Note: Descriptions are shown in the official language in which they were submitted.
A8146172CA
METHOD AND APPARATUS FOR REFINING HYDROCARBONS
WITH ELECTROMAGNETIC ENERGY
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of priority of U.S.
Provisional Patent
Application No. 62/120,670 filed February 25, 2015.
FIELD
[0002] The present disclosure relates generally to refining of
hydrocarbons. More
particularly, the present disclosure relates to refining of hydrocarbons by
exposure to
electromagnetic energy.
BACKGROUND
[0003] Hydrocarbons, including heavy crude oil and bitumen, have
previously been
upgraded by exposure to microwaves as described in, for example, Mohammed et
al.,
"Upgrading Heavy Crude Oil Potentials through Microwave Assisted
Distillation", (2011),
Journal of Innovative Research in Engineering and Science 2(3), 137, and
Britten et al.,
"Heavy petroleum upgrading by microwave irradiation", (2005), WIT Transactions
on
Modelling and Simulation, 41, 103.
[0004] United States Patent No. 8,431,015 to Banerjee et al. describes
applying
microwaves to hydrocarbons, such as heavy oil or bitumen, recovered from
underground
reservoirs. The microwaves heat the hydrocarbons to temperatures of between
250 C and
450 C to upgrade the hydrocarbons by cracking. This process lowers the
viscosity of the
hydrocarbons for transportation in a pipeline to offsite locations, such as a
refinery.
[0005] Banerjee et al. adds a microwave energy absorbing substance to
the
hydrocarbons before applying the microwaves. The energy absorbing substance
may include
halides of Na, Al, Fe, Ni, and Zn, particulate carbon graphite particles,
metal particles, or
semiconductor materials. Banerjee et al. states that utilizing the microwave
energy absorbing
substance to absorb microwave energy and transfer heat to the hydrocarbons
through
conduction makes attaining the desired temperatures feasible.
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[0006] United States Publication No. 2011/0094738 to Safinya describes
use of an
upgrader which applies microwave radiation to reduce the viscosity of and
increase the API
gravity of crude oil. Hydrocarbons, such as crude oil or heavy oil, are
transported on a
perforated belt and microwave radiation from antennas at least partially
upgrades heavy oil
into upgraded oil, such as medium-gravity oil and/or light-gravity oil.
Safinya also uses an
upgrader with an upstream reboiler to heat the oil to between 250 C and 500 C
prior to
irradiation. Safinya adds an electron activator to the oil prior to heating it
for faster, more
efficient absorption of microwaves, resulting in more efficient cracking of
the oil.
[0007] United States Publication No. 2011/0294223 to Safinya et al.
describes a
reaction vessel used for characterizing parameters useful for designing and
executing
production and upgrading plans for hydrocarbons. Samples of hydrocarbons are
placed in
the vessel and electromagnetic radiation is used to provide rapid, even, and
tunable heating
to the hydrocarbons. An electromagnetic radiation attenuating material is
included either as
part of the vessel or dispersed within the hydrocarbons. The electromagnetic
radiation is
absorbed by the electromagnetic radiation attenuating material, resulting in
an increase in
heat of the electromagnetic radiation attenuating material. The increase in
heat is passed on
to the hydrocarbons and the hydrocarbons are recovered as gases which are
analyzed to
determine the makeup of the gases. This data, among other data, facilitates
planning and
execution of production and upgrading of hydrocarbons.
[0008] The prior art carries out upgrading of hydrocarbons at high
temperatures and
generally uses an electromagnetic radiation absorbing material to reach these
temperatures.
The prior processes reduce the viscosity of the hydrocarbons. There is
therefore a need for a
system and apparatus to treat hydrocarbons at lower temperatures and for
producing
hydrocarbons with a higher viscosity than the feedstock.
SUMMARY
[0009] It is an object of the present disclosure to obviate or mitigate
at least one
disadvantage of previous methods of refining hydrocarbons by exposure to
electromagnetic
(EM) energy.
[0010] Herein disclosed are methods of refining hydrocarbons where
feedstock
hydrocarbons are exposed to EM energy, resulting in vaporization of selected
hydrocarbons.
Exposure to the EM enemy occurs at temperatures, for example about 250 C or
lower,
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below a reference vaporization temperature of at least some of the vaporized
selected
hydrocarbons. The feedstock hydrocarbons are exposed to the EM energy without
the need
for any added catalyst, significant water content, or other EM energy
absorbing material.
Refining of the hydrocarbons by the EM energy may be carried out to an
intermediate stage
or a complete stage by applying the EM energy for a longer period of time, at
a greater EM
power, or both. The EM energy may be microwave energy.
[0011] The methods may be applied to a variety of feedstock
hydrocarbons. The
feedstock hydrocarbons may include hydrocarbons having an API of 24 or lower
such as
heavy oil or bitumen. The feedstock hydrocarbons may also include lighter
hydrocarbons
including crude oil. The feedstock hydrocarbons may also include byproducts of
other
processes, such as coke, asphalt, bunker oil, or pyrolysis bunker oil.
[0012] Refining the feedstock hydrocarbons may result in separation of
the selected
hydrocarbons from a secondary product. The selected hydrocarbons may include
light and
medium carbon chain lengths, such as about C6 to about C30.
[0013] Refining heavier feedstock hydrocarbons to an intermediate stage may
result
in a secondary product including an intermediate hydrocarbon product having a
higher
viscosity than the hydrocarbon feedstock. The higher viscosity intermediate
product has an
increased viscosity compared with the feedstock hydrocarbons. The higher
viscosity
intermediate product may be solid or substantially solid at room temperature.
The higher
.. viscosity intermediate product may be hardened bitumen which is essentially
solid at 20 C.
The higher viscosity intermediate product may also be refined to obtain
asphalt as a
byproduct.
[0014] Refining to a complete or substantially complete stage results
in recovery of
the selected hydrocarbons and a secondary product which includes a residual
product. The
residual product includes a high proportion of carbon, such as 90% or greater.
[0015] The methods may be applied in a vessel. The vessel may be
divided into an
EM exposure zone and a recovery zone above the EM exposure zone. The vessel
may
include a shield positioned between the EM exposure zone and the recovery
zone. EM
energy is provided to the EM exposure zone. The shield may be gas-permeable
and EM
energy-impermeable to contain the EM energy in the EM exposure zone and allow
the
selected hydrocarbons to flow as gases into the recovery zone. The recovery
zone facilitates
condensation and recovery of the selected hydrocarbons.
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[0016] The methods disclosed herein facilitate refining hydrocarbons
comprising the
steps of treating feedstock hydrocarbons at an EM exposure temperature with EM
energy to
produce selected hydrocarbons. At least a portion of the selected hydrocarbons
may be
vaporized at a vaporization temperature below a reference vaporization
temperature of at
least one hydrocarbon species present in the selected hydrocarbons. The
reference
vaporization temperature would be the normal vaporization temperature at 760
mmHg, the
standard vaporization temperature at 1 bar (750.06 mmHg), or the otherwise
calculated
vaporization temperature in view of the pressure during vaporization by
exposure to the EM
energy. Vaporizing separates the selected hydrocarbons from the feedstock
hydrocarbons
and any secondary product. The selected hydrocarbons may be recovered, for
example by
condensing the selected hydrocarbons.
[0017] In some aspects, the present disclosure describes a method and
apparatus
for refining hydrocarbons. The method includes treating feedstock hydrocarbons
at a low
temperature with EM energy for vaporizing selected hydrocarbons. The selected
hydrocarbons are vaporized at temperatures below reference vaporization
temperatures of at
least a portion of the species included within the selected hydrocarbons. The
vaporized
hydrocarbons may be condensed from the vapour phase for recovery. A remaining
secondary product may include a higher viscosity hydrocarbon product with a
greater
viscosity than the feedstock hydrocarbons, such as a hardened bitumen that is
substantially
solid at ambient temperature.
[0018] In some aspects, the present disclosure describes a method of
refining
hydrocarbons including: treating feedstock hydrocarbons with EM energy at a
first EM
exposure temperature for vaporizing selected hydrocarbons at a first
vaporization
temperature. The first vaporization temperature is equal to or lower than the
first EM
exposure temperature. The first vaporization temperature is lower than a
reference
vaporization temperature of at least one hydrocarbon species of the selected
hydrocarbons.
[0019] In some aspects, the present disclosure describes a vessel for
treating
feedstock hydrocarbons with EM energy, the vessel including: a body; an EM
exposure zone
defined within the body for receiving the hydrocarbons; an EM energy source in
communication with the EM exposure zone for providing the EM energy to the EM
exposure
zone for exposing the feedstock hydrocarbons to the EM energy to vaporize
selected
hydrocarbons; a recovery zone in communication with the EM exposure zone for
receiving
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the selected hydrocarbons from the EM exposure zone; and a first shield
positioned within
the body between the EM exposure zone and the recovery zone. The first shield
is gas-
permeable and EM energy-impermeable for allowing the selected hydrocarbons to
flow from
the EM exposure zone to the recovery zone and for maintaining the EM energy in
the EM
exposure zone.
[0020] In some aspects, the present disclosure describes a method of
transporting
hydrocarbons comprising: providing feedstock hydrocarbons having an API
gravity of about
24 or lower; at a first location, treating the feedstock hydrocarbons with EM
energy at a first
EM exposure temperature for vaporizing first selected hydrocarbons at a first
vaporization
temperature and resulting in a higher viscosity hydrocarbon product having a
greater
viscosity than the feedstock hydrocarbons and substantially maintaining its
shape at 20 C;
and transporting the higher viscosity hydrocarbon product from the first
location to a second
location. The first vaporization temperature is lower than a reference
vaporization
temperature of at least one hydrocarbon species of the first selected
hydrocarbons. The first
vaporization temperature is lower than a reference vaporization temperature of
at least one
hydrocarbon species of the selected hydrocarbons.
[0021] In some aspects, the present disclosure describes a hardened
hydrocarbon
product prepared from a feedstock bitumen or heavy oil by exposure of
feedstock bitumen or
heavy oil to EM energy, the hardened hydrocarbon product substantially
maintaining its
.. shape at 20 'C. The hardened hydrocarbon product may have a kinematic
viscosity of about
5,000,000,000 cSt at 20 C and may have an initial boiling temperature
corresponding to a
temperature of at least 250 C for 5% mass recovery as determined by high
temperature
simulated distillation.
[0022] Other aspects and features of the present disclosure will become
apparent to
those ordinarily skilled in the art upon review of the following description
of specific
embodiments in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Embodiments of the present disclosure will now be described, by
way of
example only, with reference to the attached figures, in which features
sharing reference
numerals with the final two digits in common correspond to similar features
across multiple
figures (e.g. the waveguide 20, 120, 220, 320, 420, etc.).
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[0024] Fig. 1 is a partial cutaway perspective view of vessel for
exposing
hydrocarbons to electromagnetic energy (EM energy);
[0025] Fig. 2 is a cross-sectional elevation view of the vessel of Fig.
1;
[0026] Fig. 3 is a cross-sectional elevation view of the vessel of Fig.
1 in operation;
[0027] Fig. 4 is a cross-sectional perspective view of a further vessel for
exposing
hydrocarbons to EM energy;
[0028] Fig. 5 is a cross-sectional elevation view of a further vessel
for exposing
hydrocarbons to EM energy;
[0029] Fig. 6 is a cross-sectional elevation view of a further vessel
for exposing
hydrocarbons to EM energy;
[0030] Fig. 7 is a schematic of a method of transporting a high-
viscosity intermediate
product;
[0031] Fig. 8 is a schematic of a method of transporting a high-
viscosity intermediate
product for further refinement;
[0032] Fig. 9 is a schematic of a test-scale vessel;
[0033] Fig. 10 is a graph of temperature in a liquid bitumen sample
during the course
of an example application of a method disclosed herein;
[0034] Fig. 11 is a graph of carbon chain length population
distributions in selected
hydrocarbons recovered during the example application of Fig. 10;
[0035] Fig. 12 is a graph of carbon chain length population distributions
in feedstock
bitumen and hardened bitumen in the example application of Fig. 10;
[0036] Fig. 13 is high temperature distillation data from hardened
bitumen resulting
from an example application of a method disclosed herein;
[0037] Fig. 14 is a graph of the carbon chain length population
distribution of light
hydrocarbons recovered during an example application of a method disclosed
herein;
[0038] Fig. 15 is a graph of temperatures in a vessel during the course
of an example
application of a method disclosed herein;
[0039] Fig. 16 is a graph of the carbon chain length population
distributions in light
hydrocarbons recovered and other data acquired during the example application
of Fig. 15;
[0040] Fig. 17 is a graph of carbon chain length population distributions
in feedstock
bitumen, recovered selected hydrocarbons, and hardened bitumen from the
example
application of Fig. 15;
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[0041] Fig. 18 is a graph of carbon chain length population
distributions in feedstock
bitumen, recovered selected hydrocarbons, and hardened bitumen from the
example
application of Fig. 15;
[0042] Fig. 19 is a graph of carbon chain length population
distributions in feedstock
bitumen, recovered selected hydrocarbons, and hardened bitumen from the
example
application of Fig. 15;
[0043] Fig. 20 is a graph of carbon chain length population
distributions in feedstock
bitumen and hardened bitumen from the example application of Fig. 15;
[0044] Fig. 21 is a graph of carbon chain length population
distributions in feedstock
bitumen and hardened bitumen from the example application of Fig. 15; and
[0045] Fig. 22 is high temperature distillation data from hardened
bitumen resulting
from the example application of Fig. 15.
DETAILED DESCRIPTION
[0046] Generally, the present disclosure provides methods and apparatuses
for
refining hydrocarbons using electromagnetic energy (EM energy).
[0047] The methods may be used to refine produced hydrocarbons, and may
be
used for example with crude oil. The hydrocarbons may have an API gravity of
24 or less,
such as heavy oil or bitumen. The methods may also be applied to hydrocarbons
with diluent
added, such as Western Canadian Select. The methods may also be applied to
byproducts
of other processes, such as coke, asphalt, bunker oil, or pyrolysis bunker
oil.
[0048] In the methods disclosed herein, feedstock hydrocarbons are
exposed to EM
energy. The EM energy may be any high frequency EM energy, such as radio waves
from
about 3 kHz to about 3000 GHz, The EM energy may be radio waves having a
frequency
from 3 kHz to 300 MHz. The EM energy may be high to ultra high frequency radio
waves
having frequencies in the range of about 8 kHz to about 300 MHz. The EM energy
may be
microwaves, which may have frequencies in the range of about 300 MHz to about
300 GI-1z.
Commonly used commercial and industrial microwave frequencies are 915 MHz and
2,450
MHz.
[0049] The methods disclose herein may be carried out inside a vessel.
[0050] Figs. 1 to 3 show a vessel 10. The vessel 10 includes a body 12.
A plate 14
extends across a cavity defined within the body 12, separating the cavity into
an EM
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exposure zone 16 and a recovery zone 18. The EM exposure zone 16 is below the
recovery
zone 18.
[0051] The vessel 10 includes a waveguide 20. The waveguide 20 extends
into the
EM exposure zone 16 for providing EM energy into the EM exposure zone 16. In
the
embodiment shown in Figs. 1 to 3, the waveguide 20 extends into the reaction
16, passing
through the recovery zone 18 and the plate 14. However, the waveguide does not
need to be
positioned above the recovery zone as shown in these figures. Other
configurations are
shown in Figs. 4 and 5 and other configurations will be known to a person
skilled in this field.
The waveguide 20 includes a window 22. The window 22 functions as an EM energy
permeable gas impermeable shield at a portion of the waveguide 20 within the
EM exposure
zone 16 for providing the EM energy into the EM exposure zone 16 but
preventing potentially
combustible gases (e.g. gaseous selected hydrocarbons, etc.) from flowing into
the
waveguide 20. The window 22 may be made from any suitable material, such as
glass,
which allows passage of EM energy and which blocks gases. An EM energy source
24 is
connected to the waveguide 20 for providing the EM energy to the waveguide 20.
[0052] The plate 14 includes apertures 15 for allowing flow of fluids
across the plate
14 (e.g. gaseous selected hydrocarbons, etc.). Figure 1 shows only exemplary
apertures on
one side of the plate 14 but generally the plate will include multiple
apertures positioned
throughout. The plate 14 functions as a gas permeable, EM energy impermeable
shield.
Confining the EM energy to the EM exposure zone 16 facilitates increased
efficiency in
exposure of hydrocarbons to the EM energy and mitigates the risk that gaseous
selected
hydrocarbons will be ignited in the recovery zone 18. As shown in the figures,
the plate 14
includes metals or other conductive materials which will prevent passage of
the EM energy
into the recovery zone 18 and confine the EM energy to the EM exposure zone
16. The
apertures 15 may be smaller than the wavelength of the EM energy being used in
the vessel
10.
[0053] A lower outlet 26 and an upper outlet 28 are both positioned in
the body 12 in
the recovery zone 18 and may be connected to a collection vessel (not shown)
to recover
selected hydrocarbons by condensation after the selected hydrocarbons are
vaporized in the
EM exposure zone 16. The number and location of outlets is determined by the
properties of
the selected hydrocarbons to be recovered from the feedstock. The vessel may
include one
outlet, two outlets as shown in the figures, or more than two outlets. A lower
cooling coil 27
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and an upper cooling coil 29 are shown in Figs. 2 and 3 but are not required.
The cooling
coils 27, 29 facilitate condensation and recovery of the selected hydrocarbons
at the lower
outlet 26 and the upper outlet 28, respectively. The outlets 26, 28 and
cooling coils 27, 29
facilitate condensing and recovering the selected hydrocarbons in the recovery
zone 18.
[0054] The feedstock hydrocarbons may contain other components or
contaminants
such as sulfur. The vessel 10 may also collect these contaminants. For
example, the vessel
may include copper or other catalysts to capture sulfur (not shown).
[0055] An injection port may be included to selectively provide motive
flow to
vaporized selected hydrocarbons in the EM exposure zone 16, for example non-
condensible
gases may be injected into the vessel 10 to urge vaporized selected
hydrocarbons to cross
the plate 14 into the recovery zone 18. Injection of non-condensible gases to
provide motive
flow may for example be used with alternative vessel designs in which the
recovery zone is
offset in the body horizontally from the EM exposure zone but not vertically
from the EM
exposure zone, in which the recovery zone and the EM exposure zone are located
in
separate vessel bodies, or in which the recovery zone is otherwise not located
above the EM
exposure zone, and in which normal flow of vapour upwards is not applied for
condensation
as in the vessel 10.
[0056] Fig. 3 shows the vessel 10 being used to refine feedstock
hydrocarbons 40 in
the EM exposure zone 16 by exposure to EM energy 42 provided into the EM
exposure zone
16 through the waveguide 20. The feedstock hydrocarbons 40 interact with the
EM energy
42 in the EM exposure zone 16, resulting in gaseous selected hydrocarbons 44
and a higher
viscosity hydrocarbon product 48. The gaseous selected hydrocarbons 44 flow
through the
plate 14 into the recovery zone 18, and condense as liquid selected
hydrocarbons 46 near
the lower and upper cooling coils 27, 29. Although the cooling coils 27, 29
are included in the
.. vessel 10, cooling coils are optional and not required. Condensation of the
liquid selected
hydrocarbons 46 may be facilitated by selecting an appropriate location for
the outlets 26, 28
along the body 12 based on the expected reaction conditions and the feedstock
hydrocarbons 40 which are intended to be used. The liquid selected
hydrocarbons 46 are
recovered through the lower and upper outlets 26, 28. Where the methods are
applied to a
vessel other than the vessel 10 with additional outlets, the additional
outlets would also serve
as recovery points for the liquid selected hydrocarbons 46. Once the liquid
selected
hydrocarbons 46 have been recovered, the higher viscosity hydrocarbon product
48 remains
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in the bottom of the EM exposure zone 16. The higher viscosity hydrocarbon
product 48 is
shown at the bottom of EM exposure zone 16, however, during the reaction, the
higher
viscosity hydrocarbon product 48 may be in liquid form and mixed with any
feedstock
hydrocarbons 40 remaining in the EM exposure zone 16.
[0057] If the reaction is continued through prolonged exposure to the EM
energy 42,
additional gaseous selected hydrocarbons 44 will volatize from the higher
viscosity
hydrocarbon product 48, leaving a carbon residue (not shown). As described
above, the
carbon residue includes primarily elemental carbon, and may include common
minor
components such as sulfur (about 1 to 10% by mass) and metals (below about 500
mg/kg).
[0058] Fig. 4 shows an alternate configuration fora vessel 110 wherein the
waveguide 120 enters the body 112 at the EM exposure zone 116 directly, rather
than
passing through the recovery zone and plate as shown in Figs. 1 to 3.
[0059] Fig. 5 shows an alternate configuration fora vessel 210 which
includes a
secondary waveguide, a secondary EM exposure zone, a secondary recovery zone,
and
additional plates to function as EM shields. The vessel 210 includes a
secondary EM
exposure zone waveguide 230 and window 231 in communication with a secondary
EM
exposure zone 232 defined between a first secondary EM exposure zone plate 234
and a
second secondary EM exposure zone plate 236. A secondary recovery zone 237 is
defined
above the second secondary EM exposure zone plate 236. A secondary recovery
zone outlet
238 extends through the body 212 into the secondary recovery zone 237 for
providing fluid
communication with the secondary recovery zone 237. The secondary recovery
zone outlet
238 and a secondary EM exposure zone cooling coil 239 facilitate recovery of
additional
selected hydrocarbons resulting from exposure of selected hydrocarbons in the
secondary
EM exposure zone 232 to secondary EM energy from the secondary EM exposure
zone
waveguide 230.
[0060] The first secondary EM exposure zone plate 234 and second
secondary EM
exposure zone plate 236 each provide a gas permeable EM energy impermeable
shield. The
plates 234, 236 each include apertures 235 for allowing flow of fluids across
the plates 234,
236. The plates 234, 236 each include metals or other conductive materials
which prevent
passage of the EM energy from the secondary EM exposure zone waveguide 230
into the
recovery zone 218 and confine the EM energy to the secondary EM exposure zone
232. The
plates 234, 236 define the secondary EM exposure zone 232 and the secondary
recovery
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zone 237 and confine secondary EM energy from the secondary EM exposure zone
waveguide 230 to the secondary EM exposure zone 232. Confinement of the
secondary EM
energy to the secondary EM exposure zone 232 facilitates increased efficiency
in exposure
of selected hydrocarbons in the secondary EM exposure zone 232 to the
secondary EM
energy and mitigates the risk that gaseous selected hydrocarbons will be
ignited in the
recovery zone 218.
[0061] In operation of the vessel 210, the waveguide 220 provides EM
energy to the
EM exposure zone 216 to treat feedstock hydrocarbons in the EM exposure zone
216 (not
shown in the vessel 210, but similar to the feedstock hydrocarbons 40 in the
EM exposure
zone 16 of the vessel 10 shown in Fig. 3). Selected hydrocarbons are vaporized
during
exposure of the feedstock hydrocarbons to the EM energy in the EM exposure
zone 216.
The selected hydrocarbons flow upwards and a portion are recondensed and
recovered at
the outlets 226, 228. Any remaining vaporized selected hydrocarbons flow
through the
apertures 235 in the first secondary EM exposure zone plate 234 into the
secondary EM
exposure zone 232. In the secondary EM exposure zone 232, treatment of the
selected
hydrocarbons with the secondary EM energy results in additional selected
hydrocarbons.
Without being bound by any theory, the additional selected hydrocarbons are
understood to
arise from catabolic chemical reactions induced in the selected hydrocarbons
by the
secondary EM energy. The additional selected hydrocarbons may be condensed in
the
secondary recovery zone 237 and recovered through the secondary recovery zone
outlet
238.
[0062] EM energy may be applied to the secondary EM exposure zone
waveguide
230 independently of the waveguide 220 in the first EM exposure zone 216. The
waveguide
220 and the secondary EM exposure zone waveguide 230 may be connected to
separate
EM sources, a single EM source with separate outputs, or a single EM source
with one.
Correspondingly, a secondary EM source for the secondary waveguide 230 may be
the
same EM source used for the waveguide 220 or a separate EM source. Regardless
of
whether the secondary EM source is the same EM source is applied to the
waveguide 220,
the EM energy provided to the waveguide 220 and the additional EM energy
applied to the
secondary waveguide 230 may have the same or distinct properties depending on
the
application.
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[0063] Fig. 6 shows an alternate configuration fora vessel 310 which
includes a
secondary waveguide, a secondary EM exposure zone, and an additional plate to
function as
an EM shield. The secondary EM exposure zone waveguide 330 and window 331 are
in
communication with a secondary EM exposure zone 370 defined between an EM
exposure
zone plate 372 and a recovery zone plate 374. The recovery zone 318 is defined
above the
recovery zone plate 374.
[0064] The EM exposure zone plate 372 and the recovery zone plate 374
each
provide a gas permeable EM energy impermeable shield. The plates 372, 374 each
include
apertures 375 for allowing flow of fluids across the plates 372, 374. The
plates 372, 374 each
include metals or other conductive materials which prevent passage of the EM
energy from
the secondary EM exposure zone waveguide 330 into the recovery zone 318 and
confine the
EM energy to the secondary EM exposure zone 370. The plates 372, 374 define
the
secondary EM exposure zone 370 and the recovery zone 318 and confine secondary
EM
energy from the secondary EM exposure zone waveguide 330 to the secondary EM
exposure zone 370. Confinement of the secondary EM energy to the secondary EM
exposure zone 370 facilitates increased efficiency in exposure of selected
hydrocarbons in
the secondary EM exposure zone 370 to the secondary EM energy and mitigates
the risk
that gaseous selected hydrocarbons will be ignited in the recovery zone 318.
[0065] In operation of the vessel 310, the waveguide 320 provides EM
energy to the
EM exposure zone 316 to treat feedstock hydrocarbons in the EM exposure zone
316 (not
shown in the vessel 310, but similar to the feedstock hydrocarbons 40 in the
EM exposure
zone 16 of the vessel 10 shown in Fig. 3). Selected hydrocarbons are vaporized
during
exposure of the feedstock hydrocarbons to the EM energy in the EM exposure
zone 316.
The selected hydrocarbons flow upwards through the apertures 375 into the
secondary EM
.. exposure zone 370. In the secondary EM exposure zone 370, treatment of the
selected
hydrocarbons with the secondary EM energy results in additional selected
hydrocarbons.
The additional selected hydrocarbons may be condensed in the recovery zone 318
and
recovered through the recovery zone outlets 326, 328.
[0066] As with the vessel 210, EM energy may be applied to the
secondary EM
exposure zone waveguide 330 independently of the waveguide 320 in the first EM
exposure
zone 316. The waveguide 320 and the secondary EM exposure zone waveguide 330
may be
connected to separate EM sources, a single EM source with separate outputs, or
a single
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EM source with one. Correspondingly, a secondary EM source for the secondary
waveguide
330 may be the same EM source used for the waveguide 320 or a separate EM
source.
Regardless of whether the secondary EM source is the same EM source is applied
to the
waveguide 320, the EM energy provided to the waveguide 320 and the secondary
waveguide 330 may have the same or distinct properties depending on the
application.
[0067] Additional EM exposure zones, recovery zones, or both, either
above or below
those shown in Figs. 5 and 6, may be defined in a vessel as desired for any
given application
by adding the corresponding secondary plate(s), secondary waveguide(s), and
secondary
recovery port(s). For example, with reference to the vessel 210, an additional
EM exposure
zone may also be defined between the plate 214 and the lower secondary EM
exposure
zone plate 234 by introducing an additional waveguide between the plate 214
and the lower
secondary EM exposure zone plate 234, providing a total of three EM exposure
zones and
one recovery zone (not shown). Similarly, designs in which the EM exposure
zone(s) and
recovery zone(s) are arranged horizontally may be applied, in some cases using
non
.. condensible gases to move vaporized selected hydrocarbons between the
various zones. In
addition, vessels in accordance with the description herein may include EM
exposure zone(s)
and recovery zone(s) in separate vessels, for example as shown in the
schematics of
methods of transportation shown in Figs. 7 and 8.
[0068] Exposure of the feedstock hydrocarbons to the EM energy
vaporizes mainly
light and medium chain hydrocarbons from the feedstock hydrocarbons. The
vaporized
hydrocarbons rise through the vessel into the recovery zone and are recovered
through
known means, such as condensation. Depending on the desired products, exposure
of the
feedstock hydrocarbons to the EM energy may be carried out to refine the
feedstock
hydrocarbons to an intermediate stage of refinement or a complete stage of
refinement.
[0069] The chain length of the hydrocarbons which are vaporized and
recovered can
be controlled using a number of factors such as the temperature and pressure
in the vessel
and exposure time of the hydrocarbons to the EM energy. For example, recovery
of longer
chain hydrocarbons may be facilitated by reducing the exposure time of the
vapor phase to
the EM energy through a shorter EM exposure zone, applying a vacuum to
evacuate the
vapor phase more quickly, increasing the temperature of the EM exposure zone,
or a
combination thereof. Further, recovery of hydrocarbons having selected chain
lengths may
be facilitated by increasing the exposure time of the vapor phase to the EM
energy in the EM
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exposure zone, recovery and condensation of vapors at different heights in the
recovery
zone, including additional EM exposure zones and waveguides within the
recovery zone, or a
combination thereof. Selected hydrocarbons may be further exposed to EM
energy, either by
retaining the selected hydrocarbons in the EM exposure zone or by treating the
selected
hydrocarbons in a secondary EM exposure zone, resulting in secondary selected
hydrocarbons with shorter chain lengths. For example, if the selected
hydrocarbons include a
large proportion of hydrocarbons having C20 carbon chain length or longer,
these selected
hydrocarbons may be further processed, either by retaining them in the EM
exposure zone or
by treating them in a secondary EM exposure zone, resulting in secondary
selected
hydrocarbons having shorter carbon chain lengths, such as C7 and 08 chain
length
fractions.
[0070] The selected hydrocarbons are generally more valuable
hydrocarbons that
can be sold at higher prices than the feedstock hydrocarbons. For example, the
selected
hydrocarbons may include light hydrocarbons having chain lengths from C2 to
C30, from C4
to 022, from C5 to 020, from C6 to C15, or from C7 to C12, or may include at
least 50% by
volume 07 and C8. The selected hydrocarbons may include for example one or
more of
gasoline, naphtha, diesel, and kerosene fractions. Although the meaning of
light
hydrocarbons as defined in the industry may differ somewhat, as referred to
herein light
hydrocarbons means hydrocarbons generally having a carbon chain length of
about C2 to
about 030.
[0071] Exposure to the EM energy results in an increase in temperature
of the
feedstock hydrocarbons and vaporization of the selected hydrocarbons from the
feedstock
hydrocarbons. Wthout being bound by any theory, the selected hydrocarbons are
believed
include hydrocarbons already present in the feedstock hydrocarbons,
hydrocarbons which
are the result of chemical reactions induced by the EM energy, or a
combination of both.
[0072] An EM exposure temperature is the maximum temperature in any
component
of the system during vaporization of the selected hydrocarbons. The EM
exposure
temperature is expected to be observed in a liquid phase of heavier chain
hydrocarbons from
the feedstock hydrocarbons and any developing liquid phase selected
hydrocarbons or
secondary products. Vaporization of the selected hydrocarbons may occur at a
vaporization
temperature at or below the EM exposure temperature. The vaporization
temperature for at
least some of the selected hydrocarbons may be lower than an expected
reference
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vaporization temperature which would be observed through convection or other
heating
methods which do not include exposure to the EM energy.
[0073] Once exposure to the EM energy begins, the liquid temperature of
the
feedstock hydrocarbons increases until a threshold liquid phase temperature is
reached. The
threshold liquid phase temperature is the liquid phase temperature of the
feedstock
hydrocarbons at the onset of the selected hydrocarbons being vaporized. A
corresponding
threshold vapour phase temperature may be observed above the liquid phase
feedstock
hydrocarbons. As EM energy exposure continues, there may be an increase in
both liquid
phase and vapour phase temperatures until a plateau temperature or range of
temperatures
is reached. Plateau temperatures may be identified in each of the liquid and
vapour phases
and may be at different values at different location within a given system
being treated with
the EM energy. At the plateau temperatures, vaporization of the selected
hydrocarbons may
occur at a greater rate than at temperatures below the plateau temperatures.
If the feedstock
hydrocarbons are pre-heated by convection or other means other than the EM
energy to the
threshold liquid temperature or the plateau liquid temperature, vaporization
of the selected
hydrocarbons begins sooner after the onset of the treatment with the EM
energy.
[0074] The vaporization temperature at which at least some of the
hydrocarbons
vaporize may be significantly lower than the a reference temperature at which
at least one
species from the selected hydrocarbons would be expected to vaporize in
conventional
methods such as by convection or other heating, and below the conventionally
recognized
boiling points for these hydrocarbons. For example, where the reaction is
carried out at 760
mmHg, the vaporization temperatures may be lower than the normal boiling
points of at least
some of the selected hydrocarbons. In another example, where the reaction is
carried out at
1 bar, the vaporization temperatures may be lower than the standard boiling
points of at least
some of the selected hydrocarbons. Similarly, where the reaction is carried
out under
vacuum or under pressure, the vaporization temperatures may be lower than an
expected
reference vaporization temperature at the pressure of the reaction of at least
some of the
selected hydrocarbons.
[0075] Previous methods which applied EM energy to hydrocarbons for
upgrading
required high temperatures, in some cases of 450 C and higher. In contrast,
the refining
methods described herein may be carried out by exposing the feedstock
hydrocarbons to EM
energy, and vaporization of the selected hydrocarbons, at or below EM exposure
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temperatures. The EM exposure temperatures for vaporization of the selected
hydrocarbons
may be lower than a reference temperature required to vaporize at least one of
the selected
hydrocarbons in conventional refining methods, Olin previous microwave-based
upgrading
methods. In the present methods, the EM exposure temperatures may be below 250
C,
below 200 C, below 150 C, below 100 C, or below 60 C. The feedstock
hydrocarbons may
be exposed to the EM energy without the need for any added catalyst,
significant water
content, or other EM energy absorbing material. Since higher temperatures are
not required
and may be avoided, these added EM energy absorbing materials are not
necessary in the
present methods.
[0076] In the present methods, the EM exposure temperature may be below the
normal vaporization temperatures of at least some of the vaporized selected
hydrocarbons
are observed both in the liquid-phase feedstock hydrocarbons and in the vapor-
phase light
hydrocarbons. Table 1 shows normal (i.e. at normal atmospheric pressure of 760
mmHg)
vaporization temperatures for linear saturated hydrocarbons having carbon
chain lengths
from 4 to 15 when using convection or other heating means. These and
additional normal
boiling points are also illustrated graphically in Fig. 16 alongside data from
Example 5.
Table 1
n-Hydrocarbon Normal Vaporization Temperature ( C)
Butane -1
Pentane 36
Hexane 69
Heptane 98
Octane 125
Nonane 151
Decane 174
Undecane 196
Dodecane 216
Tridecane 235
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n-Hydrocarbon Normal Vaporization Temperature ( C)
Tetradecane 254
Pentadecane 270
[0077] The temperatures observed in the method of Example 1 are shown
in Table 2
and discussed in detail below. Briefly, the highest liquid-phase temperature
observed during
Example 1 was 106 C and the highest vapour-phase temperature observed during
Example
1 was 74 C. The observed threshold and plateau liquid phase temperatures and
the
observed threshold and plateau vapor phase temperatures were below these
temperatures
of 106 C and 74 C. However, Fig. 11 and Table 3 show that the majority of
the
hydrocarbons recovered by condensation in Example 1 had carbon chain lengths
between
C4 and C14, and that at least about 40% of the recovered hydrocarbons were of
chain
lengths from C8 to C14. As shown above in Table 1, the normal vaporization
temperature of
n-octane is 125 C and the normal vaporization temperature of tetradecane is
254 C. Thus,
by exposure of the feedstock hydrocarbons to EM energy, these fractions are
vaporized
under atmospheric pressure at significantly lower temperatures than would
typically be
required using convection or other conventional heating methods. When using
convection
heating under normal conditions, vaporization of carbon chain lengths of CO (n-
octane having
a boiling point of 125 C) or greater would not be expected at the low
temperatures at which
vaporization of selected hydrocarbons may be achieved with the present
methods, such as a
maximum EM exposure temperature of 106 C in Example 1.
[0078] The temperatures observed in the method of Example 5 are shown
in Table 4
and discussed in detail below. Briefly, the EM exposure temperature was the
highest liquid-
phase temperature observed during Example 5 was 125 C and the highest vapour-
phase
temperature observed during Example 5 was 107 C. The observed threshold and
plateau
liquid phase temperatures and the observed threshold and plateau vapor phase
temperatures were below these temperatures of 125 C and 107 C, However,
Figs. 16 to 19
show that the about 85% (w/w) of the hydrocarbons recovered by condensation in
Example 5
had carbon chain lengths between C7 and C10, and that about 35% (w/w) of the
recovered
hydrocarbons were of chain lengths from C9 to C14. As shown above in Table 1,
the normal
vaporization temperature of nonane is 151 C and the normal vaporization
temperature of
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tetradecane is 254 C. Thus, by exposure of the feedstock hydrocarbons to EM
energy,
these fractions are vaporized under atmospheric pressure at significantly
lower temperatures
than would typically be required using convection or other conventional
heating methods,
since the EM exposure temperature was 125 C. When using convection heating
under
normal conditions, vaporization of carbon chain lengths of C9 (n-nonane having
a boiling
point of 151 C) or greater would not be expected at the low temperatures seen
in the
present methods, such as a maximum EM exposure temperature of 125 C in
Example 5.
[0079] As set out above, it has been found by the present inventor that
the high
temperatures in conventional methods are not necessary to refine feedstock
hydrocarbons
and obtain the selected recovered hydrocarbons. Previous methods were directed
to
upgrading the hydrocarbons by thermally cracking long chain hydrocarbon
molecules and
providing in deasphalted oil. Such previous methods result in a hydrocarbon
product having
a reduced viscosity, which was advantageous for pipeline transport of the
hydrocarbon. In
contrast, the present methods refine the hydrocarbons, and any upgrading of
the feedstock
hydrocarbons which results from the refining procedure is at EM exposure
temperatures
below the temperatures at which comparable thermal cracking reactions would be
expected.
When refining a heavier feedstock hydrocarbon such as heavy oil or bitumen,
the present
methods may produce an intermediate product having a higher viscosity then the
feedstock
hydrocarbons. The higher viscosity intermediate product produced by the
present methods
may be transported as a solid product at ambient temperature rather than
pipelined. Further,
when the present refining methods are carried to completion, the methods are
able to extract
more hydrocarbons from the feedstock, leaving only a carbon ash residual
product, as
compared to the prior processes which leave petroleum coke as a waste
byproduct. Wthout
being bound by any theory, it is thought that the use of the lower
temperatures in
combination with the EM energy results in the production of the increased
viscosity
hydrocarbon product and more complete refining of the hydrocarbon product.
[0080] The EM energy is applied to the feedstock hydrocarbons for a
period of time
selected to result in either the higher viscosity intermediate product or to
fully refine the
hydrocarbons, leaving the carbon residue in the vessel (in addition to
recovering the selected
hydrocarbons in either case). The period of time is determined with reference
to a number of
factors including the power and frequency of the EM energy source, the
properties and
volume of feedstock hydrocarbons, the properties and volume of the selected
hydrocarbons,
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and the temperature. For example, for a barrel of bitumen at about 20 C, 10
hours of
exposure to EM energy at a frequency of 915 MHz may result in recovery of the
selected
hydrocarbons and the intermediate hardened bitumen product, with a maximum EM
exposure temperature of between about 105 C and 125 C in the liquid phase of
the
reaction mixture. The longer time frame is required since the barrel of
bitumen begins the
process at ambient temperature. If the barrel of bitumen is preheated to about
60 C, the
treatment time frame may be reduced to about 5 hours with some loss of lighter
fractions,
particularly where pentane diluent is included in the bitumen. If the barrel
of bitumen is
preheated to about 80 C, the treatment time frame may be further reduced to
about 4 hours.
By preheating the barrel of bitumen, less treatment time is required since the
barrel will
already be closer to the EM exposure temperature and the vaporization
temperature once
treatment with the EM energy begins.
[0081] Refining heavier feedstock hydrocarbons, such as those having an
API gravity
of about 24 or lower, to the intermediate stage results in recovery of the
selected
hydrocarbons described herein and a higher viscosity intermediate hydrocarbon
product. The
higher viscosity intermediate product has a higher viscosity than the
feedstock hydrocarbons.
The higher viscosity intermediate product may be hardened or solid at room or
ambient
temperature (about 20 C). Where the feedstock hydrocarbon is bitumen, the
higher viscosity
intermediate product may be hardened bitumen which is essentially solid at 20
C. Reference
to hardened or solid is meant to also include substantially hardened or
substantially solid.
The higher viscosity intermediate hydrocarbon product may maintain its form at
room
temperature, although it may still be somewhat malleable.
[0082] Previous methods that applied EM energy to hydrocarbons resulted
in
upgraded hydrocarbons with a lower viscosity and higher API gravity than the
starting
hydrocarbons, essentially synthetic crude. In contrast to previous methods
which applied
microwaves, often in combination with microwave absorbing additives, to
thermally upgrade
and increase the API gravity of hydrocarbons, the methods described herein
produce the
higher viscosity intermediate product which has a greater viscosity and lower
API gravity
than the feedstock hydrocarbons.
[0083] Where the higher viscosity intermediate product is in a hardened or
solid form,
it may be transported as a solid product. This provides an alternative to
pipelining the
hydrocarbons. Transporting a solid may have less environmental concerns than
transporting
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a liquid hydrocarbon. The hardened or solid intermediate product may be
transported in
containers designed for solid cargo, such as tractor trailers, train cars, or
shipping containers.
Costs may be reduced since there is no need to add diluent or otherwise treat
the
hydrocarbons to meet pipeline requirements.
[0084] Fig. 7 shows a schematic of a method 50 of refining feedstock
hydrocarbons
60 and transporting a resulting higher viscosity intermediate product 62 from
a first location
51 to a second location 61. In the method 50, the feedstock hydrocarbons 60
are provided to
a first reactor vessel 52 and exposed to EM energy in the first reactor vessel
52, resulting in
the higher viscosity intermediate product 62 and vaporization of selected
hydrocarbons 64.
The selected hydrocarbons 64 may be recovered, for example through
condensation in a
separate condensing vessel 54 or in the first reactor vessel 52 (for example
if using one of
the vessels shown in Figs. 1 to 6), and may be stored in a first storage
facility 55. The higher
viscosity intermediate product 62 is loaded on to a transport 56 (e.g, a rail
car, cargo
container, etc.). Where the feedstock hydrocarbons 60 include bitumen, the
higher viscosity
intermediate product 62 may substantially maintain its shape at 20 C to
simplify transport in
solid form on the transport 56. The transport 56 may be used to convey the
higher viscosity
intermediate product 62 to a second location in solid form.
[0085] The intermediate product may also be further refined. It may be
refined using
conventional methods or may be exposed to additional EM energy as set out
above to
recover additional selected hydrocarbons, until only a carbon ash residue is
left as a
byproduct. In contrast, previous refining methods typically result in
petroleum coke, asphalt,
other residue, or combinations as byproducts. The intermediate product may
also be refined
to obtain asphalt by varying intensity, duration, wavelength, or other
properties of the EM
energy applied.
[0086] Refining of the feedstock hydrocarbons to a complete or
substantially
complete stage results in the selected hydrocarbons described above and a
carbon ash
residue. When the complete stage is reached, essentially all recoverable
hydrocarbons in the
feedstock hydrocarbons may be recovered as selected hydrocarbons, leaving the
carbon
residue. The carbon residue includes primarily elemental carbon, with common
minor
components including sulfur (about 1 to 10% by mass), and metals (below about
500 mg/kg).
The complete stage may be reached by exposure of the feedstock hydrocarbons to
the EM
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energy for a greater period of time, at greater EM energy power, or both,
relative to the conditions
applied for the intermediate stage.
[0087] This carbon residue is in contrast to the petroleum coke
produced as a byproduct of
conventional upgrading which consists of heavier hydrocarbons and asphaltenes.
The present
methods are able to refine those heavier hydrocarbons and asphaltenes into
selected
hydrocarbons and leave less byproduct.
[0088] Fig. 8 shows a method 150 of refining the feedstock
hydrocarbons 160 and
transporting (e_g. via a transport 156) the higher viscosity intermediate
product 162 from the first
vessel 152 at the first location 151 to a second vessel 158 at a second
location 161. As in Fig. 7,
selected hydrocarbons 164 may be recovered, for example through condensation
in a separate
condensing vessel 154 or in the first reactor vessel 152, and may be stored in
a first storage facility
155. In the second vessel 158, the higher viscosity intermediate product 162
may be exposed to
EM energy in the second vessel 158, resulting in vaporization of additional
selected hydrocarbons
167. The additional selected hydrocarbons 167 may be recovered, for example
through
condensation in the second vessel 158 or in a separate condensing vessel 157,
and may be stored
in a second storage facility 159. After vaporization of substantially all of
the additional selected
hydrocarbons 166, a residual product 168 substantially comprised of carbon ash
may remain.
[0089] The methods may be applied to a variety of feedstock
hydrocarbons. The feedstock
hydrocarbons may include hydrocarbons having an API gravity of 24 or lower
such as heavy oil or
bitumen. Diluent is often added to bitumen prior to transport by pipeline to a
refinery. If the
feedstock hydrocarbons are bitumen with diluent or other solvents, the methods
may also be used
to recover the diluent or solvent. The feedstock hydrocarbons may also include
lighter
hydrocarbons including crude oil with an API gravity of above 24 . The
feedstock hydrocarbons
may also include byproducts of other processes, such as coke, asphalt, bunker
oil, or pyrolysis
bunker oil.
[0090] Example 1
[0091] In one example application of the methods, a one-barrel
equivalent sample (159
liters) of feedstock diluted bitumen was treated with EM energy in a test-
scale vessel. The
feedstock bitumen was purchased with diluent, some of which had evaporated
during storage prior
to Example 1. The feedstock bitumen was placed in a test-scale vessel and
exposed to
microwaves with a frequency of 915 MHz for about 10.5 hours.
[0092] In summary, during this example application, liquid feedstock
diluted bitumen
temperatures reached about 100 C during exposure to EM energy. Vapour
temperatures of up
to between about 25 C and about 75 C were observed, depending on the location
in the
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test-scale vessel. The selected hydrocarbons were recovered by condensation at
vapour
temperatures of between about 30 C and about 50 C. Onset of collection of the
selected
hydrocarbons at condensation vapour temperatures of about 30 C began when the
feedstock bitumen temperature reached about 60 C. As the feedstock bitumen was
further
treated with the EM energy, temperatures in the feedstock bitumen increased to
about 100 C
and recovery of the selected hydrocarbons increased.
[0093] Fig. 9 shows a schematic of the test scale vessel 410
identifying collection
zones and associated outlets, and temperature sensors, which are referenced
below. The
waveguide 420 and other features have been excluded from Fig. 9 for
simplicity. The test
scale vessel 410 includes the following temperature sensors, which have
numeral in the
figures and the indicated annotated names in the below Tables 2 and 4:
1) sensor 490 in the EM exposure zone 416 below the resting point of the
liquid
bitumen in the EM exposure zone 416 ("Bit");
2) sensor 491 in the EM exposure zone 416 above the resting point of the
liquid
bitumen within the EM exposure zone 416 ("Vap1");
3) sensor 492 in the recovery zone 418 below the first outlet 480 ("Vap2");
4) sensor 494 in the recovery zone 418 at the first outlet 480 ("R1"),
5) sensor 496 in the recovery zone 418 at a second outlet 482 ("R2"), and
6) sensor 498 in the recovery zone 418 at a third outlet 484 ("R3").
[0094] At the top of the vessel 410, a fourth outlet 486 is present without
a
temperature sensor.
[0095] Table 2 provides a timeline of observations taken at intervals
during the
method. In Table 2, the temperatures provided are taken from temperature
sensors in the
test-scale vessel described above with reference to Fig. 9.
Table 2: Observations during Example 1
Time Observation Temperature ( C)
(hr)
Bit Vapl Vap2 RI R2 R3
0.0 Microwave power exposure 15 17 17 17 17 18
begins at 1 kw and ramps upward
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Time Observation Temperature ( C)
(hr)
Bit Vapl Vap2 121 R2 R3
4.5 Recovery of selected 50 44 37 27 21 23
hydrocarbons by condensation
begins at highest recovery port
5.5 Recovery of selected 60 49 41 30 22 22
hydrocarbons by condensation
begins at lowest recovery port
6.0 Microwave power reaches 8 kw 66 52 43 31 22 23
6.75 Continuous recovery of selected 76 56 47 33 26
26
hydrocarbons by condensation at
all recovery ports
8.25 Cooling coils run briefly 94 67 60 50 40 38
8.5 Significant recovery of selected 95 68 60 50 40
37
hydrocarbons by condensation at
all recovery ports
10.5 Prior to Microwave power being 102 74 62 45 31
26
deactivated
10.6 Microwave power deactivated 106 68 59 39 30 30
11.25 All recovery ports closed and (no data)
hardened bitumen remaining in
test vessel left to cool
21.25 Test vessel opened and hardened (no data)
bitumen recovered from test
vessel
[0096] As indicated above, the test-scale vessel included four recovery
ports.
Temperature sensors 494, 496, 498 were located at three of the four ports only
(the three
data sets reported below at 480, 482, 484). However, selected hydrocarbons
were recovered
at all four ports 480, 482, 484, and 486, and the selected hydrocarbons from
all four ports
were analyzed to assess the chain lengths of the selected hydrocarbons (see
Fig. 11).
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[0097] With the exception of the temperatures reported at Bit, all
temperatures in the
above table are vapour temperatures (Vap1, Vap2, R1, R2, and R3). The
temperatures
reported at Bit are measured within the liquid feedstock bitumen and, as the
reaction
progresses, within liquid-phase hardened bitumen mixed with the feedstock
bitumen.
[0098] Fig. 10 is a graph of the Bit temperature readings throughout
Example 1. The
maximum observed temperature of the liquid bitumen was 106 'C. The bitumen had
a
temperature 0160 C when production of selected hydrocarbons began and when
significant
recovery of selected hydrocarbons was observed, the liquid bitumen temperature
was 95 C.
The highest vapour temperature observed over the liquid bitumen in the EM
exposure zone
was 74 C. The lowest vapour temperature at which selected hydrocarbons were
condensed
and recovered was 26 C.
[0099] Fig. 11 is a
graph of the population distribution by volume of carbon chain
lengths in the recovered selected hydrocarbons at each of the outlets 480,
482, 484, and
486. About 99% of the recovered carbon chain lengths ranged from C4 to C14,
with at least
40% being C8 to C14. The measured volumes shown in Fig. 11 can be further
summarized
as follows for each of outlets :
Table 3: Summary of Population Distributions in Fig. 11
Chain Lengths 480 482 484 486
C4-C14 99% 99% 99% 99%
C6-C10 91% 91% 94% 88%
C7-C8 70% 71% 74% 63%
C8-C14 45% 44% 41% 71%
[00100] Ports 480, 482, and 484 are the same ports for which temperature
data is
shown for selected points in time in Table 2. Port 486 is at a higher position
on the test-scale
vessel than 484. The selected hydrocarbons recovered at each port were
predominantly
heptanes and octanes. No vacuum was applied to the test-scale vessel during
the
experiment of Example 1.
[00101] The most common fractions of selected hydrocarbons recovered at all
four
ports were C7 and C8. Significant amounts (at least 1% by volume) of the
selected
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hydrocarbons having chain lengths of each of C9 to C14 were also observed,
with amounts
of between 2% and 16% by volume for each of C9 and C10. The boiling points of
n-heptane
and n-octane are 98 C and 125 C, respectively. The boiling points of n-nonane
and n-
decane are 151 C and 175 C, respectively. The boiling points of n-undecane
through
tetradecane range between 196 C and 254 C. While heptane would boil at the
highest
observed Bit temperatures, it is unexpected that the gaseous hydrocarbons
would include
the recovered quantifies of octane, nonane, decane, undecane, dodecane,
tridecane, or
tetradecane. Convection or other heating to 106 C would not be expected to
result in
vaporization of C8 or greater chain lengths without application of vacuum or
otherwise
altering the pressure or other conditions relevant to vaporization.
[00102] Fig. 12 is the population of hydrocarbons by chain length in
feedstock bitumen
(black squares) and hardened bitumen following exposure to EM energy (white
diamonds).
The population percentages are assessed by volume. For each of the feedstock
bitumen and
the hardened bitumen, the solid lines show the percentage present of a given
hydrocarbon
chain length. The dashed lines show the total percentage of hydrocarbons of a
given chain
length or shorter. The hardened bitumen had a greater percentage of C18 and
longer chain
lengths, and a lower percentage of 017 and shorter chain lengths, than the
feedstock
bitumen.
[00103] The data in Figs. 10 to 12 show that exposure of bitumen or
other
hydrocarbons to EM energy results in vaporization and recovery of selected
hydrocarbons
including light hydrocarbons (C14 or below in Example 1) from the bitumen at
vapour
temperatures far below the normal vaporization temperature for hydrocarbons
with these
chain lengths. The data also shows that the remaining hardened bitumen has an
increased
population of all fractions beginning with C20, and a decreased population of
C19 and all
fractions below 019. Recovery of the selected hydrocarbons had an onset
temperature in the
bitumen 0160 C and 49 C immediately above the bitumen (time 5.5 hours). The
temperature at the first recovery port to produce condensed selected
hydrocarbons was
C. At peak recovery of the selected hydrocarbons (time 8.5 hours), the
temperature in the
bitumen was 95 C, the vapour temperature immediately above the bitumen was 68
C, and
30 the temperature proximate the recovery ports for the selected
hydrocarbons were between
37 and 50 C (time 8.5 hours). These temperatures are far below the boiling
points of C14 (n-
tetradecane having a boiling point of 254 C) and C8 (n-octane having a boiling
point of
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125 C), each of which were recovered by condensation (in addition to C9 to C13
fractions;
see Fig. 11).
[00104] Fig. 10 shows that the feedstock in this sample took about 8
hours to reach 60
C, at which point the selected hydrocarbons were recovered. However, if the
feedstock
bitumen is initially heated to about 60 C with corresponding vapour
temperatures from about
20 C to about 50 C, recovery of the selected hydrocarbons begins about one
hour following
exposure to EM energy. However, preheating alone without exposure to the EM
energy does
not result in vaporization of the selected hydrocarbons.
[00105] At the temperatures observed in the EM exposure zone, which did
not exceed
106 C, no hydrocarbons above C7 to would be expected to be vaporized ad
distilled, and
yet chain lengths as high as 012 were present in amounts over 1% in the
selected
hydrocarbons recovered in Example 1.
[00106] At the temperatures observed in the recovery zone, it would not
be expected
that hydrocarbons with unbranched chain lengths as high as those observed
would remain
gaseous to travel upwards and condense above the shield between the EM
exposure zone
and the recovery zone. It would be expected that such hydrocarbons would
either not pass
the shield or would condense directly on top of the shield. However, recovery
of carbon
chains of C7 to C12 in amounts over 1 % w/w was observed at recovery ports 480
and 482,
and recovery of carbon chains of C7 to C10 in amounts over 2 % w/w was
observed at all
three recovery ports 480, 482, and 484.
[00107] In Example 1, vaporization of hydrocarbons, and maintenance of
the vapor
state, were each observed at much lower temperatures for the carbon chain
lengths
vaporized and recovered than would be expected at atmospheric pressure based
on the
normal vaporization temperatures shown in Table 1. Vaporization of the
selected
hydrocarbons resulted from a total of about 10 hours of exposure to 915 MHz
microwave
energy at about 8 kw peak power.
[00108] Example 2
[00109] Fig. 13 shows high temperature simulated distillation ( HTSD")
data of
hardened bitumen prepared by a second example application of the methods
provided
herein. The hardened bitumen is shown as a plot of white diamonds. Control
groups of
Checham bitumen (black "x"), Albian bitumen (black triangles), and Western
Canadian Select
bitumen (black horizontal bars) are also included in Fig. 13. A mass recovery
of 5% is
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observed at over 270 C in the hardened bitumen. A dashed line on the graph
shows 270 C
for comparison with the control samples. The control samples showed 5% mass
recovery at
38 C (Western Canadian Select), 41 C (Albian), and 100 C (Canadian Select).
At 270 C,
the control samples showed between 20 and 30 % of mass recovered. The
relatively higher
distillation temperatures of early mass recovery in the hardened bitumen
compared with the
temperatures observed in the three control samples is indicative of the lower
population of
short chain hydrocarbons in the hardened bitumen compared to the feedstock
bitumen.
[00110] Example 3
[00111] Fig. 14 is the population of hydrocarbons by chain length in the
recovered
selected hydrocarbons from a third example application of the methods. The
data in Fig. 14
is analogous to that of Fig. 11 but with the population distribution centered
on a higher
carbon chain length than in Example 1. The chain lengths of the recovered
selected
hydrocarbons in Example 3 ranged from C6 to C30, with the most populated
fractions being
C13 to C18, particularly C16. Compared with Example 1, the reaction in Example
3 was
taken to a stage of refinement where the byproduct is the carbon residue. As
described
above, the carbon residue observed in Example 3 was primarily elemental
carbon, and also
included 6.23% by mass sulfur, and below about 500 mg/kg metals.
[00112] Compared with Example 1, the total time spent in the reaction
was greater in
Example 3 than in Example 1. However, the vessel used in Example 3 essentially
lacked the
recovery zone of the vessel of Example 1. Rather, vacuum was applied to the
vessel
immediately above the gas permeable EM energy impermeable shield to draw off
any volatile
fractions. Without being bound by any theory, the longer chain lengths of the
selected
hydrocarbons in Example 3 may have been due to a shorter residence time in the
EM
exposure zone of the vessel of Example 3. With a shorter residence time in the
EM exposure
zone, the feedstock hydrocarbons would have less exposure to the EM energy.
[00113] Example 4
[00114] In a fourth example application of the methods, feedstock
bitumen was refined
to hardened bitumen. The hardened bitumen had a kinematic viscosity of about
5,000,000,000 cSt at 20 C and about 17,000,000 cSt at 40 C.
[00115] Example 5
[00116] In another example application of the methods, a one-barrel
equivalent
sample (159 liters) of feedstock diluted bitumen was treated with EM energy in
the same
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test-scale vessel as used in Example 1. About 2.55% pentane diluent was
present in the
bitumen. The feedstock bitumen was placed in the test-scale vessel and exposed
to
microwaves with a frequency of 915 MHz for about 10.5 hours.
[00117] In summary, during this example application, liquid feedstock
diluted bitumen
temperatures reached a maximum of about 125 C during exposure to EM energy.
Vapour
temperatures of up to between about 100 C and about 105 C were observed,
depending on
the location in the test-scale vessel. The selected hydrocarbons were
recovered by
condensation at vapour temperatures in the range of between about 44 C and
about 64 C.
Onset of collection of the selected hydrocarbons at condensation vapour
temperatures of
between 55 and 60 C began when the feedstock bitumen temperature reached
about 75 C,
with similar vapour temperatures immediately above the feedstock bitumen. As
the feedstock
bitumen was further treated with the EM energy, temperatures in the feedstock
bitumen
increased to about 125 C and recovery of the selected hydrocarbons increased.
[00118] Table 4 provides a timeline of observations taken at intervals
during Example
5. In Table 4, the temperatures provided are taken from temperature sensors in
the test-
scale vessel. The temperature sensors are positioned as indicated above in
respect of Table
2 described in Example 1.
Table 4: Observations during Example 5
Time Temperature ( C)
Observation
(hr) Bit Vap1 Vap2 R1 R2 R3
0.0 Microwave power exposure 19 19 19 16 15 16
begins at 1 kw and ramps upward
4.0 Recovery of selected 65 64 61 46 38 38
hydrocarbons by condensation
begins
6.0 Significant recovery of selected 79 74 69 59 56
58
hydrocarbons by condensation at
all recovery ports
10.5 Prior to Microwave power being 121 97 86 48 40 40
deactivated
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Time Temperature ( C)
Observation
(hr) Bit Vap1 Vap2 R1 R2 R3
10.6 Microwave power deactivated 120 96 85 48 40 41
[00119] As indicated above, the test-scale vessel included four recovery
ports.
Temperature sensors 494, 496,498 were located at three of the four ports only
(the three
data sets reported below at 480, 482, 484). However, selected hydrocarbons
were recovered
at all four ports 480, 482, 484, and 486, and the selected hydrocarbons from
all four ports
were analyzed to assess the chain lengths of the selected hydrocarbons (see
Fig. 16).
Unlike Example 1, carbon chain distribution data for Example 5 is a pool of
the fractions
collected at all four ports 480, 482, 484, and 486.
[00120] With the exception of the temperatures reported at Bit, all
temperatures in the
above table are vapour temperatures (Vap1, Vap2, R1, R2, and R3). The
temperatures
reported at Bit are measured within the liquid feedstock bitumen and, as the
reaction
progresses, within liquid-phase hardened bitumen mixed with the feedstock
bitumen.
[00121] Fig. 15 is a graph of the (Vap1, Vap2, R1, R2, and R3)
temperature readings
throughout Example 5. The maximum observed temperature of the liquid bitumen
was 125
C. The highest value graphed on Fig. 15 is 121, but at a higher resolution
than Fig. 15, data
up to 125 C was observed. The bitumen had a temperature of about 65 C when
production
of selected hydrocarbons began and when significant recovery of selected
hydrocarbons was
observed, the liquid bitumen temperature was 79 C. The highest vapour
temperature
observed over the liquid bitumen in the EM exposure zone was 107 C at 10.0
hours.
[00122] Fig. 15 shows that the feedstock in this sample took about 3.5
hours to reach
60 C, at which point the selected hydrocarbons were recovered. As above,
preheating the
bitumen by convection or other heating may abridge this time.
[00123] Fig. 16 is a graph of the population distribution by volume of
carbon chain
lengths in the recovered selected hydrocarbons (white circles). The
populations for the same
carbon lengths are also shown for the feedstock hydrocarbon (black squares)
and the
hardened bitumen secondary product (white diamonds). The normal boiling points
are also
shown as a bar graph for each of the carbon lengths on a separate y axis. The
maximum
temperature observed at any points in the experiment is shown for reference
(solid line at
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125 C). The range of the lower condensation temperatures observed (dashed
lines between
44 C and 64 C).
[00124] About 97% w/w of the recovered carbon chain lengths ranged from
C6 to C14,
with 35% w/w being C9 to C14, which have boiling points beginning at 151 C,
above the
maximum temperature of 125 C observed in the EM exposure zone. The selected
hydrocarbons recovered at each port were predominantly heptane (27 %) and
octane (32 %).
No vacuum was applied to the test-scale vessel during the experiment of
Example 1.
[00125] The boiling point of n-octane is 98 C. While octane would boil
at the highest
observed Bit temperatures, it is unexpected that the gaseous hydrocarbons
would include
the recovered quantifies of nonane, decane, undecane, dodecane, tridecane,
tetradecane, or
pentadecane. Convection or other heating to 125 C would not be expected to
result in
vaporization of C9 or greater chain lengths without application of vacuum or
otherwise
altering the pressure or other conditions relevant to vaporization.
[00126] At the temperatures observed in the EM exposure zone, which did
not exceed
125 C, no hydrocarbons above C8 to would be expected to be vaporized ad
distilled, and
yet chain lengths as high as C14 were present in amounts over 1% in the
selected
hydrocarbons recovered in Example 5.
[00127] Figs. 17 to 21 show the w/w% populations of hydrocarbons by
chain length in
feedstock bitumen (black squares), hardened bitumen following exposure to EM
energy
(white diamonds), and selected hydrocarbons (white circles). The population
percentages
are assessed by volume. For each of the feedstock bitumen and the hardened
bitumen, the
solid lines show the percentage present of a given hydrocarbon chain length.
The dashed
lines show the total percentage of hydrocarbons of a given chain length or
shorter.
[00128] Fig. 22 shows HTSD data of hardened bitumen prepared in Example
5.
HTSD data is shown for feedstock bitumen (black squares), hardened bitumen
following
exposure to EM energy (white diamonds), and selected hydrocarbons (white
circles). A
mass recovery of 5% is observed at 259 C in the hardened bitumen. The
feedstock bitumen
showed 5% mass recovery at 74 C and at 253 C showed 21% mass recovery. The
relatively higher distillation temperatures of early mass recovery in the
hardened bitumen
compared with the temperatures observed in the feedstock bitumen is indicative
of the lower
population of short chain hydrocarbons in the hardened bitumen compared to the
feedstock
bitumen.
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[00129] The data in Figs. 15 to 22 show that exposure of bitumen or
other
hydrocarbons to EM energy results in vaporization and recovery of selected
hydrocarbons
including light hydrocarbons (C14 or below in Example 1) from the bitumen at
vapour
temperatures far below the normal vaporization temperature for hydrocarbons
with these
chain lengths.
[00130] The data in Figs. 17 to 21 also shows that the remaining
hardened bitumen
has an increased population relative to the feedstock hydrocarbons of the all
fractions
beginning with C13, a decreased population of C8 to C12, and no C7 or lower.
Recovery of
the selected hydrocarbons had an onset temperature in the bitumen of 65 C and
immediately above the bitumen of 64 C (time 4.0 hours). At peak recovery of
the selected
hydrocarbons (time 6.0 hours), the temperature in the bitumen was 79 C, the
vapour
temperature immediately above the bitumen was 74 C, and the temperature above
the plate
414 and proximate the recovery ports for the selected hydrocarbons were
between 56 and
59 C (time 6.0 hours). These temperatures are far below the boiling points of
C14 (n-
tetradecane having a boiling point of 254 C) and C8 (n-octane having a
boiling point of 125
C), each of which were recovered by condensation (in addition to CO to C13
fractions).
Vaporization of the selected hydrocarbons resulted from a total of about 10.5
hours of
exposure to 915 MHz microwave energy at about 5 kw set-point peak power.
[00131] In the preceding description, for purposes of explanation,
numerous details
are set forth to provide a thorough understanding of the embodiments. However,
it will be
apparent to one skilled in the art that these specific details are not
required.
[00132] The above-described embodiments are intended to be examples
only.
Alterations, modifications and variations can be effected to the particular
embodiments by
those of skill in the art. The scope of the claims should not be limited by
the particular
embodiments set forth herein, but should be construed in a manner consistent
with the
specification as a whole.
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