U.S. patent application number 10/938003 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, Bruce E. Reynolds.
Application Number | 20060058174 10/938003 |
Document ID | / |
Family ID | 36034814 |
Filed Date | 2006-03-16 |
United States Patent
Application |
20060058174 |
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 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.
Inventors: |
Chen; Kaidong; (Albany,
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: |
36034814 |
Appl. No.: |
10/938003 |
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: |
C10G 2300/1033 20130101;
B01J 37/20 20130101; B01J 27/0515 20130101; C10G 2300/703 20130101;
C10G 2300/1022 20130101; C10G 45/08 20130101; C10G 49/02 20130101;
Y10T 428/2982 20150115; C10G 47/26 20130101; C07F 15/045 20130101;
C10G 49/04 20130101; C10G 49/12 20130101; C10G 2300/1074 20130101;
C10G 2300/1003 20130101; C10G 45/04 20130101; C07F 11/005 20130101;
C10G 2300/207 20130101; C10G 45/16 20130101; Y10S 502/517 20130101;
B01J 27/049 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
hydrocarbon oil having a viscosity of at least 2 cSt @ 212.degree.
F. to form Mixture X; (e) combining Mixture X with hydrogen gas in
a second reaction zone, under conditions which maintain the water
in Mixture X in a liquid phase, thereby forming an active catalyst
composition admixed with a liquid hydrocarbon; and (f) recovering
the active catalyst composition.
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 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 20, 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 ratio of Group
VI B metal oxide to oil is at least less than 1.0.
10. The catalyst composition of claim 1, wherein the hydrocarbon
oil is a vacuum gas oil.
11. The catalyst composition of claim 1, 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 100 psig to about 3000
psig.
12. The catalyst composition of claim 11, 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 200 psig to about 1000
psig.
13. The compositions of claim 12, wherein hydrogen is continuously
added to the second reaction zone, and high shear mixing is
employed in order to maintain a homogenous slurry.
14. The catalyst composition of claim 1, which is recovered by
means of a high pressure separator.
15. The catalyst composition of claim 1, which exist in an active
and concentrated state.
16. The catalyst of claim 14, which is continuously mixed in a
storage tank to maintain a homogenous slurry.
17. The catalyst composition of claim 9, wherein the ratio of Group
VI B metal oxide to oil is at least less than 0.5.
18. The catalyst composition of claim 17, wherein the ratio of
Group VI B metal oxide to oil is at least less than 0.1.
19. The catalyst composition of claim 8, wherein the Group VI B
metal is selected from the group consisting of tungsten and
molybdenum.
20. 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, 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 in a second reaction
zone, under conditions which maintain the water in Mixture X in a
liquid phase, thereby forming an active catalyst composition
admixed with a liquid hydrocarbon; and (f) recovering the active
catalyst composition.
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. Nos. 5,164,075 and 5,484,755 (the latter patent
being 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. These patents do not,
however, demonstrate the criticality of the oil viscosity in the
formation of a highly active catalyst composition, nor the
significance of maintaining water in the liquid phase in a crucial
reaction step.
[0006] In the inventions disclosed in U.S. Pat. Nos. 5,164,075 and
5,484,755, 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 application discloses a new slurry catalyst composition
that is highly active. This activity results from preparation of
the catalyst using a process employing a single hydrocarbon oil
(preferably a vacuum gas oil) having an appropriate viscosity range
at 212.degree. F.
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 VIB 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
VIB metal to from a slurry; [0011] (c) promoting the slurry with a
Group VIII metal compound; [0012] (d) mixing the slurry of step (c)
with 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 in a second reaction zone, under
conditions which maintain the water in Mixture X in a liquid phase,
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 combination of a slurry
comprising Group VIB and Group VIII metals and a hydrocarbon oil
having a viscosity of at least 2 cSt (or 32.8 SSU) @ 212.degree. F.
The preferred viscosity range for the 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 VIB 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 35 psig. The Group VIB 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 VIB 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 VIB
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 18
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 hour per pound of Group VIB
metal oxide. 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 slurry is
the catalyst precursor in an aqueous slurry phase.
[0020] The resultant 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 slurry containing the Group VIII metal promoter 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 slurry and a 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.
[0022] The hydrocarbon oil has a kinetic viscosity of at least 2
cSt (32.8 SSU) @ 212.degree. F. The kinetic viscosity can generally
range from about 2 cSt (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 hydrocarbon oil causes
the initial transformation of the catalyst precursor to an oil base
from a water base. The ratio of Group VIB 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 (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. This mixture is known in the claims as Mixture X.
[0023] The material from mixing zone 30 (Mixture X) moves to
reaction zone 40 via line 35. Hydrogen is continuously added to the
mixture reaction zone 40, and high shear mixing is employed in the
reaction zone 40 in order to maintain a homogenous slurry. Hydrogen
is added at low pressure prior to reactor 40 and at high pressure
following reactor 40. This is done in order to keep water in liquid
phase in reactor 40, change water to vapor phase after reactor 40
in order to flash off the water. When the low H2 rate is used in
reactor 40, water is still in liquid phase. Following reactor 40,
more H2 is added, so the water changes to vapor phase, permitting
separation from oil slurry in high pressure separator. The process
conditions of reactor 40 are critical to forming the final
catalyst. The water in the mixture must be maintained in a liquid
phase.
[0024] The temperature of the reaction zone 40 generally ranges
from about 300.degree. F. to 600.degree. F., preferably from about
350.degree. F. to about 500.degree. F., and most preferably from
about 350.degree. F. to about 450.degree. F. The pressure of the
reaction zone 40 generally ranges from about 100 psig to about 3000
psig, preferably from about 200 psig to about 1000 psig, and most
preferably from about 300 psig to about 500 psig. The hydrogen flow
to the reaction zone 40 generally ranges from about 300 SCFB to
about 2000 SCFB, preferably from about 300 SCFB to about 1000 SCFB,
and most preferably from about 300 SCFB to about 500 SCFB. The
reaction time in the reaction zone 40 ranges from about 10 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 admixture with the
hydrocarbon oil.
[0025] The slurry mixture is passed, through line 55, to high
pressure separator 50. More hydrogen is added in line 55 so the
water changes to vapor phase. It can then be separated from oil
slurry in the high pressure separator. The high pressure separator
operates in a range from 300.degree. F. to 700.degree. F. Gases and
water are removed overhead through line 45 and passed to a three
phase separator. 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.
[0026] 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
Catalyst Preparation
[0027] 540 gram MoO.sub.3 is mixed with 79 gram of NH.sub.3 and
2381 gram of H.sub.2O to form a solution of total 3000 gram. 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 gram NiSO.sub.4 solution which contains 36 gram of Ni
is added to the above obtained slurry. The obtained slurry mixture
is then mixed with 8000 gram 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 tanked reactor
(perfectly mixed flow reactor) with H.sub.2. The H.sub.2 gas rate
is 300 SCF/B. The reactor pressure is 400 psig and reactor
temperature is 400.degree. F., the total reaction time is 1 hour.
The reaction products are mixed with more H.sub.2 at a gas rate of
1500 SCF/B and then go to a hot high pressure separator, which is
also maintained at a pressure of 400 psig, with temperature
500.degree. F. to separate gas and liquid slurry. The obtained
liquid slurry contains the highly active catalyst component.
* * * * *