U.S. patent application number 10/938202 was filed with the patent office on 2006-03-16 for highly active slurry catalyst composition.
This patent application is currently assigned to Chevron U.S.A. Inc.. Invention is credited to Kaidong Chen, Pak C. Leung, Bruce E. Reynolds.
Application Number | 20060058175 10/938202 |
Document ID | / |
Family ID | 36034815 |
Filed Date | 2006-03-16 |
United States Patent
Application |
20060058175 |
Kind Code |
A1 |
Chen; Kaidong ; et
al. |
March 16, 2006 |
Highly active slurry catalyst composition
Abstract
The instant invention 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 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.
Inventors: |
Chen; Kaidong; (Albany,
CA) ; Leung; Pak C.; (Lafayette, CA) ;
Reynolds; Bruce E.; (Martinez, CA) |
Correspondence
Address: |
CHEVRON TEXACO CORPORATION
P.O. BOX 6006
SAN RAMON
CA
94583-0806
US
|
Assignee: |
Chevron U.S.A. Inc.
|
Family ID: |
36034815 |
Appl. No.: |
10/938202 |
Filed: |
September 10, 2004 |
Current U.S.
Class: |
502/3 ; 502/159;
502/216; 502/219; 502/220; 502/221; 502/222; 502/223 |
Current CPC
Class: |
B01J 27/053 20130101;
C10G 65/04 20130101; C10G 67/0454 20130101; C10G 2300/1033
20130101; B01J 37/20 20130101; B01J 27/0515 20130101; C10G 2300/703
20130101; C10G 2300/1003 20130101; C10G 47/26 20130101; C10G 49/04
20130101; C10G 2300/1022 20130101; C10G 49/12 20130101; B01J 35/12
20130101; C10G 2300/1074 20130101; C10G 2300/207 20130101 |
Class at
Publication: |
502/003 ;
502/159; 502/216; 502/219; 502/220; 502/221; 502/222; 502/223 |
International
Class: |
B01J 35/12 20060101
B01J035/12; B01J 31/00 20060101 B01J031/00; B01J 27/02 20060101
B01J027/02 |
Claims
1. A catalyst composition suitable for the hydroconversion of heavy
oils, which is prepared by: (a) mixing a Group VI B metal oxide and
aqueous ammonia to form a Group VI B metal compound aqueous
mixture; (b) sulfiding, in a first 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 VI
B metal to form a slurry; (c) promoting the slurry with a Group
VIII metal compound; (d) mixing the slurry of step (c) with a first
hydrocarbon oil having a viscosity of at least 2 cSt @ 212.degree.
F. to form Mixture X; (e) combining Mixture X with hydrogen gas and
a second hydrocarbon oil in a second reaction zone, the second
hydrocarbon oil having a boiling point in the range from 50.degree.
F. to 300.degree. F. and having a lower viscosity that the first
hydrocarbon oil, thereby forming an active catalyst composition
admixed with a light hydrocarbon; and (f) recovering the active
catalyst composition by separation from the light hydrocarbon
oil.
2. The catalyst composition of claim 1, wherein conditions in the
first reaction zone comprise a temperature in the range from at
least about 80.degree. F. to about 200.degree. F., and a pressure
in the range from at least about 100 psig to about 3000 psig.
3. The catalyst composition of claim 2, wherein conditions in the
first reaction zone comprise a temperature in the range from at
least about 100.degree. F. to about 180.degree. F., and a pressure
in the range from at least about 200 psig to about 1000 psig.
4. The catalyst composition of claim 3, wherein conditions in the
first reaction zone comprise a temperature in the range from at
least about 130.degree. F. to about 160.degree. F., and a pressure
in the range from at least about 300 psig to about 500 psig.
5. The catalyst composition of claim 1, wherein the first
hydrocarbon oil viscosity ranges from at least about 2 cSt @
212.degree. F. to about 15 cSt @ 212.degree. F.
6. The catalyst composition of claim 1, wherein the Group VIII
metal compound of step (c) is selected from the group consisting of
nickel sulfates and cobalt sulfates.
7. The catalyst composition of claim 4, wherein high shear mode
occurs, in the range from 100 RPM to 1600 RPM.
8. The catalyst composition of claim 6, in which the weight ratio
of nickel or cobalt to Group VI B metal oxide ranges from 1:100 to
about 1:2.
9. The catalyst composition of claim 1, wherein the second
hydrocarbon oil boils in the range from at least about 50.degree.
F. to about 300.degree. F.
10. The catalyst composition of claim 9, wherein the second
hydrocarbon oil boils in the range from at least about 75.degree.
F. to about 250.degree. F.
11. The catalyst composition of claim 1, wherein the ratio of the
volume of the second oil to the first oil is greater than 1.
12. The catalyst composition of claim 1, wherein the ratio of Group
VI B metal oxide to oil is at least less than 1.0.
13. The catalyst composition of claim 1, wherein the first
hydrocarbon oil is a vacuum gas oil.
14. The catalyst composition of claim 1, wherein the second
hydrocarbon oil possess a kinetic viscosity of less than 0.3 cSt at
212.degree. F.
15. The catalyst composition of claim 1, wherein the second
hydrocarbon oil is a light naphtha.
16. The catalyst composition of claim 15, wherein the conditions of
the second reaction zone comprise a temperature in the range from
at least about 350.degree. F. to about 600.degree. F., and a
pressure in the range from at least about 1000 psig to about 3500
psig.
17. The catalyst composition of claim 16, wherein the conditions of
the second reaction zone comprise a temperature in the range from
at least about 350.degree. F. to about 600.degree. F., and the
pressure in the range from at least about 1500 psig to about 3000
psig.
18. The catalyst composition of claim 1, wherein the light
hydrocarbon comprises a mixture of the first hydrocarbon oil and
the second hydrocarbon oil.
19. The catalyst composition of claim 1, which is recovered by
means of a high pressure separator.
20. The catalyst composition of claim 1, which exists in an active
and concentrated state.
21. The catalyst composition of claim 11, wherein the ratio of the
volume of the second oil to the first oil is greater than 5.
22. The catalyst composition of claim 21, wherein the ratio of the
volume of the second oil to the first oil is greater than 10.
23. The catalyst composition of claim 12, wherein the ratio of
Group VI B metal oxide to oil is at least less than 0.5.
24. The catalyst composition of claim 23, wherein the ratio of
Group VI B metal oxide to oil is at least less than 0.1.
25. The catalyst composition of claim 8, wherein the Group VI B
metal is selected from the group consisting of tungsten and
molybdenum.
26. A catalyst composition suitable for the hydroconversion of
heavy oils, which is prepared by: (a) mixing a Group VI B metal
oxide and aqueous ammonia to form a Group VI B metal compound
aqueous mixture; (b) sulfide in a first 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 VI
B metal to form a slurry; (c) promoting the slurry with a Group
VIII metal compound; (d) mixing, at high shear mode, the slurry of
step (c) with a first hydrocarbon oil having a viscosity of at
least 2 cSt @ 212.degree. F. to form Mixture X; (e) combining
Mixture X at high shear mode with hydrogen gas and a second
hydrocarbon oil in a second reaction zone, the second hydrocarbon
oil having a boiling point in the range from 50.degree. F. to
300.degree. F. and having a lower viscosity that the first
hydrocarbon oil, thereby forming an active catalyst composition
admixed with a light hydrocarbon; and (f) recovering the active
catalyst composition by separation from the light hydrocarbon oil.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to the preparation of slurry
catalyst compositions useful in the processing of heavy oils. These
oils are characterized by low hydrogen to carbon ratios and high
carbon residues, asphaltenes, nitrogen, sulfur and metal
contents.
BACKGROUND OF THE INVENTION
[0002] Slurry catalyst compositions and means for their preparation
are known in the refining arts. Some examples are discussed
below.
[0003] U.S. Pat. No. 4,710,486 discloses a process for the
preparation of a dispersed Group VIB metal sulfide hydrocarbon oil
hydroprocessing catalyst. Process steps include reacting aqueous
ammonia and a Group VIB metal compound, such as molybdenum oxide or
tungsten oxide, to form a water soluble oxygen-containing compound
such as ammonium molybdate or tungstate.
[0004] U.S. Pat. No. 4,970,190 discloses a process for the
preparation of a dispersed Group VIB metal sulfide catalyst for use
in hydrocarbon oil hydroprocessing. This catalyst is promoted with
a Group VIII metal. Process steps include dissolving a Group VIB
metal compound, such as molybdenum oxide or tungsten oxide, with
ammonia to form a water soluble compound such as aqueous ammonium
molybdate or ammonium tungstate.
[0005] U.S. Pat. No. 5,164,075 and U.S. Pat. No. 5,484,755, which
are incorporated by reference, disclose processes for preparation
of high activity slurry catalysts for hydroprocessing heavy
hydrocarbon oils produced from Group VIB metal compounds. An
aqueous mixture of the metal compound is sulfided with from greater
than about 8 to about 14 standard cubic feet of hydrogen sulfide
per pound of Group VIB metal. These patents demonstrate a process
of forming a slurry catalyst precursor and adding it to a heavy
feed oil to form the active catalyst.
[0006] These patents do not demonstrate the criticality of the oil
viscosity in the formation of a highly active catalyst composition,
nor the significance of using two distinctly different oils in
forming such catalyst composition. In the inventions disclosed in
these patents, the failure to form the oil and water emulsion or
the slurry phase results in an inactive catalyst or a catalyst
having low activity.
[0007] This invention discloses a new slurry catalyst composition
that is highly active. This activity results from preparation of
the catalyst using a process employing two hydrocarbon oils having
appropriate viscosity ranges at 212.degree. F. The first heavier
oil is preferably a vacuum gas oil (VGO) and the second is
preferably a light naphtha.
SUMMARY OF THE INVENTION
[0008] This invention is directed to a highly active catalyst
composition which is suitable for processing heavy hydrocarbon
oils. The catalyst is prepared by the following steps, resulting in
a catalyst composition suitable for the hydroconversion of heavy
oils, which is prepared by:
[0009] (a) mixing a Group VI B metal oxide and aqueous ammonia to
form a Group VI metal compound aqueous mixture;
[0010] (b) sulfiding, in an initial reactor, 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 VI B metal to
form a slurry;
[0011] (c) promoting the slurry with a Group VIII metal
compound;
[0012] (d) mixing the slurry of step (c) with a first hydrocarbon
oil having a viscosity of at least 2 cSt (or 32.8 SSU) @
212.degree. F. to form Mixture X;
[0013] (e) combining Mixture X with hydrogen gas and a second
hydrocarbon oil in a second reaction zone, the second hydrocarbon
oil having a boiling point in the range from 50.degree. F. to
300.degree. F. and having a lower viscosity than the first
hydrocarbon oil; thereby forming an active catalyst composition
admixed with a liquid hydrocarbon; and
[0014] (f) recovering the active catalyst composition.
[0015] This new highly active slurry catalyst composition may be
stored in an active and concentrated state. The catalyst
composition can be directly introduced into any of the known heavy
oil or residuum upgrading processes under the existing conditions
of that process. The catalyst can upgrade the very high viscosity
carbonaceous and/or highly paraffinic feedstocks with or without
dilution of the feedstock.
BRIEF DESCRIPTION OF THE DRAWING
[0016] The FIGURE illustrates the steps involved in the preparation
of the catalyst composition.
DETAILED DESCRIPTION OF THE INVENTION
[0017] This invention relates to a new highly active slurry
catalyst composition formed from the addition of a first
hydrocarbon oil having a viscosity of at least 2 cSt (or 32.8 SSU)
@ 212.degree. F., and a second hydrocarbon oil having a boiling
point in the range from 50.degree. F. to 300.degree. F. The
preferred viscosity range for the first hydrocarbon oil is from at
least about 2 cSt (or 32.8 SSU) @ 212.degree. F. to 15 cSt (or 77.9
SSU) @ 212.degree. F.
[0018] The FIGURE illustrates the steps involved in the process of
this invention. The active slurry catalyst composition is prepared
by mixing line 5, containing an oxide of Group VI B metal such as
tungsten or molybdenum, and line 7, containing aqueous ammonia, in
a mixing zone 10. The temperature of the mixing zone is generally
in the range from about 80.degree. F. to about 200.degree. F.,
preferably from about 100.degree. F. to about 150.degree. F., and
most preferably from about 110.degree. F. to about 120.degree. F.
The pressure of the mixing zone 10 is generally from about
atmospheric pressure to about 100 psig, preferably from about 5
psig to about 35 psig, and most preferably from about 10 psig to
about 20 psig. The Group VI B metal oxide is dissolved in water
containing the ammonia. The amount of ammonia added is based on the
ratio of NH.sub.3 to Group VI B oxide in lbs/lbs and generally
ranges from 0.1 lbs/lbs to about 1.0 lbs/lbs, preferably from about
0.15 lbs/lbs to about 0.50 lbs/lbs, and most preferably from about
0.2 lbs/lbs to about 0.30 lbs/lbs. The dissolved metal oxide in
aqueous ammonia is moved via line 15 to the first reaction
zone.
[0019] The amount of hydrogen sulfide (line 9) added to the
reaction zone 20 is based on the ratio of H.sub.2S to Group VI B
metal oxide in SCF/lbs and generally ranges from 4.0 SCF/lbs to
about 20 SCF/lbs, preferably from about 8.0 SCF/lbs to about 15
SCF/lbs, and most preferably from about 12 to 14 SCF/lbs. The
reaction time in the first reaction zone ranges from about 1 hour
to 10 hours, preferably from 3 hours to 8 hours, and most
preferably from about 4 hours to 6 hours. Conditions include a
temperature in the range from 80.degree. F. to 200.degree. F.,
preferably in the range from 100.degree. F. to 180.degree. F., and
most preferably in the range from 130.degree. F. to 160.degree. F.
Pressure is in the range from 100 to 3000 psig, preferably in the
range from 200 to 1000 psig, and most preferably from 300 to 500
psig. The resultant aqueous slurry is the catalyst precursor.
[0020] The aqueous slurry is combined with a Group VIII metal
compound such as Ni or Co, as disclosed in U.S. Pat. No. 5,484 755.
As an enhancement of the denitrogenation activity of the active
slurry catalyst of the present invention, it is preferred that a
Group VIII metal compound be added to the slurry before mixing the
slurry with feed oil and a hydrogen containing gas at elevated
temperature and pressure. Such Group VIII metals are exemplified by
nickel and cobalt. It is preferred that the weight ratio of nickel
or cobalt to molybdenum range from about 1:100 to about 1:2. It is
most preferred that the weight ratio of nickel to molybdenum range
from about 1:25 to 1:10, i.e., promoter/molybdenum of 4-10 weight
percent. The Group VIII metal, exemplified by nickel, is normally
added in the form of the sulfate, and preferably added to the
slurry after sulfiding at a pH of about 10 or below and preferably
at a pH of about 8 or below. Group VIII metal nitrates, carbonates
or other compounds may also be used. In view of the high activity
of the slurry catalyst of the present invention, the further
promotion by Group VIII metal compounds is very advantageous.
[0021] The aqueous slurry is moved, via line 25, to mixing zone 30.
Mixing zone 30 employs an inert atmosphere which can comprise
nitrogen, refinery gas, or any other gas having little or no
oxygen. The aqueous slurry and a first hydrocarbon oil (line 11),
such as VGO, are mixed continuously in a high shear mode to
maintain a homogeneous slurry in mixer 30. High shear mixing
encompasses a range from 100 to 1600 RPM. Preferably the mixing
rate is greater than 500 RPM and most preferably greater than 1500
RPM. The first hydrocarbon oil has a kinetic viscosity of at least
2 cSt (or 32.8 SSU) @ 212.degree. F. The kinetic viscosity can
generally range from about 2 cSt (or 32.8 SSU) @ 212.degree. F. to
about 15 cSt (77.9 SSU) @ 212.degree. F., preferably from about 4
cSt (39.5 SSU) @ 212.degree. F. to about 10 cSt (59.2 SSU) @
212.degree. F., and most preferably from about 5 cSt (42.7 SSU) @
212.degree. F. to about 8 cSt (52.4 SSU) @ 212.degree. F. The first
hydrocarbon oil causes the initial transformation of the catalyst
precursor to an oil base from a water base. The ratio of Group VI B
metal oxide to oil is at least less than 1.0, preferably less than
0.5, and more preferably less than 0.1. If the kinetic viscosity of
the oil is below about 2 cSt (or 32.8 SSU) @ 212.degree. F. or
above about 15 cSt (77.9 SSU) @ 212.degree. F., the first
transformation of the catalyst precursor will result in catalyst
particles agglomerating or otherwise not mixing.
[0022] The material from mixing zone 30 moves to reaction zone 40
via line 35. Prior to entering reaction zone 40, the material may
be combined with makeup oil of the viscosity range of the first
hydrocarbon oil. Hydrogen is also added to the mixture before it
enters reaction zone 40.
[0023] In reaction zone 40, a second, lighter hydrocarbon oil is
added to the material from mixing zone 30. The second oil,
preferably a light naphtha, preferably possesses a kinetic
viscosity of less than 0.3 cSt at 212.degree. F. One source of this
second oil may be recycle material from the high pressure separator
50 (line 45). High shear mixing is also employed in the reaction
zone 40 in order to maintain a homogenous slurry.
[0024] The second hydrocarbon oil has a boiling point generally in
the range from about 50.degree. F. to about 300.degree. F.,
preferably from about 75.degree. F. to about 250.degree. F., and
most preferably from about 100.degree. F. to about 150.degree. F.
The ratio of the volume of the second oil to the first oil is
greater than 1, preferably greater than 5, and most preferably
greater than 10. The temperature of the reaction zone 40 generally
ranges from about 300.degree. F. to 700.degree. F., preferably from
about 350.degree. F. to about 600.degree. F., and most preferably
from about 350.degree. F. to about 500.degree. F. The pressure of
the reaction zone 40 generally ranges from about 1000 psig to about
3500 psig, preferably from about 1500 psig to about 3000 psig, and
most preferably from about 2000 psig to about 3000 psig. The
hydrogen flow to the reaction zone 40 generally ranges from about
500 SCFB to about 10,000 SCFB, preferably from about 1000 SCFB to
about 8000 SCFB, and most preferably from about 3000 SCFB to about
6000 SCFB. The reaction time in the reaction zone 40 ranges from
about 11 minutes to 5 hours, preferably from 30 minutes to 3 hours,
and most preferably from about 1 hour to 1.5 hours. The resultant
slurry mixture is the active catalyst composition in a mixture of
the first hydrocarbon oil and the second hydrocarbon oil. The
slurry mixture is passed, through line 55, to high pressure
separator 50. The high pressure separator operates in a range from
300.degree. F. to 700.degree. F. The second hydrocarbon oil is
removed overhead through line 45 and recirculated back to the third
reaction zone 40. The active catalyst composition is moved through
line 65 to storage tank 60. The active catalyst composition is
continuously mixed in storage tank 60 to maintain a homogenous
slurry in a hydrogen atmosphere with little or no oxygen. In this
way, the catalyst activity and stability are maintained.
[0025] The catalyst composition is useful for upgrading
carbonaceous feedstocks which include 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. The catalyst composition is useful for but not
limited to hydrogenation upgrading processes such as thermal
hydrocracking, hydrotreating, hydrodesulphurization,
hydrodenitrification, and hydrodemetallization.
EXAMPLES
Example 1
For Catalyst Preparation (with Light Oil)
[0026] 540 gram MoO.sub.3 is mixed with 79 grams of NH.sub.3 and
2381 grams of H.sub.2O to form a solution of total 3000 grams. The
solution is then reacted with 10.71 SCF of H.sub.2S by passing a
gas mixture of 20% H.sub.2S in H.sub.2 into the solution under
strong mixing. The reactor temperature is 150.degree. F. and the
total pressure is 400 psig, and the reaction time is 4 hours. After
reaction, 460 grams NiSO.sub.4 solution which contains 36 grams of
Ni is added to the above obtained slurry. The obtained slurry
mixture is then mixed with 3500 grams of vacuum gas oil at
100.degree. F. The viscosity of the VGO is 5 cSt @ 212.degree. F.
The resulting mixture is then pumped into a continuously flow
stirred tanked reactor (perfectly mixed flow reactor) and mixed
with heptane and H.sub.2, the ratio of heptane/VGO is 9:1 and
H.sub.2 gas rate is 5000 SCF/B. The reactor pressure is 2500 psig
and reactor temperature is 400.degree. F., the total reaction time
is 1 hour. The reaction products go to a hot high pressure
separator with temperature 500.degree. F. (HPS is also at 2500
psig) to separate gas and liquid slurry. The obtained liquid slurry
contains the highly active catalyst component.
* * * * *