2.0 or larger,
and further comprising mixing the thermal cracked oil product
with heavy oil recovered at well-site for pipeline
transportation, not treated by thermal cracking.
Detailed explanation of the invention
The invention method of partially upgrading heavy oil
may further includes thermal cracking of the heavy oil at a
pressure of 0 to 0.1 MPaG at a temperature of 370 to 440deg C
for 15 to 150 minutes in a soaking drum (R1) and at the same
time the produced stripping steam is injected into the soaking
drum to separate a thermal cracked oil, generated in a liquid
phase of the soaking drum, as a gaseous thermal cracked oil,
from a thermal cracked residue, to obtain a thermal cracked oil
product, provided that the liquid phase of the soaking drum is
maintained to have an S-value of 2.0 keep adequate stability of
thermal cracked oil product.
The invention method of partially upgrading heavy oil
may further includes steps of flowing out the thermal cracked
oil together with a thermal cracked gas and stripping steam
through a discharging line (L1), provided at top of the soaking
drum, the effluents is cooled directly with a heavier fraction
of the thermal cracked oil at a discharging line (L1), a non-
condensed lighter fraction, a thermal cracked gas, steam and a
condensed heavier fraction of the thermal cracked oil are
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separated in an upgraded oil heavy fraction separator (D1), the
heavier fraction of the thermal cracked oil is discharged from
a bottom of the separator (D1), the starting heavy oil is
heated with a heat-exchanger (C2) for heat-recovering, steam is
generated at a heat-exchanger (03), part of the heavier
fraction of the thermal cracked oil is recycled as a cooling
medium to the discharging line (L1), the rest is discharged as
a heavier fraction product, the non-condensed lighter fraction,
the thermal cracked gas and steam is cooled with the heat-
exchanger (air cooler) (C1), a condensed lighter fraction is
separated¨from water in an oil/water separator (D2), the
condensed lighter fraction is mixed with the heavier fraction
product to obtain a thermal cracked oil product which will be
mixed with heavy oil recovered from reservoir, for pipeline
transportation.
The invention provides the above shown thermal
cracking method or step for a partially upgrading heavy oil.
In the invention, thermal cracking of heavy oil by
the HSC (High conversion Soaker Cracking) process produces
upgraded oil with a lowered viscosity, a raised API gravity and
less impurities. It improves the transportability of heavy oil
and separates the thermal cracked residue which is used as the
fuel to generate the assist steam into heavy oil reservoir.
These directly relate to the reduction of investment cost of
heavy oil upgrading at well-site and operating cost of heavy
oil recovery by injecting steam into reservoir.
The invention is below explained in comparison with
issues of conventional.
1. Heavy oils have higher viscosity and lower API gravity than
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conventional crudes and are hard to be pipelined. Moreover,
heavy oils have high contents of impurities such as sulfur,
nitrogen and heavy metals like nickel and vanadium and TAN.
Thermal cracking of heavy oil by HSC (High conversion Soaker
Cracking) process produces upgraded oil with a lowered
viscosity, a raised API gravity and less impurities and
separates the thermal cracked residue.
2. Visbreaker, a conventional thermal cracking process, is
avoided from a high conversion from the reason that the
coexistence of the lighter fraction and the cracked residue in
the same liquid phase in the reactor has much propensity of
asphaltene precipitation, which leads to coking of a reactor
and plugging of pipes.
HSC thermal cracking can attain a higher conversion by
avoiding the coexistence of the lighter fraction and the
cracked residue in the same liquid phase.
3. Heavy oils are highly viscous and low in fluidity so that
they have to be pipelined after diluted by diluent or
condensate. A diluent cost and related costs to pipeline are
reduced by a less volume of the diluent by means of HSC. The
ultimate case of no dilution requires no diluent-returning
pipeline.
4. The cost of natural gas for steam generation amounts to more
than half of the total operating cost for heavy oil recovering.
Replacing the natural gas for steam generation with the thermal
cracked residue, by-product of the HSC, reduces the energy
cost.
5. Such conventional processes as thermal cracking, solvent
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deasphalting (SDA) and hydrocracking, which are commonly used
to process atmospheric or vacuum residues in refinery
configuration, are not suitable for partial upgrading of heavy
oil at well-site from the view points of economically feasible
plant scale, obtainable upgrading margin and product oil
specifications for pipeline transportation. The HSC process
with simplified scheme is more economically feasible than
conventional processes and thus suitable for partial upgrading
of heavy oil and for making heavy oil transportable at well-
site.
The invention solves the above shown issues as
follows:
(1) HSC thermal cracking can be operated stably, attaining a
higher conversion, in which asphaltenes are kept well-dispersed
in the reaction liquid phase by simultaneous separation of
thermal cracked oil from the reaction liquid phase, avoiding
the coexistence with cracked residue in the same liquid phase.
(2) The HSC produces upgraded oil with a lowered viscosity, a
raised API gravity and less impurities such as sulfur, nitrogen
and heavy metals like nickel and vanadium and reduced TAN.
(3) A process scheme in which heavy oil is thermally cracked by
the HSC to produce the thermal cracked oil product as upgraded
oil with a lowered viscosity, a raised API gravity and less
impurities and separates cracked residue. The thermal cracked
oil product as upgraded oil is mixed with heavy oil recovered
from reservoir for pipeline transportation.
(4) In the method and scheme, the separated cracked residue is
used as the fuel to generate the assist steam for recovering
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heavy oil from reservoir.
(5) The quantity of cracked residue corresponding to the
required assist steam quantity by SOR (Steam to Oil Ratio=
volume of water to volume of oil, converted to assist steam for
one unit volume of heavy oil) at reservoir injection for heavy
oil recovery is adjusted by the feeding rate of heavy oil to
the HSC.
The invention relates preferably to a partial
upgrading by thermal cracking of heavy oils in order to improve
their properties and transportability at well-site at which
heavy oils, whose API gravity is less than 20 such as Oil Sands
Bitumen and Orinoco Tar, or heavy crude, are recovered by
injecting assist steam into heavy oil reservoir.
In the invention, the thermal cracking and injection
of stripping steam are carried out in a drum or reactor. The
heavy oil is easily separated into a thermal cracked oil
product and a thermal cracked residue. The invention can be
preferably carried out at well-site of heavy oil source, that
is, provides preferably a well-site upgrading method by thermal
cracking.
In the invention, the thermal cracked oil product has
sulfur, nitrogen and heavy metals like nickel and vanadium in
reduced amounts. The thermal cracking is preferably carried out
at 400deg C to 440deg C and the thermal cracked oil product has
a reduced total acid number (TAN). The thermal cracked oil
product has so reduced viscosity as to be suitable for pipeline
transportation. The thermal cracked oil product has a larger
API gravity than the original heavy oil. The thermal cracked
oil product is stable in properties by avoiding contact with
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air during storage or transportation.
The invention method may further comprise firing the
separated thermal cracked residue in a boiler to generate
assist steam and the assist steam is used for recovering heavy
oil in SAGD, CSS or Steam Flooding. The separated thermal
cracked residue is used in an amount to generate in an amount
of assist steam required for SOR (Steam to Oil Ratio) at well-
site. The separated thermal cracked residue is obtained by
thermal cracking heavy oil recovered at well-site.
The invention method may further comprise mixing the
thermal cracked product with heavy oil recovered at well-site
for pipeline transportation.
It is preferable that the heavy oil has an API
gravity of 20 or less. It is more preferable that the heavy oil
has an API gravity of 10 or less and a total acid number (TAN)
of 2.0 or larger, such as Oil Sands Bitumen or Orinoco Tar.
Brief description of Drawings
Fig. 1, shows a conventional visbreaker (a) and the HSC (b) in
comparison. Fig. 2 shows the flow scheme of HSC process at a
well-site. Fig. 3 shows mixing schemes, including part 3.1
showing commonly used scheme, part 3.2-1 showing all recovered
heavy oil processed by the HSC and part 3.2-2 showing part of
recovered heavy oil processed by the HSC. Fig. 4 shows a simple
flow diagram of auto-cave experimental apparatus. Fig. 5 is a
graph showing thermal cracking yield and TAN of upgraded oil.
Fig. 6 is a graph showing reaction temperature and TAN of
upgraded oil.
The invention will be explained more in details in
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reference to examples and drawings.
Fig. 1 shows conventional Visbreaker (a) and the HSC
(b) in comparison. The visbreaker, both coil type and soaker
type, is operated at elevated pressure and the thermal cracked
oil and the thermal cracked residue coexist in the same
reaction liquid phase, which leads to the situation to
accelerate the sedimentation of asphaltenes in the liquid
phase. In order to avoid this situation, visbreaker process has
intrinsically conversion limitation. In the HSC process, the
thermal cracking reaction is carried out under atmospheric
pressure and the thermal cracked oil product is simultaneously
stripped away from the reaction liquid phase by the vapor
pressure reducing effect of the injected stripping steam in the
reaction liquid phase. This allows the HSC proceed the thermal
cracking beyond the conversion limit of the conventional
visbreaker process.
One of the evaluation methods of the stability of
thermal cracked oil product is known as S-value. S-value is
determined by diluting an oil sample with toluene to fully
disperse asphaltene and then adding n-heptane to the diluted
liquid until asphaltene starts to precipitate. In ASTM D-7157-
05, asphaltene precipitated point is optically detected by
automatic titration with n-heptane of a toluene-diluted sample.
Based on this principle, this invention adopted to detect the
asphaltene precipitated point by observing the appearance of a
dark spot mark at the center of the spot on the chromatograph
paper dropping small amounts of sample specimen at every
addition of known amount of n-heptane to toluene diluted
sample. The higher S-value shows the more stably asphaltenes
are dispersed. When precipitation of asphaltene is observed
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without adding any n-heptane, it is denoted S-value as 1Ø The
visbreaker is said to require S-value of minimum 2.0 for the
stable process operation.
Fig. 2 shows the flow scheme of the HSC for upgrading
heavy oil at well-site. In Fig. 2, HVO: Heavy Oil Feed, UGO:
Upgraded Oil (thermal cracked oil product), Pl: Feed Pump, P2:
Upgraded Oil Heavy Fraction Circulation Pump, P3: Upgraded Oil
Light Fraction Draw-out Pump, P4: Condensed Water Draw-out
Pump, P5: Thermal Cracked Residue Circulation Pump, Hi: Furnace
Heater, Cl: Heat Exchanger 1, C2: Heat Exchanger 2, C3: Heat
Exchanger 3, C4: Heat Exchanger 4, C5: Heat Exchanger 5, R1:
Soaking Drum, Dl: Upgraded Oil Heavy Fraction Separato, D2:
Oil/Water Separator, Si: Steam, Li: Line 1. HVO is first
supplied by a Pump P1 through Heat Exchanger C2 for heating and
fed to Charge Heater H1 for designed temperature. The heated
HVO is fed to Soaking Drum R1 in which thermal cracking
reactions occur in the liquid zone where steam Si superheated
at H1 is injected. The thermal cracked oil (upgraded oil),
which is stripped away from the liquid zone as vapors by the
vapor pressure reducing effect of the injected stripping steam
in the reaction liquid phase, flows out of the top of R1
together with cracked gas and stripping steam to Upgraded Oil
Heavy Fraction Separator D1 through Discharging Line Li. The
effluents is directly quenched by circulated cool heavier
fraction of thermal cracked oil at Li from R1 to Dl. Condensed
heavier fraction of thermal cracked oil is separated from
vapors of the lighter fraction of thermal cracked oil, thermal
cracked gas and stripping steam at Dl. Vapors of the lighter
fraction of thermal cracked oil, thermal cracked gas and
stripping steam are cooled further by Heat Exchanger Cl and
uncondensed thermal cracked gas flows out of Oil/Water
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Separator D2. Condensed steam and the lighter fraction of
thermal cracked oil are separated by density at D2 and
condensate water is drawn out by Pump P4. The separated lighter
fraction of thermal cracked oil is drawn out by Pump P3 and
mixed with the heavier fraction of thermal cracked oil. The
separated heavier fraction of thermal cracked oil at D1 is
circulated by Pump P2, after which is cooled by Heat Exchangers
C2 and C3, and used for direct quenching of thermal cracked
gas, thermal cracked oil and stripping steam which come out
from top of Rl. A part of the heavier fraction of thermal
cracked oil cooled by C3 is mixed with the lighter fraction of
thermal cracked oil as the product upgraded oil UGO (thermal
cracked oil product). The upgraded oil(UGO=Thermal cracked oil)
can be pipelined itself, also can be used as a diluent for
pipelining the heavy oil recovered from reservoir.
It is also possible to pre-cut the lighter faction
originally contained in HVO before the above processing scheme
and to mix it with UGO.
A mixing scheme will be explained below in reference
to Fig. 3.
Part 3.1 shows the commonly used scheme using natural
gas for assist steam production and dilution of recovered heavy
oil by diluent for pipelining. The water separated from the
mixture of heavy oil and hot water came out from subterranean
zone is re-circulated and reused for boiler feed water after
required treatment.
Part 3.2-1 shows a schematic diagram for the case in
which all of the recovered heavy oil is processed by the HSC
and the upgraded oil (thermal cracked oil product) which meets
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pipelineable specifications is pipelined without dilution. The
thermal cracked residue is used as the fuel for assist steam
generation in place of natural gas.
Part 3.2-2 shows a schematic diagram for the case in which the
quantity of thermal cracked residue corresponding to the
required assist steam quantity by SOR at reservoir injection
for heavy oil recovery is adjusted by the feeding rate of heavy
oil to the HSC. The rest of untreated heavy oil is mixed with
the upgraded oil (thermal cracked oil product) by the aforesaid
method and the mixture is diluted by a diluent to adjust
specifications for pipelining.
In this case, the water is also re-circulated and
reused after required treatment of separated water from the
mixture of heavy oil and hot water came out from subterranean
zone.
Fig. 4 is a simple flow of an experimental autoclave
(ACR) apparatus. About 500g of heavy oil is charged into 1
(one) liter autoclave ACR and precisely weighed. After closing
the cover flange of the ACR and purging the system by nitrogen,
the system was adjusted to the objected vacuum by Vacuum Pump
VPUMP. ACR is immersed into the molten tin bath and the
agitator is started above the melting point of heavy oil in
ACR. The reaction time counting is started when the heavy oil
sample in ACR reached at objected reaction temperature. During
the reaction, the effluents from ACR are first cooled at hot
water condenser HC and condensed heavier fraction of thermal
cracked oil is collected in Heavy Oil Receiver HOR. Lighter
fraction of thermal cracked oil is collected in Light oil
Receiver LOR after cooling by cold water and chilled water Cold
Trap CC. All of thermal cracked gas is collected in Tedler Bag
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after measuring the volume by Gas Meter GM.
After the reaction, the bath is lowered rapidly to
cool ACR and stop the reaction. Having been cooled to room
temperature, the cover flange is taken out and the ACR is
weighed. The weight of the content is determined by reducing
the weight of the ACR itself as a weight of the thermal cracked
residue.
The oils in HOR and LOR are weighed in total as an
amount of the thermal cracked oil product.
Taking a part of the thermal cracked gas in BAG, the
concentration of hydrogen sulfide was measured by detecting
tube and the rest of gas components was analyzed by gas
chromatography. The weight of thermal cracked gas was obtained
from gas volumes and gas composition.
Properties of heavy oils, Oil Sands Bitumen and
Orinoco Tar, used for the experiments, are listed in Table 1.
Both feedstocks are extra heavy oil with API gravity less than
10.
Comparison with conventional visbreaking is explained
below.
Examples are listed in Table 2(1). Examples 1, 2 and
3 are conducted varying the reaction time to obtain different
cracking yields at constant vacuum and temperature conditions,
118mmHg and 410deg C, respectively. S-values of the thermal
cracked residue the mixture of upgraded oil and the thermal
cracked residue were measured and compared, the former
simulating the reaction liquid phase of the HSC in which the
upgraded oil simultaneously separated as vapor by stripping
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steam from the liquid phase, and the latter simulating the
reaction liquid phase of visbreaker.
As in Example 1, S-value of the mixture of upgraded
oil and the thermal cracked residue at the thermal cracking
yield (gas + upgraded oil) of 58.3 wt% is 1.9 which is lower
than 2.0 of the limit value for the stable operation of
visbreaker process. This means that further cracking brings
risky situation which may lead to the contamination, plugging
and ultimately coking of the reactor by asphaltene
sedimentation. On the other hands, S-value of the thermal
cracked residue is 2.8 at the same thermal cracking yield,
which implies the well dispersed asphaltenes.
S-value of the mixture of upgraded oil and the
thermal cracked residue of Example 2 is 1.6 at thermal cracking
yield (gas + upgraded oil) of 62.4 wt%, which means worse
dispersion of asphaltenes. However, S-value of the thermal
cracked residue is 2.5 at the same thermal cracking yield,
which means asphaltene dispersion is kept satisfactorily.
S-value of the mixture of upgraded oil and the thermal cracked
residue of Example 3 is 1.4 at thermal cracking yield (gas +
upgraded oil) of 67.4 wt%, which means worse dispersion of
asphaltenes. However, S-value of the thermal cracked residue is
2.0 at the same thermal cracking yield meaning asphaltene
dispersion kept still within the allowable range of visbreaker.
From above Examples the HSC is evidently has the advantage to
conventional visbreker keeping asphaltene stability in the
reaction liquid phase even above the limit of visbreaker.
Table 2(2) shows S-values of thermal cracked residues
from Middle Eastern vacuum residue. Although the softening
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point of thermal cracked residue of Comparative Example 1 is
same as that of Example 1, S-value of Comparative Example 1 is
2.2, which is lower than that of Example 1, namely 2.8.
In the same way, although the softening point of
thermal cracked residue of Comparative Example 2 is the same as
that of Example 2, S-value of Comparative Example 2 is 1.7,
which is lower than that of Example 2, this time namely 2.5.
Thus, the HSC is a superior technology to upgrade heavy oil,
especially for Oil Sands Bitumen.
Reduction of Contents of Impurities will be explained
below. As shown in Table 3(1), contents of nitrogen of 0.4 wt%,
sulfur of 5.02 wt% and nickel/vanadium of 85/220 wppm of
feedstock Oil Sands Bitumen are improved to 0.1-0.2 wt%, 3.4-
3.66 wt% and <1/<1 wppm, respectively, in the upgraded oils.
Also as shown in Table 3(2), contents of nitrogen of
0.58 wt%, sulfur of 3.61 wt% and nickel/vanadium of 92/439 wppm
of feedstock Oil Sands Bitumen are improved to 0.2-0.3 wt%,
3.29-3.52 wt% and <1/<1 wppm, respectively, in the upgraded
oils (thermal cracked oil product).
Reduction of TAN will be explained below.
Results of TAN reduction of Examples 1, 2, 3, 4, 5
and 6 are shown in Table 4(1), Figs. 5 and 6. When Oil Sands
Bitumen with TAN of 2.80 mgKOH/g is treated by the HSC, TAN of
the upgraded oil (thermal cracked oil product) is reduced to
2.12-1.66 mgKOH/g.
It is observed that the reduction rate of thermal
cracking at 390 C is the least and tends to increase reduction
rate with the increase of temperature. Temperature higher than
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400 C is effective for the reduction of TAN.
Table 4(2) shows the results of Examples 11 and 12
for Orinoco Tar. Orinoco Tar with TAN of 3.3 mgKOH/g is treated
by the HSC, TAN of the upgraded oils is reduced to 2.0 mgKOH/g.
Storage Stability of Upgraded Oil (thermal cracked oil product)
will be explained below.
Table 5 shows test results of storage stability of
upgraded oil. The API gravity and kinematic viscosity of
upgraded oil increased with the increase of storage duration in
air atmosphere as in Comparative Example 4. However, properties
of upgraded oil stored in nitrogen atmosphere are unchanged
after 60 days storage as in Example 9. The stability of
upgraded oil is kept avoiding the contact with air during long
time storage.
Reduction of Diluent and Property Improvement by Heavy Oil
Upgrading
In Canada, viscosity not more than 350 mm2/s and API
gravity more than 19 is the pipelineable specifications for
heavy oil. Respective viscosities of Examples 1, 2 and 3 are
158, 142 and 130 mm2/s even at 7.5 C (the climate yearly lowest
reference temperature), which are sufficiently below 350 mm2/s,
as shown in Table 3(1).
Respective API gravities of upgraded oil (thermal
cracked oil product) of Examples 1, 2 and 3 of Table 3(1) are
19.0, 19.1 and 19.3, which satisfy the requirement of
pipelineable specification without dilution.
Table 6 shows the dilution ratios when API gravity of
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21 is required as pipelineable specification. Against
Comparative Example 3 for which the diluent of 29.8 vol% is
necessary for the case without upgrading, the upgraded oil by
the HSC requires the diluent of 18 vol% at SOR 3.0 (Example 7)
and the diluent of 11.5 vol% at SOR 4.0 (Example 8). Thus when
the bitumen processed by the HSC, less amount of the diluent is
necessary for pipelineable specification of API gravity 21.
At the same time, sulfur, nitrogen, nickel/vanadium
and TAN of the blended oils of Examples 7 and 8 are lower than
those of Comparative Example 3, thus properties of blended oils
are improved.
Table 1, Table 1 (continued), Table 2(1), Table 2(2),
Table 3(1), Table 3(1) (continued), Table 3(2), Table 3(2)
(continued), Table 4(1), Table 4(2), Table 5 and Table 6 are
below described.
19
=
0,
0-1
=¨)
o
N)
i
, Table 1 Feedstock Properties01
1---,
Oil Sands
Orinoco Tar
Bitumen
Cerro Negro Analytical Method
. . = Athabasca
=
JIS K2249
Density @15 C g/cm3 1.0164 1.0133
Worden Pycnometer
API 7.6 8.1
C wt% 83.60 78.26
0
H wt% 10.50 10.68
JPI-5S-65
0
. N wt% 0.40 0.58
IV
,1
S wt% 5.02 3.61
JIS K2541-3 ..3
w
Ni wPPm 85 92
g
iv
JPI-5S-59 0
0V wPPm 220 439
1.)
nC7Insols. wt% 10.4 10.0
ASTM D6560 0
1-`
MCR wt% 14.08 12.34
JIS IC2270 0,
i
0
JIS K2501
N)
TAN 2.8 3.3
'
1.)
Potentiometric Titration
1.)
Kinematic Viscosity @7.5 C mm2/s - -
@50 C mm2/s 6,970 -
JIS K2283
@75 C mm2/s 874 -
@100 C mm2/s 182 -
Absolute Viscosity @100 C mPa.s 203 140
@160 C mPa = s 23 6
Brookfield Rheometer
@220 C mPa.s 8 -
=
,
o-
,
cri
--...]
c)
tv
1
Table 1 Feedstock Properties (continued) CP
CM
I-'
Oil Sands
Orinoco Tar
Bitumen
Analytical Method
Cerro Negro
Athabasca
. .
Gross Heating Value ' J/g
42,530 . .
40,800
JIS K2279
Net Heating Value J/g 40,140
38,650
Stability (S-value) . 3.7 -
acc. to ASTM D7157
._
JIS K2275
Water % 0.3 -
Karl Fisher Coulometric Titration
Dry Sludge wt% 0.23
0.28 ISO 10307-1 0
JIS K2254
0
Distillation %
N.,
Gas Chromatography Method
--3
=
--3
IBP C 194
145 w
0
_
0
N) 5 C =276
238 c)
10 C 318285 0
_
1-,
20 C 385 360 0,
1
0
30 C 442 441
1
40 C 500 490
N.,
45 C - 520
50 C 548 -
60 C 598
70 C 652 -
80 C 714 - _
90 C - -
95 C .. _
EP C - -
, .
m
(xi
,
--]
o
Iv
1
Table 2(1) Thermal Cracking Test Results
ui
(5)
1¨
Oil Sands Bitumen Athabasca Example 1
Example 2 Example 3
_
_
Upgraded Oil
Upgraded Oil Upgraded Oil
= Vacuum. =
mmHg 118 118 118 .
Stripping Steam Injection Ratio
wt% on Feed 13
15 15.5
equivalent to Vacuum
-
Reaction Temp. C 410
410 410
¨
Reaction Duration min 20
31 47 0
Thermal Cracking Yield wt% :
0
Gas 1.0
1.11.6 1.)
..3
'
,1
Upgraded Oil . 57.3
61.3 _ 65.8 w
0
N.)
.
N) Thermal Cracked residue 41.7
37.6 ., 32.6
.
1.)
,
Softening Point of
. C 85
99 125
0,
Thermal Cracked Residue
I
0
1.)
Thermal Conversion of I%
30.6 37.4 45.8 "
1.)
500 C+ Farction
Thermal Conversion of 500 C+ Farction % =
(Yield of (Gas+Upglided Oil) wt%-500 C- Fraction of Feed wt%))/(100-500 C.
Fraction of Feed vvt%)x100
S-value -
Thermal Cracked Residue - 2.8
2.5 2
,
Mixture of Upgraded Oil &
- 1.9 1.6 1.4
Thermal Cracked Residue
,
CA 02773000 2016-02-22
65702-561
Table 2(2) S-value of Thermal Cracked Residue of Middle Eastern Vacuum Residue
Comparative Example 1
Comparative Example 2 _
Softening Point of
Thermal Cracked Residue C 85 99
S-value 2.2 1.7
=
23
o-)
01
---)
c)
Table 3(1) Thermal Cracking Test Results =
' N)
. 1
cri
o-)
Feed
Example 1 Example 2 Example 3 Example 1 Example 2
Example 3 i--
I
Oil Sands
Thermal Thermal Thermal
Upgraded Upgraded Upgraded
=Bitumen
Cracked Cracked Cracked
Oil Oil Oil
Athabasca
Residue Residue Residue
. . .
Vacuum mmHg _ 118 118 118
118 118 118
'
Stripping Steam Injection
wt% on Feed . 13 15 15.5
13 15 15.5
Ratio equivalent to Vacuum
Reaction Temp. C - 410 410 410
410 410 410
n -
Reaction Duration mm - 20 31 47
_ 20 31 47
N.)
-
--3
Opaque Slightly Slightly
Slightly --3
w
0
Blackish Transparent, Transparent,
Transparent, 0
Apprearante
Black Solid Black Solid Black Solid 0
N) Brown, Dark Brown Dark Brown Dark
Brown 1..)
.i. = Highly Viscous
Liquid Liquid Liquid 0
1-,
Oil Classification Extra Heavy . Heavy
Heavy Heavy Extra Heavy Extra Heavy
Extra Heavy_ 1
-
0
Density @15 C g/cm3 1.0164 0.9403
0.9388 0.938 1.091 1.1104 1.1276 I "
1
_
_
. -
N.)
API = 7.6 19 19.1 19.3
- - - N.)
_ -
_
N wt% _ 0.40 0.1 = 0.2 0.1
0.9 0.9 1.1
S wt% _ 5.02 3.4 3.51 3.66
6.11 6.08 6.12
Ni wPPIn . 85 <1 <1 <1
200 _ 230 .260
' V 1313113 220 <1 =<1 -
<1
530 590 680
nC7 Insols. wt% 10.4 0.03 <0.01 0.05
27.5 30.8 31.3
_
-
MCR wt% 14.08 0.36 0.39 0.41 ,
36.02 40.33 46.94
TAN'=mgKOHig 2.8 1.8 1.73 1.66
- -
=
=
,
o-)
cri
--..]
cz)
N)
1
cn
cs-)
Table 3(1) Thermal Cracking Test Results (continued)
i¨
Feed Example 1 Example 2
Example 3 Example 1 Example 2 Example 3
_
. Oil .Sands
Thermal Thermal Thermal
Upgraded Upgraded Upgraded
'
Bitumen
Cracked Cracked Cracked
Oil Oil Oil
Athabasca
Residue Residue Residue
. -
Kinematic Viscosity @7.5 C mm2/S - 157.7 141.7
129.7 - - -
=
@50 C mm2/s 6,970 15.75 14.9
14.21 - - -
o
@75 C mm2/s 874 7.042 6.723 6.51
- - -
@100 C mm2/3 182 3.916 3.794 3.695
- - _ _ 0
1..)
-4
Absolute Viscosity @100 C mPa = s 203 - - -
- - - ..3
w
0
@160 C mPa = s 23 . _ _
_ _ - 0
iv -
_ 0
0-1 @220 C mPa = s 8 - - -
77 141 534 1..)
0
@260 C mPa = s - - -
-29 46 108
0,
_
1
@280 C mPa= s - -- -
19 29 60 0
1..)
_
1
Softening Point of Thermal Cracked
1..)
C - - -
85 99 125 1..)
Residue
Stability (S-value) - = 33 = no spot-no spot
no spot - - = -
Dry Sludge wt% = 0.01 0.01
<0.01 - -
_
o.)
cn
-.1
CD
N)
Table 3(2) Thermal Cracking Test Results
1
cp
c5)
Feed
ExampleExample 11 Example 12 Example 11 Example 12
Thermal Thermal
Orinoco Tar Upgraded Upgraded
Cracked Cracked
Cerro Negro Oil
Oil
Residue
Residue
=
= =
Vacuum mmHg - 118
140 118 140
Stripping Steam Injection Ratio equivalent to Vacuum wt% on Feed
, 13 15 13 15
,
Reaction Temp. oc _ 410
420 410 420
Reaction Duration min - 20
10 20 10
Thermal Cracking Yield wt%
o
_
_
Gas - 0.3
0.4 -
_
- 0
Upgraded Oil _ 54.1
60.4 - - "
=4
Thermal Cracked residue - 45.6
39.2 - - --3
w
0
Softening Point of Thermal Cracked Residue C - 88
116 -- 0
N)
0
o-, 500 C+ Farction Thermal Conversion % , 29.6
39.5 -
0
500 C+Farction Thermal Conversion %=
1-,
0,
I
(Yield of (Gas+Upgraded Oil) wt%-500 C-Fraction of Feed wt%))/(100-500 C-
Fraction of Feed wt%)x100 0
1.)
1
= Opaque
1.)
Slightly Slightly 1.)
Blackish
Transparent, Transparent,
Apprearance Brown,
Black Solid Black Solid
Dark Brown Dark Brown
Highly
Liquid Liquid
Viscous
Oil Classification Extra Heavy
Heavy Heavy Extra Heavy Extra Heavy
Density @15 C g/cm3 1.0133
0.9279 0.9304 1.0960 1.1250
- .
API 8.1 20.9
20.5 - -
o-)
Cl
--..]
c)
N)
Table 3(2) Thermal Cracking Test Results (continued)
1
cn
o-)
Feed
Example 11 Example 12 Example 11 Example 12 1--µ
Thermal Thermal
Orinoco Tar Upgraded Upgraded
Cracked Cracked
Cerro Negro .Oil -
Oil
' =
Residue Residue
=
N wt% 0.58 0.2
0.3 1.2 0.9
S = ' wt% 3.61 3.52
3.29 4.22 , 6.08
Ni wPPm 92 <I
<1 202 230
IV wPPm 439 <1
<1 871 590
nC7 Insols. wt% 10.0 <0.01
<0.01 - ' - 30.8 (1
MCR wt% 12.34 0.23
0.26 33.6 40.33 4=,
TAN mgKOH/g 3.3
2.0 , 2.0 - 0
1..)
...1
Kinematic Viscosity @7.5 C mm2/5 -
- - ...1
W
-
0
N.) @50 C 1:0M2/S - 16.2
13.5 - -
c:._
--..]
@75 C mm2/s -
- - 7.2 6.2 1..,
c:.
' @100 C mm2is _ -
4.2 3.5 - -
0,
1
Absolute Viscosity @100 C mPa - = s 150
- - - c:.
1..,_
1
-
@160 C _ mPa= s 11 -
- - 1..,
1..,
@220 C mPa = s 3 -
- 90 320
@260 C mPa = s - -
- 31 80
-
@280 C mPa = s - - -
- 20 45 .
'
Softening Point of Thermal Cracked Residue C_ -
- 88 116
Stability (S-value) -
, - - -
Dry Sludge wt% 0.28 -
- - -
cs,
N.)
(5)
Table 4(1) Total Acid Number of Upgraded Oil
Feed Example 1 Example 2 Example 3
Example 4 Example 5 Example 6
Oil Sands.
Upgraded Upgraded Upgraded Upgraded Upgraded Upgraded
Bitumen.
Oil Oil Oil
Oil Oil Oil
Athabasca
Vacuum mmHg 118 118 118
70 87 140
Reaction Temp. C 410 410 410
390 400 420 0
Reaction Duration min 20 31 47
91 56 17
0
TAN mgKOH/g 2.8 1.8 1.73 1.66
2.12 1.77 1.73 0
0
co
0
0
CA 02773000 2016-02-22
65702-561
Table 4(2) Total Acid Nnmber of Upgraded Oil
Feed Example 11
Example 12
Orinoco Tar Upgraded Upgraded
Cerro Negro Oil Oil
Vacuum mmHg 118 140
Reaction Temp. 410 420
Reaction Duration mm 20 10
TAN mgKOH/g _ 3.3 _ 2.0 2.0
29
=
C3.1
(II
--1
0
N)
I
cri
cs)
Hr
Table 5 Storage Stability Test
=
' = Comparative Example 4 =
Example 9 .
Atmosphere Air
N2
Temperature , C , 37
37
= ________________________________________________________________________
Storage Duration ____________ -
day 0 , 10 30 60 0
11 30 60
hour 0 240 720 1440 0 '
164 720 1440
o
Dark Brown Dark Brown Dark Brown Dark Brown
Dark Brown Dark Brown Dark Brown Dark Brown 0
Apperearance Slightly Slightly Slightly
Slightly
Transparent Transparent Transparent Transparent .4
Transparent Transparent Transparent Transparent .4
u)
i
_______________________________________________________________________________
_____________________________________ 0
cp Density @ 15 C g/cm3 0.9388 0.943 0.9449
0.9464 0.9383 , 0.9386 0.9384 0.9384 0
'API Gravity ' - 19.1 ' 18.5 18.2 17.9
: 19.2 __ 19.2 19.2 ' 19.2
0
.
1-,
Kinematic Viscosity
0,
mm2
@50 C /s 14.9 17.81 19.68 21.31
14.87 14.53 14.47 14.49 '
0
i
T
Dry Sludge wt% 0.01 0.02 <0.01 <0.01
<0.01 <0.01 0.05 , <0.01 "
IV
=
,
,
=
CA 02773000 2016-02-22
65702-561
Table 6 Blending Ration for API 21 and Properties of Blended Oil
Comparative
Example 3 Example 7 Example 8
SOR 3.0 4.0
without Ungraded Ungraded
Upgrading by HSC by HSC
Diluent vol% 29.8 18.0 11.5
Oil Sands
vol% 70.2 37.4 19.2
Bitumen
Upgraded Oil vol% 44.6 69.3
Properties of
Blended Oil
API 21 21 21
wt% 191 3.64 3.73
wt% 0.31 0.15 0.21
Ni/V wppm 73/170 22/47 40/91
TAN mgKOH/g 2.15 1.75 1.90
API Gravity. Diluent 65, Oil Sands Bitumen 7.6, Upgraded Oil 19.3
=
=
=
31
