# Patent

## Title
Conversion of fine catalyst into coke-like material

## Abstract

A process for converting fine catalyst slurried in heavy oil into a coke-like material from which catalytic metals can be recovered comprises mixing fine catalyst slurried in heavy oil with solvent, which causes asphaltenes in the heavy oil to precipitate from the heavy oil; separating fine catalyst and precipitated asphaltenes from the heavy oil and solvent; and converting precipitated asphaltenes to a coke-like material by pyrolizing fine catalyst and precipitated asphaltenes separated from the heavy oil.

## Background
BACKGROUND
Traditional light oil reserves are being depleted due to high oil production. Oil fields are requiring substantial new investment in secondary and tertiary oil recovery technology. On the other hand, the cost of producing and refining heavy crude has decreased due to new production and refining technologies. Most of the heavy crude reserves all over the world have not yet been exploited. Considering the continuously increasing demand in oil and the large difference in price between light oil and heavy crude, heavy crude reserves are emerging as a very attractive source of energy.
Heavy crude contains 40-70% high boiling range material that boils over 1000° F. (i.e., vacuum resid) and very low amounts of fuels in high demand such as, for example, gasoline and diesel. Therefore, in order to convert vacuum resid to valuable light products, new and more cost effective technologies are needed. Heavy crude can be converted into lighter products via conventional processes such as coking (e.g., delayed coking and/or fluid coking) and hydroconversion (e.g., LC Fining and H-OIL). However, such conventional processes produce large amounts of undesirable byproducts such as, for example, coke or fuel oil and also are very sensitive to the contaminants such as, for example, V, Ni, and S.
Most hydroconversion technologies utilize novel catalysts composed predominantly of metals of Group VA, VIA, VIIA, or VIII metal sulfides especially compounds such as molybdenum disulfide (MoS2) and nickel sulfide (NiS). Such metals are highly active in hydroconversion of heavy crudes but also are very expensive. In order to minimize the amount of catalyst required, and minimize the diffusion effects, catalyst is often unsupported.
In hydroconversion of vacuum resid and related feedstocks, the remaining portion of unconverted material, which may range from 0 to 10% of fresh feed, shows low API gravity (−10 to 29), high remaining microcarbon residue (MCR) (0 to 60%), very high viscosity and asphaltenes content, and likely also contains catalyst. Therefore, the separation scheme utilized to recover valuable active metals such as, for example, MoS2 and NiS is a critical step in making the process economically attractive. Catalyst remaining in the unconverted slurry bleed oil (USBO) is to be removed and sent for reprocessing to recover the metals and also to recover the unconverted portion of the residue in order to be recycled or further processed.
Expensive spent catalyst contained in the USBO is coated with USBO and is not leachable by conventional technologies of metals extraction that basically are effective for water-based slurries. Therefore, without additional processing, the valuable metals cannot be recovered. Technologies employing microfiltration, ultrafiltration, or nanofiltration; gravity based separation, such as centrifugation or hydrocycloning; and chemical recovery, which may be effective for water-based slurries, similarly do not provide acceptable results for catalyst coated with USBO.
Provided is a process for recovery of spent slurry catalysts from USBO.
SUMMARY
Provided is a process for converting fine catalyst slurried in heavy oil into a coke-like material from which catalytic metals can be recovered. The process comprises mixing fine catalyst slurried in heavy oil with solvent, which causes asphaltenes in the heavy oil to precipitate from the heavy oil. Fine catalyst and precipitated asphaltenes are separated from the heavy oil and solvent. Precipitated asphaltenes are converted to a coke-like material by pyrolizing fine catalyst and precipitated asphaltenes separated from the heavy oil.


DETAILED DESCRIPTION
As used herein, “heavy oil” refers to an oil characterized by low hydrogen to carbon ratios and high carbon residues, asphaltenes, nitrogen, sulfur and metal contents. Examples 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 heavy oil can comprise microcarbon residue (MCR) in the range of about 15 to 30 weight % and (C7) asphaltenes in the range of about 5 to 20 weight %.
The presently claimed process for converting fine catalyst slurried in heavy oil into a coke-like material from which catalytic metals can be recovered comprises: mixing fine catalyst slurried in heavy oil with solvent (“dilution”), which causes asphaltenes in the heavy oil to precipitate from the heavy oil; separating fine catalyst and precipitated asphaltenes from the heavy oil and solvent (“separation”); and converting precipitated asphaltenes to a coke-like material by pyrolizing fine catalyst and precipitated asphaltenes separated from the heavy oil (“coking”).
A heavy crude oil feedstock containing greater than 50 weight % of vacuum resid with an asphaltene level of greater than 3 weight % subjected to a high severity conversion process can result in a vacuum reside or asphaltene conversion level in the range of about 80 to 99 weight %. To achieve such conversion levels, temperatures in the range of about 420 to 450° C. and pressures in the range of about 500 to 3000 psi hydrogen partial pressure are required. An effect of high severity conversion processes is that a large fraction of the heavier components, such as, for example, asphaltenes, are converted to lighter fractions leaving a small amount of dishydrogenated asphaltenes with a high degree of condensation that are incompatible within the hydroconverted product and, therefore, have a tendency to precipitate, especially when mixed with solvent.
Heavy Oil Upgrading
Suitable feeds to a process for upgrading heavy oils using a slurry catalyst composition, include, for example, 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. The feed is supplied to a reactor, wherein the feed is reacted with a catalyst slurry described in further detail below and preferably hydrogen. In an embodiment, the reactor is a liquid recirculating reactor, although other types of upflow reactors may be employed. The catalyst slurry can be useful for, but not limited to, hydrogenation upgrading processes such as thermal hydrocracking, hydrotreating, hydrodesulphurization, hydrodenitrification, and hydrodemetalization. Effluent streams from the reactor, perhaps following downstream processing, such as, for example, separation(s), can include one or more valuable light products as well as a stream containing unsupported catalyst in unconverted feed.
Processing of an effluent steam containing unsupported catalyst in unconverted feed is described herein. In particular, the cost of the catalyst, and more specifically the expensive metal(s) that comprise the catalyst, may necessitate the recovery of catalyst from unconverted feed to ensure an economical heavy oil upgrading process. Additionally, the recovery of catalyst from unconverted feed may allow for 90-100% conversion of heavy oil, as described in further detail, below. However, the high molecular weight of the unconverted heavy oil feed makes it difficult to separate unsupported catalyst therefrom. Further, conventional filtration processes may not be suitable to separate catalyst from unconverted feed, as the unsupported fine catalyst may cause plugging or fouling of filters.
Catalyst Slurry
The presently described method utilizes catalysts in the conversion (in particular, hydroconversion) of heavy oil (i.e., reaction of a slurry comprising unsupported fine catalyst in heavy oil) into one or more light oil products. In an embodiment, the catalysts are composed predominantly of compounds such as a Group VI and/or Group VIII metal compound sulfide, for example, molybdenum sulfide (MoS2) and nickel sulfide (NiS), as described in U.S. Pat. No. 5,484,755 and U.S. Patent Application Publication Nos. 2006/0054534 A1, 2006/0054535 A1, 2006/0058174 A1, and 2006/0058175 A1, the contents of which are hereby incorporated by reference in their entireties. The highly active, unsupported catalysts typically exhibit particle size distributions in the range of about 1-8 microns, with some smaller and larger particles existing on either end of the range. In particular, the catalyst particles can have a size distribution in the range of about 0.2-20 microns, and a mean particle size of about 4-5 micron, with the mode being about 6-7 micron.
In particular, the feedstock to the deep catalyst cracking can be the catalyst bleed stream from a vacuum resid unit, which is primarily made-up of spent finely divided unsupported slurry catalyst, carbon fines, and metal fines in unconverted resid hydrocarbon oil. The solids content of the feedstock can be in the range of about 5-40 weight %, for example about 15-30 weight % or about 20-25 weight %.
Dilution
Solvent is mixed with fine catalyst slurried in heavy oil in a volume ratio of about 0.5/1 to 5/1. The catalyst can have a particle size distribution in the 0.01-40 micron range, with the majority of the particles being in the 1-10 micron size range. The current tendency is to maximize the fraction of submicron particles. The solvent can comprise a paraffinic solvent, such as, for example, light naphtha, heavy naphtha, and/or kerosene. Mixing the fine catalyst slurried in heavy oil with solvent reduces viscosity and promotes partial asphaltenes precipitation to flocculate part of the asphaltenes and the very fine particles of the expensive catalyst.
Separation
The flocculated asphaltenes and catalyst are next separated from the heavy oil and solvent. Conventional separation techniques such as, for example, gravity decanting and/or centrifugal decanting may be used. Catalyst recovery can be in the range of 90 to 99.9 weight %. Additional processes for separation of a particulate solid material from a hydrocarbon liquid can be found in U.S. application Ser. No. 11/618,244, entitled “A PROCESS FOR RECOVERING ULTRAFINE SOLIDS FROM A HYDROCARBON LIQUID” and filed on Dec. 29, 2006, the contents of which are hereby incorporated by reference in its entirety.
Coking
Coking, or pyrolysis, technologies are then used to crack the asphaltenes containing spent slurry catalyst producing a petroleum coke-like byproduct with a yield not larger than 0.25 weight % to 0.6 weight % based on fresh feed. Thus, the amount of coke produced is substantially minimized compared to coking of the complete unconverted vacuum residue. As a result, the solids handling cost is much lower, and the liquid yield is higher. When the MCR or asphaltenes in the heavy oil are exposed to extreme temperatures, ranging from 700 to 1000+° F., the petroleum molecules are “thermally cracked” in such a way as to produce some portion of lighter oil product and some portion of condensed asphaltenes and heavy molecules as petroleum coke. The coke-like matrix preferably is leachable, such that valuable metals (e.g., Mo, Ni, and V) can be recovered therefrom.
The coking unit can be, for example, a standard delayed coking unit, a modified delayed coking unit, a screw reactor type of pyrolyzer, a screw coker, a rotary kiln, or a rotary calciner. In the coking reaction, cracked liquid and gas products as well as coke are produced. The coke contains slurry catalyst.
A large amount of coke deposited onto the catalyst can block access to the nickel and molybdenum that are desired to be leached. The amount of coke generated in the coking step can be many times (e.g., about 3 to about 6 times) greater than the amount of coke present on the used catalyst as it exits heavy oil upgrading. Nevertheless, according to the present process the coke deposited in the coking step does not encapsulate the metals.
Grinding
Thus, prior to metals recovery, the coke-like material can be ground, and the ground particles retain enough porosity to be leachable. For example, the coke-like material can be ground to a particle size ranging from about greater than 1 to less than 50 microns.
Metals Recovery
The process of recovering metals, specifically molybdenum, nickel, and deposited vanadium, from coked, ground catalyst comprises the steps of autoclave-based ammoniacal metals leach, vanadium metal recovery, nickel metal solvent extraction, and molybdenum metal solvent extraction. Coked ground catalyst, containing MOS2 and slurried in water, enters an autoclave, along with ammonia and enriched air containing additional oxygen. Leaching reactions occur in the autoclave, producing ammonium molybdate and nickel ammonium sulfate, which remain in solution and pass to a leach residue filter press. The ammonium metavanadate precipitates out as a solid in the leach slurry. Solid/liquid separation occurs in the leach residue filter press.
More specifically, a stream of coked, ground catalyst slurried with water is pumped to an ammoniacal pressure leaching autoclave. This autoclave is a multi-chambered, agitated vessel, in which both ammonia and oxygen are supplied to induce leaching reactions. These reactions can occur at various temperatures, for example, in the range from about 20° C. through about 315° C., in the range from about 35° C. through about 250° C., or in the range from about 90° C. through about 200° C. Autoclave vessel pressure ranges can be, for example, in the range from about 0 psig through about 1200 psig, in the range from about 100 psig through about 900 psig, or in the range from about 300 psig through about 700 psig, sufficient to suppress flashing in the vessel. Process pH values range from about 7 through about 12, for example, from about 8 through about 11 or from about 9 through about 10. Leaching reactions occur as specified in the equations below.

MoS2+4.5O2+6NH3+3H2O→(NH4)2MoO4−+2(NH4)2SO4 

V2S3+7O2+8NH3+4H2O→2NH4VO3+3(NH4)2SO4 

NiS+2O2+6NH3→Ni(NH3)6SO4 

Further details of metals recovery, for example, vanadium extraction, nickel extraction, and molybdenum removal, can be found in U.S. Patent Application Publication No. 2007/0025899, the contents of which are hereby incorporated by reference in its entirety.
The following examples are intended to be illustrative and are not meant to be limiting in any way.
EXAMPLES
Vacuum residue containing spent catalyst was diluted with heavy naphtha in a volume ratio of solvent/residue of 3/1. Separation via centrifugal force in a centrifuge at 1600 g-force and 2 minutes residence time yielded 99.8 weight % of the spent catalyst having particle size lower than 10 microns.
The separated solids and asphaltenes (i.e., 50 weight % of the asphaltenes of the feed) were heated up to a temperature of 950° F. at atmospheric pressure, with a residence time of 1 hour. The recovered solids (coke and catalyst) were ground, or milled, to a particle size range of about greater than 1 to less than 50 microns, yielding a milled material amenable to metals recovery in a 99.8 weight % of Mo and Ni. Specifically, the material was amenable to pressure leaching in an ammoniacal solution to recover valuable metals such as, for example, Mo, Ni, V, and other Group VA, VIA, VIIA, and VIII metals.
In another example, a vacuum residue containing about 5 weight % MoS2 and NiS catalyst. The residue stream was contacted with a heavy naphtha in a volume ratio of solvent/residue of 2/1 with a 2000 g-force and 1 minute residence time, yielding a paste containing 99.9 weight % of the catalyst and 50 weight % of the original asphaltenes (less than 1 weight % based on fresh feed to the hydrocracking unit). The paste was processed in a microcoker unit and exposed to coking conditions from around 950° F. Products from the microcoker operation included a cracked gas stream (13 weight %), a coker liquid product stream (26 weight %), and a solid coke product (61 weight %). The solid coke product was analyzed and it was determined that the coke contained appreciable quantities of Mo, Ni, and V. The coke product was milled to 100% passing 325 mesh (44 microns) in a ceramic ball mill, and then was subjected to a pressure leach test under conditions disclosed in U.S. Patent Application Publication No. 2007/0025899 A1, the contents of which are hereby incorporated by reference in its entirety.
Several runs were conducted and in each, extraction of Mo was greater than 99 weight %, Ni greater than 87 weight %, and V greater than 70 weight %, as outlined below.
Example
Pressure Leach Test on Coked Sample


    Charge: 115.0 g dry ground coked catalyst sample, 100%-44 μm 2.0 L solution (6 M NH3 and 30 g/L (NH4)2SO4), 2 drops Aerosol OT-75
    Temperature: 150° C.
    Total Pressure: 2800 kPa (gauge)
    Oxidant: Compressed air, through sparger on demand to maintain pressure
    Vent Rate: 1.0 L/min
    Equipment: 4 L stainless steel batch autoclave, baffled, agitation supplied by dual axial flow impellers (7.6 cm diameter) rotating at 1120 revolutions/minute, vented through condenser and rotameter











TABLE 2









Time, min















Head
0
30
60
120
180
Final (240)


















Slurry Sample









Weight, g

112.6
98.3
84.2
77.6
79.5
1247


Volume, mL

114
98
84
78
79
1180


Pulp Density, g/L

998
1003
1002
995
1006
1056


Solids, g
115
6.2
4.2
3.6
3.3
3.5
66.6


Solids, g/L
58
54
43
43
42
44
56


Solids, %
5.4
5.5
4.3
4.3
4.3
4.4
5.3


Solution Analysis


pH

11.5
11.2
11.1
11.2
11.3
11.1


NH3 (free)*, g/L
102
82
75
72
66
65
63


Mo

0.96
4.20
4.45
4.46
4.51
4.79


Ni

0.19
0.47
0.48
0.48
0.48
0.50


V

0.09
0.14
0.15
0.14
0.15
0.15


NH3 (total)

87.2
81.6
78.8
75.4
72.6
71.5


S
7.3
8.3
10.1
10.0
10.1
10.1
10.6


NH4NH2SO3

0.78
0.54
0.31
<0.1
<0.1
<0.1


(NH4)2SO4
30
32.9
39.9
39.7
40.4
40.4
42.4


Inorganic C

0.027
0.048
0.069
0.090
0.115
0.167


Total Organic C

0.033
0.039
0.063
0.104
0.118
0.123


Solids Analysis, %


Mo
8.29
6.61
0.60
0.082
<0.05
<0.05
0.059


Ni
0.99
0.66
0.16
0.11
0.12
0.14
0.12


V
0.41
0.22
0.11
0.096
0.096
0.090
0.088


Fe
0.13
0.14
0.13
0.12
0.11
0.09
0.10


C
68
72
80
80
80
79
79


S
8.84
7.37
3.35
3.05
2.94
2.78
3.03


Extraction, % (basis)

(C tie)
(C tie)
(C tie)
(C tie)
(C tie)
(C tie)


Mo

24.7
93.9
99.2
99.5
99.5
99.4


Ni

36.6
85.9
90.6
89.3
88.2
89.5


V

48.5
76.1
79.9
79.9
80.9
81.3


S

21.3
67.8
70.7
71.7
72.9
70.5





*titrated with 2.94 N H2SO4 in Research lab






Example
Pressure Leach Test on Coked Sample


    Charge: 50.6 g dry ground coked catalyst sample, 100%-44 μm 2.0 L solution (80 g/L NH3 and 30 g/L (NH4)2SO4), 2 drops Aerosol OT-75
    Temperature: 150° C.
    Total Pressure: 2800 kPa (gauge)
    Oxidant: Compressed air, through sparger on demand to maintain pressure
    Vent Rate: 0.5 L/min
    Equipment: 4 L stainless steel batch autoclave, baffled, agitation supplied by dual axial flow impellers (7.6 cm diameter) rotating at 1120 revolutions/minute, vented through condenser and rotameter











TABLE 3









Time, min















Head
0
30
60
120
180
Final (240)


















Slurry Sample









Weight, g

34.3
73.3
71.3
75.1
75.7
1373


Volume, mL

40
74
71
76
77
1340


Pulp Density, g/L

858
991
1004
988
983
1024


Solids, g
50.6
0.7
1.3
1.3
1.4
1.4
32.6


Solids, g/L
25.3
18
18
18
18
18
24


Solids, %
2.5
2.0
1.8
1.8
1.9
1.8
2.4


Solution Analysis


pH

11.3
11.1
11.0
11.0
10.9
10.9


NH3 (free)*, g/L
80
68
67
63
59
59
58


Mo

0.15
1.64
1.61
1.61
1.62
1.69


Ni

0.03
0.19
0.18
0.18
0.18
0.19


V

<0.01
0.048
0.052
0.050
0.052
0.053


NH3 (total)

78.8
75.1
71.8
69.5
67.4
68.6


S
7.3
7.4
8.2
8.0
8.0
8.0
8.4


NH4NH2SO3






<0.0.1


(NH4)2SO4
30





34.2


Inorganic C

0.023
0.036
0.038
0.049
0.056
0.086


Total Organic C

0.092
0.084
0.086
0.103
0.142
0.167


Solids Analysis, %


Mo
6.06
5.88
0.16
0.045
0.043
0.038
0.039


Ni
0.75
0.62
0.13
0.11
0.12
0.12
0.11


V
0.21
0.21
0.077
0.071
0.069
0.067
0.067


Fe
<0.09
0.22
0.18
0.15
0.15
0.16
0.18


C
75
72
78
78
78
77
77


S
7.2
7.0
3.1
3.0
2.8
2.8
2.7


Extraction, % (basis)


(C tie)
(C tie)
(C tie)
(C tie)
(C tie)


Mo


97.4
99.3
99.3
99.4
99.4


Ni


83.0
85.4
84.8
83.9
86.3


V


64.7
67.5
68.4
68.9
68.9


S


58.6
59.9
62.6
62.1
63.5





*titrated with 2.94 N H2SO4 in Research lab






Many modifications of the exemplary embodiments disclosed herein will readily occur to those of skill in the art. Accordingly, the present disclosure is to be construed as including all structure and methods that fall within the scope of the appended claims.

## Claims

1. A process for converting spent fine catalyst slurried in heavy oil into a coke-like material from which metals can be recovered, the process comprising:
mixing the spent fine catalyst comprising a Group VI metal sulfide and/or a Group VIII metal sulfide slurried in heavy oil with solvent, which causes asphaltenes in the heavy oil to precipitate from the heavy oil;
separating the spent fine catalyst and precipitated asphaltenes from the heavy oil and solvent; and
Converting precipitated asphaltenes to a coke-like material containing metals to be recovered by pyrolizing by thermal cracking the spent fine catalyst and precipitated asphaltenes separated from the heavy oil and solvent.

2. The process of claim 1, further comprising recovering catalytic metals from the coke-like material.

3. The process of claim 1, further comprising separating heavy oil and solvent.

4. The process of claim 1, wherein the solvent comprises a solvent selected from the group consisting of light naphtha, heavy naphtha, kerosene, and mixtures thereof.

5. The process of claim 1, wherein the heavy oil is mixed with solvent in a volume ratio of solvent/heavy oil between 0.5/1 and 5/1.

6. The process of claim 1, wherein the heavy oil is mixed with solvent at a temperature between 25 and 80° C.

7. The process of claim 1, wherein separating fine catalyst and precipitated asphaltenes from the heavy oil comprises a separation process selected from the group consisting of gravity decanting, centrifugal decanting, and combinations thereof.

8. The process of claim 1, wherein separating fine catalyst and precipitated asphaltenes from the heavy oil comprises using centrifugal force between 500 and 5000 g-force.

9. The process of claim 1, wherein separating fine catalyst and precipitated asphaltenes from the heavy oil comprises using centrifugal force for 0.5 to 4 minutes.

10. The process of claim 1, wherein separating fine catalyst and precipitated asphaltenes from the heavy oil yields about 90 to 99.9 weight % of the fine catalyst in the heavy oil.

11. The process of claim 1, wherein pyrolizing is conducted in a reactor selected from the group consisting of standard delayed coking unit, a modified delayed coking unit, a screw reactor type of pyrolyzer, a screw coker, a rotary kiln, and a rotary calciner.

12. The process of claim 1, wherein pyrolizing fine catalyst and precipitated asphaltenes comprises heating to a temperature of greater than 700° F.

13. The process of claim 1, wherein pyrolizing fine catalyst and precipitated asphaltenes comprises heating for greater than 0.5 hours.

14. The process of claim 1, wherein the coke-like material has sufficient porosity to allow leaching of catalytic metals in the fine catalyst.

15. The process of claim 1, wherein the fine catalyst comprises particles having a size of less than 10 microns.

16. The process of claim 1, further comprising grinding the coke-like material.

17. The process of claim 1, further comprising grinding the coke-like material to a particle size ranging from about greater than 1 to less than 50 microns.

18. The process of claim 2, wherein recovering catalytic metals from the coke-like material comprises subjecting the coke-like material to leaching reactions.

19. The process of claim 1, wherein the fine catalyst slurried in heavy oil comprises particles having a mean particle size of 4-5 micron.