U.S. patent application number 12/212005 was filed with the patent office on 2009-03-05 for process for upgrading heavy oil using a highly active slurry catalyst composition.
Invention is credited to Darush Farshid, Bruce Reynolds.
Application Number | 20090057193 12/212005 |
Document ID | / |
Family ID | 38172202 |
Filed Date | 2009-03-05 |
United States Patent
Application |
20090057193 |
Kind Code |
A1 |
Farshid; Darush ; et
al. |
March 5, 2009 |
Process for upgrading heavy oil using a highly active slurry
catalyst composition
Abstract
The instant invention is directed to a new residuum full
hydroconversion slurry reactor system that allows the catalyst,
unconverted oil and converted oil to circulate in a continuous
mixture throughout an entire reactor with no confinement of the
mixture. The mixture is partially separated in between the reactors
to remove only the products and hydrogen, while permitting the
unconverted oil and the slurry catalyst to continue on into the
next sequential reactor where a portion of the unconverted oil is
converted to lower boiling point hydrocarbons, once again creating
a mixture of unconverted oil, converted oil, and slurry catalyst.
Further hydroprocessing may occur in additional reactors, fully
converting the oil. The oil may alternately be partially converted,
leaving a highly concentrated catalyst in unconverted oil which can
be recycled directly to the first reactor.
Inventors: |
Farshid; Darush; (Larkspur,
CA) ; Reynolds; Bruce; (Martinez, CA) |
Correspondence
Address: |
CHEVRON CORPORATION
P.O. BOX 6006
SAN RAMON
CA
94583-0806
US
|
Family ID: |
38172202 |
Appl. No.: |
12/212005 |
Filed: |
September 17, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11305377 |
Dec 16, 2005 |
7431823 |
|
|
12212005 |
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Current U.S.
Class: |
208/56 |
Current CPC
Class: |
C10G 49/12 20130101;
C10G 65/02 20130101 |
Class at
Publication: |
208/56 |
International
Class: |
C10G 45/00 20060101
C10G045/00 |
Claims
1. A process for the hydroconversion of heavy oils, said process
employing at least two upflow reactors in series, a first reactor
and a reactor other than the first reactor, and at least two
separators, a first separator and a separator other than the first
separator, with a separator in between each reactor, said process
comprising: (a) combining a heated heavy oil feed, an active slurry
catalyst composition having particle sizes of 1-10 micron and a
hydrogen-containing gas to form a mixture; (b) passing the mixture
of step (a) to the bottom of the first reactor, which is maintained
at hydroprocessing conditions, including elevated temperature and
pressure; (c) removing a vapor stream comprising products,
hydrogen, unconverted material and slurry catalyst from the top of
the first reactor and passing it to the first separator; (d) in the
first separator, removing the products and hydrogen to further
processing and passing a liquid bottoms stream, comprising
unconverted material and slurry catalyst, to the bottom of the
reactor other than the first reactor, which is maintained at slurry
hydroprocessing conditions, including elevated temperature and
pressure; (e) removing a vapor stream comprising products and
hydrogen unconverted material and slurry catalyst from the top of
the reactor other than the first reactor and passing it to the
separator other than the first separator; (f) in the separator
other than the first separator, removing the products and hydrogen
overhead as a vapor stream to further processing and passing a
bottoms stream comprising unconverted material and slurry catalyst
to further processing; wherein the heavy oil is selected from the
group consisting of atmospheric residuum, vacuum residuum, tar from
a solvent deasphlating unit, atmospheric gas oils, vacuum gas oils,
deasphalted oils, olefins, oils derived from tar sands or bitumen,
oils derived from coal, heavy crude oils, synthetic oils from
Fischer-Tropsch processes, and oils derived from recycled oil
wastes and polymers.
2. The process of claim 1, wherein the bottoms material from a
separator other than the first separator is recycled to step (a),
the mixture of step (a) further comprising recycled unconverted
material and slurry catalyst.
3. The process of claim 1, wherein the bottoms material of step (f)
is passed to the bottom of a third reactor which is maintained at
hydroconversion conditions, including elevated temperature and
pressure.
4. The process of claim 1, in which at least one of the reactors is
a liquid recirculating reactor.
5. The process of claim 4, in which the recirculating reactor
employs a pump.
6. The process of claim 1, in which hydroprocessing conditions
employed in each reactor comprise a total pressure in the range
from 1500 through 3500 psia and temperature from 700 through 900
F.
7. The process of claim 1, in which the total pressure is
preferably in the range from 2000 through 3000 psia and temperature
is preferably in the range from 775 through 850 F.
8. The process of claim 1, wherein the separator located between
each reactor is a flash drum.
9. (canceled)
10. The hydroconversion process of claim 1, wherein the process is
selected from the group consisting of hydrocracking, hydrotreating,
hydrodesulphurization, hydrodenitrification, and
hydrodemetalization.
11. The process of claim 1, wherein the active slurry catalyst
composition of claim 1 is prepared by the following steps: (a)
mixing a Group VIB metal oxide and aqueous ammonia to form a Group
VI B metal compound aqueous mixture; (b) sulfiding, in an initial
reaction zone, the aqueous mixture of step (a) with a gas
comprising hydrogen sulfide to a dosage greater than 8 SCF of
hydrogen sulfide per pound of Group VIB metal to form a slurry; (c)
promoting the slurry with a Group VIII metal compound; (d) mixing
the slurry of step (c) with a hydrocarbon oil having a viscosity of
at least 2 cSt @212.degree. F. to form an intermediate mixture; (e)
combining the intermediate mixture with hydrogen gas in a second
reaction zone, under conditions which maintain the water in the
intermediate mixture in a liquid phase, thereby forming an active
catalyst composition admixed with a liquid hydrocarbon; and (f)
recovering the active catalyst composition.
12. The process of claim 1, in which about 98 wt % of heavy oil
feed is converted to lighter products.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 11/305,377 with a filing date of Dec. 16,
2005, the disclosure of which is incorporated herein by
reference.
FIELD OF THE INVENTION
[0002] The instant invention relates to a process for upgrading
heavy oils using a slurry catalyst composition.
BACKGROUND OF THE INVENTION
[0003] There is an increased interest at this time in the
processing of heavy oils, due to increased worldwide demand for
petroleum products. Canada and Venezuela are sources of heavy oils.
Processes which result in complete conversion of heavy oils feeds
to useful products are of particularly interest.
[0004] The following patents, which are incorporated by reference,
are directed to the preparation of highly active slurry catalyst
compositions and their use in processes for upgrading heavy
oil:
[0005] U.S. Ser. No. 10/938,202 is directed to the preparation of a
catalyst composition suitable for the hydroconversion of heavy
oils. The catalyst composition is prepared by a series of steps,
involving mixing a Group VIB metal oxide and aqueous ammonia to
form an aqueous mixture, and sulfiding the mixture to form slurry.
The slurry is then promoted with a Group VIII metal. Subsequent
steps involve mixing the slurry with a hydrocarbon oil and
combining the resulting mixture with hydrogen gas and a second
hydrocarbon oil having a lower viscosity than the first oil. An
active catalyst composition is thereby formed.
[0006] U.S. Ser. No. 10/938,003 is directed to the preparation of a
slurry catalyst composition. The slurry catalyst composition is
prepared in a series of steps, involving mixing a Group VIB metal
oxide and aqueous ammonia to form an aqueous mixture and sulfiding
the mixture to form a slurry. The slurry is then promoted with a
Group VIII metal. Subsequent steps involve mixing the slurry with a
hydrocarbon oil, and combining the resulting mixture with hydrogen
gas (under conditions which maintain the water in a liquid phase)
to produce the active slurry catalyst.
[0007] U.S. Ser. No. 10/938,438 is directed to a process employing
slurry catalyst compositions in the upgrading of heavy oils. The
slurry catalyst composition is not permitted to settle, which would
result in possible deactivation. The slurry is recycled to an
upgrading reactor for repeated use and products require no further
separation procedures for catalyst removal.
[0008] U.S. Ser. No. 10/938,200 is directed to a process for
upgrading heavy oils using a slurry composition. The slurry
composition is prepared in a series of steps, involving mixing a
Group VIB metal oxide with aqueous ammonia to form an aqueous
mixture and sulfiding the mixture to form a slurry. The slurry is
then promoted with a Group VIII metal compound. Subsequent steps
involve mixing the slurry with a hydrocarbon oil, and combining the
resulting mixture with hydrogen gas (under conditions which
maintain the water in a liquid phase) to produce the active slurry
catalyst.
[0009] U.S. Ser. No. 10/938,269 is directed to a process for
upgrading heavy oils using a slurry composition. The slurry
composition is prepared by a series of steps, involving mixing a
Group VIB metal oxide and aqueous ammonia to form an aqueous
mixture, and sulfiding the mixture to form a slurry. The slurry is
then promoted with a Group VIII metal. Subsequent steps involve
mixing the slurry with a hydrocarbon oil and combining the
resulting mixture with hydrogen gas and a second hydrocarbon oil
having a lower viscosity than the first oil. An active catalyst
composition is thereby formed.
SUMMARY OF THE INVENTION
[0010] A process for the hydroconversion of heavy oils, said
process employing at least two upflow reactors in series with a
separator in between each reactor, said process comprising the
following steps: [0011] a) combining a heated heavy oil feed, an
active slurry catalyst composition and a hydrogen-containing gas to
form a mixture; [0012] b) passing the mixture of step (a) to the
bottom of first reactor, which is maintained at slurry
hydroprocessing conditions, including elevated temperature and
pressure; [0013] c) removing a vapor stream comprising products,
hydrogen, unconverted material and slurry catalyst from the top of
the first reactor and passing it to a first separator; [0014] d) in
the first separator, removing the products and hydrogen overhead as
a vapor stream to further processing and passing a liquid bottoms
stream, comprising unconverted material and slurry catalyst, to the
bottom of the second reactor, which is maintained at slurry
hydroprocessing conditions, including elevated temperature and
pressure; [0015] e) removing a vapor stream comprising products and
hydrogen, unconverted material and slurry catalyst from the top of
the second reactor and passing it to a second separator; [0016] f)
in the second separator, removing the products and hydrogen
overhead as a vapor stream to further processing and passing a
bottoms stream, comprising unconverted material and slurry catalyst
to further processing.
BRIEF DESCRIPTION OF THE FIGURE
[0017] The FIGURE depicts a process scheme of this invention,
employing three reactors.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The process for the preparation of the catalyst slurry
composition used in this invention is set forth in U.S. Ser. No.
10/938,003 and U.S. Ser. No. 10/938,202 which are incorporated by
reference. The catalyst composition is useful for but not limited
to hydrogenation upgrading processes such as thermal hydrocracking,
hydrotreating, hydrodesulphurization, hydrodenitrification, and
hydrodemetalization.
[0019] The feeds suitable for use in this invention are set forth
in U.S. Ser. No. 10/938,269 and include atmospheric residuum,
vacuum residuum, tar from a solvent deasphalting unit, atmospheric
gas oils, vacuum gas oils, deasphalted oils, olefins, oils derived
from tar sands or bitumen, oils derived from coal, heavy crude
oils, synthetic oils from Fischer-Tropsch processes, and oils
derived from recycled oil wastes and polymers. Suitable feeds also
include atmospheric residuum, vacuum residuum and tar from a
solvent deasphlating unit.
[0020] The preferred type of reactor in the instant invention is a
liquid recirculating reactor, although other types of upflow
reactors may be employed. Liquid recirculating reactors are
discussed further in copending application Ser. No. 11/305,359 or
US Patent Publication No. US2007140927 (T6493) which is
incorporated by reference.
[0021] A liquid recirculation reactor is an upflow reactor to which
is fed heavy hydrocarbon oil admixed with slurry catalyst and a
hydrogen rich gas at elevated pressure and temperature, for
hydroconversion.
[0022] Hydroconversion includes processes such as hydrocracking and
the removal of heteroatom contaminants (such sulfur and nitrogen).
In slurry catalyst use, catalyst particles are extremely small
(1-10 micron). Pumps are not generally needed for recirculation,
although they may be used. Sufficient motion of the catalyst is
usually established without them.
[0023] The FIGURE illustrates the preferred embodiment of this
invention. The instant invention is directed to a process for
catalyst activated slurry hydrocracking. Stream 1 comprises a heavy
feed, such as vacuum residuum. This feed enters furnace 80 where it
is heated, exiting in stream 4. Stream 4 combines with a hydrogen
containing gas (stream 2), and a stream comprising an active slurry
composition (stream 23), resulting in a mixture (stream 24). Stream
24 enters the bottom of the first reactor 10. Vapor stream 5 exits
the top of the reactor 10, comprising slurry, products and
hydrogen, and unconverted material. Stream 5 passes to separator
40, which is preferably a flash drum. Products and hydrogen are
removed overhead as stream 6. Liquid stream 7 is removed through
the bottom of the flash drum. Stream 7 contains slurry in
combination with unconverted oil.
[0024] Stream 7 is combined with a gaseous stream comprising
hydrogen (steam 15) to create stream 25. Stream 25 enters the
bottom of second reactor 20. Vapor stream 8, comprising products,
hydrogen, slurry and unconverted material passes to separator 50,
preferably a flash drum. Product and hydrogen, in a vapor stream is
removed overhead as stream 9. Liquid stream 11 is removed through
the bottom of the flash drum. Stream 11 contains slurry in
combination with unconverted oil.
[0025] Stream 11 is combined with a gaseous stream comprising
hydrogen (stream 16) to create stream 26. Stream 26 enters the
bottom of third reactor 30. Vapor stream 12, comprising products,
hydrogen, slurry and unconverted material passes overhead from
reactor 30 to separator 60, preferably a flash drum. Products and
hydrogen are removed overhead as vapor stream 13. Liquid stream 17
is removed through the bottom of the flash drum. Stream 17 contains
slurry in combination with unconverted oil. A portion of this
stream may be drawn off through stream 18.
[0026] Overhead streams 6, 9 and 13 create stream 14, which passes
to high pressure separator 70. Stream 21, comprising a lean oil
such as vacuum gas oil enters the top portion of high pressure
separator 70. Products and hydrogen exit lean oil contactor 70
overhead as vapor stream 22, while liquid stream 19 exits at the
bottom. Stream 19 comprises a mixture of slurry and unconverted
oil. Stream 19 is combined with stream 17, which also comprises a
mixture of slurry and unconverted oil. Fresh slurry is added in
stream 3, and stream 23 is created. Stream 23 is combined with the
feed to first reactor 10.
* * * * *