BACKGROUND
Technical Field
[0001] This invention relates to hydrocarbon processing, and more particularly to methods
for efficiently upgrading heavy crude oil.
Background Information
Introduction to Heavy Crude Oil
[0002] The average weight or density of crude oils extracted from oil fields globally has
been increasing very gradually over time, a trend expected to continue indefinitely.
However, the existence of large reserves of heavy and extra-heavy crude oils in some
countries means that the as-produced weight of crude oil can increase much more rapidly
on a regional basis. Of particular importance are the tar oils in the Orinoco Belt
in Venezuela and oil sand bitumen in Alberta, Canada, which in aggregate are currently
estimated as being 2-3 times the size of the oil reserves in Saudi Arabia. The density
of Saudi Arabian crude oils, expressed as API gravity or °API, may typically fall
in the range of about 27 - 34 °API, in the center of which falls the current global
average. By contrast, the deposits in Venezuela and Alberta are generally characterized
as being heavy crude oils (HCO) or extra-heavy crude oils (EHCO) for which the corresponding
densities may be regarded generally as being below about 22.3 °API and about 10 °API,
respectively. (The lower the °API value, the higher the density.) For deposits that
are heavier still, such as in the case of some natural bitumen deposits in Alberta,
the term ultra-heavy crude oil (UHCO) is sometimes applied. In most cases, the densities
of native, unmodified heavy crude oils produced in Venezuela and Alberta are below
about 15 °API, and even below 10 °API. (Though the classification scheme used herein
to differentiate crude oils in terms of °API will be recognized by those skilled in
the art, other conventions and criteria exist, which may apply different terms and
°API ranges and/or include other criteria such as viscosity and percent sulfur. Therefore,
definitions used herein should not be regarded as limiting but only illustrative.)
[0003] From the viewpoint of crude oil production and transport, HCO, EHCO, and UHCO, the
entire group of which shall hereinafter be referred to inclusively as heavy crude
oils (HCO) without limitation as regards exact composition or geological or geographic
origin, are problematic because the same physico-chemical characteristics that cause
their elevated density produce a corresponding increase in viscosity. By way of illustration
that is neither bound by theory nor intended to be complete or applicable to all crude
oils, asphaltenes are a class of diverse compounds known to affect density and viscosity
directly and to have concentrations in HCO that are generally higher than in medium
and light crudes. Having molecular weights that are high relative to other compounds
in crude oils generally, increasing asphaltene concentration is generally accompanied
by an increase in both density and viscosity. This may be due to the tendency of asphaltenes
to self-associate, or it may be due to the formation of dense microscopic particles
comprising a dense core of aggregated asphaltenes surrounded by layers of other crude
oil components. Regardless of the mechanisms by which composition and microscopic
structure cause elevated density and viscosity, HCO is generally not amenable to the
methods of transportation and storage commonly applied to medium crude oils (about
22.3 °API to about 31.1 °API) and light crude oils (greater than about 31.1 °API).
For example, if crude oil were required to have a minimum °API value of about 20 to
be pipelineable, and if transport by rail tank car is precluded on the grounds of
practical economics and logistics, then delivery to market of crude oil extracted
from Albertan oil sands requires that it be somehow upgraded to meet pipeline specifications
for density and viscosity.
Approaches to Upgrading Heavy Crude Oils
[0004] Commercially relevant upgrading strategies currently applied in Alberta fall into
two general categories. In the first, coking, hydrocracking, or other techniques are
applied to HCO to chemically convert asphaltenes and other heavy components into lighter
materials, which are recovered through distillation and blended to produce pipeline
quality synthetic crude oil. The various conversion and recovery processes are related
to those employed in oil refining and the overall approach is correspondingly capital
intensive, adding an estimated $14 per barrel. Furthermore, economic considerations
preclude an implementation strategy whereby smaller-scale upgrading facilities may
be located in or near numerous production fields.
[0005] Producers therefore rely on another, simpler strategy whereby the bitumen and heavy
oil are mixed with higher-value, lighter petroleum products at the wellhead to produce
diluted bitumen (dilbit) that can be easily transported through pipelines. However,
several significant issues are associated with dilbit. First, the diluent must be
transported by rail or pipeline to production fields from distant refineries or gas
processing plants where it is produced. Second, dilbit in pipelines may typically
contain about 20% to 40% diluent, effectively reducing the net capacity of pipelines
to carry unrefined crude. Compounding these issues, the net cost for diluent in terms
of both the material itself and the facilities required to handle it adds $10 - $16
per barrel of dilbit. However, beyond infrastructure and cost considerations looms
a broader problem, namely, that diluent-based upgrading may not be a practical way
to meet future growth of Canadian HCO production. Absent an alternative approach,
Canada will be required to import ever increasing quantities of diluents. Currently,
efforts are underway to expand the pipeline infrastructure from the Gulf Coast of
the United Stated all the way to Alberta via Illinois to carry the "pentane plus"
condensate by-product of shale gas production.
[0006] The need exists in the art for a new approach that requires lower initial capital
investment, has lower ongoing operating costs, and combines the best features of the
two main upgrading methods used currently: reduction of the density and viscosity
of the native crude through conversion of asphaltenes and other heavy components into
lighter ones; and scalability that permits distributed implementation at or near the
wellhead to minimize or eliminate the reliance on diluent from remote sources
[0007] US2008/099378 discloses the upgrading of heavy oil at supercritical conditions.
SUMMARY
[0008] According to one aspect of the present invention, a method is provided for upgrading
a continuously flowing process stream including heavy crude oil (HCO), as defined
in claim 1.
[0009] The features and advantages described herein are not all-inclusive and, in particular,
many additional features and advantages will be apparent to one of ordinary skill
in the art in view of the drawings, specification, and claims. Moreover, it should
be noted that the language used in the specification has been principally selected
for readability and instructional purposes, and not to limit the scope of the inventive
subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention is illustrated by way of example and not limitation in the
figures of the accompanying drawings, in which like references indicate similar elements
and in which:
Fig. 1 is a schematic diagram of a representative embodiment of a hydrothermal heavy
crude oil (HCO) upgrading system used in the method of the present invention;
Fig. 2 is a schematic diagram of the embodiment of Fig. 1, with various optional features;
Fig. 3 is a schematic diagram of the embodiment of Fig. 2, with further optional features;
Fig. 4 is a schematic diagram of the embodiment of Fig. 3, with additional optional
features;
Fig. 5 is a schematic diagram of the embodiment of Fig. 4, with an additional optional
feature;
Fig. 6A is a schematic diagram of the embodiment of Fig. 3, with an additional optional
feature;
Fig. 6B is a view similar to that of Fig. 6A, with other optional features;
Fig. 7 is a schematic cross-sectional view of a reactor suitable for use in one or
more of the embodiments of Figs. 1-6B, with temperature represented graphically thereon;
Fig. 8 is a view similar to that of Fig. 7, of an alternate reactor;
Fig. 9 is a schematic diagram of another alternate reactor portion usable with embodiments
of the present invention;
Fig. 10 is a schematic diagram of still other reactor portions usable with embodiments
of the present invention;
Fig. 11 is a schematic diagram of still other reactor portions usable with embodiments
of the present invention;
Fig. 12 is a schematic diagram of an alternate embodiment of a hydrothermal heavy
crude oil (HCO) upgrading system of the present invention;
Fig. 13 is a schematic diagram of yet another alternate embodiment of a hydrothermal
heavy crude oil (HCO) upgrading system of the present invention;
Fig. 14 is a schematic diagram of another embodiment of a hydrothermal heavy crude
oil (HCO) upgrading system of the present invention;
Fig. 15 is a schematic diagram of another embodiment of a hydrothermal heavy crude
oil (HCO) upgrading system of the present invention;
Fig. 16 is a graphical representation of aspects of the embodiments of Figs. 12-15;
Fig. 17 is a graphical representation of additional aspects of the present invention;
Fig. 18 is a graphical representation of additional aspects of the present invention;
and
Fig. 19 is a graphical representation of still further aspects of the present invention.
DETAILED DESCRIPTION
[0011] In the following detailed description, reference is made to the accompanying drawings
that form a part hereof, and in which is shown by way of illustration, specific embodiments
in which the invention may be practiced. These embodiments are described in sufficient
detail to enable those skilled in the art to practice the invention, and it is to
be understood that other embodiments may be utilized. In addition, well-known structures,
circuits and techniques have not been shown in detail in order not to obscure the
understanding of this description. The following detailed description is, therefore,
not to be taken in a limiting sense, and the scope of the present invention is defined
by the appended claims and their equivalents.
[0012] As will now be described in detail, embodiments of the present invention relate to
upgrading a continuously flowing stream including heavy crude oils, extra-heavy crude
oils, ultra-heavy crude oils, bitumen, and the like without limitation in regard to
exact composition or geologic or geographic origin, which hereinafter are referred
to inclusively as heavy crude oils or simply HCO. Indeed, as used herein, the term
"heavy crude oil" and/or "HCO" refers to substantially any crude oil or hydrocarbon-containing
material measuring at or below about 22.3 °API, with lower °API values corresponding
to higher densities. Referring to Fig. 1, in one example, a system 20 is provided
for the hydrothermal upgrading of a process stream (reaction mixture) 22 (HCO and
water) by a reactor portion (section) 24 configured to progressively heat the process
stream 22 as a function of the reaction coordinate (R.C.) 26. The R.C. 26 may be calculated
as (a) the relative distance between an inlet 28 and outlet 30 traversed by the process
stream 22 within the reactor section 24, or (b) the time elapsed after the reaction
mixture 22 enters the reactor section at 28, times flow rate divided by the total
volume of the fluid flow path within the reactor section 24. In Fig. 1, the rate of
heat applied (rate of heat transfer or thermal flux) to the reaction mixture 22 is
shown graphically as temperature (T) of the process mixture 22 (on the y-axis), as
a function of the R.C. 26 (on the x-axis.) Moreover, in particular embodiments, the
thermal flux or temperature applied at the reactor 24 is increased progressively along
the downstream direction a. This progressively increasing thermal flux may be provided,
for example, by an otherwise conventional counter-flow heat exchanger such as the
shell-and-tube heat exchanger shown and described hereinbelow with respect to Figs.
7, 8 and 11. It should be recognized, however, that substantially any type of heater
known to those skilled in the art, e.g., arranged in series with one another along
the process fluid flow path may be used, without departing from the scope of the present
invention.
[0013] In particular embodiments, the reactor section 24 includes one or more process flow
tubes each having an interior cross-sectional dimension (e.g., diameter) in a plane
extending transversely to the downstream direction
a therethrough. In this regard, it should be recognized that the process flow tubes
may be disposed in series, such as shown and described hereinbelow with respect to
Fig. 7, and/or in parallel, as shown in Fig. 11. Regardless of whether the flow tubes
are disposed in series, in parallel, or in a combination thereof, the flow tubes are
provided with a combined length of at least about 30 times the aggregated interior
cross-sectional dimension. For purposes of computing the aggregated interior cross-sectional
dimension, flow tubes disposed in series are treated as a single tube. Therefore,
for example, a reactor having one or more flow tubes in series, each with a diameter
of 5 cm would have an aggregated cross-sectional dimension of 5 cm and a total length
of at least 30 x 5 cm or about 150 cm. Similarly, a reactor having three parallel
flow tubes each having a diameter of 5 cm, would have an aggregated cross-sectional
dimension of 15 cm and a length of at least about 450 cm. Moreover, although these
examples contemplate flow tubes of circular cross-section, one skilled in the art
will recognize that tubes of substantially any shape cross-section, such as square,
oblong, etc., may be used without departing from the scope of the present invention.
[0014] The reactor 24 is configured to apply heat to the reaction mixture flowing therethrough,
to progressively heat the reaction mixture 22 so that the reaction mixture is disposed
at a lower temperature at an upstream or inlet portion of the reactor, e.g., at 28,
than at a downstream or outlet portion of the reactor, e.g., at 30. In particular
examples, the reactor 24 is configured to progressively heat the reaction mixture
22 from an inlet 28 temperature of about 60 °C to 200 °C, to an outlet 30 temperature
(T(max)1) of between about 260 °C and 400 °C. It should be noted that this progressive
heating may be accomplished either substantially continuously, as shown in Figs. 1-7,
or discontinuously, as will be discussed in greater detail hereinbelow with respect
to Figs. 8-10. It is also noted that the reactor 24 is configured to maintain the
reaction mixture 22 at a pressure sufficient to ensure that the reaction mixture remains
a single phase at T(max)1, i.e., to substantially prevent formation of a gas phase
separate from the liquid phase of the reaction mixture 22. In various exemplary embodiments,
pressure within reactor 24 may be maintained within a range of about 1500 to about
3000 psia (10.34 to 20.68 MPa), with particular embodiments being maintained within
a range of 1500 to 2000 psia (10.34 to 13.79 MPa), and other embodiments being maintained
within a range of about 2000 to 3000 psia (13.79 to 20.68 MPa).
[0015] As also shown, system 20 may also include a controller 32, e.g., in the form of a
conventional closed-loop programmable logic controller (PLC) or process automation
controller (PAC) such as the model T2750 commercially available from Foxboro (Invensys
Systems, Inc., Foxborough, MA, USA), optionally augmented with model predictive control
(MPC) capability, communicably coupled to reactor 24, including a flowmeter and temperature
and pressure probes associated therewith (not shown) for capturing the flow rate,
temperature and pressure of the process stream 22. The controller 32 is configured
to adjust both the rate of flow of reaction mixture 22 into the reactor 24, and/or
the rate of heat applied (rate of heat transfer or thermal flux) to the reaction mixture
22 in the reactor 24 (e.g., by controlling operation of hardware commonly associated
with process flow, such as pumps, valves, heaters, etc. (not shown)). In particular
embodiments, controller 32 is configured to ensure that the flow rate is sufficiently
high and the rate of heat transfer is sufficiently low to minimize or substantially
prevent coke formation, while maintaining a total residence time of the reaction mixture
22 within the reactor 24 of greater than about 1 minute and less than about 25 minutes,
calculated as the total volume of the fluid flow path within the reactor divided by
the flow rate, to form a product mixture 34 exiting the reactor at 30. It is noted
that both the flow rate and the thermal flux from the inside surface of the tube or
tubes in the reactor section may be optimized to minimize or prevent coke formation
while achieving the desired level of upgrading and maximizing throughput, while taking
into consideration the thermal conductivity of the reaction mixture 22.
[0016] As also shown, system 20 includes a recovery portion (section) 38 configured to receive
the process stream, which has now been transformed into product mixture 34, exiting
the reactor section at 30. Recovery section 38 is configured to reduce the temperature
of the product mixture 34, e.g., to between 60 °C and 200 °C, and to also effect a
corresponding reduction in the vapor pressure of the mixture 34. It is also noted
that in particular embodiments, recovery section 38 includes a water separator 40
configured to separate water from the upgraded crude oil, which exit the recovery
section 38 at 42 and 44, respectively.
[0017] An aspect of the present invention is thus the gradual heating of reaction mixture
22, including an HCO stream and water, flowing through reactor section 24, on a time
scale configured to promote, at relatively low temperatures, the disaggregation of
HCO components and their substantially uniform distribution in the matrix of the reaction
mixture, and additionally at higher temperatures upgrading reactions, all the while
minimizing or preventing coking. It is noted that the use of tube reactors in petrochemical
processing to effect chemical transformations is commonplace. For example, it is the
standard approach for cracking of gas-phase naphtha at temperatures in excess of 800
°C to produce ethylene. It is noted, however, that the use of tube reactors to effect
the chemical transformation of liquids at the relatively lower temperatures is rather
uncommon or absent in commercially relevant processes used in either in refining or
petrochemical operations.
[0018] Another aspect of the present invention is that instead of the reactor having a substantially
uniform temperature distribution, the flowing mixture 22 instead experiences a deliberately
non-uniform application of heat (thermal flux) between the inlet 28 and the outlet
30. Though not wishing to be bound by any particular theory of operation, the belief
is that the aforementioned approach facilitates upgrading by fostering sequentially
two different physico-chemical processes. First, as discussed briefly above, the use
of time and the application of progressively increasing temperatures between the inlet
and outlet of the reactor section serves to disintegrate physical structures in HCO
and/or effect the dissolution of HCO components to yield a substantially uniform dispersion
by the point where the mixture reaches a temperature of about 80% to about 90% of
the predetermined maximum temperature at some point before the outlet. The process
of disaggregation, disintegration, or destructuring of assemblages of HCO components
and the dispersing and/or dissolution of the same will be inclusively referred to
hereinafter as the disaggregation reaction or simply disaggregation. Through disaggregation,
asphaltenes and other heavy compounds that are generally associated in HCO are thought
to be dispersed and nominally separated from one other, predisposing them to undergo
upgrading reactions involving water and minimizing the possibility that they thereafter
will undergo retrograde reactions with each other that lead to the formation of more
and larger asphaltenes molecules and possibly coke. The process that yields product
qualities such as density and viscosity that are improved over those of the HCO feed
due to upgrading reactions involving heavy components originating in HCO will be referred
to inclusively as the upgrading reaction or simply upgrading.
[0019] It will be understood that the embodiments shown and described herein for upgrading
HCO do not purport to selectively and/or exclusively promote first the initial disaggregation
reaction and subsequently the upgrading reaction, nor is there a presumption that
the latter occurs only when the temperature of the reaction mixture reaches and exceeds
temperatures of between about 80% and 90% of the predetermined maximum temperature.
Rather, the reaction mixture will predominantly undergo disaggregation reactions at
lower temperatures in the reactor section while upgrading reactions occur predominantly
at the higher temperatures in the reactor section. Indeed, as shown in Fig. 10 (discussed
in greater detail hereinbelow) an aspect of embodiments of the present invention is
the fostering of the disaggregation of HCO components prior to their being subjected
to conditions of elevated temperature at which upgrading reactions occur, maximizing
the efficiency and extent of upgrading at the highest temperatures while minimizing
undesirable side reactions that lead to coke formation.
[0020] Turning now to Fig. 2, the controlled, progressive increase in the temperature of
the reaction mixture between the reactor section inlet and outlet is but one aspect
of the present invention that preferentially promotes, first, the disaggregation reaction
and then the upgrading reaction. An additional approach for promoting disaggregation
and upgrading reactions associated with various embodiments of the present invention
involves the selection and contacting of the HCO stream in a premix section with materials
selected to promote one or both of those reactions. In one embodiment of the invention,
HCO flowing through a premix section 50 is contacted with a material including either
water or steam at a temperature at or below the desired predetermined inlet 28 temperature
of the process stream 22, e.g., at a temperature at or below about 200 °C. In another
embodiment the temperature of the water or steam contacting HCO flowing through the
premix section may be as high as about T(max)1 or about 350 °C, whichever is lower
so as to avoid the promotion of localized cracking of HCO components at or near the
point of contacting, which is thought to lead to coke formation. The mixture of HCO
and this water or steam becomes the process stream 22 that is fed to the reactor section
24 at inlet 28.
[0021] Not wishing to be bound by any particular theory of operation, it is believed that
the contacting of HCO, which has not substantially undergone disaggregation, with
water whose temperature is greater than about 325 °C may promote coking due to localized
high rates of cracking at or near the point of contacting followed by retrograde intermolecular
reactions of components that are not substantially disaggregated within the reaction
mixture 22. Thus, while coke formation by this mechanism may be minimized by ensuring
that HCO components are substantially disaggregated prior to contacting with water
that is supercritical (temperature and pressure are equal to or greater than about
374 °C and 3200 psia (22.06 MPa)) or near-supercritical (e.g. temperature and pressure
are in the range of about 325 °C to 374 °C and 2000 psia to 3200 psia (13.79 to 22.06
MPa), respectively), it is expected to be reduced even further through the promoting
of disaggregation and the contacting with water whose temperature is less than about
325 °C.
[0022] Thus, as shown, system 220 of Fig. 2 is substantially similar to system 20 of Fig.
1, while also including an optional premix section 50 for contacting the HCO with
water or steam to form the process stream 22. As also shown, the recovery section
of system 220 includes an optional energy recovery subsection (e.g., heat exchanger)
52, which is configured to recover thermal energy from the product mixture 34 and
to distribute the recovered energy to the reactor section 24 as shown at 56. The energy
removed from the mixture 34 is shown graphically as a reduction in temperature (T)
as a function of R.C. 26. Still further, system 220 may include an optional water
recycling loop 58 configured to recirculate the water 42 recovered at water separator
40, to the premix section 50, although it will be understood that other embodiments
water used in contacting HCO in the premix section and/or the reaction mixture in
the reactor section (discussed in greater detail hereinbelow) may be from sources
instead of or in addition to water from the recycling loop.
[0023] Turning now to Fig. 3, in another variation of the foregoing, a system 320 is substantially
similar to system 220, with the addition to the recovery section of an optional light
hydrocarbon removal device 62. An example of a suitable device 62 may include a conventional
flash drum configured for recovering light hydrocarbons (e.g., naphtha, distillates,
condensates and the like, hereinafter referred to simply as LHC) from the product
mixture 34. The recovered LHC may then be recirculated via hydrocarbon recycling loop
64 back to the premix section 50, to help promote the disaggregation reaction.
[0024] Turning now to Fig. 4, in yet another variation of the foregoing embodiments, a system
420 is substantially similar to system 320, with the optional injection of water or
steam (e.g., from recycling loop 58) at one or more points in reactor section 24 instead
of the premix section 50. This effectively provides for contacting the HCO stream
with the hydrocarbons, and therefore promoting the disaggregation reaction, prior
to contacting the HCO with water or steam, which may be particularly effective for
predisposing the reaction mixture 22 toward mixing with injected water or steam and
undergoing upgrading reactions involving water at the higher temperatures found in
the reactor section 24.
[0025] In another variation shown in Fig. 5, a system 520 is substantially similar to system
420, with the optional injection of light hydrocarbon from recycling loop 64 into
the reactor section 24 as well as premix section 50. It is noted that in particular
embodiments, the injection of light hydrocarbon occurs at one or more points 68 prior
to where the reaction mixture 22 has reached a temperature T
85 of between about 80% to 90% of the temperature T(max)1. In other embodiments, the
injection of light hydrocarbon occurs at one or more points 68 prior to where the
reaction mixture 22 has reached a temperature T
65 of between about 60% to 70% of the temperature T(max) 1.
[0026] Turning now to Fig. 6A, system 620 is substantially similar to system 520, with the
injection of light hydrocarbon and water/steam into reactor 24 without any injection
into premix section 50. Thus, in this embodiment, no material is mixed with the HCO
in the premix section (the premix section 50 is thus not required, although shown),
although the HCO may contain water and/or LHC as the result of the steam assisted
gravity drainage (SAGD) process in widespread use in Alberta for extracting and producing
HCO from oil sands deposits, which HCO may be upgraded by embodiments of the present
invention. Rather, water or steam are injected at one or more points in the reactor
section 24 prior to the T
85 or T
65 points as discussed hereinabove. In this embodiment, it is also noted that at the
point of injection the temperatures of the water or steam supplied by loop 58 may
be equal to or less than about 80% to 90% of the predetermined maximum temperature
in the reactor section T(max) 1. In another embodiment, the temperature of the water
injected into the reactor section may have temperatures greater than T(max)1 but less
than about 350 °C. System 620' of Fig. 6B is substantially similar to system 620,
but with the additional injection of water/steam and hydrocarbon via loops 58 and
64, respectively, into premix section 50.
[0027] It is noted that in any of the embodiments shown and described herein, the contacting
of water/steam and/or hydrocarbon with the HCO may be facilitated by a variety of
conventional means including but not limited to mechanical stirring, inline mixing,
static mixing, a mixing eductor, a radial (vortex) premixer, and/or a pump that continuously
drives the reaction mixture 22 from the premix section 50 into the reactor section
24. Moreover, the examples shown and described herein are not intended to be limiting,
with other combinations of injecting water/steam and hydrocarbons into the premix
and reactor sections being included within the scope of the present invention.
[0028] Still further, in various embodiments described herein, the amount of water/steam
and hydrocarbon supplied to the HCO in process stream 22 is configured to provide
a final ratio of HCO to water (HCO:water) ranges from about 1:1 and 20:1, while the
ratio of native HCO to LHC not native to the HCO (HCO:LHC) ranges from about 1:2 and
20:1. It is noted that the non-native LHC may be present in the HCO stream flowing
into the premix section 50 or may be that which is introduced in either the premix
section 50 or the reactor section 24.
[0029] The selection of the particular final value for HCO:water may be based on the balancing
of two opposing factors. Higher relative concentrations of water may be beneficial
in that they foster improved heat transfer from the walls of tube in the reactor section
24, suppress coke formation by quenching or preventing reactions between HCO components,
and improve the kinetics of upgrading reactions involving water. Some disadvantages
of relatively high water concentrations relate to the fact that displacement of HCO
by water reduces the effective throughput of HCO while increasing operating costs
due to the need to invest thermal energy to heat not only HCO but also water. Given
that the heat capacity of the latter is approximately twice that of HCO and other
hydrocarbons, each incremental increase in the water content of the reaction mixture
requires proportionately more thermal energy to heat the reaction mixture to T(max)
1. Because, in comparison with water, added light hydrocarbon is thought to be particularly
effective for promoting the disaggregation reaction while suppressing the formation
of coke, particular embodiments of the present invention, as discussed hereinabove,
involve the initial contacting of the HCO by light hydrocarbon in the premix section
50 and the injection at one or more points later in the process (e.g., in the reactor
section 24) of a minimum amount of water required to effect the desired level of upgrading
without formation of unacceptable levels of coke. It will be understood that examples
given hereinabove, which depict the contacting of HCO in the premix section and/or
the reaction mixture in the reactor section by LHC recovered directly from the product
mixture by the LHC removal device 62, are nonlimiting. In other embodiments, LHC may
be used for such purpose which come from sources other than or in addition to the
optional device 62.
[0030] Referring now to Fig. 7, in a nonlimiting example, the reactor section 24 is a conventional
shell-and-tube heat exchanger in which the reaction mixture 22 flowing through a central
tube is heated by a heating fluid 70 flowing in the direction opposite that of the
reaction mixture 22. The heating fluid 70 flowing into the shell has a temperature
sufficient to ensure that the temperature of the reaction mixture 22 at the outlet
30 of the reactor section 24 is at about the predetermined maximum temperature T(max)1.
The flow rate and temperature of the heating fluid are adjusted to create a continuously-varying
temperature profile along the length of the reactor section 24 as shown and described
hereinabove with respect to the graphical components of the Figures. The temperatures
of the reaction mixture 22 and the heating fluid 70 are shown graphically as a function
of the reaction coordinate 26. The graphical component of Fig. 7 also indicates that
the occurrence of the disaggregation reactions predominates at the inlet/low temperature
end 28 of the reaction section 24, while the upgrading reactions predominate at the
outlet/high temperature end 30 of the reaction section 24.
[0031] As also mentioned hereinabove, although reactor section 24 may take the form of a
single-tube heat exchanger, the skilled artisan will recognize that reactor section
24 may alternatively include a heat exchanger having a plurality of parallel tubes
within the shell, wherein the inlets of all the tubes are communicably coupled by
a common inlet chamber and the outlets are communicably coupled by a common outlet
chamber, such as shown in Fig. 11.
[0032] Turning now to Fig. 8, an alternate reactor section shown at 24' may take the form
of a series of shell-and-tube subsections 72, where T(hf)
i is the temperature of the heating fluid 70 at the inlet to each subsection. Reactor
section 24 is otherwise substantially similar to reactor section 24, such as described
with respect to Fig. 7.
[0033] Referring to Fig. 9, an optional reactor section 24" is substantially similar to
reactor section 24', but with the interposition of thermal-soak chambers 74 disposed
serially between the subsections 72. As shown graphically, the thermal-soak chambers
74 are configured as insulated, unheated flow-through chambers that effectively lengthen
the residence time of the reaction mixture 22 at various temperatures as the mixture
22 flows through the reactor section 24". As shown graphically, the thermal-soak chambers
74 effectively provide a substantially step-wise increase in temperature as a function
of the R.C. 26, e.g., along the length of the reactor section 24". The particular
temperatures and the resulting residence time at those temperatures may be selected
to facilitate kinetics related to the disaggregation and upgrading reactions. Moreover,
although in particular embodiments the thermal-soak chambers 74 will be unheated,
it should be recognized that in particular applications, it may be appropriate to
apply some amount of heat to the thermal-soak chambers, such as may be desired to
maintain the reaction mixture flowing therethrough at an approximately uniform temperature.
[0034] As discussed above, the graphical component indicates that the occurrence of the
disaggregation reactions predominates at the inlet/low temperature end 28 of the reaction
section 24", while the upgrading reactions predominate at the outlet/high temperature
end 30 of the reaction section 24". It should be recognized that any number of the
reactor subsections 72 of Figs. 8 and 9 may be used, depending on the particular application.
It should also be recognized that in various embodiments, pressure within the various
components of reactors 24, 24', 24", is maintained at levels sufficient to prevent
the formation of a phase separate from the liquid phase of reaction mixture 22, as
discussed hereinabove.
[0035] Turning now to Fig. 10, any of the aforementioned reactor portions 24, 24', 24" may
be further modified to include a supplemental reactor section 80 serially disposed
at outlet 30 thereof. It is noted that supplemental reactor section 80 may be substantially
similar to reactor section 24, 24', 24" and/or one or more reactor subsections 72.
As shown, reactor section 24, 24', 24" effectively brings the reaction mixture 22
to T(max)1 as described hereinabove, while the supplemental reactor section 80 is
configured so that the reaction mixture flowing therethrough achieves a predetermined
maximum temperature T(max)2 . In particular embodiments, T(max)2 is within a range
of approximately 1.0 to 1.1 times T(max)1, and in other embodiments, is within a range
of approximately 1.1 to 1.4 times T(max) 1, as will be discussed in greater detail
hereinbelow. Examples of reactor sections 24, 24', 24" and energy recovery sections
52 which include multiple parallel process flow paths as discussed hereinabove, disposed
in series, are shown in Fig. 11.
[0036] In the foregoing embodiments employing serial heat exchangers, the temperature and
rate of heating fluid flow through each shell may be individually controlled to control
the temperature and rate of heat applied to the reactions mixture 22. Moreover, as
also discussed hereinabove, the reaction mixture is maintained at pressure sufficient
to maintain the reaction mixture as a single phase throughout the reactor section.
Doing so is important from the viewpoint of process energetics because in general,
liquid-to-gas phase changes consume significant energy as a function of the heat of
vaporization, ΔH
vap. The importance of this issue is particularly acute given that ΔH
vap for water may be 5-9 times higher than for many lower molecular weight hydrocarbons.
Therefore, in a particular embodiment of the present invention, the reactor section
is operated at pressures in excess of those required to maintain the reaction mixture
in liquid phase when the reaction mixture experiences the maximum temperature in the
reactor section. Higher pressures may also enhance the kinetics of the disaggregation
reaction, the upgrading reaction, or both. Yet, any such benefit may be offset by
higher equipment costs and operating costs, which include equipment maintenance. Therefore,
in a particular embodiment of the present invention the reactor section is maintained
at an operating pressure that is approximately 5% to 10% in excess of that required
to maintain the reaction mixture as a liquid phase. That pressure varies as a function
of the predetermined maximum temperature in the reactor section; the amount and chemical
composition of LHC in the reaction mixture, whether they are native to the HCO, added
to enhance disaggregation reactions, or generated through upgrading reactions; and
the amount of water in the reaction mixture. Various embodiments use pressures within
a range of from about 1500 to about 3000 psia (10.34 to 20.68 MPa). Under some conditions
of temperature and reaction mixture composition, the required operating pressure may
be approximately 2000 psia (13.79 MPa), while under other conditions the required
pressure may be from about 1500 psia to about 2000 psia (10.34 to 13.79 MPa), while
under yet other conditions the required pressure may be from about 2000 psi to approximately
3000 psia (13.79 to 20.68 MPa).
[0037] In various embodiments of the present invention, the predetermined maximum temperature
at the outlet from the reactor section is kept as low as possible in consideration
of energy costs, the aforementioned costs associated with building and maintaining
processing equipment, and of the desire to minimize coke formation. However, doing
so works at cross-purposes to the promotion of the disaggregation and upgrading reactions,
which are enhanced as a function of increasing temperature. Consequently, another
processing variable that plays a role in chemical kinetics must be exploited, namely,
time.
[0038] The shell-and-tube configuration of the reactor section provides two important benefits,
one stated and one implied. The former relates to the possibility for creating a deliberately
non-isothermal temperature regime to preferentially promote disaggregation before
applying maximum thermal energy to achieve predetermined maximum temperatures and
drive upgrading reactions involving water. The implied benefit is the well-known enhancement
of heat transfer by means of the high ratio of surface area to volume (surface:volume)
available in tubular reactors. Yet, the latter benefit is achieved at the price of
pressure drop between the inlet and outlet as a function of increasing tube length
and decreasing tube cross-sectional dimension, both of which increase surface:volume.
Therefore, the idea of increasing the total time spent by the reaction mixture in
the reactor section by increasing the tubing length seems dubious. And though the
problem may be mitigated by a variety of means, it ultimately is bounded by the interplay
between three variables: the number and lengths of the tubes inside of a shell-and-tube
system; the viscosity of the mixture flowing through them; and flow rate. The possibilities
for reducing viscosity by increasing temperature or decreasing the amount of HCO relative
to added light hydrocarbon or water are limited, as these measures tend to work in
opposition to other considerations related to upgrading optimization. Similarly, reducing
the flow rate serves primarily to reduce the throughput of HCO.
[0039] The present inventor's solution to the problem resides in an approach that reduces
pressure drop by effectively increasing the diameters of tubes in the reactor section,
which at first seems counterintuitive and even contrary to a key benefit noted for
tubular reactors, namely, that they offer a high ratio of surface area to volume.
However, in particular embodiments of the present invention, one or more flow-through
chambers (thermal soak chambers) 74, that are only insulated and not heated will be
interposed between individual reactor subsections, where the volume of the flow-through
chambers 74 is equal to about the desired increase in residence time multiplied by
the flow rate through the reactor section. For example, a single such chamber 74 of
volume V
C located in the reactor section before the T
85 point could increase by an average of one minute the time for the disaggregation
reaction if V
C = 1 minute x F
RM, where F
RM = the flow rate of the reaction mixture through the reactor section in units of volume/minute.
(This does not take into account, of course, the consequence of flow-based mixing
that might occur in the flow-through chamber.) Similarly, in another particular embodiment
of the invention, the reactor section 24, 24', 24" is extended by the location of
an insulated, unheated flow-through chamber 74 of volume V
C = m x F
RM at the outlet of the last shell-and-tube subsection in the reactor section where
the reaction mixture is heated to about the predetermined maximum temperature T(max)1,
resulting in the increase by m minutes the time available for upgrading reactions,
where F
RM is the flow rate of the reaction mixture in units of volume/minute. In yet another
particular embodiment, the throughput of the upgrading system may be increased without
significantly increasing the pressure drop across the reactor section by increasing
the size of the flow-through chamber 74 installed at the outlet from the last shell-and-tube
subsection, the size and number of flow-through chambers 74 interposed between the
inlet and outlet, and the number of tubes contained in the shell-and-tube subsections
72. More than one shell-and-tube subsection 72 may be installed between the chambers
74.
[0040] Though not wishing to be bound by any particular theoretical reasoning, upgrading
reactions in the reactor section of the instant invention are thought to be of two
general types discussed briefly hereinabove. In the heterolytic scission of the covalent
bond between two atoms, the electron pair is divided asymmetrically whereas homolytic
scission results in the bonding electron pair being divided equally between the two
bonded atoms. For convenience, the heterolytic and homolytic reactions of HCO components
are discussed herein will be referred to hereinafter as upgrading reactions Type I
and Type II, respectively. In the absence of catalysts, homolytic reactions may be
promoted at elevated temperatures, an important example being the production of ethylene
through the gas-phase cracking of naphtha at temperatures of about 850 °C. Being highly
endothermic (ΔH° has a high positive value), the entropy term of the Gibbs Free Energy
equation ΔG° = ΔH° - TΔS° prevails under such conditions. By contrast, heterolytic
reactions may be promoted by catalysts that facilitate reactions by lowering the activation
energy, which is generally desirable as this allows reactions to occur at lower temperatures
than would be possible without a catalyst. An example is fluidized catalytic cracking
(FCC) in refineries where FCC units play a vitally important role by increasing the
yields of gasoline obtained from crude oil through the cracking of heavier hydrocarbons
to form lighter ones. FCC catalysts are fine powders that function as a substrate
onto which hydrocarbons adsorb in order for catalysis to occur. Other catalysts may
be molecules that promote reactions by participating in them, in some cases being
chemically integrated into reaction intermediates, but always being regenerated. The
ability of water to function in this way is well known, and in a particular embodiment
of the present invention, the reaction mixture in the reactor section is heated to
a final predetermined temperature T(max)1 of about 260 °C to about 325 °C (or about
260 °C to about 400 °C in some embodiments) such that the upgrading rates due to water-catalyzed
Type I reactions are thought to become significant when the reaction mixture reaches
a temperature of about 80% to about 90% of T(max)1, where significant levels of homolytic
cracking do not occur.
[0041] Though not wishing to be bound by any particular theory of operation, in particular
embodiments of the invention the reaction mixture flows through a primary reactor
section 24, 24', 24" and is heated to the predetermined maximum temperature T(max)1
where water-catalyzed Type I reactions are thought to occur without Type II reactions
occurring at an appreciable rate, and then flows into a supplemental reactor section
80 (Fig. 10) appended to the primary reactor section where heating of the reaction
mixture continues to a second predetermined maximum temperature of T(max)2. In this
particular embodiment, the flow rate of, and the thermal flux into the reaction mixture
are controlled to minimize or prevent coke formation in the reaction mixture as it
is heated progressively while flowing through both the primary and the supplemental
reactor sections.
[0042] In a particular embodiment, the predetermined maximum temperature T(max)2 of the
supplemental reactor section 80 is between about 1.0 and 1.1 times T(max)1, the principal
purpose of the supplemental reactor section being in this case to further drive Type
I reactions to an extent beyond that which might have been achieved in the primary
reactor section without appreciably fostering Type II reactions. In yet another embodiment,
the supplemental reactor section raises the reaction mixture to a predetermined maximum
temperature T(max)2 of between about 1.1 and 1.4 times T(max)1 to promote further
upgrading by means of Type II reactions in addition to Type I reactions. Though not
wishing to be limited by any particular theoretical reasoning, it is suspected that
the benefit of such a strategy is that promoting first the Type I upgrading reactions
in the primary reactor section reduces the average molecular weight of components
in the reaction mixture to produce lighter compounds, which in turn serve to promote
further disaggregation and even the dissolution of heavy components, minimizing the
potential for coke formation or the retrograde formation of asphaltenes and other
heavy components when subjected to thermal conditions conducive to Type II upgrading
reactions in the supplemental reactor section.
[0043] In particular embodiments as discussed hereinabove, the recovery section 38 reduces
the temperature of the product mixture to between about 60 °C and 200 °C. The reduction
in temperature results in a corresponding reduction in the vapor pressure of the product
mixture and an increase in viscosity. Moreover, the product mixture 34 (Fig. 3) may
flow under pressure through water separator 40, which may take the form of one or
more liquid-liquid separators for the purpose of removing water. As discussed, recovered
water can then be recycled in the process at 58 or used elsewhere, for example, it
may be combined with water that is converted to steam for downhole injection in the
context of the SAGD process for extracting HCO form oil sands. And as also discussed,
in various embodiments, the product mixture from which water has been substantially
removed flows into flash drum 62, having had its temperature reduced to a level appropriate
to remove desired quantities of LHC at 64, e.g., by flash distillation of vapors,
which LHC are referred to as condensate. The flash drum 62 may be appropriately configured
to recover other volatile components in the product mixture that are lighter than
condensate, which may include methane ethane, propane, hydrogen sulfide, CO
2, COS, CS
2, SO
x, and possibly nitrogenous compounds. In various embodiments as discussed above, the
recovered condensate is used to facilitate the disaggregation reaction by contacting
with HCO in the premix section 50 or injection into the reactor section 24, 24', 24".
[0044] Scalability is another among the many aspects of the present invention that have
already been identified, and which are believed to be novel, non-obvious and beneficial.
In particular, embodiments of the invention may be scaled without substantially changing
the basic design to permit the construction of upgrading systems with capacities ranging
from < 1barrel per day (bpd) to >10,000 bpd (<0.15 to >1500 m
3/d). This feature means that the present invention combines the best features of the
two upgrading methodologies that enjoy broad use in Canada today. First, like the
large, expensive technology used to produce synthetic crude oil, it offers the possibility
to upgrade HCO to meet pipeline specifications without relying on dilution. Second,
like diluent-based upgrading, the system and method described herein is suitable for
distributed implementation on a smaller scale at or near wellheads and remote production
fields.
[0045] Another aspect of the present invention is that particular embodiments maximize energy
efficiency and ecofriendliness. For example, the recovery section 38 captures and
recycles thermal energy and also water for reuse in the system and method described
herein for upgrading HCO. Particularly beneficial is the ability to substantially
minimize the thermal energy required to heat the reaction mixture to T(max)1, or to
T(max)2, by substantially maximizing the ratio HCO:water. When the reaction mixture
comprises only HCO and water, relatively large amounts of the latter are required
because, apart from being involved in upgrading reactions, it is thought to be important
for facilitating the dissociation and dispersal of HCO components in a water-dominated
matrix. This latter function would not merely expose individual molecules such as
asphaltenes to the upgrading reactions, but also suppress counterproductive retrograde
or intramolecular reactions that could lead to the formation of undesirable products
such as coke. By this strategy, the required amount of water relative to HCO is much
greater than the minimum required only for actual upgrading reactions, and an energy
penalty attaches to it because the heat capacity of water is approximately twice that
of HCO. Embodiments of the instant invention address this dilemma by the mixing of
HCO in the premix 50 and/or reactor 24, 24', 24" sections with LHC, e.g. those optionally
recovered from the product mixture and recycled to the front end of the process, which
are thought to facilitate disaggregation reactions without themselves being subject
to appreciable additional chemical transformation in the reactor section. Subsequently,
only the amount of water required to foster water-based upgrading reactions is added
to the reaction mixture flowing through the reactor section. Not only does this approach
help minimize energy requirements, but it offers the possibility to improve the kinetics
of the disaggregation reaction because the LHC are presumably more effective than
water in that regard.
[0046] Additional aspects of the invention concern the specific, deliberate design of the
reactor section(s) to effect the gradual heating of the reaction mixture for the explicit
purpose of a) avoiding levels of thermal flux into reaction mixture from the inside
walls of the reactor to minimize or prevent coking; b) promoting disaggregation reactions
by means of optionally contacting of HCO with LHC in the premix section and/or the
reactor section; c) promoting disaggregation reactions prior to the reaction mixture
reaching a temperature slightly below (e.g., between about 80% and about 90% of) the
predetermined maximum temperature T(max)1; d) promoting upgrading reactions in a reactor
section at temperatures between that point (e.g., about 80% to 90% of T(max)1) and
about T(max)1 where Type I upgrading reactions are thought to occur; e) avoiding subjecting
the HCO to localized heating at the point of injection of and contacting by water
that has been heated to supercritical or near-supercritical temperatures when the
HCO has not already undergone disaggregation, under which conditions the localized
rate of heating exceeds the rate of disaggregation and instead promotes the formation
of coke due to intermolecular reactions between HCO components and/or localized high
rates of cracking, ostensibly by homolytic mechanisms; and f) optionally promoting
further upgrading reactions in the reaction mixture flowing through a supplemental
reaction section whose predetermined maximum temperature T(max)2 is between (i) 1.0
and 1.1 times T(max)1 where Type I reactions are thought to predominate, or (ii) 1.1
to 1.4 times T(max) 1 where Type II upgrading reactions are thought to occur at the
point in the supplemental reactor when the reaction mixture reaches a temperature
greater than about 1.1 times T(max)1. It should be noted the various means described
by which the invention minimizes the formation of coke effectively increase the yield
of upgrading because coking converts HCO components into a low-value byproduct that
has little value other than as fuel.
[0047] Heretofore the underlying concept of the instant invention has been to introduce
the HCO feed to an upgrading process that is more or less linear: the feed flows continuously
into a reactor or a series of reactor subsections after optionally flowing through
a premix section; a reaction mixture is generated by contacting the HCO with LHC and/or
water/steam at one or a plurality of points in the premix and/or reactor sections;
the mixture is progressively heated in the reactor or plurality of reactor subsections
to a predetermined maximum temperature T(max)1; it optionally flows through a supplemental
reactor section where it is heated progressively to a second predetermined maximum
temperature T(max)2; and the product mixture flowing therefrom is processed through
a recovery section designed to remove water from the upgraded HCO product, recover
thermal energy, and optionally recover LHC to be recycled to one or more upstream
points for contacting with the HCO to aid in disaggregation believed to be an important
for predisposing HCO to upgrading reactions with water. (The foregoing summary is
provided by way of illustration, is not intended to describe all possible embodiments,
and therefore is not limiting.) However, in other embodiments of the invention, one
or more additional elements may be added into the process flowpath to create one or
more branch points in the flowpath. These embodiments, which will now be described
in greater detail, are intended to increase yet further the selectivity, efficiency,
and effectiveness of the upgrading process. This in turn tends to increase control
over the range and quality of products that can be obtained from the process, thereby
opening up distinctive, new possibilities to enhance the economics of producing HCO
by the SAGD process and upgrading it for transport to market.
[0048] Referring to Figure 12, the reaction mixture flows through the reactor section 24,
24', 24" such as shown and described hereinabove, including one or more subsections
and optional thermal soak chambers interposed in the flow path. The product mixture
then flows from the outlet 30 of the primary reactor section 24, etc., into a flash
distillation column 90, also designated FDC1, wherein the product mixture is separated
into two product fractions differentiated on the basis of the boiling point ranges
for their respective components, which for simplicity will be referred to as light
and heavy fractions 92 and 94, respectively. The light fraction 92 includes water
and light hydrocarbons (LHC), the latter being designated LHC1 and having boiling
points at atmospheric pressure below a predetermined maximum value of BP(LHC1), which
in one embodiment is below about 280 °C, while in yet another particular embodiment
BP(LHC1) may be below about 220 °C, and in yet another particular embodiment, it may
be less than about 160 °C. The heavy fraction 94, which may be referred to as the
predominantly heavy hydrocarbon (HHC) product stream, the HHC residue, or simply HHC1,
includes components in the product mixture 34 whose boiling points are higher than
BP(LHC1). Components in light fraction 92 from FDC1 90 are cooled in a condenser (not
shown) to yield liquid mixture that is separated into an aqueous phase and a hydrocarbon
phase. By contrast, the HHC1 94, flows without having been cooled from the bottom
of the distillation column 90 into an optional premix section 50' configured in the
flow path between FDC1 90 and a supplemental reactor section 80 such as shown and
described hereinabove.
[0049] Not wishing to be bound by any particular theory of operation, it is believed that
LHC in the light fraction 92 includes compounds generated through upgrading reactions
in the primary reactor 24, etc., in addition to LHC compounds that may be native to
the HCO and any that may have been added in the premix 50, 50' and/or reactor 24,
24', 24" sections to promote disaggregation reactions. Additionally, it is believed
that the HHC1 94 flowing from FDC1 90 includes compounds that either have undergone
varying degrees of upgrading upstream from FDC1 90 but which on the whole may be susceptible
to further upgrading. As such, they are the appropriate object of further upgrading
in the supplemental reactor section 80. Due to their higher molecular weight (MW)
compared with LHCs, the viscosity of HHC1 94 will vary directly as a function of LHCs
removed by FDC1 90. Therefore, the operation of FDC1 90 should be optimized to ensure
facile flow of HHC1 94 in a downstream manner from FDC1 90 and prevent HHCs from becoming
so concentrated and highly associated as to reduce their proclivity to undergo further
upgrading reactions in the supplemental reactor section 80.
[0050] Turning again to Figure 12, HHC1 94 flowing downstream through premixer 50' to the
supplemental reactor section 80 is heated progressively in a particular embodiment
to a predetermined maximum temperature T(max)2 before reaching the outlet of the same,
which temperature is between about 1.0 and 1.1 times T(max)1, the predetermined maximum
temperature to which the reaction mixture is heated in the primary reactor section.
Though not wishing to be bound by a particular theory of operation, in this embodiment
the principal objective is to further drive Type I reactions, described previously
in this specification, to an extent beyond that which might have been achieved in
the primary reactor section, yet without fostering appreciable upgrading by means
of Type II reactions in addition to Type I reactions. Given that much or most of the
water present in the product mixture flowing into FDC1 90 is removed in the light
fraction 92, HHC1 94 may be contacted with water or steam (such as recycled from light
fraction 92) at one point or a plurality of points downstream of FDC1 94, e.g. in
the supplemental reactor section 80 and/or the optional premix section 50' as shown.
[0051] In another particular embodiment, the supplemental reactor section progressively
raises the reaction mixture to a predetermined maximum temperature T(max)2 of between
about 1.1 and 1.4 times T(max)1 where Type II reactions are believed to occur. Given
that such reactions are thought to be thermolytic instead of involving Type I hydrolytic
mechanisms, the contacting of the HHC1 by water and/or steam in the premix section
50' and/or the supplemental reactor section 80 is optional. Nevertheless, said contacting
may offer benefits aside from the possibility to promote further upgrading by Type
I mechanisms. First, given that the thermal conductivity of water may be about 3-4
times higher than that of hydrocarbons including bitumen, the presence of just 5%
to 10% water in the reaction mixture may increase the efficiency of thermal energy
transfer from the walls of the shell-and-tube reactor to the HHC residue flowing therethrough,
which is believed to minimize or prevent coke formation that would otherwise occur,
for example at the walls of the shell-and-tube reactor. Additionally, not being bound
by a particular theory of operation, the addition of water in controlled amounts may
serve helpfully to prevent HHC components from becoming so concentrated and highly
associated as to reduce their proclivity to undergo further upgrading reactions in
the supplemental reactor section 80. However, as has been explained in detail elsewhere,
the heat capacity of water is approximately twice that of hydrocarbons. Thus, in a
particular embodiment of the present invention, the economics of HHC residue upgrading
in the supplemental reactor section may be optimized by taking into consideration
the quality and quantity of HHC residue fed thereinto; the quality and quantity of
the upgraded hydrocarbon product flowing therefrom; and the amount of thermal energy
applied, where the latter depends on 1) controlling the amount of LHC removed in FDC1
90 and the amount of water or steam mixed with the HHC residue flowing through the
supplemental reactor section 80; and 2) the predetermined temperature T(max)2 to which
the reaction mixture is heated.
[0052] Compared with the approach described earlier in this specification, at least four
benefits may accrue through the removal of LHC from the reaction mixture flowing into
FDC1 90 from the primary reactor section 24, 24', 24". First, it results in a reduction
of the quantity of material that must be heated to a temperature of T(max)2. In the
particular case where T(max)2 equals about 1.1 to 1.4 times T(max)1, this reduction
results in a corresponding reduction in thermal energy that must be invested to heat
the HHC residue 94 compared with the case where no FDC1 90 is used to reduce LHC.
Second, corresponding to this reduction in material mass is a reduction in material
volume, which reduces the hydraulic capacity, or throughput, required of the supplemental
reactor section 80. This reduces not only the energy input required, but the size
and cost of the capital equipment associated with the supplemental reactor section.
Third, regardless of the value of T(max)2, removal by FDC1 90 of LHC in the product
mixture 34 avoids subjecting components in the same to higher-severity conditions,
which may cause them to undergo further reactions to yield undesirable, lower-molecular-weight
products. Finally, by way of corollary with the preceding benefit, removal of LHC
from the product mixture 34 provides the possibility to improve selectivity of the
upgrading process toward those components that do not initially yield readily to upgrading
under lower-severity conditions.
[0053] In a particular embodiment, the product mixture 34' exiting the outlet of the supplemental
reactor section 80 may flow into a recovery section 38, 52, etc., such as described
hereinabove with respect to Figs. 1-6B and 11. Turning once again to Figure 12, in
another particular embodiment the product mixture flows optionally into a second flash
distillation column 96, also designated as FDC2. As with FDC1, FDC2 obtains two fractions
from the product mixture flowing thereinto from the supplemental reactor section:
a light fraction 98 including water and light hydrocarbons, the latter being designated
LHC2; and a heavy fraction 100, designated HHC2. As in the case of FDC1, these two
fractions are differentiated from each other on the basis of the boiling point of
the light fraction, in this case being designated BP(LHC2), which in one embodiment
is below about 280 °C, while in yet another particular embodiment BP(LHC2) may be
below about 220 °C, and in yet another particular embodiment, it may be less than
about 160 °C. LHC1 and LHC2 may be combined to obtain a single LHC product stream
(not shown).
[0054] Referring again to Figure 12, in a particular embodiment a portion of HHC2 100 may
be optionally recycled, e.g., at 102, to an upstream point in the supplemental reactor
section, e.g. to the premix section 50', where it is combined with HHC1 94. And in
yet another embodiment, a portion of the light hydrocarbons from 92 and/or 98, may
in particular embodiments be optionally recycled and mixed with HCO feed 22 at points
in the primary reactor section 24, 24', 24" before the reaction mixture reaches a
temperature of about 60% to 70% of T(max)1, and/or in the premix section 50. Though
thought to be desirable to minimize the amount of LHC that is subjected to higher-severity
upgrading conditions, the mixing of limited amounts of LHC with HHC1 in the premix
section 50 may beneficially permit reduction in the amount of water required to ensure
that heavy components in the reaction mixture flowing through the supplemental reactor
section 80 are sufficiently disaggregated, the benefit including a corresponding reduction
in the energy required to heat the reaction mixture to T(max)2. Though not wishing
to be bound by a particular theory of operation, it is believed that components in
HHC2 100 may undergo further upgrading if again subjected to the upgrading conditions
in the supplemental reactor section 80 by recycling at 102. As in the case of HHC1
94, this approach enables the additional, selective upgrading of heavy components
while minimizing or avoiding the subjecting of lighter components 98, removed in FDC2
96, to higher-severity conditions in the supplemental reactor section. This helps
to minimize the risk of undesirable decomposition of LHCs that might reduce overall
upgrading yield and provides the means to promote further upgrading without increasing
the predetermined maximum temperature T(max)2 in the supplemental reactor section.
[0055] Referring now to Figure 13, in another particular embodiment, product mixture outputs
from the primary reactor subsection 24, 24', 24" and supplemental reactor subsection
80 feed into a single flash distillation column 96, while a portion of the HHC residue
100' is recycled at 102 to serves as a feed to the supplemental reactor section 80,
e.g., via premix 50' as shown. By way of example, suppose that the flash distillation
column 96 is operated in such a way that the HHC residue includes components whose
boiling points are greater than about 280 °C, and that the LHC 98' and HHC residue
100' each represents about 50% of the combined product mixture flowing into the flash
distillation column 96. In a particular embodiment the supplemental reactor has the
capacity to process up to about 80% of the HHC residue, and therefore would have a
throughput of about 40% that of the primary reactor section. Again, the benefit of
this processing scheme is that it provides the possibility to optimize the economics
of upgrading through the control of multiple process variables, including but not
limited to the maximum predetermined temperatures T(max)1 and T(max)2; the operation
of the flash distillation column to determine the maximum boiling point of components
in the LHC fraction, BP(LHC); and the residue recycle rate (the fraction of the residue
that is processed through the supplemental reactor section). Other variables, discussed
elsewhere, include flow rate, the amounts of LHC and water or steam in the reaction
mixture flowing through the primary reactor section (or subsections); and the size
and number of thermal soak chambers, which in combination with flow rate determine
the length of time that reaction mixtures in the primary or supplemental reactor sections
experience the predetermined maximum temperatures T(max) 1 and T(max)2, respectively.
[0056] Turning now to Figure 14, the reaction mixture proceeds in a linear sequence from
the premix section 50 and then through the primary reactor section 24, 24', 24", the
optional supplemental reactor section 80, including optional thermal soak chambers
74. Finally, the product mixture flows into a flash distillation column 96, which,
as in the cases of FDC1 and FDC2 described previously, yields LHC 98' and HHC residue
100' products streams whose components are differentiated on the basis of boiling
point. In a particular embodiment a portion of the HHC residue 100' from the flash
distillation column is recycled at 102' to the premix section 50 disposed upstream
from the primary reactor section where it combines with HCO feed 22 and with LHC (e.g.,
recycled from 98') and/or water. In another particular embodiment depicted in Figure
15, the residue recycle 102 instead flows into an optional premix section 51' disposed
between the primary reactor section 24, 24', 24" and supplemental reactor section
80 where it combines with the reaction mixture flowing from the primary reactor section,
and optionally with LHC and/or water supplied to premix section 50. In contrast with
embodiments depicted in Figures 12 and 13, the capacity of the supplemental reactor
section 80 corresponding to the embodiment shown in Figure 14 is substantially the
same as that of the primary reactor section 24, 24', 24", whereas the capacity of
the supplemental reactor section used in Figure 15 would be larger in order to handle
the recycled residue 100'.
[0057] As discussed above, in the embodiments depicted in Figures 12 - 15, flash distillation
columns yield two fractions: a light fraction including water and light hydrocarbons
(LHCs), and a HHC fraction referred to alternatively as HHC residue or simply as residue,
which includes hydrocarbons that are differentiated from the LHCs on the basis of
boiling point: LHC components have boiling points below about BP(LHC) while HHC components
have boiling points that are higher than about BP(LHC). Though the flash distillation
columns serve to separate LHCs from HHC residue on the basis of boiling point, that
separation is not absolute. Rather, some compounds with boiling points below BP(LHC)
remain in the HHC residue and some with boiling points above BP(LHC) distill with
the LHC. In consideration of process optimization objectives, the value of BP(LHC)
and the extent of overlap between the two curves (Fig. 16) are determined by (i) the
design of the distillation column, including the number of theoretical plates; (ii)
the flow rate of the product mixture into the column; and (iii) the temperature of
the product mixture flowing into the column; and (iv) the operating pressure inside
of the column. Referring to Figure 16, BP(LHC) effectively represents a temperature
range in which compounds contained in both LHC and HHC residue distill, the nominal
value of BP(LHC) corresponding to the intersection 110 of the distillation yield curves
for LHC and HHC residue, shown at 112 and 114, respectively. The process optimization
objectives may consider among other things the yield and quality of LHC desired and
the composition of the HHC residue. Not wishing to be bound by a particular theory
of operation, the flash distillation columns in the embodiments depicted in Figures
12-15 should be controlled so that the quantity of LHC removed is not so great as
to either permit the re-aggregation of higher MW compounds in the HHC residue to such
an extent that they would resist subsequent upgrading, or cause the viscosity of the
HHC residue to become intractably high.
[0058] A person possessing common knowledge regarding the design and operation of distillation
columns will recognize that flash distillation columns provide a high-throughput,
coarse separation between components in a mixture on the basis of their boiling points,
in contrast with distillation columns that provide sharper resolution in regard to
boiling point by dint of having more theoretical plates. However, the repeated reference
in this specification to the use of flash distillation columns is not intended to
limit the optional use of higher-resolution columns to serve a process optimization
goal such as minimizing the range of the boiling point overlap between heavy and light
fractions. Similarly, the portrayal in Figures 12-15 of flash distillation columns
with only two cutpoints for obtaining light and heavy fractions, e.g. water/LHC and
HHC residue, respectively, is not meant to preclude the optional configuration of
a distillation column to have three or more cutpoints to obtain from a product mixture
two or more LHC fractions in addition to the HHC residue. An additional feature of
the process whose importance would be understood by those skilled in the art, and
therefore not detailed in the present specification, is the removal from LHC of any
relatively high-volatility compounds that might accompany LHC and water in the light
fraction obtained by the flash distillation column, which removal may be desirable
to make the LHC suitable for purposes described herein.
[0059] As already has been discussed in some detail with respect to embodiments represented
in Figures 12 and 13, the embodiments depicted in Figures 12-15 afford possibilities
to optimize the upgrading process. Referring now to Figure 17, in a particular embodiment
of the present invention all LHC and HHC residue outputs are combined to produce a
type of synthetic crude whose °API, distillation yield, and other properties resemble
those of conventional crude and make it pipelineable and suitable as a refinery feedstock.
The objective of optimization is to maximize efficiency, a circumscribed view of which,
by this embodiment, considers only the quantity and value of process outputs obtained
from a given quantity and value of inputs that principally include energy and HCO.
In a particular embodiment, the upgrading process is designed and operated at a severity
such that substantially all LHC and HHC residue products obtained from HCO feed of
a given quality are consumed to produce a synthetic crude oil whose properties meet
but do not exceed the minimum values that define pipelineability. Embedded in this
definition of efficiency is the concept of yield, which is understood in terms of
the amount of high-value, pipelineable material produced relative to HCO and thermal
energy input into the process. This efficiency objective may be achieved by a number
of means including but not limited to controlling (i) values for the predetermined
maximum temperatures T(max)1 and T(max)2 to minimize the net energy applied per-barrel
for upgrading and/or (ii) the residue recycle ratio (the fraction of HHC residue exiting
the bottom of a flash distillation column that is directed to a point upstream from
the flash distillation column where it is combined with the reaction mixture) and/or
(iii) the number and size of thermal soak chambers interposed in the flow path.
[0060] The constrained view of efficiency just described may be useful to a point, but it
is also incomplete. Another particular embodiment takes a holistic view of efficiency
that includes all aspects of the constrained view, but also gives consideration to
additional negative-value inputs and outputs, examples of which include coke (also
referred to as petroleum coke, pet coke, or petcoke when derived from petroleum) and
light gases such as methane, ethane, and propane, all of which are generated in significant
quantities by the HCO upgrading processes discussed hereinabove. These by-products
have value as fuel that may be used to generate thermal energy required to drive the
upgrading process. However, greenhouse gas emissions per unit energy produced by petcoke
is similar to that for coal. The additional production of pollutants such as SO
2 and NO
X further exacerbates the problem. Thus, production of coke both reduces the yield
of positive-value upgraded HCO and disproportionately increases the amount of negative-value
emissions.
[0061] Referring now to Figures 18 and 19, in other particular embodiments the unconstrained
definition of HCO upgrading efficiency expands to include production of LHC in excess
of that required to produce pipelineable synthetic crude oil as described above in
relation to Figure 17. In these particular embodiments of the present invention, processes
depicted in Figures 12-15 are designed and operated so as produce said excess quantities
of LHC by, for example, designing and controlling the upgrading process to operate
at higher severity while also minimizing coke formation, the designing and controlling
being accomplished through means including but not limited to (i) increasing values
for the predetermined maximum temperatures T(max)1 and T(max)2 in the primary and
supplemental reactor sections, respectively; and/or (ii) interposing a plurality of
thermal soak chambers in the flow path upstream from flash distillation columns; and/or
(iii) increasing the size of said chambers to increase the residence time that the
reaction mixture experiences upgrading conditions; and/or (iv) increasing the residue
recycle ratio. Excess LHC also may be generated by designing and operating flash distillation
columns so as to increase the amount of LHC recovered from the reaction mixture while
respecting previously discussed cautions against removing too much LHC in flash distillation
columns.
[0062] Referring again to Figure 18, excess LHC obtained by such means is, in a particular
embodiment, blended with HCO that has not been upgraded to produce diluted bitumen
(dilbit), which is another type of upgraded HCO that is pipelineable. This dilbit
production can be performed by means of blending operations that are either proximate
to or distant from the location of the hydrothermal upgrader, the LHC being transported
in the latter case by truck, rail, or pipeline.
[0063] Turning again to Figure 19, all or a portion of the excess LHC may be blended with
any combination of (i) HHC residue generated by an upgrading process such as those
depicted in Figures 12-15, and (ii) HCO that has not been subjected to upgrading.
In a particular embodiment, substantially all of the excess LHC is mixed with all
HHC residue generated by the upgrading process and with an amount of HCO corresponding
to the maximum that can be combined with the other blending components to produce
synthetic crude oil that meets the requirements for pipelineability. In yet another
embodiment, excess LHC not consumed in the production of synthetic crude oil may be
used for dilbit production, whether in proximity to or at a location remote from the
point of LHC production.
[0064] The invention described heretofore with reference to specific exemplary embodiments
for the purposes of illustration and description is not intended to be exhaustive
or to limit the invention to the precise form disclosed. Many modifications and variations
are possible in light of this disclosure. For example embodiments of the present invention
corresponding to depictions in Figures 12-15 may be provided with a recovery section
wherein some portion of the thermal energy invested into the process may be captured
from the product mixture stream or from the LHC/water and HHC residue product streams
and used to facilitate the heating of the reaction mixture upstream from the flash
distillation column, such as shown and described hereinabove with respect to Figs.
1-6B and 11. Similarly, the embodiments of Figures 12-15 may supply water, e.g., which
is separated from LHC after removal from the flash distillation column, to the HHC
residue product stream 94, 100, to remove undesirable water-soluble materials therefrom,
which may include compounds of vanadium and nickel. Also, it should be recognized
that water removed from the LHC downstream of the flash distillation column(s) may
be recovered and fed back to the HCO or the reaction mixture at an upstream point
in the flowpath of the reaction mixture, such as shown and described with respect
to Figs. 2-6B. Moreover, it should be understood that a controller 32 (Fig. 1) may
be used to control operation, including optimizing the blending of HHC residue and
LHC, or of HHC residue, LHC, and HCO, or of LHC and HCO to produce synthetic crude
oil or dilbit that meets the minimum requirements of pipelineability as described
herein. It is intended that the scope of the invention be limited not by this detailed
description, but rather by the claims appended hereto.
[0065] The understanding of process efficiency now has been expanded to encompass upgraded
HCO obtained by means of embodiments depicted in Figures 12-15, through the simple
dilution with excess LHC as depicted in Figures 18 and 19, and by blending with HHC
residue and excess LHC according to Figure 19. Consider now that the SAGD (Steam Assisted
Gravity Drainage) oil recovery process used widely in Alberta is known to be energy
intensive, owing primarily to the generation and downhole injection into oil sands
deposits of large quantities of high pressure steam to produce water-bitumen emulsions
that are recovered by pumping to the surface where water is separated to yield HCO.
Extraction by the SAGD process of bitumen in oil sand deposits involves complex thermodynamic,
physical chemistry, and mass transfer phenomena which others have shown can be advantageously
altered by addition into the steam of hydrocarbon, the core principle being simply
that the bitumen in the oil sands does not mix efficiently with water but does with
added hydrocarbons. The enhancement is the increasing of the yield of recovered HCO
per unit energy invested, one measure being the cumulative steam-to-oil ratio (CSOR),
which is the amount of steam as liquid water that must be generated and injected downhole
to produce a barrel of HCO. Currently in the range of 2:1 to 3:1, a solvent-enhanced
SAGD (SAGD/SE) process has the potential to reduce the CSOR by 25% to 50%, resulting
in a corresponding reduction in energy consumption and greenhouse gas emissions associated
steam generation.
[0066] Generally, hydrocarbons employed to recover HCO by means of SAGD/SE are "imported"
to the wellhead. That is, they are not generated at the wellhead, but instead must
be purchased in the marketplace and transported to the wellhead. Because cost is an
issue, and lower molecular-weight hydrocarbons such as propane or butane generally
are cheaper than equivalent quantities of pentanes, gasoline, or distillates, economics
of SAGD/SE dictate use of the former. A stated advantage of doing so is that HCO produced
by SAGD/SE has °API values that typically are in the range of 13-17, compared with
values that are typically below 10 for the conventional SAGD process. However appealing
those numbers may be, they belie the reality that conventional SAGD/SE is selective
against heavier hydrocarbons that also have value. In effect, SAGD/SE that uses light,
three- and four-carbon solvents actually may have a lower yield than conventional
SAGD, yield being defined in terms of the amount of HCO removed from oil sand deposits
relative to the total available HCO that is resident in those deposits. Though not
wishing to be bound by a particular theory concerning mechanisms by which SAGD/SE
operates, the higher °API values for the HCO obtained by it are consistent with the
fact that compounds in crude oils whose polarity, MW, and aromaticity are high, e.g.
asphaltenes, have relatively low solubility in low-MW alkanes such as n-pentane, much
less propane and butanes, compared with hydrocarbons that have both higher MW and
diverse chemical functionality. Accordingly, SAGD/SE employing low-MW alkanes may
be selective against compounds that otherwise have fuel value and may readily form
emulsions with water to enable their recovery. Of course, the relatively lower level
of heavy components in the HCO recovered by SAGD/SE is an advantage when no convenient,
economical means exists to upgrade those components, such as that afforded by the
present invention. Thus, the purported advantage of conventional SAGD/SE comes at
the expense of reduced overall recovery from oil sands deposits of hydrocarbons contained
therein.
[0067] In a particular embodiment of the present invention, excess LHC produced as described
hereinabove is injected with steam into oil sand deposits. Though not wishing to be
bound by a particular theory of operation, such an LHC-enhanced SAGD process (SAGD/LHC)
is thought to have an important advantage over SAGD/SE that relies on propane, butanes,
or pentanes. The chemical composition LHC is thought to include compounds whose molecular
weights and molecular weight ranges are higher, and which have diverse chemical structures
including but not limited hydrocarbons containing various straight-chain, branched,
and aromatic moieties. As cess LHC generated by means of the ins afford higher yields
than SAGD/SE that relies on aliphatic hydrocarbons with just 3-4 or even 5 carbons.
Of some concern is the possibility for fugitive emissions of light hydrocarbons such
as propane from oil sand deposits where SAGD/SE is being applied, such emissions being
considered greenhouse gases. By contrast, such emissions from SAGD/LHC process are
expected to be substantially lower due to the lower vapor pressure of LHCs.
[0068] Also, the recovery of low MW solvents used for SAGD/SE, which are contained in the
water-HCO mixture extracted from oil sand deposits, is an economic necessity, as doing
so reduces the amount of solvent that must be purchased and transported to the wellhead.
Additionally, pipelineability specifications relating to vapor pressure effectively
limit the quantities of propane and butanes that may be contained in crude oils. Yet,
the recovery and reuse of such solvents relies on equipment for their handling, purification,
and storage, representing an additional capital burden. By contrast, LHC used in SAGD/LHC
and recovered with HCO is compatible with pipelineable crude oil and therefore does
not need to be removed, e.g. when dilbit is produced from HCO. Equally important,
LHC used in SAGD/LHC does not need to be purchased on the open market and transported
to the wellhead, but instead can be produced by means of the instant invention when
installed and operating in relatively close proximity to the wellhead.
[0069] In yet another particular embodiment, excess LHC generated by means of the instant
invention may be transported by truck, rail, or pipeline to a site where SAGD/SE is
being used to extract HCO from oil sand deposits, the purpose being to supplement
the low-MW hydrocarbons conventionally used in SAGD/SE, or to replace the same in
the event that supplies thereof are limited, or if market value of the same, relative
to that of LHC, fluctuates in a manner that warrants such a hybridized strategy. Thus,
this particular embodiment serves to mitigate market-based risks associated with a
one-dimensional SAGD/SE approach.
[0070] In the preceding specification, the invention has been described with reference to
specific exemplary embodiments for the purposes of illustration and description. It
is not intended to be exhaustive or to limit the invention to the precise form disclosed.
Many modifications and variations are possible in light of this disclosure. It is
intended that the scope of the invention be limited not by this detailed description,
but rather by the claims appended hereto.
[0071] It should be further understood that any of the features described with respect to
one of the embodiments described herein may be similarly applied to any of the other
embodiments described herein without departing from the scope of the present invention.
1. A method for upgrading a continuously flowing process stream including heavy crude
oil (HCO), comprising:
conveying the process stream continuously through a fluid flow path in a downstream
direction, the flow path including a reactor;
the reactor receiving the process stream in combination with water, at an inlet temperature
within a range of about 60 °C to about 200 °C;
the reactor including one or more process flow tubes defining an aggregated interior
cross-sectional dimension in a plane extending transversely to the downstream direction
therethrough, the one or more flow tubes having a combined length of at least about
30 times the aggregated interior cross-sectional dimension;
the reactor applying heat to the process stream flowing therethrough, to progressively
heat the process stream from the inlet temperature at an upstream portion of the reactor,
to an outlet temperature T(max)1 within a range of between about 260 °C to about 400
°C at a downstream portion of the reactor;
the reactor maintaining the process stream at a pressure within a range of about 103
to about 207 bar (about 1500 to about 3000 psia), sufficient to ensure that the process
stream remains a single phase at T(max) 1;
selectively adjusting by means of a controller a rate of flow of the process stream
through the reactor to maintain a total residence time of the process stream in the
reactor of greater than about 1 minute and less than about 25 minutes;
wherein said rate of flow, said flow tube lengths, and said application of heat, minimize
or prevent coke formation; and
separating water, light hydrocarbons (LHC) and any other volatile components having
boiling points at atmospheric pressure below a BP(LHC1) value of about 280 °C, by
means of a recovery unit disposed downstream of the reactor in the fluid flow path
and including one or more separators, wherein the process stream retains heavy hydrocarbons
(HHC) components having boiling points higher than BP(LHC1) to form an HHC process
stream.
2. The method of claim 1, wherein the recovery unit comprises a flash distillation column.
3. The method of claim 1, wherein the recovery unit recovers thermal energy and water
from the process stream, to reduce the temperature of the process stream flowing through
the recovery unit to said inlet temperature, and to reduce vapor pressure of the process
stream flowing through the recovery unit.
4. The method of claim 3, wherein the one or more separators comprises a flash drum.
5. The method of claim 3, wherein the one or more separators comprises a fractionation
column for separating LHC into two or more fractions to produce recovered LHC product
streams differentiated on the basis of boiling point range of their components.
6. The method of claim 1, wherein one or more materials are added to the process stream
upstream of the recovery unit, to form a substantially uniform dispersion.
7. The method of claim 6, wherein the one or more materials are added to the process
at one or more points upstream of a point at which the process stream reaches a temperature
within a range of about 80% to about 90% of T(max)1.
8. The method of claim 6, wherein maintaining and supplying the process stream to the
reactor at said inlet temperature, and further adding the one or more materials to
the process stream is realized by means of a premixer disposed in the fluid flow path
upstream of the reactor.
9. The method of claim 6, wherein the one or more materials is selected from a group
consisting of water, steam, hydrocarbons, and combinations thereof.
10. The method of claim 6, wherein water is supplied to the process stream to provide
a ratio of HCO to water (HCO:water) within a range of from about 1:1 to 20:1.
11. The method of claim 6, wherein the ratio between HCO that has not been upgraded and
hydrocarbons added to the process stream (HCO:added hydrocarbons) is within a range
of from about 1:2 to 20:1.
12. The method of claim 6, wherein hydrocarbons are added to the process stream at a location
upstream of a location at which water is added to the process stream.
13. The method of claim 6, wherein the recovery unit is configured to recover LHC from
the process fluid for recycling to the process stream upstream of the recovery unit.
14. The method of claim 1, wherein variables including (i) values for T(max)1 and T(max)2
and/or (ii) a recycle ratio including the percentage of the process stream exiting
the recovery unit that is recycled to the process stream upstream of the recovery
unit; and/or (iii) the total residence time of the process stream in the reactor are
selectively adjusted by means of the controller.
15. The method of claim 1, wherein the outlet temperature T(max)1 is within a range of
between about 260 °C to about 325 °C.
16. The method of claim 1, wherein the reactor is divided into a series of reactor sub-portions
spaced along the flow path.
17. The method of claim 16, wherein HCO in the process stream disaggregates to form a
substantially uniform dispersion at a temperature in a range of about 80% to 90% of
T(max)1 and one or more primary reactor sub-portions heat the process stream to a
predetermined maximum temperature of T(max) 1, and one or more supplemental reactor
sub-portions heat the process stream to a second predetermined maximum temperature
(T(max)2).
18. The method of claim 17, wherein the primary and supplemental reactor sub-portions
feed the process stream in parallel into the recovery unit.
19. The method of claim 17, wherein a portion of the HHC product stream from the recovery
unit is recycled back to the process stream upstream of the supplemental reactor sub-portion.
20. The method of claim 17, wherein another recovery unit is disposed between the primary
reactor sub-portion and the supplemental reactor sub-portion.
21. The method of claim 20, wherein a portion of the HHC product stream from the other
recovery unit is recycled back to the process stream upstream of the supplemental
reactor sub-portion.
22. The method of claim 17, wherein the second predetermined maximum temperature T(max)2
is within a range of about 1.0 to 1.4 times T(max)1.
23. The method of claim 17, wherein one or more unheated flow-through chambers are disposed
within the reactor flow path at the outlet from one or more reactor sub-portions,
said one or more flow-through chambers being insulated, sized and shaped to facilitate
kinetics associated with disaggregation and/or upgrading of HCO in the process stream
flowing thereinto by lengthening residence time spent by the process stream at about
the temperature at said outlet or outlets.
24. The method of claim 23, wherein the one or more flow-through chambers are configured
to be heated so that the temperature of the process stream flowing from the outlet
of each chamber is about the same as at the inlet thereto.
1. Verfahren zur Aufbereitung eines kontinuierlich strömenden Prozessstroms, der schweres
Rohöl (HCO) enthält, umfassend:
Fördern des Prozessstroms kontinuierlich durch einen Fluidströmungsweg in einer stromabwärtigen
Richtung, wobei der Strömungsweg einen Reaktor enthält;
wobei der Reaktor den Prozessstrom in Kombination mit Wasser bei einer Einlasstemperatur
in einem Bereich von etwa 60°C bis etwa 200°C aufnimmt;
wobei der Reaktor ein oder mehrere Prozessströmungsrohre aufweist, die eine aggregierte
innere Querschnittsabmessung in einer Ebene definieren, die sich quer zur stromabwärtigen
Richtung durch sie erstreckt, wobei das eine oder die mehreren Strömungsrohre eine
kombinierte Länge von mindestens etwa dem 30-fachen der aggregierten inneren Querschnittsabmessungen
aufweisen;
wobei der Reaktor Wärme auf den durchströmenden Prozessstrom aufbringt, um den Prozessstrom
schrittweise von der Einlasstemperatur in einem stromaufwärtigen Abschnitt des Reaktors
auf eine Auslasstemperatur T(max)1 in einem Bereich zwischen etwa 260°C bis etwa 400°C
an einem stromabwärtigen Abschnitt des Reaktors zu erwärmen;
wobei der Reaktor den Prozessstrom auf einem Druck in einem Bereich von ungefähr 103
bis ungefähr 207 bar (ungefähr 1500 bis ungefähr 3000 psia) hält, der ausreicht, um
sicherzustellen, dass der Prozessstrom bei T(max)1 eine einzelne Phase bleibt;
selektives Einstellen einer Strömungsgeschwindigkeit des Prozessstroms durch den Reaktor
mittels eines Controllers, um eine Gesamtverweilzeit des Prozessstroms im Reaktor
von mehr als etwa 1 Minute und weniger als etwa 25 Minuten aufrechtzuerhalten;
wobei die Strömungsgeschwindigkeit, die Strömungsrohrlängen und die Wärmeanwendung
Koksbildung minimieren oder verhindern; und
Trennen von Wasser, leichten Kohlenwasserstoffen (LHC) und anderen flüchtigen Bestandteilen
mit Siedepunkten bei Atmosphärendruck unter einem BP(LHC1)-Wert von etwa 280°C mittels
einer Rückgewinnungseinheit, die stromabwärts des Reaktors im Fluidströmungsweg angeordnet
ist und einen oder mehrere Separatoren aufweist, wobei der Prozessstrom schwere Kohlenwasserstoff-(HHC)-Komponenten
mit höheren Siedepunkten als BP(LHC1) hält, um einen HHC-Prozessstrom zu bilden.
2. Verfahren nach Anspruch 1, wobei die Rückgewinnungseinheit eine Flash-Destillationskolonne
aufweist.
3. Verfahren nach Anspruch 1, wobei die Rückgewinnungseinheit Wärmeenergie und Wasser
aus dem Prozessstrom zurückgewinnt, um die Temperatur des durch die Rückgewinnungseinheit
strömenden Prozessstroms auf die Einlasstemperatur zu senken und den Dampfdruck des
durch die Rückgewinnungseinheit strömenden Prozessstroms zu verringern.
4. Verfahren nach Anspruch 3, wobei der eine oder die mehreren Separatoren eine Flash-Trommel
umfassen.
5. Verfahren nach Anspruch 3, wobei der eine oder die mehreren Separatoren eine Fraktionierungskolonne
zum Trennen von LHC in zwei oder mehr Fraktionen umfasst, um zurückgewonnene LHC-Produktströme
zu erzeugen, die auf der Basis des Siedepunktbereichs ihrer Komponenten differenziert
sind.
6. Verfahren nach Anspruch 1, wobei dem Prozessstrom stromaufwärts der Rückgewinnungseinheit
ein oder mehrere Materialien zugesetzt werden, um eine im wesentlichen gleichmäßige
Dispersion zu bilden.
7. Verfahren nach Anspruch 6, wobei das eine oder die mehreren Materialien dem Prozess
an einem oder mehreren Punkten stromaufwärts eines Punkts zugesetzt werden, an dem
der Prozessstrom eine Temperatur in einem Bereich von etwa 80% bis etwa 90% von T(max)1
erreicht.
8. Verfahren nach Anspruch 6, wobei das Aufrechterhalten und Zuführen des Prozessstroms
zum Reaktor bei der Einlasstemperatur und das weitere Hinzufügen des einen oder der
mehreren Materialien zum Prozessstrom mittels eines Vormischers realisiert werden,
der in dem Fluidströmungsweg stromaufwärts des Reaktors angeordnet ist.
9. Verfahren nach Anspruch 6, wobei das eine oder die mehreren Materialien ausgewählt
sind aus einer Gruppe, die aus Wasser, Dampf, Kohlenwasserstoffen und Kombinationen
davon besteht.
10. Verfahren nach Anspruch 6, wobei dem Prozessstrom Wasser zugeführt wird, um ein Verhältnis
von HCO zu Wasser (HCO: Wasser) in einem Bereich von etwa 1: 1 bis 20: 1 bereitzustellen.
11. Verfahren nach Anspruch 6, wobei das Verhältnis zwischen dem HCO, das nicht aufbereitet
ist, und den Kohlenwasserstoffen, die dem Prozessstrom hinzugesetzt sind, (HCO: zugesetzte
Kohlenwasserstoffe) in einem Bereich von etwa 1: 2 bis 20: 1 liegt.
12. Verfahren nach Anspruch 6, wobei dem Prozessstrom Kohlenwasserstoffe an einem Ort
stromaufwärts eines Orts zugesetzt werden, an dem dem Prozessstrom Wasser zugesetzt
wird.
13. Verfahren nach Anspruch 6, wobei die Rückgewinnungseinheit konfiguriert ist, um LHC
aus dem Prozessfluid zur Rückführung in den Prozessstrom stromaufwärts der Rückgewinnungseinheit
zurückzugewinnen.
14. Verfahren nach Anspruch 1, wobei Variablen, die (i) Werte für T(max)1 und T(max)2
und/oder (ii) ein Rückführungsverhältnis enthalten, das den Prozentsatz des Prozessstroms
aufweist, der aus der Rückgewinnungseinheit austritt und der in den Prozessstrom stromaufwärts
der Rückgewinnungseinheit rückgeführt wird; und/oder (iii) die Gesamtverweilzeit des
Prozessstroms im Reaktor mittels des Controllers selektiv eingestellt werden.
15. Verfahren nach Anspruch 1, wobei die Auslasstemperatur T(max)1 in einem Bereich zwischen
etwa 260°C bis etwa 325°C liegt.
16. Verfahren nach Anspruch 1, wobei der Reaktor in eine Reihe von Reaktorunterabschnitten
unterteilt ist, die entlang des Strömungsweges beabstandet sind.
17. Verfahren nach Anspruch 16, wobei HCO in dem Prozessstrom disaggregiert, um eine im
wesentlichen gleichmäßige Dispersion bei einer Temperatur in einem Bereich von etwa
80% bis 90% von T (max)1 zu bilden, und ein oder mehrere primäre Reaktorteilabschnitte
den Prozessstrom auf eine vorbestimmte maximale Temperatur von T(max)1 erwärmen, und
ein oder mehrere zusätzliche Reaktorunterabschnitte den Prozessstrom auf eine zweite
vorbestimmte maximale Temperatur (T(max)2) erwärmen.
18. Verfahren nach Anspruch 17, wobei die primären und zusätzlichen Reaktorteilabschnitte
den Prozessstrom parallel in die Rückgewinnungseinheit einspeisen.
19. Verfahren nach Anspruch 17, wobei ein Abschnitt des HHC-Produktstroms von der Rückgewinnungseinheit
in den Prozessstrom stromaufwärts des zusätzlichen Reaktorunterabschnitts zurückgeführt
wird.
20. Verfahren nach Anspruch 17, wobei eine andere Rückgewinnungseinheit zwischen dem primären
Reaktorteilabschnitt und dem zusätzlichen Reaktorteilabschnitt angeordnet ist.
21. Verfahren nach Anspruch 20, wobei ein Teil des HHC-Produktstroms von der anderen Rückgewinnungseinheit
in den Prozessstrom stromaufwärts des zusätzlichen Reaktorunterabschnitts zurückgeführt
wird.
22. Verfahren nach Anspruch 17, wobei die zweite vorbestimmte maximale Temperatur T(max)2
innerhalb eines Bereichs des etwa 1,0- bis 1,4-fachen T(max)1 liegt.
23. Verfahren nach Anspruch 17, wobei ein oder mehrere unerwärmte Durchflusskammern innerhalb
des Reaktorströmungsweges am Auslass von einem oder mehreren Reaktorunterabschnitten
angeordnet sind, wobei die eine oder mehreren Durchflusskammern isoliert, dimensioniert
und geformt sind, um die Kinetik zu erleichtern, die mit der Disaggregation und/oder
Aufbereitung von HCO im Prozessstrom, der darin strömt, in Verbindung steht, indem
die Verweilzeit verlängert wird, die der Prozessstrom bei der Temperatur an dem Auslass
oder den Auslässen verbringt.
24. Verfahren nach Anspruch 23, wobei die eine oder mehreren Durchflusskammern so konfiguriert
sind, dass sie erwärmt werden, so dass die Temperatur des Prozessstroms, der aus dem
Auslass jeder Kammer strömt, ungefähr gleich ist wie am Einlass dazu.
1. Procédé pour la valorisation d'un courant de processus s'écoulant en continu incluant
du pétrole brut lourd (HCO), comprenant :
acheminer le courant de processus en continu à travers un chemin d'écoulement de fluide
dans une direction en aval, le chemin d'écoulement incluant un réacteur ;
le réacteur recevant le courant de processus en combinaison avec de l'eau, à une température
d'entrée dans une plage d'environ 60 °C à environ 200 °C ;
le réacteur incluant un ou plusieurs tubes d'écoulement de processus définissant une
dimension de section transversale intérieure agrégée dans un plan s'étendant transversalement
à la direction en aval à travers celui-ci, l'un ou plusieurs tubes d'écoulement ayant
une longueur combinée d'au moins environ 30 fois la dimension de section transversale
intérieure agrégée ;
le réacteur appliquant de la chaleur au courant de processus s'écoulant à travers
celui-ci, pour chauffer progressivement le courant de processus à partir de la température
d'entrée en correspondance d'une partie en amont du réacteur, jusqu'à une température
de sortie T(max)1 dans une plage comprise entre environ 260 °C et environ 400 °C en
correspondance d'une partie en aval du réacteur ;
le réacteur maintenant le courant de processus à une pression dans une plage d'environ
103 à environ 207 bar (environ 1500 à environ 3000 psia), suffisante pour garantir
que le courant de processus reste une seule phase à T(max)1 ;
ajuster sélectivement au moyen d'un contrôleur un débit de courant de processus à
travers le réacteur pour maintenir un temps de séjour total du courant de processus
dans le réacteur supérieur à environ 1 minute et inférieur à environ 25 minutes ;
dans lequel ledit débit de courant, ladite longueur de tubes d'écoulement, et ladite
application de chaleur, minimisent ou empêchent la formation de coke ; et
séparer de l'eau, des hydrocarbures légers (LHC) et tout autre composant volatil ayant
des points d'ébullition à une pression atmosphérique inférieurs à une valeur BP(LHC1)
d'environ 280 °C, au moyen d'une unité de récupération disposée en aval du réacteur
dans le chemin d'écoulement de fluide et incluant un ou plusieurs séparateurs, dans
lequel le courant de processus retient des composants d'hydrocarbures lourds (HHC)
ayant des points d'ébullition supérieurs à BP(LHC1) pour former un courant de processus
de HHC.
2. Procédé de la revendication 1, dans lequel l'unité de récupération comprend une colonne
de distillation flash.
3. Procédé de la revendication 1, dans lequel l'unité de récupération récupère de l'énergie
thermique et de l'eau du courant de processus, pour réduire la température du courant
de processus s'écoulant à travers l'unité de récupération à ladite température d'entrée,
et pour réduire la pression de vapeur du courant de processus s'écoulant à travers
l'unité de récupération.
4. Procédé de la revendication 3, dans lequel l'un ou plusieurs séparateurs comprend
un ballon de détente.
5. Procédé de la revendication 3, dans lequel l'un ou plusieurs séparateurs comprend
une colonne de fractionnement pour séparer des LHC en deux ou plusieurs fractions
pour produire des courants de produits de LHC récupérés différentiés sur la base d'une
plage de point d'ébullition de leurs composants.
6. Procédé de la revendication 1, dans lequel un ou plusieurs matériaux sont ajoutés
au courant de processus en amont de l'unité de récupération, pour former une dispersion
sensiblement uniforme.
7. Procédé de la revendication 6, dans lequel l'un ou plusieurs matériaux sont ajoutés
au processus en correspondance d'un ou plusieurs points en amont d'un point en correspondance
duquel le courant de processus atteint une température dans une plage d'environ 80
% à environ 90 % de T(max)1.
8. Procédé de la revendication 6, dans lequel maintenir et approvisionner le courant
de processus du réacteur à ladite température d'entrée, et ajouter en outre l'un ou
plusieurs matériaux au courant de processus est réalisé au moyen d'un prémélangeur
disposé dans le chemin d'écoulement de fluide en amont du réacteur.
9. Procédé de la revendication 6, dans lequel l'un ou plusieurs matériaux sont sélectionnés
parmi un groupe constitué d'eau, vapeur, hydrocarbures, et leurs combinaisons.
10. Procédé de la revendication 6, dans lequel de l'eau est approvisionnée au courant
de processus pour fournir un rapport de HCO à eau (HCO:eau) dans une plage d'environ
1:1 à 20:1.
11. Procédé de la revendication 6, dans lequel le rapport entre le HCO qui n'a pas encore
été valorisé et les hydrocarbures ajoutés au courant de processus (HCO:hydrocarbures
ajoutés) est dans une plage d'environ 1:2 à 20:1.
12. Procédé de la revendication 6, dans lequel des hydrocarbures sont ajoutés au courant
de processus en correspondance d'une position en amont d'une position en correspondance
de laquelle de l'eau est ajoutée au courant de processus.
13. Procédé de la revendication 6, dans lequel l'unité de récupération est configurée
pour récupérer des LHC du fluide de processus pour les recycler dans un courant de
processus en amont de l'unité de récupération.
14. Procédé de la revendication 1, dans lequel des variables incluant (i) des valeurs
pour T(max)1 et T(max)2 et/ou (ii) un rapport de recyclage incluant le pourcentage
du courant de processus sortant de l'unité de récupération qui est recyclé dans le
courant de processus en amont de l'unité de récupération ; et/ou (iii) le temps de
séjour total du courant de processus dans le réacteur sont sélectivement ajustées
au moyen du contrôleur.
15. Procédé de la revendication 1, dans lequel la température de sortie T(max)1 est dans
une plage comprise entre environ 260 °C et environ 325 °C.
16. Procédé de la revendication 1, dans lequel le réacteur est divisé en une série de
sous-parties de réacteur espacées le long du chemin d'écoulement.
17. Procédé de la revendication 16, dans lequel un HCO dans le courant de processus se
désagrège pour former une dispersion sensiblement uniforme à une température dans
une plage d'environ 80 % à 90 % de T(max)1 et une ou plusieurs sous-parties de réacteur
primaires chauffent le courant de processus à une température maximale prédéterminée
de T(max)1, et une ou plusieurs sous-parties de réacteur supplémentaires chauffent
le courant de processus à une deuxième température maximale prédéterminée (T(max)2).
18. Procédé de la revendication 17, dans lequel les sous-parties de réacteur primaires
et supplémentaires alimentent le courant de processus en parallèle dans l'unité de
récupération.
19. Procédé de la revendication 17, dans lequel une partie du courant de produits d'HHC
de l'unité de récupération est recyclée dans le courant de processus en amont de la
sous-partie de réacteur supplémentaire.
20. Procédé de la revendication 17, dans lequel une autre unité de récupération est disposée
entre la sous-partie de réacteur primaire et la sous-partie de réacteur supplémentaire.
21. Procédé de la revendication 20, dans lequel une partie du courant de produits d'HHC
de l'autre unité de récupération est recyclée dans le courant en amont de la sous-partie
de réacteur supplémentaire.
22. Procédé de la revendication 17, dans lequel la deuxième température maximale prédéterminée
T(max)2 est dans une plage d'environ 1,0 à 1,4 fois T(max)1.
23. Procédé de la revendication 17, dans lequel une ou plusieurs chambres d'écoulement
traversant non chauffées sont disposées à l'intérieur du chemin d'écoulement de réacteur
à la sortie d'une ou plusieurs sous-parties de réacteur, lesdites une ou plusieurs
chambres d'écoulement traversant étant isolées, dimensionnées et conformées pour faciliter
une cinétique associée avec une désagrégation et/ou une valorisation de HCO dans le
courant de processus s'écoulant dans celles-ci en allongeant le temps de séjour passé
par le courant de processus à environ la température en correspondance de ladite ou
desdites sorties.
24. Procédé de la revendication 23, dans lequel l'une ou plusieurs chambres d'écoulement
traversant sont configurées pour être chauffées de sorte que la température du courant
de processus s'écoulant de la sortie de chaque chambre est environ la même qu'en correspondance
de l'entrée de celle-ci.