U.S. patent application number 11/400628 was filed with the patent office on 2006-10-19 for systems, methods, and catalysts for producing a crude product.
Invention is credited to Opinder Kishan Bhan.
Application Number | 20060231457 11/400628 |
Document ID | / |
Family ID | 36636339 |
Filed Date | 2006-10-19 |
United States Patent
Application |
20060231457 |
Kind Code |
A1 |
Bhan; Opinder Kishan |
October 19, 2006 |
Systems, methods, and catalysts for producing a crude product
Abstract
Methods and systems for contacting of a crude feed with one or
more catalysts to produce a total product that includes a crude
product are described. The crude product is a liquid mixture at
25.degree. C. and 0.101 MPa. The crude product has a nitrogen
content of at most 90% of the nitrogen content of the crude feed.
One or more other properties of the crude product may be changed by
at least 10% relative to the respective properties of the crude
feed.
Inventors: |
Bhan; Opinder Kishan; (Katy,
TX) |
Correspondence
Address: |
SHELL OIL COMPANY
P O BOX 2463
HOUSTON
TX
772522463
US
|
Family ID: |
36636339 |
Appl. No.: |
11/400628 |
Filed: |
April 7, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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60670136 |
Apr 11, 2005 |
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Current U.S.
Class: |
208/85 ;
502/100 |
Current CPC
Class: |
C10G 45/08 20130101;
B01J 23/882 20130101; B01J 35/10 20130101; B01J 35/1042 20130101;
B01J 35/108 20130101; C10G 45/04 20130101; B01J 37/0009 20130101;
B01J 35/1061 20130101; B01J 23/883 20130101; B01J 21/04 20130101;
B01J 37/20 20130101; B01J 21/12 20130101; C10G 45/10 20130101; C10G
65/04 20130101; B01J 35/1019 20130101; B01J 23/28 20130101 |
Class at
Publication: |
208/085 ;
502/100 |
International
Class: |
C10G 71/00 20060101
C10G071/00 |
Claims
1. A method of producing a crude product, comprising: contacting a
crude feed with one or more catalysts to produce a total product
that includes the crude product, wherein the crude product is a
liquid mixture at 25.degree. C. and 0.101 MPa; the crude feed has a
nitrogen content of at least 0.0001 grams per gram of crude feed;
and at least one of the catalysts is a Column 6 metal catalyst that
comprises: one or more metals from Column 6 of the Periodic Table
and/or one or more compounds of one or more metals from Column 6 of
the Periodic Table; a pore size distribution with a median pore
diameter of greater than 110 .ANG.; and a pore volume in which
pores having a pore diameter of at least 350 .ANG. provide at most
10% of the pore volume, wherein pore diameter and pore volume are
as determined by ASTM Method D4282; and controlling contacting
conditions such that the crude product has a nitrogen content of at
most 90% of the nitrogen content of the crude feed, wherein
nitrogen content is as determined by ASTM Method D5762.
2. The method as claimed in claim 1, wherein pores having a pore
diameter of at least 350 .ANG. provide at most 5% of the pore
volume.
3. The method as claimed in claims 1, wherein the nitrogen content
of the crude product is at most 50% of the nitrogen content of the
crude feed.
4. The method as claimed in claim 1, wherein the nitrogen content
of the crude product is in a range from 0.1% to 75% of the nitrogen
content of the crude feed.
5. The method as claimed in claim 1, wherein the crude feed has
from 0.0001 grams to 0.1 grams, 0.001 grams to 0.05 grams of
nitrogen per gram of crude feed.
6. The method as claimed in claim 1, wherein the crude product has
from 0.00001 grams to 0.05 grams of nitrogen per gram of crude
product.
7. The method as claimed in claim 1, wherein the Column 6 metal
catalyst has, per gram of catalyst, from 0.0001 grams to 0.3 grams
of one or more of the Column 6 metals and/or one or more of the
Column 6 metal compounds, calculated as total weight of Column 6
metal.
8. The method as claimed in claim 1, wherein the Column 6 metal
catalyst comprises in addition one or more metals from Columns 7-10
of the Periodic Table and/or one or more compounds of one or more
metals from Columns 7-10 of the Periodic Table.
9. The method as claimed in claim 8, wherein the Column 6 metal
catalyst has, per gram of catalyst, from 0.001 grams to 0.1 grams
of one or more of the Columns 7-10 metals and/or one or more of the
Columns 7-10 metal compounds, calculated as total weight of Columns
7-10 metals.
10. The method as claimed in claim 1, wherein the Column 6 metal
catalyst comprises in addition one or more metals from Column 10 of
the Periodic Table and/or one or more compounds of one or more
metals from Column 10 of the Periodic Table.
11. The method as claimed in claim 1, wherein the Column 6 metal
catalyst comprises molybdenum and/or tungsten.
12. The method as claimed in claim 11, wherein the Column 6 metal
catalyst comprises nickel.
13. The method as claimed in claim 11, wherein the Column 6 metal
catalyst comprises nickel and iron.
14. The method as claimed in claim 13, wherein a molar ratio of
total molybdenum to total nickel and iron is at least 1.5.
15. The method as claimed in claim 1, wherein the Column 6 metal
catalyst comprises in addition one or more elements from Column 15
of the Periodic Table and/or one or more compounds of one or more
elements from Column 15 of the Periodic Table.
16. The method as claimed in claim 15, wherein the catalyst has,
per gram of catalyst, from 0.000001 grams to 0.1 grams of one or
more of the Column 15 elements and/or one or more of the Column 15
element compounds, calculated as total weight of Column 15
element.
17. The method as claimed in claim 1, wherein the Column 6 metal
catalyst comprises in addition phosphorus.
18. The method as claimed in claim 1, wherein the Column 6 metal
catalyst has, per gram of catalyst, from 0.001 grams to 0.15 grams
of molybdenum and/or one or more compounds of molybdenum,
calculated as total weight of molybdenum; and from 0.001 grams to
0.05 grams of nickel and/or one or more compounds of nickel,
calculated as total weight of nickel.
19. The method as claimed in claim 18, wherein the Column 6 metal
catalyst has in addition, per gram of catalyst, from 0.001 grams to
0.05 grams of phosphorus and/or one or more compounds of
phosphorus, calculated as total weight of phosphorus.
20. The method as claimed in claim 19, wherein the Column 6 metal
catalyst has in addition, per gram of catalyst, from 0.001 grams to
0.05 grams of iron and/or one or more compounds of iron, calculated
as total weight of iron.
21. The method as claimed in claim 1, wherein the Column 6 metal
catalyst has at most 0.001 grams per gram of catalyst of one or
more metals from Column 5 of the Periodic Table and/or one or more
compounds of one or more metals from Column 5 of the Periodic
Table, calculated as total weight of Column 5 metal.
22. The method as claimed in claim 1, wherein the Column 6 metal
catalyst has a median pore diameter of at least 120 .ANG. or at
most 300 .ANG., wherein pore size distribution is as determined by
ASTM Method D4282.
23. The method as claimed in claim 1, wherein the Column 6 metal
catalyst has a pore size distribution such that at least 60% of the
total number of pores in the pore size distribution are within 45
.ANG. of the median pore diameter of the pore size
distribution.
24. The method as claimed in claim 1, wherein the Column 6 metal
catalyst comprises in addition a support, and the support has, per
gram of support, at least 0.8 grams of gamma alumina.
25. The method as claimed in claim 24, wherein the support has, per
gram of support, at most 0.1 grams of silica.
26. The method as claimed in claim 1, wherein the Column 6 metal
catalyst is obtainable by combining a mixture with one or more of
the Column 6 metals and/or one or more of the Column 6 metal
compounds, and the mixture comprises: one or more metals from
Columns 7-10 of the Periodic Table and/or one or more compounds of
one or more metals from Columns 7-10 of the Periodic Table; and a
support.
27. The method as claimed in claim 26, wherein at least one of the
Columns 7-10 metals comprises nickel, cobalt, iron, or mixtures
thereof.
28. The method as claimed in claim 1, wherein crude feed also has a
C.sub.5 asphaltenes content, and the crude product has a C.sub.5
asphaltenes content of at most 90% of the C.sub.5 asphaltenes
content of the crude feed, wherein C.sub.5 asphaltenes content is
as determined by ASTM Method D2007.
29. The method as claimed in claim 1, wherein the crude product has
a viscosity at 37.8.degree. C. (100.degree. F.) of at most 90% of
the viscosity at 37.8.degree. C. of the crude feed, wherein
viscosity is as determined by ASTM Method D445.
30. The method as claimed in claim 1, wherein the crude feed also
has a sulfur content, and the crude product has a sulfur content of
at most 90% of the sulfur content of the crude feed, wherein sulfur
content is as determined by ASTM Method D4294.
31. The method as claimed in claim 1, wherein the crude feed also
has a residue content, and the crude product has a residue content
of at most 90% of the residue content of the crude feed, wherein
residue content is as determined by ASTM Method D5307.
32. The method as claimed in claim 1, wherein the contacting is
performed in the presence of a hydrogen source.
33. The method as claimed in claim 1, wherein the contacting
conditions comprise: a temperature within the range of 50.degree.
C. to 500.degree. C.; a total pressure within a range of 0.1 MPa to
20 MPa; a liquid hourly space velocity of at least 0.05 h.sup.-1;
and a ratio of a gaseous hydrogen source to the crude feed in a
range from 0.1 Nm.sup.3/m.sup.3 to 100,000 Nm.sup.3/m.sup.3.
34. The method as claimed in claim 33, wherein the total pressure
is at most 18 MPa.
35. The method as claimed in claim 33, wherein the temperature is
at most 430.degree. C.
36. The method as claimed in claim 1, wherein a crude feed/total
product mixture has a P-value of at least 1.5 during
contacting.
37. The method as claimed in claim 1, wherein the method further
comprises combining the crude product with a crude that is the same
as or different from the crude feed to form a blend.
38. The method of claim 1 or claim 37 further comprising the step
of processing the crude product or blend to produce transportation
fuel, heating fuel, lubricants, or chemicals.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional
Application 60/670,136 filed on Apr. 11, 2005, herein incorporated
by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention generally relates to systems, methods,
and catalysts for treating crude feed. More particularly, certain
embodiments described herein relate to systems, methods, and
catalysts for conversion of a crude feed to a total product,
wherein the total product includes a crude product that is a liquid
mixture at 25.degree. C. and 0.101 MPa, and has one or more
properties that are changed relative to the respective property of
the crude feed.
DESCRIPTION OF RELATED ART
[0003] Crudes that have one or more unsuitable properties that do
not allow the crudes to be economically transported, or processed
using conventional facilities, are commonly referred to as
"disadvantaged crudes".
[0004] Disadvantaged crudes may include acidic components that
contribute to the total acid number ("TAN") of the crude feed.
Disadvantaged crudes with a relatively high TAN may contribute to
corrosion of metal components during transporting and/or processing
of the disadvantaged crudes. Removal of acidic components from
disadvantaged crudes may involve chemically neutralizing acidic
components with various bases. Alternately, corrosion-resistant
metals may be used in transportation equipment and/or processing
equipment. The use of corrosion-resistant metal often involves
significant expense, and thus, the use of corrosion-resistant metal
in existing equipment may not be desirable. Another method to
inhibit corrosion may involve addition of corrosion inhibitors to
disadvantaged crudes before transporting and/or processing of the
disadvantaged crudes. The use of corrosion inhibitors may
negatively affect equipment used to process the crudes and/or the
quality of products produced from the crudes.
[0005] Disadvantaged crudes often contain relatively high levels of
residue. Disadvantaged crudes having high levels of residue tend to
be difficult and expensive to transport and/or process using
conventional facilities.
[0006] Disadvantaged crudes often contain organically bound
heteroatoms (for example, sulfur, oxygen, and nitrogen).
Organically bound heteroatoms may, in some situations, have an
adverse effect on catalysts used to process disadvantaged
crudes.
[0007] Disadvantaged crudes may include relatively high amounts of
metal contaminants, for example, nickel, vanadium, and/or iron.
During processing of such crudes, metal contaminants and/or
compounds of metal contaminants, may deposit on a surface of the
catalyst or in the void volume of the catalyst. Such deposits may
cause a decline in the activity of the catalyst.
[0008] Disadvantaged crudes may have components that contribute
coke and/or to thermal degradation of the disadvantaged crude. The
coke and/or thermally degraded components may form and/or deposit
on catalyst surfaces at a rapid rate during processing of
disadvantaged crudes. It may be costly to regenerate the catalytic
activity of a catalyst contaminated with coke and/or thermally
degraded crude. Additionally, high temperatures used during
regeneration of a catalyst may also diminish the activity of the
catalyst and/or cause the catalyst to deteriorate.
[0009] Disadvantaged crudes may include metals (for example,
calcium, potassium and/or sodium) in metal salts of organic acids.
Metals in metal salts of organic acids are not typically separated
from disadvantaged crudes by conventional production processing,
for example, desalting and/or acid washing.
[0010] Problems are often encountered in conventional catalytic
processing of crudes when metals in metal salts of organic acids
are present. In contrast to nickel and vanadium, which typically
deposit near the external surface of the catalyst, metals in metal
salts of organic acids may deposit preferentially in void volumes
between catalyst particles, particularly at the top of the catalyst
bed. The deposit of contaminants, for example, metals in metal
salts of organic acids, at the top of the catalyst bed, generally
results in an increase in pressure drop through the bed and may
effectively plug the bed. Moreover, the metals in metal salts of
organic acids may cause rapid deactivation of catalysts.
[0011] Disadvantaged crudes may include organic oxygen compounds.
Treatment facilities that process disadvantaged crudes with an
oxygen content of at least 0.002 grams of oxygen per gram of
disadvantaged crude may encounter problems during processing.
Organic oxygen compounds, when heated during processing, may form
higher oxidation compounds (for example, ketones and/or acids
formed by oxidation of alcohols, and/or acids formed by oxidation
of ethers) that are difficult to remove from the treated crude
and/or may corrode/contaminate equipment during processing and
cause plugging in transportation lines.
[0012] Disadvantaged crudes may include hydrogen deficient
hydrocarbons. When processing hydrogen deficient hydrocarbons,
consistent quantities of hydrogen generally need to be added,
particularly if unsaturated fragments resulting from cracking
processes are produced. Hydrogenation during processing, which
typically involves the use of an active hydrogenation catalyst, may
be needed to inhibit unsaturated fragments from forming coke.
Hydrogen is costly to produce and/or costly to transport to
treatment facilities.
[0013] Disadvantaged crudes also tend to exhibit instability during
processing in conventional facilities. Crude instability tends to
result in phase separation of components during processing and/or
formation of undesirable by-products (for example, hydrogen
sulfide, water, and carbon dioxide).
[0014] Conventional processes for treating disadvantaged crudes may
reduce the amount of components that contribute to high viscosity,
thermal degradation of the disadvantaged crude, and/or coking.
Removal of these components, however, may cause instability in the
crude, thus causing separation of the crude during transportation.
During conventional processing, components that contribute to high
viscosity and/or coking are typically removed when the crude is
treated with a catalyst that has a large pore size, a high surface
area, and a low hydrotreating activity. The resulting crude may
then be further treated to remove other unwanted components in the
crude.
[0015] Some processes for improving the quality of crude include
adding a diluent to disadvantaged crudes to lower the weight
percent of components contributing to the disadvantaged properties.
Adding diluent, however, generally increases costs of treating
disadvantaged crudes due to the costs of diluent and/or increased
costs to handle the disadvantaged crudes. Addition of diluent to a
disadvantaged crude may, in some situations, decrease stability of
such crude.
[0016] U.S. Pat. No. 6,547,957 to Sudhakar et al.; U.S. Pat. No.
6,277,269 to Myers et al.; U.S. Pat. No. 6,203,695 to Harle et al.;
U.S. Pat. No. 6,063,266 to Grande et al.; U.S. Pat. No. 5,928,502
to Bearden et al.; U.S. Pat. No. 5,914,030 to Bearden et al.; U.S.
Pat. No. 5,897,769 to Trachte et al.; U.S. Pat. No. 5,744,025 to
Boon et al.; U.S. Pat. No. 4,212,729 to Hensley, Jr., and U.S. Pat.
No. 4,048,060 to Riley; and U.S. Patent Application Publication No.
US 2004/0106516 to Schulz et al., all of which are incorporated
herein by reference, describe various processes, systems, and
catalysts for processing crudes. The processes, systems, and
catalysts described in these patents, however, have limited
applicability because of many of the technical problems set forth
above.
[0017] In sum, disadvantaged crudes generally have undesirable
properties (for example, relatively high TAN, a tendency to become
unstable during treatment, and/or a tendency to consume relatively
large amounts of hydrogen during treatment). Disadvantaged crudes
may also include relatively high amounts of undesirable components
(for example, components that contribute to thermal degradation,
residue, organically bound heteroatoms, metal contaminants, metals
in metal salts of organic acids, and/or organic oxygen compounds).
Such properties and components tend to cause problems in
conventional transportation and/or treatment facilities, including
increased corrosion, decreased catalyst life, process plugging,
and/or increased usage of hydrogen during treatment. Thus, there is
a significant economic and technical need for improved systems,
methods, and/or catalysts for conversion of disadvantaged crudes
into crude products with more desirable properties. There is also a
significant economic and technical need for systems, methods,
and/or catalysts that can change selected properties in a
disadvantaged crude while minimizing changes to other properties in
the disadvantaged crude.
SUMMARY OF THE INVENTION
[0018] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa; the crude feed has a micro-carbon
residue ("MCR") content of at least 0.0001 grams per gram of crude
feed; and at least one of the catalysts is a Column 6 metal
catalyst that comprises: one or more metals from Column 6 of the
Periodic Table and/or one or more compounds of one or more metals
from Column 6 of the Periodic Table; a pore size distribution with
a median pore diameter of greater than 110 .ANG.; and a pore volume
in which pores having a pore diameter of at least 350 .ANG. provide
at most 10% of the pore volume, wherein pore volume and pore
diameter are as determined by ASTM Method D4282; and controlling
contacting conditions such that the crude product has a MCR content
of at most 90% of the MCR content of the crude feed, wherein MCR
content is as determined by ASTM Method D4530.
[0019] In some embodiments, the invention also provides a catalyst,
comprising: a support; and one or more metals from Column 6 of the
Periodic Table and/or one or more compounds of one or more metals
from Column 6 of the Periodic Table; wherein the catalyst has a
pore size distribution with a median pore diameter greater than 110
.ANG. and a pore volume in which pores having a pore diameter of at
least 350 .ANG. provide at most 10% of the pore volume, wherein
pore diameter and pore volume are as determined by ASTM Method
D4282.
[0020] In some embodiments, the invention also provides a method of
making a catalyst, comprising: combining a support with a metal
solution comprising one or more metals from Column 6 of the
Periodic Table and/or one or more compounds of one or more metals
from Column 6 of the Periodic Table, wherein the support has an
average pore diameter of at least 90 .ANG. and a pore volume in
which pores having a pore diameter of at least 350 .ANG. provide at
most 15% of the pore volume of the support, wherein pore diameter
and pore volume are as determined by ASTM Method D4282.
[0021] In some embodiments, the invention also provides a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed has a MCR content of at
least 0.0001 grams per gram of crude feed, and at least one of the
catalysts is a Columns 6-10 catalyst that has, per gram of
catalyst, at least 0.3 grams of one or more metals from Columns
6-10 of the Periodic Table and/or one or more compounds of one or
more metals from Columns 6-10 of the Periodic Table; and a binder;
and controlling contacting conditions such that the crude product
has a MCR content of at most 90% of the MCR content of the crude
feed, wherein MCR content is as determined by ASTM Method
D4530.
[0022] In some embodiments, the invention also provides a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed comprises one or more
alkali metal salts of one or more organic acids, alkaline-earth
metal salts of one or more organic acids, or mixtures thereof, the
crude feed has, per gram of crude feed, a total content of alkali
metal and alkaline-earth metal in metal salts of organic acids of
at least 0.00001 grams, and at least one of the catalysts is a
Columns 5-10 metal catalyst that comprises: a support, the support
comprising theta alumina; and one or more metals from Columns 5-10
of the Periodic Table and/or one or more compounds of one or more
metals from Columns 5-10 of the Periodic Table; and controlling
contacting conditions such that the crude product has a total
content of alkali metal and alkaline-earth metal in metal salts of
organic acids of at most 90% of the content of alkali metal and
alkaline-earth metal in metal salts of organic acids in the crude
feed, wherein content of alkali metal and alkaline-earth metal in
metal salts of organic acids is as determined by ASTM Method
D11318.
[0023] In some embodiments, the invention also provides a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa; the crude feed has a nitrogen content
of at least 0.0001 grams per gram of crude feed; and at least one
of the catalysts is a Column 6 metal catalyst that comprises: one
or more metals from Column 6 of the Periodic Table and/or one or
more compounds of one or more metals from Column 6 of the Periodic
Table; a pore size distribution with a median pore diameter of
greater than 110 .ANG.; and a pore volume in which pores having a
pore diameter of at least 350 .ANG. provide at most 10% of the pore
volume, wherein pore diameter and pore volume are as determined by
ASTM Method D4282; and controlling contacting conditions such that
the crude product has a nitrogen content of at most 90% of the
nitrogen content of the crude feed, wherein nitrogen content is as
determined by ASTM Method D5762.
[0024] In some embodiments, the invention also provides a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa; the crude feed has a nitrogen content
of at least 0.0001 grams per gram of crude feed; wherein at least
one of the catalysts is a Column 6 metal catalyst that is
obtainable by heating a Column 6 metal catalyst precursor in the
presence of one or more sulfur containing compounds at a
temperature below about 500.degree. C., wherein the Column 6 metal
catalyst precursor comprises: one or more metals from Column 6 of
the Periodic Table and/or one or more compounds of one or more
metals from Column 6 of the Periodic Table; and a support; and
controlling contacting conditions such that the crude product has a
nitrogen content of at most 90% of the nitrogen content of the
crude feed, wherein nitrogen content is as determined by ASTM
Method D5762.
[0025] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, the Column 6
metal catalyst: (a) in which pores having a pore diameter of at
least 350 .ANG. provide at most 5%, at most 3%, at most 1%, or at
most 0.5% of the pore volume; (b) has a pore size distribution with
a median pore diameter of at least 120 .ANG., at least 130 .ANG.,
at least 150 .ANG., at least 180 .ANG., at least 200 .ANG., at
least 250 .ANG., or at most 300 .ANG., wherein pore size
distribution is as determined by ASTM Method D4282; and/or (c) has
a pore size distribution such that at least 60% of the total number
of pores in the pore size distribution are within about 45 .ANG.,
about 35 .ANG., or about 25 .ANG. of the median pore diameter of
the pore size distribution.
[0026] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, that the
Column 6 metal catalyst: (a) has, per gram of catalyst, from about
0.0001 grams to about 0.3 grams, about 0.005 grams to about 0.2
grams, or about 0.01 grams to about 0.1 grams of one or more of the
Column 6 metals and/or one or more of the Column 6 metal compounds,
calculated as total weight of Column 6 metal; (b) comprises one or
more metals from Columns 7-10 of the Periodic Table and/or one or
more compounds of one or more metals from Columns 7-10 of the
Periodic Table; and has, per gram of catalyst, from about 0.001
grams to about 0.1 grams or about 0.01 grams to about 0.05 grams of
one or more of the Columns 7-10 metals and/or one or more of the
Columns 7-10 metal compounds, calculated as total weight of Columns
7-10 metals; (c) comprises one or more metals from Column 10 of the
Periodic Table and/or one or more compounds of one or more metals
from Column 10 of the Periodic Table; (d) comprises molybdenum
and/or tungsten; (e) comprises nickel and/or cobalt; (f) comprises
nickel and/or iron; (g) comprises one or more elements from Column
15 of the Periodic Table and/or one or more compounds of one or
more elements from Column 15 of the Periodic Table; and has, per
gram of catalyst, from about 0.000001 grams to about 0.1 grams,
about 0.00001 grams to about 0.06 grams, about 0.00005 grams to
about 0.03 grams, or about 0.0001 grams to about 0.001 grams of one
or more of the Column 15 elements and/or one or more of the Column
15 element compounds, calculated as total weight of Column 15
element; (h) comprises phosphorus; and/or (i) has, per gram of
catalyst, at most 0.001 grams of one or more metals from Column 5
of the Periodic Table and/or one or more compounds of one or more
metals from Column 5 of the Periodic Table, calculated as total
weight of Column 5 metal.
[0027] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, that the
Column 6 metal catalyst or Column 6 metal solution has, per gram of
catalyst or Column 6 metal solution: (a) from about 0.01 grams to
about 0.15 grams of molybdenum and/or one or more compounds of
molybdenum, calculated as total weight of molybdenum; and from
about 0.001 grams to about 0.05 grams of nickel and/or one or more
compounds of nickel, calculated as total weight of nickel; and (b)
optionally, from about 0.001 grams to about 0.05 grams of iron
and/or one or more compounds of iron, calculated as total weight of
iron; and (c) optionally, from about 0.0001 grams to about 0.05
grams of phosphorus and/or one or more compounds of phosphorus,
calculated as total weight of phosphorus.
[0028] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, that the
Columns 5-10 metal catalyst: (a) comprises molybdenum; (b)
comprises tungsten; (c) comprises vanadium; (d) has, per gram of
catalyst, from about 0.001 grams to about 0.1 grams or about 0.01
grams to about 0.05 grams of one or more metals from Columns 7-10
of the Periodic Table and/or one or more compounds of one or more
metals from Columns 7-10 of the Periodic Table; (e) comprises one
or more elements from Column 15 of the Periodic Table and/or one or
more compounds of one or more elements from Column 15 of the
Periodic Table; (f) comprises phosphorus; and/or (g) has a pore
size distribution with a median pore diameter of at least 180
.ANG., at least 200 .ANG., at least 230 .ANG., at least 250 .ANG.,
or at least 300 .ANG..
[0029] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, that the
Column 6 metal catalyst is a supported catalyst, in which the
support has, per gram of support: (a) at least 0.8 grams, at least
0.9 grams, or at least 0.95 grams of gamma alumina; (b) at most 0.1
grams, at most 0.08 grams, at most 0.06 grams, at most 0.04 grams,
or at most 0.02 grams of silica, or (c) at least 0.3 grams or at
least 0.5 grams of theta alumina.
[0030] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, contacting
the crude feed with one or more catalysts in which at least one or
more of the catalysts is a Column 6 metal catalyst that is
obtainable by combining a mixture with one or more of the Column 6
metals and/or one or more of the Column 6 metal compounds, and the
mixture comprises: one or more metals from Columns 7-10 of the
Periodic Table and/or one or more compounds of one or more metals
from Columns 7-10 of the Periodic Table; and a support. In some
embodiments, in combination with one or more of the above
embodiments, at least one of the Columns 7-10 metals comprises
nickel, cobalt, iron, or mixtures thereof.
[0031] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a crude feed
that has: (a) from about 0.0001 grams to about 0.5 grams, about
0.005 grams to about 0.1 grams, or about 0.01 grams to about 0.05
grams of MCR per gram of crude feed; (b) from about 0.0001 grams to
about 0.1 grams, about 0.001 grams to about 0.05 grams, or about
0.005 grams to about 0.01 grams of nitrogen per gram of crude feed;
and/or (c) from about 0.00001 grams to about 0.005 grams, about
0.00005 grams to about 0.05 grams, or about 0.0001 grams to about
0.01 grams of alkali metal and alkaline-earth metal in metal salts
of organic acids per gram of crude feed.
[0032] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a crude
product that has: (a) a MCR content of at most 80%, at most 50%, at
most 30%, or at most 10% of the MCR content of the crude feed; (b)
a nitrogen content of at most 80%, at most 50%, at most 30%, or at
most 10% of the nitrogen content of the crude feed; (c) a total
content of alkali metal, and alkaline-earth metal in metal salts of
organic acids in the crude product of at most 80%, at most 50%, at
most 30%, or at most 10% of the content of alkali metal, and
alkaline-earth metal, in metal salts of organic acids in the crude
feed; (d) a MCR content in a range from about 0.1% to about 75%,
about 0.5% to about 45%, about 1% to about 25%, or about 2% to
about 9% of the MCR content of the crude feed; (e) a nitrogen
content in a range from about 0.1% to about 75%, about 0.5% to
about 45%, about 1% to about 25%, or about 2% to about 9% of the
nitrogen content of the crude feed; (f) a total content of alkali
metal and alkaline-earth metal in metal salts of organic acids in
the crude product in a range from about 0.1% to about 75%, from
about 0.5% to about 45%, about 1% to about 25%, or about 2% to
about 9% of the content of alkali metal and alkaline-earth metal in
metal salts of organic acids in the crude feed; (g) from about
0.00001 grams to about 0.1 grams, about 0.0001 grams to about 0.05
grams, or about 0.001 grams to about 0.005 grams of MCR per gram of
crude product; (h) from about 0.00001 grams to about 0.05 grams,
about 0.0001 grams to about 0.01 grams, or about 0.0005 grams to
about 0.001 grams of nitrogen per gram of crude product; (i) from
about 1.times.10.sup.-7 grams to about 5.times.10.sup.-5 grams,
about 5.times.10.sup.-7 grams to about 1.times.10.sup.-5 grams, or
about 1.times.10.sup.-6 grams to about 5.times.10.sup.-6 grams of
alkali metal and alkaline-earth metal in metal salts of organic
acids per gram of crude product; (j) a viscosity at 37.8.degree. C.
(100.degree. F.) of at most 90%, at most 80%, at most 70%, at most
50%, at most 30%, or at most 10% of the viscosity at 37.8.degree.
C. (100.degree. F.) of the crude feed, wherein viscosity is as
determined by ASTM Method D445; (k) a C.sub.5 asphaltenes content
of most 90%, at most 80%, at most 70%, at most 50%, at most 30%, or
at most 10% of the C.sub.5 asphaltenes content of the crude feed,
wherein C.sub.5 asphaltenes content is as determined by ASTM Method
D2007; (1) a residue content of at most 90%, at most 80%, at most
70%, at most 50%, at most 30%, or at most 10% of the residue
content of the crude feed, wherein residue content is as determined
by ASTM Method D5307; and/or (m) a sulfur content of at most 90%,
at most 80%, at most 70%, at most 50%, at most 30%, or at most 10%
of the sulfur content of the crude feed, wherein sulfur content is
as determined by ASTM Method D4294.
[0033] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, contacting
the crude feed with one or more catalysts and one or more
additional catalysts, at least one of the catalysts is the Column 6
metal catalyst, and one or more of the additional catalysts has a
median pore diameter of at least 60 .ANG., at least 90 .ANG., at
least 110 .ANG., at least 180 .ANG., at least 200 .ANG., or at
least 250 .ANG.; and the Column 6 metal catalyst is contacted with
the crude feed prior to and/or after contact of the crude feed with
at least one of the additional catalysts.
[0034] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, at least one
of the catalysts is the Columns 5-10 metal catalyst; and contacting
the crude feed with an additional catalyst having a median pore
diameter of at least 60 .ANG., and the additional catalyst is
contacted with the crude feed subsequent to contact of the crude
feed with the Columns 5-10 metal catalyst.
[0035] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, contacting
the crude feed with one or more catalysts to produce a total
product in which, during contact, a crude feed/total product
mixture has a P-value of at least 1.5.
[0036] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, contacting
in the presence of a hydrogen source.
[0037] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, the
contacting conditions which comprise: (a) a temperature within the
range of about 50.degree. C. to about 500.degree. C.; (b) a
temperature of at most 430.degree. C., at most 420.degree. C., or
at most 410.degree. C.; (c) a total pressure within a range of
about 0.1 MPa to about 20 MPa; (d) a total pressure of at most 18
MPa, at most 16 MPa, or at most 14 MPa; (e) a liquid hourly space
velocity of at least 0.05 h.sup.-1; and/or (f) a ratio of a gaseous
hydrogen source to the crude feed in a range from about 0.1
Nm.sup.3/m.sup.3 to about 100,000 Nm.sup.3/m.sup.3.
[0038] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
that comprises contacting a crude feed with one or more catalysts
to produce a total product that includes a crude product, the
method further comprising combining the crude product with a crude
that is the same as or different from the crude feed to form a
blend suitable for transporting.
[0039] In some embodiments, the invention provides, in combination
with one or more of the above embodiments, a method of making a
catalyst that includes combining a support with a Column 6 metal
solution: (a) that has a pH of up to about 3; (b) that has a pH in
a range from about 1 to about 3; (c) in which an amount of Column 6
metal in the metal solution is selected such that the catalyst has,
per gram of catalyst, from about 0.0001 grams to about 0.3 grams,
about 0.005 grams to about 0.2 grams, or about 0.01 grams to about
0.1 grams of one or more of the Column 6 metals and/or one or more
of the Column 6 metal compounds, calculated as total weight of
Column 6 metal; (d) that comprises one or more metals from Columns
7-10 of the Periodic Table and/or one or more compounds of one or
more metals from Columns 7-10 of the Periodic Table; and where an
amount of Columns 7-10 metals is selected such that the catalyst
has, per gram of catalyst, from about 0.001 grams to about 0.1
grams or about 0.01 grams to about 0.05 grams of one or more of the
Columns 7-10 metals and/or one or more of the Columns 7-10 metal
compounds, calculated as total weight of Columns 7-10 metals; (e)
that comprises one or more metals from Column 10 of the Periodic
Table and/or one or more compounds of one or more metals from
Column 10 of the Periodic Table; (f) that comprises molybdenum
and/or tungsten; (g) that comprises nickel and/or cobalt; (h) that
comprises nickel and iron; (i) that comprises one or more elements
from Column 15 of the Periodic Table and/or one or more compounds
of one or more elements from Column 15 of the Periodic Table; and
where an amount of Columns 15 elements is selected such that the
catalyst has, per gram of catalyst, from about 0.000001 grams to
about 0.1 grams, about 0.00001 grams to about 0.06 grams, about
0.00005 grams to about 0.03 grams, or about 0.0001 grams to about
0.001 grams of one or more of the Column 15 elements and/or one or
more of the Column 15 element compounds, calculated as total weight
of Column 15 element; (j) that comprises phosphorus; (k) that
comprises one or more mineral acids; (l) that comprises one or more
organic acids; (m) that comprises hydrogen peroxide; and/or (n)
that comprises an amine.
[0040] In some embodiments, the invention provides, in combination
with one or more of the above embodiments, a method of making a
catalyst that includes: heat-treating the supported metal at a
temperature in a range from about 40.degree. C. to about
400.degree. C., about 60.degree. C. to about 300.degree. C., or
about 100.degree. C. to about 200.degree. C.; and optionally
further heat-treating the supported metal at a temperature of at
least 400.degree. C.
[0041] In some embodiments, the invention provides, in combination
with one or more of the above embodiments, a Columns 6-10 metal
catalyst: (a) that comprises one or more metals from Column 6 of
the Periodic Table and/or one or more compounds of one or more
metals from Column 6 of the Periodic Table; (b) that comprises one
or more metals from Columns 7-10 of the Periodic Table and/or one
or more compounds of one or more metals from Columns 7-10 of the
Periodic Table; (c) that comprises molybdenum and/or tungsten; (d)
that comprises nickel and/or cobalt; (e) in which the binder
comprises silica, alumina, silica/alumina, titanium oxide,
zirconium oxide, or mixtures thereof; and/or (f) that is
amorphous.
[0042] In further embodiments, features from specific embodiments
may be combined with features from other embodiments. For example,
features from one embodiment may be combined with features from any
of the other embodiments.
[0043] In further embodiments, crude products are obtainable by any
of the methods and systems described herein.
[0044] In further embodiments, additional features may be added to
the specific embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0045] Advantages of the present invention will become apparent to
those skilled in the art with the benefit of the following detailed
description and upon reference to the accompanying drawings in
which:
[0046] FIG. 1 is a schematic of an embodiment of a contacting
system.
[0047] FIGS. 2A and 2B are schematics of embodiments of contacting
systems that include two contacting zones.
[0048] FIGS. 3A and 3B are schematics of embodiments of contacting
systems that include three contacting zones.
[0049] FIG. 4 is a schematic of an embodiment of a separation zone
in combination with a contacting system.
[0050] FIG. 5 is a schematic of an embodiment of a blending zone in
combination with a contacting system.
[0051] FIG. 6 is a schematic of an embodiment of a combination of a
separation zone, a contacting system, and a blending zone.
[0052] While the invention is susceptible to various modifications
and alternative forms, specific embodiments thereof are shown by
way of example in the drawings. The drawings may not be to scale.
It should be understood that the drawings and detailed description
thereto are not intended to limit the invention to the particular
form disclosed, but on the contrary, the intention is to cover all
modifications, equivalents and alternatives falling within the
spirit and scope of the present invention as defined by the
appended claims.
DETAILED DESCRIPTION
[0053] The above problems may be addressed using systems, methods,
and catalysts described herein. For example, the crude product
having reduced MCR content and/or a reduced nitrogen content
relative to the MCR content and/or the nitrogen content of the
crude feed is produced by contacting the crude feed with the
catalyst that has a pore size distribution with a median pore
diameter of greater than 110 .ANG., and a pore volume in which
pores having a pore diameter of at least 350 .ANG. provide at most
10% of the pore volume. Crude product having reduced nitrogen
content relative to the nitrogen content of the crude feed is
produced by contacting the crude feed with the uncalcined catalyst.
Crude product having reduced content of metals in metal salts of
organic acids relative to the content of metals in metal salts of
organic acids of the crude feed is produced by contacting the crude
feed with the catalyst that includes Columns 5-10 metal(s) and
theta alumina. Crude product having reduced MCR content relative to
the MCR content of the crude feed is produced by contacting the
crude feed with the bulk metal catalyst.
[0054] U.S. application Ser. Nos. 11/014,335; 11/013,553;
11/014,386; 11/013,554; 11/013,629; 11/014,318; 11/013,576;
11/013,835; 11/014,362; 11/014,011; 11/013,747; 11/013,918;
11/014,275; 11/014,060; 11/014,272; 11/014,380; 11/014,005;
11/013,998; 11/014,406; 11/014,365; 11/013,545; 11/014,132;
11/014,363; 11/014,251; 11/013,632; 11/014,009; 11/014,297;
11/014,004; 11/013,999; 11/014,281; 11/013,995; 11/013,904,
11/013,952; 11/014,299; 11/014,381; 11/014,346; 11/014,028;
11/013,826; and 11/013,622 also discuss systems, methods, and
catalysts that address the above problems, albeit with respect to
crude feeds that may differ in some respects from the crude feeds
treated in accordance with the inventions described herein.
[0055] Certain embodiments of the inventions are described herein
in more detail. Terms used herein are defined as follows.
[0056] "ASTM" refers to American Standard Testing and
Materials.
[0057] "API gravity" refers to API gravity at 15.5.degree. C.
(60.degree. F.). API gravity is as determined by ASTM Method
D6822.
[0058] Atomic hydrogen percentage and atomic carbon percentage of
the crude feed and the crude product are as determined by ASTM
Method D5291.
[0059] Boiling range distributions for the crude feed, the total
product, and/or the crude product are as determined by ASTM Method
D5307 unless otherwise mentioned.
[0060] "Binder" refers to a substrate that combines smaller
particles together to form larger substances (for example, blocks
or pellets).
[0061] "Bulk metal catalyst" refers to a catalyst that includes at
least one metal, and does not require a carrier or a support.
[0062] "C.sub.5 asphaltenes" refers to asphaltenes that are
insoluble in pentane. C.sub.5 asphaltenes content is as determined
by ASTM Method D2007.
[0063] "Column X metal(s)" refers to one or more metals of Column X
of the Periodic Table and/or one or more compounds of one or more
metals of Column X of the Periodic Table, in which X corresponds to
a column number (for example, 1-12) of the Periodic Table. For
example, "Column 6 metal(s)" refers to one or more metals from
Column 6 of the Periodic Table and/or one or more compounds of one
or more metals from Column 6 of the Periodic Table.
[0064] "Column X element(s)" refers to one or more elements of
Column X of the Periodic Table, and/or one or more compounds of one
or more elements of Column X of the Periodic Table, in which X
corresponds to a column number (for example, 13-18) of the Periodic
Table. For example, "Column 15 element(s)" refers to one or more
elements from Column 15 of the Periodic Table and/or one or more
compounds of one or more elements from Column 15 of the Periodic
Table.
[0065] In the scope of this application, weight of a metal from the
Periodic Table, weight of a compound of a metal from the Periodic
Table, weight of an element from the Periodic Table, or weight of a
compound of an element from the Periodic Table is calculated as the
weight of metal or the weight of element. For example, if 0.1 grams
of MoO.sub.3 is used per gram of catalyst, the calculated weight of
the molybdenum metal in the catalyst is 0.067 grams per gram of
catalyst.
[0066] "Content" refers to the weight of a component in a substrate
(for example, a crude feed, a total product, or a crude product)
expressed as weight fraction or weight percentage based on the
total weight of the substrate. "Wtppm" refers to parts per million
by weight.
[0067] "Crude feed/total product mixture" refers to the mixture
that contacts the catalyst during processing.
[0068] "Distillate" refers to hydrocarbons with a boiling range
distribution between 204.degree. C. (400.degree. F.) and
343.degree. C. (650.degree. F.) at 0.101 MPa. Distillate content is
as determined by ASTM Method D5307.
[0069] "Heteroatoms" refers to oxygen, nitrogen, and/or sulfur
contained in the molecular structure of a hydrocarbon. Heteroatoms
content is as determined by ASTM Methods E385 for oxygen, D5762 for
total nitrogen, and D4294 for sulfur. "Total basic nitrogen" refers
to nitrogen compounds that have a pKa of less than 40. Basic
nitrogen ("bn") is as determined by ASTM Method D2896.
[0070] "Hydrogen source" refers to hydrogen, and/or a compound
and/or compounds that when in the presence of a crude feed and a
catalyst react to provide hydrogen to compound(s) in the crude
feed. A hydrogen source may include, but is not limited to,
hydrocarbons (for example, C.sub.1 to C.sub.4 hydrocarbons such as
methane, ethane, propane, butane), water, or mixtures thereof. A
mass balance may be conducted to assess the net amount of hydrogen
provided to the compound(s) in the crude feed.
[0071] "Flat plate crush strength" refers to compressive force
needed to crush a catalyst. Flat plate crush strength is as
determined by ASTM Method D4179.
[0072] "LHSV" refers to a volumetric liquid feed rate per total
volume of catalyst, and is expressed in hours (h.sup.-1). Total
volume of catalyst is calculated by summation of all catalyst
volumes in the contacting zones, as described herein.
[0073] "Liquid mixture" refers to a composition that includes one
or more compounds that are liquid at standard temperature and
pressure (25.degree. C., 0.101 MPa, hereinafter referred to as
"STP"), or a composition that includes a combination of one of more
compounds that are liquid at STP with one or more compounds that
are solids at STP.
[0074] "Periodic Table" refers to the Periodic Table as specified
by the International Union of Pure and Applied Chemistry (IUPAC),
November 2003.
[0075] "Metals in metal salts of organic acids" refer to alkali
metals, alkaline-earth metals, zinc, arsenic, chromium, or
combinations thereof. A content of metals in metal salts of organic
acids is as determined by ASTM Method D1318.
[0076] "MCR" content refers to a quantity of carbon residue
remaining after evaporation and pyrolysis of a substrate. MCR
content is as determined by ASTM Method D4530.
[0077] "Naphtha" refers to hydrocarbon components with a boiling
range distribution between 38.degree. C. (100.degree. F.) and
200.degree. C. (392.degree. F.) at 0.101 MPa. Naphtha content is as
determined by ASTM Method D5307.
[0078] "Ni/V/Fe" refers to nickel, vanadium, iron, or combinations
thereof.
[0079] "Ni/V/Fe content" refers to the content of nickel, vanadium,
iron, or combinations thereof. The Ni/V/Fe content is as determined
by ASTM Method D5708.
[0080] "Nm.sup.3/m.sup.3" refers to normal cubic meters of gas per
cubic meter of crude feed.
[0081] "Non-carboxylic containing organic oxygen compounds" refers
to organic oxygen compounds that do not have a carboxylic
(--CO.sub.2--) group. Non-carboxylic containing organic oxygen
compounds include, but are not limited to, ethers, cyclic ethers,
alcohols, aromatic alcohols, ketones, aldehydes, or combinations
thereof, which do not have a carboxylic group.
[0082] "Non-condensable gas" refers to components and/or mixtures
of components that are gases at STP.
[0083] "P (peptization) value" or "P-value" refers to a numeral
value, which represents the flocculation tendency of asphaltenes in
the crude feed. Determination of the P-value is described by J. J.
Heithaus in "Measurement and Significance of Asphaltene
Peptization", Journal of Institute of Petroleum, Vol. 48, Number
458, February 1962, pp. 45-53.
[0084] "Pore diameter", "average pore diameter", "median pore
diameter", and "pore volume" refer to pore diameter, average pore
diameter, median pore diameter, and pore volume, as determined by
ASTM Method D4284 (mercury porosimetry at a contact angle equal to
140.degree.). A micromeritics.RTM. A9220 instrument (Micromeritics
Inc., Norcross, Ga., U.S.A.) may be used to determine these values.
Pore volume includes the volume of all pores in the catalyst.
Median pore diameter refers to the pore diameter where 50% of the
total number of pores have a pore diameter above the median pore
diameter and 50% of the total number of pores have a pore diameter
below the median pore diameter. Average pore diameter, expressed in
Angstrom units (A), is determined using the following equation:
Average pore diameter=(40,000.times.total pore volume in
cm.sup.3/g)/(surface area in m.sup.2/g).
[0085] "Residue" refers to components that have a boiling range
distribution above 538.degree. C. (1000.degree. F.), as determined
by ASTM Method D5307.
[0086] "SCFB" refers to standard cubic feet of gas per barrel of
crude feed.
[0087] "Surface area" of a catalyst is as determined by ASTM Method
D3663.
[0088] "TAN" refers to a total acid number expressed as milligrams
("mg") of KOH per gram ("g") of sample. TAN is as determined by
ASTM Method D664.
[0089] "VGO" refers to hydrocarbons with a boiling range
distribution between 343.degree. C. (650.degree. F.) and
538.degree. C. (1000.degree. F.) at 0.101 MPa. VGO content is as
determined by ASTM Method D5307.
[0090] "Viscosity" refers to kinematic viscosity at 37.8.degree. C.
(100.degree. F.). Viscosity is as determined using ASTM Method
D445.
[0091] All referenced methods are incorporated herein by reference.
In the context of this application, it is to be understood that if
the value obtained for a property of the substrate tested is
outside of limits of the test method, the test method may be
modified and/or recalibrated to test for such property.
[0092] Crudes may be produced and/or retorted from hydrocarbon
containing formations and then stabilized. Crudes are generally
solid, semi-solid, and/or liquid. Crudes may include crude oil.
Stabilization may include, but is not limited to, removal of
non-condensable gases, water, salts, solids, or combinations
thereof from the crude to form a stabilized crude. Such
stabilization may often occur at, or proximate to, the production
and/or retorting site.
[0093] Stabilized crudes include crudes that have not been
distilled and/or fractionally distilled in a treatment facility to
produce multiple components with specific boiling range
distributions (for example, naphtha, distillates, VGO, and/or
lubricating oils). Distillation includes, but is not limited to,
atmospheric distillation methods and/or vacuum distillation
methods. Undistilled and/or unfractionated stabilized crudes may
include components that have a carbon number above 4 in quantities
of at least 0.5 grams of such components per gram of crude.
Stabilized crudes also include crudes from a surface retorting
processes. For example, Canadian tar sands may be mined, and then
treated in a surface retorting process. The crude produced from
such surface retorting may be a stabilized crude. Examples of
stabilized crudes include whole crudes, topped crudes, desalted
crudes, desalted topped crudes, retorted crudes, or mixtures
thereof. "Topped" refers to a crude that has been treated such that
at least some of the components that have a boiling point below
35.degree. C. at 0.101 MPa (about 95.degree. F. at 1 atm) have been
removed. Typically, topped crudes will have a content of at most
0.1 grams, at most 0.05 grams, or at most 0.02 grams of such
components per gram of the topped crude.
[0094] Some stabilized crudes have properties that allow the
stabilized crudes to be transported to conventional treatment
facilities by transportation carriers (for example, pipelines,
trucks, or ships). Other crudes have one or more unsuitable
properties that render them disadvantaged. Disadvantaged crudes may
be unacceptable to a transportation carrier and/or a treatment
facility, thus imparting a low economic value to the disadvantaged
crude. The economic value may be such that a reservoir that
includes the disadvantaged crude is deemed too costly to produce,
transport, and/or treat.
[0095] Properties of disadvantaged crudes may include, but are not
limited to: a) TAN of at least 0.1, or at least 0.3; b) viscosity
of at least 10 cSt; c) API gravity of at most 19; d) a total NiN/Fe
content of at least 0.00002 grams or at least 0.0001 grams of
Ni/V/Fe per gram of disadvantaged crude; e) a total heteroatoms
content of at least 0.005 grams of heteroatoms per gram of
disadvantaged crude; f) a residue content of at least 0.01 grams of
residue per gram of disadvantaged crude; g) a C.sub.5 asphaltenes
content of at least 0.04 grams of C.sub.5 asphaltenes per gram of
disadvantaged crude; h) a MCR content of at least 0.0001 grams of
MCR per gram of disadvantaged crude; i) a content of metals in
metal salts of organic acids of at least 0.00001 grams of metals
per gram of disadvantaged crude; or j) combinations thereof. In
some embodiments, disadvantaged crudes includes, per gram of
disadvantaged crude, at least 0.2 grams of residue, at least 0.3
grams of residue, at least 0.5 grams of residue, or at least 0.9
grams of residue. In some embodiments, disadvantaged crudes have a
TAN in a range from about 0.1 to about 20, about 0.3 to about 10,
or about 0.4 to about 5. In certain embodiments, disadvantaged
crudes, per gram of disadvantaged crude, have a sulfur content of
at least 0.005, at least 0.01, or at least 0.02 grams.
[0096] In certain embodiments, disadvantaged crudes have, per gram
of disadvantaged crude, an MCR content of at least 0.0001 grams, at
least 0.001 grams, at least 0.003 grams, at least 0.005 grams, at
least 0.01 grams, at least 0.1 grams, or at least 0.5 grams.
Disadvantaged crudes may have, per gram of disadvantaged crude, an
MCR content in a range from about 0.0001 grams to about 0.5 grams,
from about 0.005 grams to about 0.1 grams, or from about 0.01 grams
to about 0.05 grams.
[0097] In some embodiments, disadvantaged crudes have, per gram of
disadvantaged crude, a nitrogen content of at least 0.0001 grams,
at least 0.001 grams, at least 0.01 grams, at least 0.05 grams, or
at least 0.1 grams. Disadvantaged crudes may have, per gram of
disadvantaged crude, a nitrogen content in a range from about
0.0001 grams to about 0.1 grams, from about 0.001 grams to about
0.05 grams, or from about 0.005 grams to about 0.01 grams.
[0098] In certain embodiments, disadvantaged crudes have at least
0.00001 grams, at least 0.0001 grams, at least 0.001 grams, or at
least 0.01 grams, of alkali and alkaline earth metals in metal
salts of organic acids. Disadvantaged crudes may have a content of
metals in metal salts of organic acids in a range from about
0.00001 grams to about 0.003 grams, about 0.00005 grams to about
0.005 grams, or about 0.0001 grams to about 0.01 grams of alkali
metal and alkaline-earth metal in metal salts of organic acids.
[0099] In some embodiments, disadvantaged crudes have properties
including, but not limited to: a) TAN of at least 0.5; b) an oxygen
content of at least 0.005 grams of oxygen per gram of crude feed;
c) a C.sub.5 aspnaltenes content of at least 0.04 grams of C.sub.5
asphaltenes per gram of crude feed; d) a higher than desired
viscosity (for example, greater than or equal to 10 cSt for a crude
feed with API gravity of at least 10; e) a content of metals in
metal salts of organic acids of at least 0.00001 grams of alkali
and alkaline earth metals per gram of crude; or f) combinations
thereof.
[0100] Disadvantaged crudes may include, per gram of disadvantaged
crude: at least 0.001 grams, at least 0.005 grams, or at least 0.01
grams of hydrocarbons with a boiling range distribution between
about 95.degree. C. and about 200.degree. C. at 0.101 MPa; at least
0.001 grams, at least 0.005 grams, or at least 0.01 grams of
hydrocarbons with a boiling range distribution between about
200.degree. C. and about 300.degree. C. at 0.101 MPa; at least
0.001 grams, at least 0.005 grams, or at least 0.01 grams of
hydrocarbons with a boiling range distribution between about
300.degree. C. and about 400.degree. C. at 0.101 MPa; and at least
0.001 grams, at least 0.005 grams, or at least 0.01 grams of
hydrocarbons with a boiling range distribution between about
400.degree. C. and 650.degree. C. at 0.101 MPa.
[0101] Disadvantaged crudes may include, per gram of disadvantaged
crude: at least 0.001 grams, at least 0.005 grams, or at least 0.01
grams of hydrocarbons with a boiling range distribution of at most
100.degree. C. at 0.101 MPa; at least 0.001 grams, at least 0.005
grams, or at least 0.01 grams of hydrocarbons with a boiling range
distribution between about 100.degree. C. and about 200.degree. C.
at 0.101 MPa; at least 0.001 grams, at least 0.005 grams, or at
least 0.01 grams of hydrocarbons with a boiling range distribution
between about 200.degree. C. and about 300.degree. C. at 0.101 MPa;
at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams
of hydrocarbons with a boiling range distribution between about
300.degree. C. and about 400.degree. C. at 0.101 MPa; and at least
0.001 grams, at least 0.005 grams, or at least 0.01 grams of
hydrocarbons with a boiling range distribution between about
400.degree. C. and 650.degree. C. at 0.101 MPa.
[0102] Some disadvantaged crudes may include, per gram of
disadvantaged crude, at least 0.001 grams, at least 0.005 grams, or
at least 0.01 grams of hydrocarbons with a boiling range
distribution of at most 100.degree. C. at 0.101 MPa, in addition to
higher boiling components. Typically, the disadvantaged crude has,
per gram of disadvantaged crude, a content of such hydrocarbons of
at most 0.2 grams or at most 0.1 grams.
[0103] Some disadvantaged crudes may include, per gram of
disadvantaged crude, at least 0.001 grams, at least 0.005 grams, or
at least 0.01 grams of hydrocarbons with a boiling range
distribution below 200.degree. C. at 0.101 MPa.
[0104] In certain embodiments, disadvantaged crudes include, per
gram of disadvantaged crude, up to 0.9 grams, or up to 0.99 grams
of hydrocarbons with a boiling range distribution above 300.degree.
C. In certain embodiments, disadvantaged crudes also include, per
gram of disadvantaged crude, at least 0.001 grams of hydrocarbons
with a boiling range distribution above 650.degree. C. In certain
embodiments, disadvantaged crudes include, per gram of
disadvantaged crude, up to about 0.9 grams, or up to about 0.99
grams of hydrocarbons with a boiling range distribution between
about 300.degree. C. and about 1000.degree. C.
[0105] Examples of disadvantaged crudes that might be treated using
the processes described herein include, but are not limited to,
crudes from of the following regions of the world: U.S. Gulf Coast,
southern California, north slope of Alaska, Canada tar sands,
Canadian Alberta region, Mexico Bay of Campeche, Argentinean San
Jorge basin, Brazilian Santos and Campos basins, Egyptian Gulf of
Suez, Chad, United Kingdom North Sea, Angola Offshore, China Bohai
Bay, China Karamay, Iraq Zagros, Kazakhstan Caspian, Nigeria
Offshore, Madagascar northwest, Oman, Netherlands Schoonebek,
Venezuelan Zulia, Malaysia, and Indonesia Sumatra. Treatment of
disadvantaged crudes may enhance the properties of the
disadvantaged crudes such that the crudes are acceptable for
transportation and/or treatment. A crude and/or disadvantaged crude
that is to be treated herein is referred to as "crude feed". The
crude feed may be topped, as described herein. The crude feed may
be obtainable by, but is not limited to, methods as described
herein. The crude product resulting from treatment of the crude
feed, as described herein, is generally suitable for transporting
and/or treatment. Properties of the crude product produced as
described herein are closer to the corresponding properties of West
Texas Intermediate crude than the crude feed, or closer to the
corresponding properties of Brent crude, than the crude feed,
thereby enhancing the economic value of the crude feed. Such crude
product may be refined with less pre-treatment than other crude
products from disadvantaged crude feeds, or no pre-treatment,
thereby enhancing refining efficiencies. Pre-treatment may include
desulfurization, demetallization and/or atmospheric distillation to
remove impurities.
[0106] Treatment of a crude feed in accordance with inventions
described herein may include contacting the crude feed with the
catalyst(s) in a contacting zone and/or combinations of two or more
contacting zones. In a contacting zone, at least one property of a
crude feed may be changed by contact of the crude feed with one or
more catalysts relative to the same property of the crude feed. In
some embodiments, contacting is performed in the presence of a
hydrogen source. In some embodiments, the hydrogen source is one or
more hydrocarbons that under certain contacting conditions react to
provide relatively small amounts of hydrogen to compound(s) in the
crude feed.
[0107] FIG. 1 is a schematic of contacting system 100 that includes
an upstream contacting zone 102. The crude feed enters upstream
contacting zone 102 via crude feed conduit 104. A contacting zone
may be a reactor, a portion of a reactor, multiple portions of a
reactor, or combinations thereof. Examples of a contacting zone
include a stacked bed reactor, a fixed bed reactor, an ebullating
bed reactor, a continuously stirred tank reactor ("CSTR"), a
fluidized bed reactor, a spray reactor, and a liquid/liquid
contactor. In certain embodiments, the contacting system is on or
coupled to an offshore facility. Contact of the crude feed with the
catalyst(s) in contacting system 100 may be a continuous process or
a batch process.
[0108] The contacting zone may include one or more catalysts (for
example, two catalysts). In some embodiments, contact of the crude
feed with a first catalyst of the two catalysts may reduce metals
in metal salts of organic acids of the crude feed. Subsequent
contact of the crude feed having reduced metal salts with the
second catalyst may decrease MCR content and/or heteroatoms
content. In other embodiments, TAN, viscosity, Ni/V/Fe content,
heteroatoms content, residue content, API gravity, or combinations
of these properties of the crude product change by at least 10%
relative to the same properties of the crude feed after contact of
the crude feed with one or more catalysts.
[0109] In certain embodiments, a volume of catalyst in the
contacting zone is in a range from about 10% to about 60 vol %,
about 20% to about 50 vol %, or about 30% to about 40 vol % of a
total volume of crude feed in the contacting zone. In some
embodiments, a slurry of catalyst and crude feed may include from
about 0.001 grams to about 10 grams, about 0.005 grams to about 5
grams, or about 0.01 grams to about 3 grams of catalyst per 100
grams of crude feed in the contacting zone.
[0110] Contacting conditions in the contacting zone may include,
but are not limited to, temperature, pressure, hydrogen source
flow, crude feed flow, or combinations thereof. Contacting
conditions in some embodiments are controlled to produce a crude
product with specific properties. Temperature in the contacting
zone may range from about 50.degree. C. to about 500.degree. C.,
about 60.degree. C. to about 440.degree. C., about 70.degree. C. to
about 430.degree. C., or about 80.degree. C. to about 420.degree.
C. Pressure in a contacting zone may range from about 0.1 MPa to
about 20 MPa, about 1 MPa to about 12 MPa, about 4 MPa to about 10
MPa, or about 6 MPa to about 8 MPa. LHSV of the crude feed will
generally range from about 0.05 h.sup.-1 to about 30 h.sup.-1,
about 0.5 h.sup.-1 to about 25 h.sup.-1, about 1 h.sup.-1 to about
20 h.sup.-1, about 1.5 h.sup.-1, to about 15 h.sup.-1, or about 2
h.sup.-1 to about 10 h.sup.-1. In some embodiments, LHSV is at
least 5 h.sup.-1, at least 11 h.sup.-1, at least 15 h.sup.-1, or at
least 20 h.sup.-1. In some embodiments, the total pressure is at
most 18 MPa, at most 16 MPa, at most 14 MPa, at most 12 MPa, at
most 10 MPa, or at most 8 MPa. In certain embodiments, the
temperature is at most 430.degree. C., at most 420.degree. C., at
most 410.degree. C., or at most 400.degree. C.
[0111] In embodiments in which the hydrogen source is supplied as a
gas (for example, hydrogen gas), a ratio of the gaseous hydrogen
source to the crude feed typically ranges from about 0.1
Nm.sup.3/m.sup.3 to about 100,000 Nm.sup.3/m.sup.3, about 0.5
Nm.sup.3/m.sup.3 to about 10,000 Nm.sup.3/m.sup.3, about 1
Nm.sup.3/m.sup.3 to about 8,000 Nm.sup.3/m.sup.3, about 2
Nm.sup.3/m.sup.3 to about 5,000 Nm.sup.3/m.sup.3, about 5
Nm.sup.3/m.sup.3 to about 3,000 Nm.sup.3/m.sup.3, or about 10
Nm.sup.3/m.sup.3 to about 800 Nm.sup.3/m.sup.3 contacted with the
catalyst(s). The hydrogen source, in some embodiments, is combined
with carrier gas(es) and recirculated through the contacting zone.
Carrier gas may be, for example, nitrogen, helium, and/or argon.
The carrier gas may facilitate flow of the crude feed and/or flow
of the hydrogen source in the contacting zone(s). The carrier gas
may also enhance mixing in the contacting zone(s). In some
embodiments, a hydrogen source (for example, hydrogen, methane or
ethane) may be used as a carrier gas and recirculated through the
contacting zone.
[0112] The hydrogen source may enter upstream contacting zone 102
co-currently with the crude feed in crude feed conduit 104 or
separately via gas conduit 106. In upstream contacting zone 102,
contact of the crude feed with a catalyst produces a total product
that includes a crude product, and, in some embodiments, gas. In
some embodiments, a carrier gas is combined with the crude feed
and/or the hydrogen source in conduit 106. The total product may
exit upstream contacting zone 102 and enter downstream separation
zone 108 via total product conduit 110.
[0113] In downstream separation zone 108, the crude product and gas
may be separated from the total product using generally known
separation techniques, for example, gas-liquid separation. The
crude product may exit downstream separation zone 108 via crude
product conduit 112, and then be transported to transportation
carriers, pipelines, storage vessels, refineries, other processing
zones, or a combination thereof. The gas may include gas formed
during processing (for example, hydrogen sulfide, carbon dioxide,
and/or carbon monoxide), excess gaseous hydrogen source, and/or
carrier gas. The excess gas may be recycled to contacting system
100, purified, transported to other processing zones, storage
vessels, or combinations thereof.
[0114] In some embodiments, contacting the crude feed with the
catalyst(s) to produce a total product is performed in two or more
contacting zones. The total product may be separated to form the
crude product and gas(es).
[0115] FIGS. 2-3 are schematics of embodiments of contacting system
100 that includes two or three contacting zones. In FIGS. 2A and
2B, contacting system 100 includes upstream contacting zone 102 and
downstream contacting zone 114. FIGS. 3A and 3B include contacting
zones 102, 114, 116. In FIGS. 2A and 3A, contacting zones 102, 114,
116 are depicted as separate contacting zones in one reactor. The
crude feed enters upstream contacting zone 102 via crude feed
conduit 104.
[0116] In some embodiments, the carrier gas is combined with the
hydrogen source in gas conduit 106 and is introduced into the
contacting zones as a mixture. In certain embodiments, as shown in
FIGS. 1, 3A, and 3B, the hydrogen source and/or the carrier gas may
enter the one or more contacting zones with the crude feed
separately via gas conduit 106 and/or in a direction counter to the
flow of the crude feed via, for example, gas conduit 106'. Addition
of the hydrogen source and/or the carrier gas counter to the flow
of the crude feed may enhance mixing and/or contact of the crude
feed with the catalyst.
[0117] Contact of the crude feed with catalyst(s) in upstream
contacting zone 102 forms a feed stream. The feed stream flows from
upstream contacting zone 102 to downstream contacting zone 114. In
FIGS. 3A and 3B, the feed stream flows from downstream contacting
zone 114 to additional downstream contacting zone 116.
[0118] Contacting zones 102, 114, 116 may include one or more
catalysts. As shown in FIG. 2B, the feed stream exits upstream
contacting zone 102 via feed stream conduit 118 and enters
downstream contacting zone 114. As shown in FIG. 3B, the feed
stream exits downstream contacting zone 114 via conduit 118 and
enters additional downstream contacting zone 116.
[0119] The feed stream may be contacted with additional catalyst(s)
in downstream contacting zone 114 and/or additional downstream
contacting zone 116 to form the total product. The total product
exits downstream contacting zone 114 and/or additional downstream
contacting zone 116 and enters downstream separation zone 108 via
total product conduit 110. The crude product and/or gas is (are)
separated from the total product. The crude product exits
downstream separation zone 108 via crude product conduit 112.
[0120] FIG. 4 is a schematic of an embodiment of a separation zone
upstream of contacting system 100. The disadvantaged crude (either
topped or untopped) enters upstream separation zone 120 via crude
conduit 122. In upstream separation zone 120, at least a portion of
the disadvantaged crude is separated using techniques known in the
art (for example, sparging, membrane separation, pressure
reduction, filtering, or combinations thereof) to produce the crude
feed. For example, water may be at least partially separated from
the disadvantaged crude in upstream separation zone 120. In another
example, components that have a boiling range distribution below
95.degree. C. or below 100.degree. C. may be at least partially
separated from the disadvantaged crude in upstream separation zone
120 to produce the crude feed. In some embodiments, at least a
portion of naphtha and compounds more volatile than naphtha are
separated from the disadvantaged crude. In some embodiments, at
least a portion of the separated components exit upstream
separation zone 120 via conduit 124.
[0121] The crude feed obtained from upstream separation zone 120,
in some embodiments, includes a mixture of components with a
boiling range distribution of at least 100.degree. C. or, in some
embodiments, a boiling range distribution of at least 120.degree.
C. Typically, the separated crude feed includes a mixture of
components with a boiling range distribution between about
100.degree. C. to about 1000.degree. C., about 120.degree. C. to
about 900.degree. C., or about 200.degree. C. to about 800.degree.
C. At least a portion of the crude feed exits upstream separation
zone 120 and enters contacting system 100 (see, for example, the
contacting zones in FIGS. 1-3) via additional crude feed conduit
126 to be further processed to form a crude product. In some
embodiments, upstream separation zone 120 may be positioned
upstream or downstream of a desalting unit. In certain embodiments,
upstream separation zone 120 may be positioned downstream of a
retorting process for bitumen, oil shale, and/or tar sands. After
processing, the crude product exits contacting system 100 via crude
product conduit 112.
[0122] In some embodiments, the crude product is blended with a
crude that is the same as or different from the crude feed. For
example, the crude product may be combined with a crude having a
different viscosity thereby resulting in a blended product having a
viscosity that is between the viscosity of the crude product and
the viscosity of the crude. In another example, the crude product
may be blended with crude having a TAN and/or MCR content that is
different, thereby producing a product that has a TAN and/or MCR
content that is between the TAN and/or MCR content of the crude
product and the crude. The blended product may be suitable for
transportation and/or treatment.
[0123] As shown in FIG. 5, in certain embodiments, crude feed
enters contacting system 100 via crude feed conduit 104, and at
least a portion of the crude product exits contacting system 100
via conduit 128 and is introduced into blending zone 130. In
blending zone 130, at least a portion of the crude product is
combined with one or more process streams (for example, a
hydrocarbon stream such as naphtha produced from separation of one
or more crude feeds), a crude, a crude feed, or mixtures thereof,
to produce a blended product. The process streams, crude feed,
crude, or mixtures thereof are introduced directly into blending
zone 130 or upstream of such blending zone via stream conduit 132.
A mixing system may be located in or near blending zone 130. The
blended product may meet product specifications designated by
refineries and/or transportation carriers. Product specifications
include, but are not limited to, a range of or a limit of API
gravity, TAN, viscosity, or combinations thereof. The blended
product exits blending zone 130 via blend conduit 134 to be
transported or processed.
[0124] In FIG. 6, the disadvantaged crude enters upstream
separation zone 120 through crude conduit 122, and the
disadvantaged crude is separated as previously described to form
the crude feed. The crude feed then enters contacting system 100
through additional crude feed conduit 126. At least some components
from the disadvantaged crude exit separation zone 120 via conduit
124. At least a portion of the crude product exits contacting
system 100 and enters blending zone 130 through crude product
conduit 128. Other process streams and/or crudes enter blending
zone 130 directly or via stream conduit 132 and are combined with
the crude product to form a blended product. The blended product
exits blending zone 130 via blend conduit 134.
[0125] In some embodiments, the crude product and/or the blended
product are transported to a refinery and distilled and/or
fractionally distilled to produce one or more distillate fractions.
The distillate fractions may be processed to produce commercial
products such as transportation fuel, lubricants, or chemicals.
[0126] In some embodiments, after contact of the crude feed with
the catalyst, the crude product has a TAN of at most 90%, at most
50%, at most 30%, or at most 10% of the TAN of the crude feed. In
certain embodiments, the crude product has a TAN of at most 1, at
most 0.5, at most 0.3, at most 0.2, at most 0.1, or at most 0.05.
TAN of the crude product will frequently be at least 0.0001 and,
more frequently, at least 0.001. In some embodiments, TAN of the
crude product may be in a range from about 0.001 to about 0.5,
about 0.01 to about 0.2, or about 0.05 to about 0.1.
[0127] In some embodiments, the crude product has a total Ni/V/Fe
content of at most 90%, at most 50%, at most 30%, at most 10%, at
most 5%, or at most 3% of the Ni/V/Fe content of the crude feed. In
certain embodiments, the crude product has, per gram of crude
product a total Ni/V/Fe content in a range from about
1.times.10.sup.-7 grams to about 5.times.10.sup.-5 grams, about
3.times.10.sup.-7 grams to about 2.times.10.sup.-5 grams, or about
1.times.10.sup.-6 grams to about 1.times.10.sup.-5 grams. In
certain embodiments, the crude product has at most
2.times.10.sup.-5 grams of Ni/V/Fe per gram of crude product. In
some embodiments, a total Ni/V/Fe content of the crude product is
about 70% to about 130%, about 80% to about 120%, or about 90% to
about 110% of the Ni/V/Fe content of the crude feed.
[0128] In some embodiments, the crude product has a total content
of metals in metal salts of organic acids of at most 90%, at most
50%, at most 30%, at most 10%, or at most 5% of the total content
of metals in metal salts of organic acids in the crude feed. In
some embodiments, the total content of metals in metal salts of
organic acids is in a range from about 0.1% to about 75%, from
about 0.5% to about 45%, from about 1% to about 25%, or from about
2% to about 9% of the content of metals in metal salts of organic
acids of the crude feed. Organic acids that generally form metal
salts include, but are not limited to, carboxylic acids, thiols,
imides, sulfonic acids, and sulfonates. Examples of carboxylic
acids include, but are not limited to, naphthenic acids,
phenanthrenic acids, and benzoic acid. The metal portion of the
metal salts may include alkali metals (for example, lithium,
sodium, and potassium), alkaline-earth metals (for example,
magnesium, calcium, and barium), Column 12 metals (for example,
zinc and cadmium), Column 15 metals (for example arsenic), Column 6
metals (for example, chromium), or mixtures thereof.
[0129] In some embodiments, the crude product has a total content
of alkali metal and alkaline-earth metal in metal salts of organic
acids of at most 90%, at most 80%, at most 50%, at most 30%, at
most 10%, or at most 5% of the content of alkali metal and
alkaline-earth metal in metal salts of organic acids in the crude
feed. In some embodiments, the total content of alkali metal and
alkaline-earth metal in metal salts of organic acids in the crude
product is in a range from about 0.1% to about 75%, from about 0.5%
to about 45%, from about 1% to about 25%, or from about 2% to about
9% of the total content of alkali metal and alkaline-earth metal
salts of organic acids in the crude feed.
[0130] In certain embodiments, the crude product has a total
content of zinc salts of one or more organic acids of at most 90%,
at most 80%, at most 50%, at most 30%, at most 10%, or at most 5%
of the content of zinc salts of one or more organic acids in the
crude feed. In some embodiments, the total content of zinc salts of
organic acids in the crude product is in a range from about 0.1% to
about 75%, from about 0.5% to about 45%, from about 1% to about
25%, or from about 2% to about 9% of the total content of zinc
salts of organic acids in the crude feed.
[0131] In some embodiments, the crude product has a total content
of chromium and/or arsenic in metal salts of organic acids of at
most 90% of the content of chromium and/or arsenic in metal salts
of organic acids in the crude feed.
[0132] In certain embodiments, the crude product has, per gram of
crude product, from about 1.times.10.sup.-7 grams to about
5.times.10.sup.-5 grams, about 5.times.10.sup.-7 grams to about
1.times.10.sup.-5 grams, or about 1.times.10.sup.-6 grams to about
5.times.10.sup.-6 grams of alkali metal and alkaline-earth metal in
metal salts of organic acids.
[0133] In certain embodiments, API gravity of the crude product
produced from contact of the crude feed with catalyst, at the
contacting conditions, is about 70% to about 130%, about 80% to
about 120%, about 90% to about 110%, or about 100% to about 130% of
the API gravity of the crude feed. In certain embodiments, API
gravity of the crude product is from about 14 to about 40, about 15
to about 30, or about 16 to about 25.
[0134] In certain embodiments, the crude product has a viscosity of
at most 90%, at most 80%, at most 70%, at most 50%, at most 30%, at
most 10%, or at most 5% of the viscosity of the crude feed. In some
embodiments, the viscosity of the crude product is at most 90% of
the viscosity of the crude feed while the API gravity of the crude
product is about 70% to about 130%, about 80% to about 120%, or
about 90% to about 110% of the API gravity the crude feed.
[0135] In some embodiments, the crude product has a total
heteroatoms content of at most 90%, at most 50%, at most 30%, at
most 10%, or at most 5% of the total heteroatoms content of the
crude feed. In certain embodiments, the crude product has a total
heteroatoms content of at least 1%, at least 30%, at least 80%, or
at least 99% of the total heteroatoms content of the crude
feed.
[0136] In some embodiments, the sulfur content of the crude product
may be at most 90%, at most 50%, at most 30%, at most 10%, or at
most 5% of the sulfur content of the crude feed. In certain
embodiments, the crude product has a sulfur content of at least 1%,
at least 30%, at least 80%, or at least 99% of the sulfur content
of the crude feed.
[0137] In some embodiments, total nitrogen content of the crude
product may be at most 90%, at most 80%, at most 70%, at most 50%,
at most 30% or at most 10%, or at most 5% of a total nitrogen
content of the crude feed. In certain embodiments, the crude
product has a total nitrogen content of at least 1%, at least 30%,
at least 80%, or at least 99% of the total nitrogen content of the
crude feed. In certain embodiments, the crude product has a total
nitrogen content in a range from about 0.1% to about 75%, from
about 0.5% to about 45%, from about 1% to about 25%, or about 2% to
about 9% of the total nitrogen content of the crude feed. In some
embodiments, the crude product has, per gram of crude product, a
total nitrogen content in a range from about 0.00001 grams to about
0.05 grams, about 0.0001 grams to about 0.01 grams, or about 0.0005
grams to about 0.001 grams.
[0138] In certain embodiments, basic nitrogen content of the crude
product may be at most 95%, at most 90%, at most 50%, at most 30%,
at most 10%, or at most 5% of the basic nitrogen content of the
crude feed. In certain embodiments, the crude product has a basic
nitrogen content of at least 1%, at least 30%, at least 80%, or at
least 99% of the basic nitrogen content of the crude feed.
[0139] In some embodiments, the oxygen content of the crude product
may be at most 90%, at most 50%, at most 30%, at most 10%, or at
most 5% of the oxygen content of the crude feed. In certain
embodiments, the oxygen content of crude product may be least 1%,
at least 30%, at least 80%, or at least 99% of the oxygen content
of the crude feed. In some embodiments, the total content of
carboxylic acid compounds of the crude product may be at most 90%,
at most 50%, at most 30%, at most 10%, or at most 5% of the content
of the carboxylic acid compounds in the crude feed. In certain
embodiments, the total content of carboxylic acid compounds of the
crude product may be at least 1%, at least 30%, at least 80%, or at
least 99% of the total content of carboxylic acid compounds in the
crude feed.
[0140] In some embodiments, selected organic oxygen compounds may
be reduced in the crude feed. In some embodiments, carboxylic acids
and/or metal salts of carboxylic acids may be chemically reduced
before non-carboxylic containing organic oxygen compounds.
Carboxylic acids and non-carboxylic containing organic oxygen
compounds in a crude product may be differentiated through analysis
of the crude product using generally known spectroscopic methods
(for example, infrared analysis, mass spectrometry, and/or gas
chromatography).
[0141] The crude product, in certain embodiments, has an oxygen
content of at most 90%, at most 80%, at most 70%, or at most 50% of
the oxygen content of the crude feed, and TAN of the crude product
is at most 90%, at most 70%, at most 50%, at most 30% or at most
40% of the TAN of the crude feed. In certain embodiments, the
oxygen content of the crude product may be at least 1%, at least
30%, at least 80%, or at least 99% of the oxygen content of the
crude feed, and the crude product has a TAN of at least 1%, at
least 30%, at least 80%, or at least 99% of the TAN of the crude
feed.
[0142] Additionally, the crude product may have a content of
carboxylic acids and/or metal salts of carboxylic acids of at most
90%, at most 70%, at most 50%, or at most 40% of the crude feed,
and a content of non-carboxylic acid containing organic oxygen
compounds within about 70% to about 130%, about 80% to about 120%,
or about 90% to about 110% of the non-carboxylic acid containing
organic oxygen compounds of the crude feed.
[0143] In some embodiments, the crude product includes, in its
molecular structure, from about 0.05 grams to about 0.15 grams or
from about 0.09 grams to about 0.13 grams of hydrogen per gram of
crude product. The crude product may include, in its molecular
structure, from about 0.8 grams to about 0.9 grams or from about
0.82 grams to about 0.88 grams of carbon per gram of crude product.
A ratio of atomic hydrogen to atomic carbon (H/C) of the crude
product may be within about 70% to about 130%, about 80% to about
120%, or about 90% to about 110% of the atomic H/C ratio of the
crude feed. A crude product atomic H/C ratio within about 10% to
about 30% of the crude feed atomic H/C ratio indicates that uptake
and/or consumption of hydrogen in the process is relatively small,
and/or that hydrogen is produced in situ.
[0144] The crude product includes components with a range of
boiling points. In some embodiments, the crude product includes,
per gram of the crude product: at least 0.001 grams, or from about
0.001 grams to about 0.5 grams of hydrocarbons with a boiling range
distribution of at most 100.degree. C. at 0.101 MPa; at least 0.001
grams, or from about 0.001 grams to about 0.5 grams of hydrocarbons
with a boiling range distribution between about 100.degree. C. and
about 200.degree. C. at 0.101 MPa; at least 0.001 grams, or from
about 0.001 grams to about 0.5 grams of hydrocarbons with a boiling
range distribution between about 200.degree. C. and about
300.degree. C. at 0.101 MPa; at least 0.001 grams, or from about
0.001 grams to about 0.5 grams of hydrocarbons with a boiling range
distribution between about 300.degree. C. and about 400.degree. C.
at 0.101 MPa; and at least 0.001 grams, or from about 0.001 grams
to about 0.5 grams of hydrocarbons with a boiling range
distribution between about 400.degree. C. and about 538.degree. C.
at 0.101 MPa.
[0145] In some embodiments the crude product includes, per gram of
crude product, at least 0.001 grams of hydrocarbons with a boiling
range distribution of at most 100.degree. C. at 0.101 MPa and/or at
least 0.001 grams of hydrocarbons with a boiling range distribution
between about 100.degree. C. and about 200.degree. C. at 0.101
MPa.
[0146] In some embodiments, the crude product may have at least
0.001 grams, or at least 0.01 grams of naphtha per gram of crude
product. In other embodiments, the crude product may have a naphtha
content of at most 0.6 grams, or at most 0.8 grams of naphtha per
gram of crude product.
[0147] In some embodiments, the crude product has, per gram of
crude product, a distillate content in a range from about 0.00001
grams to about 0.5 grams, about 0.001 grams to about 0.3 grams, or
about 0.002 grams to about 0.2 grams.
[0148] In certain embodiments, the crude product has, per gram of
crude product, a VGO content in a range from about 0.00001 grams to
about 0.8 grams, about 0.001 grams to about 0.5 grams, about 0.005
grams to about 0.4 grams, or about 0.01 grams to about 0.3
grams.
[0149] In some embodiments, the crude product has a residue content
of at most 90%, at most 70%, at most 50%, at most 30%, or at most
10% of the residue content of the crude feed. In certain
embodiments, the crude product has a residue content of about 70%
to about 130%, about 80% to about 120%, or about 90% to about 110%
of the residue content of the crude feed. The crude product may
have, per gram of crude product, a residue content in a range from
about 0.00001 grams to about 0.8 grams, about 0.0001 grams to about
0.5 grams, about 0.0005 grams to about 0.4 grams, about 0.001 grams
to about 0.3 grams, about 0.005 grams to about 0.2 grams, or about
0.01 grams to about 0.1 grams.
[0150] In some embodiments, the C.sub.5 asphaltenes content is at
most 90%, at most 80%, at most 70%, at most 50%, at most 30%, or at
most 10% of the C.sub.5 asphaltenes content of the crude feed. In
certain embodiments, the C.sub.5 asphaltenes content of the crude
product is at least 10%, at least 60%, or at least 70% of the
C.sub.5 asphaltenes content of the crude feed. The crude product
may have a C.sub.5 asphaltenes content in a range from about 0.1%
to about 75%, from about 0.5% to about 45%, from about 1% to about
25%, or from about 2% to about 9% of the C.sub.5 asphaltenes
content of the crude feed. The crude product has, in some
embodiments, from about 0.0001 grams to about 0.1 grams, from about
0.005 grams to about 0.08 grams, or from about 0.01 grams to about
0.05 grams of C.sub.5 asphaltenes per gram of crude product.
[0151] In certain embodiments, the crude product has an MCR content
that is at most 90%, at most 80%, at most 50%, at most 30%, or at
most 10% of the MCR content of the crude feed. In some embodiments,
the crude product has a MCR content in a range from about 0.1% to
about 75%, from about 0.5% to about 45%, from about 1% to about
25%, or from about 2% to about 9% of the MCR content of the crude
feed. The crude product has, in some embodiments, from about
0.00001 grams to about 0.1 grams, about 0.0001 grams to about 0.05
grams, or about 0.001 grams to about 0.005 grams of MCR per gram of
crude product.
[0152] In some embodiments, the C.sub.5 asphaltenes content and MCR
content may be combined to produce a mathematical relationship
between the high viscosity components in the crude product relative
to the high viscosity components in the crude feed. For example, a
sum of a crude feed C.sub.5 asphaltenes content and a crude feed
MCR content may be represented by S. A sum of a crude product
C.sub.5 asphaltenes content and a crude product MCR content may be
represented by S'. The sums may be compared (S' to S) to assess the
net reduction in high viscosity components in the crude feed. S' of
the crude product may be in a range from about 1% to about 99%,
about 10% to about 90%, or about 20% to about 80% of S. In some
embodiments, a ratio of MCR content of the crude product to C.sub.5
asphaltenes content is in a range from about 1.0 to about 3.0,
about 1.2 to about 2.0, or about 1.3 to about 1.9.
[0153] In some embodiments, the crude product includes from greater
than 0 grams, but less than 0.01 grams, from about 0.000001 grams
to about 0.001 grams, or from about 0.00001 grams to about 0.0001
grams of total catalyst per gram of crude product. The catalyst may
assist in stabilizing the crude product during transportation
and/or treatment. The catalyst may inhibit corrosion, inhibit
friction, and/or increase water separation abilities of the crude
product. Methods described herein may be configured to add one or
more catalysts described herein to the crude product during
treatment.
[0154] The crude product produced from contacting system 100 (as
shown in FIGS. 1-6) has properties different than properties of the
crude feed. Such properties may include, but are not limited to: a)
reduced TAN; b) reduced viscosity; c) reduced total Ni/V/Fe
content; d) reduced content of sulfur, oxygen, nitrogen, or
combinations thereof; e) reduced residue content; f) reduced
C.sub.5 asphaltenes content; g) reduced MCR content; h) increased
API gravity; i) a reduced content of metals in metal salts of
organic acids; j) increased stability relative to the crude feed;
or k) combinations thereof.
[0155] Catalysts used in one or more embodiments of the inventions
may include one or more bulk metals and/or one or more metals on a
support. The metals may be in elemental form or in the form of a
compound of the metal. The catalysts described herein may be
introduced into the contacting zone as a precursor, and then become
active as a catalyst in the contacting zone (for example, when
sulfur and/or a crude feed containing sulfur is contacted with the
precursor). The catalyst or combination of catalysts used as
described herein may or may not be commercial catalysts. Examples
of commercial catalysts that are contemplated to be used as
described herein include HDS22; HDN60; C234; C311; C344; C411;
C424; C344; C444; C447; C454; C448; C524; C534; DN120; DN140;
DN190; DN200; DN800; DC2118; DC2318; DN3100; DN3110; DN3300;
DN3310; RC400; RC410; RN412; RN400; RN410; RN420; RN440; RN450;
RN650; RN5210; RN5610; RN5650; RM430; RM5030; Z603; Z623; Z673;
Z703; Z713; Z723; Z753; and Z763, which are available from CRI
International, Inc. (Houston, Tex., U.S.A.).
[0156] In some embodiments, catalysts used to change properties of
the crude feed include one or more Columns 5-10 metal(s) on a
support. Columns 5-10 metal(s) include, but are not limited to,
vanadium, chromium, molybdenum, tungsten, manganese, technetium,
rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium,
osmium, iridium, platinum, or mixtures thereof. Compounds of
Columns 5-10 metal(s) include, but are not limited to, oxides,
nitrates, ammonium salts, and carbonates of the Columns 5-10
metal(s). Examples of Columns 5-10 metal compounds include, but are
not limited to, molybdenum trioxide, molybdenum ammonium oxide,
molybdenum carbonate, tungsten trioxide, nickel oxide, nickel
carbonate, nickel nitrate, cobalt carbonate, and cobalt oxide.
[0157] The catalyst may have, per gram of catalyst, a total Columns
5-10 metal(s) content in a range from at least 0.0001 grams, at
least 0.001 grams, at least 0.01 grams, at least 0.3 grams, at
least 0.5 grams, at least 0.6 grams, at least 0.8 grams, or at
least 0.9 grams. A total content of Columns 5-10 metal(s), per gram
of catalyst, may be in a range about 0.0001 grams to about 0.99
grams, about 0.0005 grams to about 0.5 grams, about 0.001 grams to
about 0.3 grams, about 0.005 grams to about 0.2 grams, or about
0.01 grams to about 0.1 grams. In some embodiments, the catalyst
includes Column 15 element(s) in addition to the Columns 5-10
metal(s). An example of a Column 15 element is phosphorus. The
catalyst may have a total Column 15 element content, per gram of
catalyst, in range from about 0.000001 grams to about 0.1 grams,
about 0.00001 grams to about 0.06 grams, about 0.00005 grams to
about 0.03 grams, or about 0.0001 grams to about 0.001 grams. In
other embodiments, the catalyst does not include a Column 15
element.
[0158] In some embodiments, the catalyst includes a combination of
Column 6 metal(s) with one or more metals from Column 5 and/or
Columns 7-10. A molar ratio of Column 6 metal to Column 5 metal may
be in a range from about 0.1 to about 20, about 1 to about 10, or
about 2 to about 5. A molar ratio of Column 6 metal to Columns 7-10
metal may be in a range from about 0.1 to about 20, about 1 to
about 10, or about 2 to about 5. In some embodiments, the catalyst
includes Column 15 element(s) in addition to the combination of
Column 6 metal(s) with one or more metals from Columns 5 and/or
7-10. In other embodiments, the catalyst includes Column 6 metal(s)
and Column 10 metal(s). A molar ratio of the total Column 10 metal
to the total Column 6 metal in the catalyst may be in a range from
about 1 to about 10, or from about 2 to about 5. In certain
embodiments, the catalyst includes Column 5 metal(s) and Column 10
metal(s). A molar ratio of the total Column 10 metal to the total
Column 5 metal in the catalyst may be in a range from about 1 to
about 10, or from about 2 to about 5.
[0159] In certain embodiments, the catalyst includes Column 6
metal(s). The catalyst may have, per gram of catalyst, a total
Column 6 metal(s) content of at least 0.00001 grams, at least 0.01
grams, at least 0.02 grams and/or in a range from about 0.0001
grams to about 0.6 grams, about 0.001 grams to about 0.3 grams,
about 0.005 grams to about 0.2 grams, or about 0.01 grams to about
0.1 grams. In some embodiments, the catalyst includes from about
0.0001 grams to about 0.2 grams, from about 0.001 grams to about
0.08 grams, or from about 0.01 grams to 0.06 grams of Column 6
metal(s) per gram of catalyst. In some embodiments, the catalyst
includes Column 15 element(s) in addition to the Column 6
metal(s).
[0160] In some embodiments, the catalyst includes a combination of
Column 6 metal(s) with one or more metals from Columns 7-10. The
catalyst may have, per gram of catalyst, a total Column 7-10
metal(s) content in a range from about 0.0001 grams to about 0.1
grams, from about 0.001 grams to about 0.05 grams, or from about
0.01 grams to about 0.03 grams. In certain embodiments, the
catalyst includes, per gram of catalyst, from about 0.01 grams to
about 0.15 grams of molybdenum and from about 0.001 grams to about
0.05 grams of nickel. The catalyst, in some embodiments, also
includes from about 0.001 grams to about 0.05 grams of iron per
gram of catalyst.
[0161] In some embodiments, the catalyst includes, per gram of
catalyst, from about 0.01 grams to about 0.15 grams of molybdenum,
from about 0.001 grams to about 0.05 grams of nickel, from about
0.001 grams to about 0.05 grams of iron, and from about 0.0001
grams to about 0.05 grams of phosphorus.
[0162] In some embodiments, Columns 5-10 metal(s) are incorporated
in, or deposited on, a support to form the catalyst. In certain
embodiments, Columns 5-10 metal(s) in combination with Column 15
element(s) are incorporated in, or deposited on, the support to
form the catalyst. In embodiments in which the metal(s) and/or
element(s) are supported, the weight of the catalyst includes all
support, all metal(s), and all element(s). The support may be
porous and may include refractory oxides, porous carbon based
materials, zeolites, or combinations thereof. Refractory oxides may
include, but are not limited to, alumina, silica, silica-alumina,
titanium oxide, zirconium oxide, magnesium oxide, or mixtures
thereof. Supports may be obtained from a commercial manufacturer
such as Criterion Catalysts and Technologies LP (Houston, Tex.,
U.S.A.). Porous carbon based materials include, but are not limited
to, activated carbon and/or porous graphite. Examples of zeolites
include Y-zeolites, beta zeolites, mordenite zeolites, ZSM-5
zeolites, and ferrierite zeolites. Zeolites may be obtained from a
commercial manufacturer such as Zeolyst (Valley Forge, Pa.,
U.S.A.). The support may be prepared and/or selected based upon a
variety of desired characteristics. Examples of characteristics
include, but are not limited to, pore volume, average pore
diameter, pore volume distribution, surface area, and percentage of
pores above or in a certain pore diameter range.
[0163] The support, in some embodiments, is prepared such that the
support has an average pore diameter of at least 90 .ANG., at least
110 .ANG., at least 130 .ANG., at least 150 .ANG., at least 170
.ANG., or at least 180 .ANG.. In certain embodiments, the support
is prepared by combining water with the support to form a paste. In
some embodiments, an acid is added to the paste to assist in
extrusion of the paste. The water and dilute acid are added in such
amounts and by such methods as required to give the extrudable
paste a desired consistency. Examples of acids include, but are not
limited to, nitric acid, acetic acid, sulfuric acid, and
hydrochloric acid.
[0164] The paste may be extruded and cut using generally known
catalyst extrusion methods and catalyst cutting methods to form
extrudates. The extrudates may be heat-treated at a temperature in
a range from about 65.degree. C. to about 260.degree. C. or from
about 85.degree. C. to about 235.degree. C. for a period of time
(for example, for about 0.5 hours to about 8 hours) and/or until
the moisture content of the extrudate has reached a desired level.
The heat-treated extrudate may be further heat-treated at a
temperature in a range from about 800.degree. C. to about
1200.degree. C. or about 900.degree. C. to about 1100.degree. C. to
form a support having an average pore diameter of at least 150
.ANG.. The supports have a pore volume distribution over a range of
pore diameters. In some embodiments, the support contains pores
that have a pore diameter of at least 350 .ANG., at least 400
.ANG., at least 500 .ANG., or at least 1000 .ANG., or in a range of
about 350 .ANG. to about 5000 .ANG., about 400 .ANG. to about 1000
.ANG., or about 500 .ANG. to about 900 .ANG., which provide at most
15%, at most 10%, at most 5% at most 3%, at most 1% or at most 0.5%
of the total pore volume of the support.
[0165] In certain embodiments, the support includes gamma alumina,
theta alumina, delta alumina, alpha alumina, or combinations
thereof. The amount of gamma alumina, delta alumina, alpha alumina,
or combinations thereof, per gram of catalyst support, may be in a
range from about 0.0001 grams to about 0.99 grams, about 0.001
grams to about 0.5 grams, about 0.01 grams to about 0.1 grams, or
at most 0.1 grams as determined by x-ray diffraction. In some
embodiments, the support includes, per gram of support, at least
0.5 grams, at least 0.8 grams, at least 0.9 grams, or at least 0.95
grams of gamma alumina. In certain embodiments, the support
contains, per gram of support, from about 0.5 grams to about 0.99
grams, from about 0.6 grams to about 0.9 grams, or from about 0.7
grams to about 0.8 grams of gamma alumina. In certain embodiments,
the support has, either alone or in combination with other forms of
alumina, a theta alumina content, per gram of support, in a range
from about 0.1 grams to about 0.99 grams, about 0.5 grams to about
0.9 grams, or about 0.6 grams to about 0.8 grams, as determined by
x-ray diffraction. In some embodiments, the support may have, per
gram of support, at least 0.1 grams, at least 0.3 grams, at least
0.5 grams, or at least 0.8 grams of theta alumina, as determined by
x-ray diffraction.
[0166] In certain embodiments, the support includes, per gram of
support, at most 0.2 grams, at most 0.1 grams, at most 0.08 grams,
at most 0.06 grams, at most 0.05 grams, at most 0.04 grams, at most
0.03 grams, at most 0.02 grams, or at most 0.01 grams of silica. In
certain embodiments, the support has, per gram of support, from
about 0.001 grams to about 0.2 grams or from about 0.01 grams to
about 0.1 grams of silica. In some embodiments, the support
includes a combination of silica and alumina.
[0167] Supported catalysts may be prepared using generally known
catalyst preparation techniques. Examples of catalyst preparations
are described in U.S. Pat. No. 6,218,333 to Gabrielov et al.; U.S.
Pat. No. 6,290,841 to Gabrielov et al.; and U.S. Pat. No. 5,744,025
to Boon et al., and U.S. Patent Application Publication No. US
2003/0111391 to Bhan, all of which are incorporated herein by
reference.
[0168] In some embodiments, the support may be combined with metal
to form a catalyst. In certain embodiments, the support is
heat-treated at temperatures in a range from about 400.degree. C.
to about 1200.degree. C., about 450.degree. C. to about
1000.degree. C., or about 600.degree. C. to about 900.degree. C.
prior to combining with a metal. In some embodiments, impregnation
aids may be used during preparation of the catalyst. Examples of
impregnation aids include hydrogen peroxide, organic acids, amines,
ethylenediaminetetraacetic acid (EDTA), ammonia, or mixtures
thereof. Examples of amines include, but are not limited to,
alkanolamines, ammonia, alkyl amines, aromatic amines, and
substituted ammonium compounds. Organic acids include, but are not
limited to, citric acid, tartaric acid, oxalic acid, malonic acid,
malic acid, or mixtures thereof.
[0169] In certain embodiments, the support may be combined with a
metal solution having a pH of up to about 3. The pH of the metal
solution may range from about 1 to about 3, or from about 1.5 to
about 2.5. Controlling the pH of the metal solution may facilitate
dispersion of metals into the support. A dispersed or substantially
dispersed metal catalyst prepared using such pH controlled
conditions may have an increased catalyst life compared to the life
of a conventional catalyst when used to process a crude feed at the
same contacting conditions.
[0170] The metal solution may include Column 6 metal(s). In some
embodiments, the metal solution includes Column 6 metal(s) in
combination with Columns 7-10 metal(s). In certain embodiments, the
metal solution includes Column 15 element(s) in combination with
Column 6 metal(s), or in combination with Column 6 metal(s) and
Columns 7-10 metal(s).
[0171] In some embodiments, the pH of the metal solution may be
adjusted to the desired pH of up to pH 3 using mineral acids and/or
organic acid components. Mineral acids include, but are not limited
to, phosphoric acid, nitric acid, sulfuric acid, or mixtures
thereof.
[0172] In certain embodiments, the metal solution is prepared by
combining one or more Columns 6-10 metal solutions having different
pH values. A Columns 6-10 metal solution having a pH in a range
from about 4 to about 7, or from about 5 to about 6, may be
combined with a different Columns 6-10 metal solution having a pH
in a range from about 0.1 to about 4, or about 1 to about 3. In
some embodiments, the Columns 6-10 metal solutions include
impregnation aids, mineral acids, organic acids, Column 15
element(s), or mixtures thereof.
[0173] In certain embodiments, a catalyst may be formed by adding
or incorporating multiple Columns 5-10 metal(s) to a support
sequentially ("overlaying"). Overlaying a metal on top of a support
that includes a substantially uniform concentration of metal often
provides beneficial catalytic properties of the catalyst.
Heat-treating the support after each overlay of metal tends to
improve the catalytic activity of the catalyst. Methods to prepare
a catalyst using overlay methods are described in U.S. Patent
Application Publication No. US 2003/0111391 to Bhan.
[0174] In some embodiments, a support/Columns 7-10 metal(s) mixture
is prepared by combining a support with one or more Columns 7-10
metal(s). In an embodiment, the resulting mixture includes about
0.01 grams to about 0.1 grams of Columns 7-10 metal(s) per gram of
the support/Columns 7-10 metal(s) mixture. The support/Columns 7-10
metal(s) mixture may be heat-treated at a temperature in a range
from about 50.degree. C. to about 100.degree. C. or about
60.degree. C. to about 90.degree. C. for several hours, and then
heat-treated at a temperature in a range from about 400.degree. C.
to about 700.degree. C., about 450.degree. C. to about 650.degree.
C., or about 500.degree. C. to about 600.degree. C. for about 2
hours. The resulting metal-containing support may be combined with
a Column 6 metal(s) and, optionally, an additional amount of
Columns 7-10 metal(s) such that the finished catalyst contains, per
gram of catalyst, at least 0.3 grams, at least 0.1 grams, or at
least 0.08 grams of the Column 6 metal(s), and a total Columns 7-10
metal(s), per gram of catalyst, in a range from about 0.01 grams to
about 0.2 grams or from about 0.05 grams to about 0.1 grams. The
resulting catalyst may be heat-treated at a temperature in a range
from about 50.degree. C. to about 100.degree. C. or from about
60.degree. C. to about 90.degree. C. for several hours, and then
heat-treated at a temperature in a range from about 350.degree. C.
to about 500.degree. C. or 400.degree. C. to about 450.degree. C.
for about 2 hours. In some embodiments, Column 15 element(s) may be
combined with the support/Columns 7-10 metal(s) mixture and/or with
the Column 6 metal(s).
[0175] Typically, the Columns 5-10 metal(s) and support may be
mixed with suitable mixing equipment to form a Columns 5-10
metal(s)/support mixture. Examples of suitable mixing equipment
include tumblers, stationary shells or troughs, Muller mixers (for
example, batch type or continuous type), impact mixers, and any
other generally known mixer or device, that will suitably provide
the Columns 5-10 metal(s)/support mixture. In certain embodiments,
the materials are mixed until the Columns 5-10 metal(s) is (are)
substantially homogeneously dispersed in the support.
[0176] In some embodiments, the catalyst is heat-treated at
temperatures from about 150.degree. C. to about 750.degree. C.,
from about 200.degree. C. to about 740.degree. C., or from about
400.degree. C. to about 730.degree. C. after combining the support
with the metal.
[0177] In some embodiments, the catalyst may be heat-treated in the
presence of hot air and/or oxygen rich air at a temperature in a
range between about 400.degree. C. and about 1000.degree. C. to
remove volatile matter such that at least a portion of the Columns
5-10 metal(s) are converted to the corresponding metal
oxide(s).
[0178] In other embodiments, however, the catalyst may be
heat-treated in the presence of air at temperatures in a range from
about 35.degree. C. to about 500.degree. C. for a period of time in
a range from 1 hour to about 3 hours to remove a majority of the
volatile components without substantially converting the Columns
5-10 metal(s) to metal oxide(s). Catalysts prepared by such a
method are generally referred to as "uncalcined" catalysts. When
catalysts are prepared in this manner, in combination with a
sulfiding method, the active metals may be substantially dispersed
on the support. Preparations of such catalysts are described in
U.S. Pat. No. 6,218,333 to Gabrielov et al. and U.S. Pat. No.
6,290,841 to Gabrielov et al.
[0179] In certain embodiments, a theta alumina support may be
combined with Columns 5-10 metal(s) to form a theta alumina
support/Columns 5-10 metal(s) mixture. The theta alumina
support/Columns 5-10 metal(s) mixture may be heat-treated at a
temperature of at least 400.degree. C. to form a catalyst having a
pore size distribution with a median pore diameter of at least 230
.ANG.. Typically, such heat-treating is conducted at temperatures
of at most 1200.degree. C.
[0180] In some embodiments, bulk metals catalysts used to change
properties of the crude feed include one or more Columns 6-10
metal(s). The bulk metal catalyst may have, per gram of catalyst, a
total Columns 6-10 metal(s) content from at least 0.3 grams, at
least 0.5 grams, at least 0.6 grams, at least 0.8 grams, or at
least 0.9 grams. The total Columns 6-10 metal(s) content, per gram
of catalyst, may be in a range from about 0.3 grams to about 0.99
grams, from about 0.5 grams to about 0.9 grams, or from about 0.6
grams to about 0.8 grams.
[0181] In some embodiments, the catalyst includes Column 15
element(s) in addition to the Columns 6-10 metal(s). The bulk metal
catalyst may have a total Column 15 element content, per gram of
catalyst, in range from about 0.000001 grams to 0.1 grams, about
0.00001 grams about 0.06 grams, about 0.00005 grams to about 0.03
grams, or about 0.0001 grams to about 0.001 grams.
[0182] The bulk metal catalyst, in some embodiments, may include a
binder. The binder may be silica, alumina oxide, zinc oxide, oxides
of the Columns 6-10 metal(s), carbon, zeolites, or mixtures
thereof. In certain embodiments, the catalyst includes at most 0.2
grams, at most 0.1 grams, at most 0.05 grams, at most 0.01 grams,
or at most 0.005 grams of binder per gram of catalyst.
[0183] The bulk metal catalyst may be prepared as described in U.S.
Pat. No. 4,937,218 to Aqudelo et al.; U.S. Pat. No. 6,162,350 to
Soled et al.; and U.S. Pat. No. 6,783,663 to Riley et al.; U.S.
Patent Application Publication Nos. US 2004/0182749 to Domokos et
al. and US 2004/0235653 to Domokos et al.; and by Landau et al. in
"Hydrosulfurization of Methyl-Substituted Dibenzothiophenes:
Fundamental Study of Routes to Deep Desulfurization, Journal of
Catalysis, 1996, Vol. 159, pp. 236-235, all of which are
incorporated herein by reference.
[0184] In some embodiments, one or more Columns 6-10 metal slurries
in water or other protic liquids are contacted at a temperature in
a range from about 25.degree. C. to about 95.degree. C. with a
slurry of water, alkaline compound, and a binder to form a Columns
6-10 metal/binder slurry. The Columns 6-10 metal slurries may
include 0.01 grams to 0.8 grams, 0.02 grams to 0.5 grams, or 0.05
grams to 0.3 grams of Columns 6-10 metal(s) per gram of slurry. In
some embodiments, the alkali compound is ammonia. An amount of
alkali compound may be at least 0.5 moles, at least 0.7 moles, at
least 0.8 moles, at least, 0.9 moles or at most 2 mole per mole of
Columns 6-10 metal(s), based on the oxide form of the Columns 6-10
metal(s). In some embodiments, the binder may be silica, alumina,
silica/alumina, titanium oxide, zirconium oxide, or mixtures
thereof.
[0185] The Columns 6-10 metal/binder slurry may be held at ambient
and/or at the slurry temperature for a period of time (for example,
at least 10 minutes, at least 30 minutes, or at least 240 minutes)
and then cooled, if necessary. The bulk metal catalyst may be
isolated from the slurry using general isolation techniques (for
example, filtration, spray dying, flash drying, evaporation, and
vacuum distillation). The bulk metal catalyst may be heat-treated
in a range from about 25.degree. C. to 95.degree. C., from about
55.degree. C. to about 90.degree. C., or from about 70.degree. C.
to about 80.degree. C. In some embodiments, the bulk metal catalyst
is further heat-treated at a temperature in a range from about
100.degree. C. to about 600.degree. C., from about 120.degree. C.
to about 400.degree. C., or at most 300.degree. C. In certain
embodiments, the bulk metal catalyst may be powdered, shaped,
and/or combined with other materials.
[0186] The bulk metal catalyst may be characterized using powder
x-ray diffraction methods. In some embodiments, the bulk metal
catalyst may exhibit no significant reflection that can be assigned
to the Columns 6-10 metal components. No significant reflection as
detected by x-ray diffraction methods may indicate that the bulk
metal catalyst is substantially amorphous, or amorphous.
[0187] In some embodiments, the support (either a commercial
support or a support prepared as described herein) may be combined
with a supported catalyst and/or a bulk metal catalyst. In some
embodiments, the supported catalyst may include Column 15
element(s). For example, the supported catalyst and/or the bulk
metal catalyst may be converted into a powder with an average
particle size from about 1 micron to about 50 microns, about 2
microns about 45 microns, or about 5 microns to about 40 microns.
The powder may be combined with a support to form an embedded metal
catalyst. In some embodiments, the powder may be combined with the
support and then extruded using standard techniques to form a
catalyst having a pore size distribution with a median pore
diameter in a range from about 80 .ANG. to about 200 .ANG. or about
90 .ANG. to about 180 .ANG., or about 120 .ANG. to about 130 .ANG..
Combining the catalyst with the support allows, in some
embodiments, at least a portion of the metal to reside under the
surface of the resulting embedded metal catalyst leading to less
metal on the surface than would otherwise occur in the unembedded
metal catalyst. In some embodiments, having less metal on the
surface of the catalyst extends the life and/or catalytic activity
of the catalyst by allowing at least a portion of the metal to move
to the surface of the catalyst during use. The metals may move to
the surface of the catalyst through erosion of the surface of the
catalyst during contact of the catalyst with a crude feed.
[0188] In some embodiments, catalysts may be characterized by pore
structure. Various pore structure parameters include, but are not
limited to, pore diameter, pore volume, surface areas, or
combinations thereof. The catalyst may have a distribution of total
quantity of pore size versus pore diameter. The median pore
diameter of the pore size distribution may be in a range from about
30 .ANG. to about 1000 .ANG., about 50 .ANG. to about 500 .ANG., or
about 60 .ANG. to about 300 .ANG.. In some embodiments, catalysts
that include at least 0.5 grams of gamma alumina per gram of
catalyst have a pore size distribution with a median pore diameter
in a range from about 50 .ANG. to about 500 .ANG., about 60 .ANG.
to about 200 .ANG., about 90 .ANG. to about 180 .ANG., about 100
.ANG. to about 140 .ANG., or about 120 .ANG. to about 130 .ANG.. In
other embodiments, catalysts that include at least 0.1 grams of
theta alumina per gram of catalyst have a pore size distribution
with a median pore diameter in a range from about 180 .ANG. to
about 500 .ANG., about 200 .ANG. to about 300 .ANG., or about 230
.ANG. to about 250 .ANG.. Such median pore diameters are typically
at most 1000 .ANG..
[0189] In certain embodiments, the median pore diameter of the pore
size distribution is greater than 110 .ANG., at least 120 .ANG., at
least 130 .ANG., at least 140 .ANG., at least 150 .ANG., at least
200 .ANG., or at least 250 .ANG.. Such median pore diameters are
typically at most 300 .ANG.. The median pore diameter of the pore
size distribution may be in a range from about 115 .ANG. to about
290 .ANG., from about 120 .ANG. to about 190 .ANG., from about 130
.ANG. to about 180 .ANG., or from about 140 .ANG. to about 160
.ANG..
[0190] In some embodiments, the catalyst having the pore size
distribution has at least 60% of a total number of pores in the
pore size distribution with a pore diameter within about 45 .ANG.,
about 35 .ANG., about 30 .ANG., about 25 .ANG., or about 20 .ANG.
of the median pore diameter of the pore distribution. In
embodiments in which the median pore diameter of the pore size
distribution is at least 180 .ANG., at least 200 .ANG., or at least
230 .ANG., greater that 60% of a total number of pores in the pore
size distribution have a pore diameter within about 50 .ANG., about
70 .ANG., or about 90 .ANG. of the median pore diameter. In some
embodiments, the catalyst has a pore size distribution with a
median pore diameter in a range from about 180 .ANG. to about 500
.ANG., about 200 .ANG. to about 400 .ANG., or about 230 .ANG. to
about 300 .ANG., with at least 60% of a total number of pores in
the pore size distribution having a pore diameter within about 50
.ANG., about 70 .ANG., or about 90 .ANG. of the median pore
diameter.
[0191] In some embodiments, pore volume of pores may be at least
0.3 cm.sup.3/g, at least 0.7 cm.sup.3/g or at least 0.9 cm.sup.3/g.
In certain embodiments, pore volume of pores may range from about
0.3 cm.sup.3/g to about 0.99 cm.sup.3/g, about 0.4 cm.sup.3/g to
about 0.8 cm.sup.3/g, or about 0.5 cm.sup.3/g to about 0.7
cm.sup.3/g. In some embodiments, pores having a pore diameter of at
least 350 .ANG., at least 400 .ANG., at least 500 .ANG., at least
1000 .ANG., at least 3000 .ANG., or at least 5000 .ANG. provide at
most 10%, at most 5%, at most 3%, at most 1%, or at most 0.5% of
the total pore volume of the catalyst. Such pore diameters may be
in a range of about 350 .ANG. to about 5000 .ANG., about 400 .ANG.
to about 1000 .ANG., or about 500 .ANG. to about 900 .ANG.. The
total pore volume provided by pores with such pore diameters may be
in a range from about 0% to about 9%, about 0.1% to about 5%, or
about 0.5% to about 1%.
[0192] The catalyst having a pore size distribution with a median
pore diameter in a range from about 60 .ANG. to about 500 .ANG.
may, in some embodiments, have a surface area of at least 100
m.sup.2/g, at least 120 m.sup.2/g, at least 170 m.sup.2/g, at least
220 m.sup.2/g, or at least 270 m.sup.2/g. Such surface area may be
in a range from about 100 m 2/g to about 300 m.sup.2/g, about 120
m.sup.2/g to about 270 m.sup.2/g, about 130 m.sup.2/g to about 250
m.sup.2/g, or about 170 m.sup.2/g to about 220 m.sup.2/g. In
certain embodiments, a surface area of a shaped bulk metal catalyst
is at least 30 m.sup.2/g, at least 60 m.sup.2/g, or in a range from
about 10 m.sup.2/g to about 350 m.sup.2/g.
[0193] In some embodiments, the bulk metal catalyst, the supported
catalyst and/or the catalyst precursor is sulfided to form metal
sulfides (prior to use) using techniques known in the art (for
example, ACTICAT.TM. process, CRI International, Inc.). In some
embodiments, the catalyst(s) and/or catalyst precursor may be dried
then sulfided. Alternatively, the catalyst(s) or catalyst precursor
may be sulfided in situ by contact of the catalyst or catalyst
precursor with a crude feed that includes sulfur-containing
compounds. In-situ sulfurization may utilize either gaseous
hydrogen sulfide in the presence of hydrogen, or liquid-phase
sulfurizing agents such as organosulfur compounds (including
alkylsulfides, polysulfides, thiols, and sulfoxides). Ex-situ
sulfurization processes are described in U.S. Pat. No. 5,468,372 to
Seamans et al. and U.S. Pat. No. 5,688,736 to Seamans et al., both
of which are incorporated herein by reference.
[0194] In certain embodiments, a first type of catalyst ("first
catalyst") includes Columns 5-10 metal(s) in combination with a
theta alumina support. The first catalyst has a pore size
distribution with a median pore diameter of at least 180 .ANG., at
least 220 .ANG., at least 230 .ANG., at least 250 .ANG., at least
300 .ANG., or at most 500 .ANG.. The support may include at least
0.1 grams, at least 0.5 grams, or at least 0.9 grams, or at most
0.999 grams of theta alumina per gram of support. In some
embodiments, the support has an alpha alumina content of below 0.1
grams of alpha alumina per gram of catalyst. The catalyst includes,
in some embodiments, at most 0.1 grams of Column 6 metal(s) per
gram of catalyst and at least 0.0001 grams of Column 6 metal(s) per
gram of catalyst. In some embodiments, the Column 6 metal(s) are
molybdenum and/or tungsten. In some embodiments, a first catalyst
may include Column 5 metal(s). The first catalyst may allow for
removal of alkali metals and alkaline-earth metals in metal salts
of organic acids. The first catalyst is generally capable of
removing at least a portion of the alkali metals and/or
alkaline-earth metal salts of organic acids, which may reduce
viscosity and/or surface tension of the crude feed. This may allow
the resulting crude feed to be more readily contacted with
catalysts positioned after the first catalyst.
[0195] In certain embodiments, a second type of catalyst ("second
catalyst") includes Columns 6-10 metal(s) in combination with a
support. The second catalyst has a median pore diameter of greater
than 110 .ANG.. The second catalyst has pores with a pore diameter
of at least 350 .ANG., which provide at most 10% of the pore volume
of the second catalyst. The second catalyst has per gram of second
catalyst, in some embodiments, a total content of Column 6 metal(s)
in a range from about 0.0001 grams to about 0.3 grams, a total
content of Columns 7-10 metal(s) in a range from about 0.0001 grams
to about 0.1 grams, and a total content of Column 15 element(s) in
a range from about 0.00001 grams to about 0.1 grams. In certain
embodiments, the second catalyst support has, per gram of support,
at least 0.9 grams of gamma alumina. The second catalyst is
generally capable of: removing at least a portion of the components
from the crude feed that contribute to thermal degradation as
measured by MCR; removing at least a portion of organic nitrogen
containing compounds; and removing at least a portion of the
C.sub.5 asphaltenes from the crude feed. The second catalyst, in
some embodiments, also removes at least a portion of the residue,
removes at least a portion of the Ni/FeN, removes at least a
portion of the components that contribute to high viscosities,
and/or removes at least a portion of the components that contribute
to low API gravity.
[0196] In some embodiments, a third type of catalyst ("third
catalyst") may have a median pore diameter of about 250 .ANG.. The
third catalyst has pores with a pore diameter of at least 350
.ANG., which provide at most 10% of the pore volume of the third
catalyst. The third catalyst is generally capable of: removing at
least a portion of the components from the crude feed that
contribute to thermal degradation as measured by MCR; removing a
portion of compounds containing heteroatoms; and/or removing a
portion of the C.sub.5 asphaltenes from the crude feed. The third
catalyst, in some embodiments, also removes components that
contribute to high viscosities and/or low API gravity.
[0197] In some embodiments, the second catalyst(s) and third
catalyst(s) have selected median pore diameters and pores having
selected pore diameters providing at most 10%, at most 5%, at most
3% or at most 1% of the pore volume. These catalysts provide
enhanced reduction of C.sub.5 asphaltenes content in the crude feed
and/or reduction of at least a portion of the components that
contribute to thermal degradation of the crude feed as measured by
MCR. Reduction of these compounds using catalysts with selected
median pore diameter and selected pore volume may allow the number
of catalysts to be minimized. Typically, the crude feed is first
treated with a conventional catalyst having relatively low
catalytic activity to remove C.sub.5 asphaltenes and/or components
that contribute to thermal degradation. These types of conventional
catalysts generally remove the C.sub.5 asphaltenes and/or other
components by allowing a relatively large portion of the C.sub.5
asphaltenes and/or other components to enter the pores of the
catalysts and fill the pores. As the pores are filled, the C.sub.5
asphaltenes and/or other components may be physically removed from
the crude feed. Once the pores are filled and/or plugged, the life
of the conventional catalyst becomes diminished. Catalysts with
selected median pore diameter and selected pore volumes remove
C.sub.5 asphaltenes and/or other components that contribute to
thermal degradation by limiting the portion, if any, of C.sub.5
asphaltenes and/or other components that enter the pores of the
catalyst. As such, the life of the catalyst may not be diminished
due to contact of the catalyst with C.sub.5 asphaltenes and/or
other components.
[0198] In some embodiments, the second catalyst(s) and/or the third
catalyst(s) may remove at least a portion of the alkali metals and
alkaline-metals in metal salts of organic acids. In certain
embodiments, the second catalyst(s) and/or the third catalyst(s)
are capable of removing at least a portion of the alkali metals
and/or alkaline-earth metal salts of organic acids that contribute
to formation of compounds that increase viscosity and/or surface
tension of the crude feed. In some embodiments, the second
catalyst(s) and/or the third catalyst(s) are capable of removing at
least a portion of the components that contribute to relatively
high viscosity of the crude feed.
[0199] In some embodiments, a fourth type of catalyst ("fourth
catalyst") may be obtainable by combining a support with Column 6
metal(s) to produce a catalyst precursor. Typically, the catalyst
precursor is heated to at least 100.degree. C. for about 2 hours.
In certain embodiments, the fourth catalyst(s) may have, per gram
of fourth catalyst(s), a Column 15 element(s) content in a range
from about 0.001 grams to about 0.03 grams, 0.005 grams to about
0.02 grams, or 0.008 grams to about 0.01 grams. The fourth
catalyst(s) may exhibit significant activity and stability when
used to treat the crude feed as described herein. In some
embodiments, the catalyst precursor is heated at temperatures below
500.degree. C. in the presence of one or more sulfur compounds. The
fourth catalyst(s) is (are) generally capable of removing a portion
of nitrogen containing compounds from the crude feed. Removal of
nitrogen containing compounds decreases the corrosive properties of
the crude product relative to the corrosive properties of the crude
feed. The fourth catalyst(s) may remove at least a portion of the
components that contribute to the TAN of the crude feed, remove at
least a portion of the metals in metal salts of organic acids,
remove at least a portion of the NiN/Fe, and/or remove at least a
portion of components contributing to a high viscosity of the crude
feed.
[0200] The fourth catalyst(s), in some embodiments, may also reduce
at least a portion of the MCR content of the crude feed, while
maintaining crude feed/total product stability. In certain
embodiments, the fourth catalyst(s) may have a Column 6 metal(s)
content in a range from about 0.0001 grams to about 0.1 grams,
about 0.005 grams to about 0.05 grams, or about 0.001 grams to
about 0.01 grams and a Column 10 metal(s) content in a range from
about 0.0001 grams to about 0.05 grams, about 0.005 grams to about
0.03 grams, or about 0.001 grams to about 0.01 grams per gram of
fourth catalyst(s). The fourth catalyst(s) may facilitate reduction
of at least a portion of the components that contribute to MCR in
the crude feed at temperatures in a range from about 300.degree. C.
to about 500.degree. C. or about 350.degree. C. to about
450.degree. C. and pressures in a range from about 0.1 MPa to about
20 MPa, about 1 MPa to about 10 MPa, or about 2 MPa to about 8
MPa.
[0201] In certain embodiments, a fifth type of catalyst ("fifth
catalyst") may be a bulk metal catalyst. The fifth catalyst(s)
includes at least 0.3 grams of Columns 6-10 metal(s) per gram of
fifth catalyst(s). In certain embodiments, the fifth catalyst(s)
also includes the binder. The fifth catalyst(s), in some
embodiments, includes Column 6 metal(s) in combination with Column
9 metal(s) and/or Column 10 metal(s). The fifth catalyst(s) is
generally capable of removing at least a portion of the components
that contribute to thermal degradation as measured by MCR. The
fifth catalyst(s), in some embodiments, is also capable of removing
at least a portion of C.sub.5 asphaltenes, at least a portion of
organic compounds containing heteroatoms, at least a portion of the
total Ni/V/Fe content, at least a portion of the components that
contribute to high viscosity, and/or at least a portion of the
components that contribute to low API gravity.
[0202] The first catalyst(s), second catalyst(s), third
catalyst(s), fourth catalyst(s), and fifth catalyst(s), may be
stable for at least 3 months, at least 6 months or at least 1 year
at temperatures of at least 370.degree. C., at least 380.degree.
C., at least 390.degree. C., at least 400.degree. C., or at least
420.degree. C., and pressures of at least 8 Nm.sup.3/m.sup.3, at
least 10 Nm.sup.3/m.sup.3, or at least 14 Nm.sup.3/m.sup.3 during
contact with the crude feed.
[0203] In some embodiments, the crude feed may be contacted with an
additional catalyst subsequent to contact with the first catalyst.
The additional catalyst may be one or more of the following: the
second catalyst, the third catalyst, the fourth catalyst, the fifth
catalyst, the commercial catalysts described herein, or
combinations thereof.
[0204] Other embodiments of the first catalyst(s), second
catalyst(s), third catalyst(s), fourth catalyst(s), and fifth
catalyst(s) may also be made and/or used as is otherwise described
herein.
[0205] Selecting the catalyst(s) of this application and
controlling operating conditions may allow a crude product to be
produced that has a MCR content, a nitrogen content, a content of
metals in metal salts of organic acids, and/or selected properties
changed relative to the crude feed. The resulting crude product may
have enhanced properties relative to the crude feed and, thus, be
more acceptable for transporting and/or refining.
[0206] Arrangement of two or more catalysts in a selected sequence
may control the sequence of property improvements for the crude
feed. For example, metals in metal salts of organic acids in the
crude feed can be reduced before at least a portion of the
components contributing to MCR and/or heteroatoms in the crude feed
are reduced.
[0207] Arrangement and/or selection of the catalysts may, in some
embodiments, improve lives of the catalysts and/or the stability of
the crude feed/total product mixture. Improvement of a catalyst
life and/or stability of the crude feed/total product mixture
during processing may allow a contacting system to operate for at
least 3 months, at least 6 months, or at least 1 year without
replacement of the catalyst in the contacting zone. A life of the
catalyst may be determined by measuring the temperature change of
the contacting zone over a period of time (for example, one month,
two months, three months, six months, and/or one year), while other
contacting conditions remain relatively constant such that certain
product specifications are maintained. A requirement for an
increase in the temperature of about 15.degree. C., about
13.degree. C., or about 10.degree. C. above the initial temperature
required for processing, may indicate that the effectiveness of the
catalyst is diminished.
[0208] Combinations of selected catalysts may allow reduction in at
least a portion of the MCR content, at least a portion of the
Ni/V/Fe, at least a portion of the C.sub.5 asphaltenes, at least a
portion of the metals in metal salts of organic acids, at least a
portion of the components that contribute to TAN, at least a
portion of the residue, or combinations thereof, from the crude
feed before other properties of the crude feed are changed, while
maintaining the stability of the crude feed/total product mixture
during processing (for example, maintaining a crude feed P-value of
above 1.5). Alternatively, C.sub.5 asphaltenes, TAN, and/or API
gravity may be incrementally reduced by contact of the crude feed
with selected catalysts. The ability to incrementally and/or
selectively change properties of the crude feed may allow the
stability of the crude feed/total product mixture to be maintained
during processing.
[0209] The first catalyst allows, in some embodiments, for removal
of at least a portion of metals in metal salts of organic acids
from the crude feed. For example, reducing at least a portion of
the metals in metal salts of organic acids in the crude feed/total
product mixture relative to the crude feed inhibits plugging of
other catalysts positioned downstream, and thus, increases the
length of time the contacting system may be operated without
replenishment of catalyst. Removal of at least a portion of the
metals in metal salts of organic acids from the crude feed may, in
some embodiments, increase a life of one or more catalysts
positioned after the first catalyst.
[0210] The second catalyst(s), the third catalyst(s), and/or the
fourth catalyst(s) may be positioned downstream of the first
catalyst. Further contact of the crude feed/total product mixture
with the second catalyst(s), third catalyst(s), and/or the fourth
catalyst(s) may reduce MCR content, reduce the content of NiN/Fe,
reduce sulfur content, reduce oxygen content, reduce viscosity,
and/or further reduce the content of metals in metal salts of
organic acids.
[0211] In some embodiments, the fifth catalyst(s) may be positioned
downstream of commercial catalysts. The commercial catalysts may be
used to remove at least a portion of the Ni/V/Fe in a crude feed.
Further contact of the crude feed/total product mixture with the
fifth catalyst(s) may reduce MCR content, reduce sulfur content,
reduce nitrogen content, and/or reduce oxygen content.
[0212] In some embodiments, catalyst selection and/or order of
catalysts in combination with controlled contacting conditions (for
example, temperature and/or crude feed flow rate) may assist in
reducing hydrogen uptake by the crude feed, maintaining crude
feed/total product mixture stability during processing, and
changing one or more properties of the crude product relative to
the respective properties of the crude feed. Stability of the crude
feed/total product mixture may be affected by various phases
separating from the crude feed/total product mixture. Phase
separation may be caused by, for example, insolubility of the crude
feed and/or crude product in the crude feed/total product mixture,
flocculation of asphaltenes from the crude feed/total product
mixture, precipitation of components from the crude feed/total
product mixture, or combinations thereof.
[0213] At certain times during the contacting period, the
concentration of crude feed and/or total product in the crude
feed/total product mixture may change. As the concentration of the
total product in the crude feed/total product mixture changes due
to formation of the crude product, solubility of the components of
the crude feed and/or components of the total product in the crude
feed/total product mixture tends to change. For example, the crude
feed may contain components that are soluble in the crude feed at
the beginning of processing. As properties of the crude feed change
(for example, TAN, MCR, C.sub.5 asphaltenes, P-value, or
combinations thereof), the components may tend to become less
soluble in the crude feed/total product mixture. In some instances,
the crude feed and the total product may form two phases and/or
become insoluble in one another. Solubility changes may also result
in the crude feed/total product mixture forming two or more phases.
Formation of two phases, through flocculation of asphaltenes,
change in concentration of crude feed and total product, and/or
precipitation of components, tends to reduce the life of one or
more of the catalysts. Additionally, the efficiency of the process
may be reduced. For example, repeated treatment of the crude
feed/total product mixture may be necessary to produce a crude
product with desired properties.
[0214] During processing, the P-value of the crude feed/total
product mixture may be monitored and the stability of the process,
crude feed, and/or crude feed/total product mixture may be
assessed. Typically, a P-value that is at most 1.5 indicates that
flocculation of asphaltenes from the crude feed generally occurs.
If the P-value is initially at least 1.5, and such P-value
increases or is relatively stable during contacting, then this
indicates that the crude feed is relatively stabile during
contacting. Crude feed/total product mixture stability, as assessed
by P-value, may be controlled by controlling contacting conditions,
by selection of catalysts, by selective ordering of catalysts, or
combinations thereof. Such controlling of contacting conditions may
include controlling LHSV, temperature, pressure, hydrogen uptake,
crude feed flow, or combinations thereof.
[0215] Catalysts described herein may facilitate reduction of MCR
content and viscosity at elevated temperatures and pressures while
maintaining the stability of the crude feed/total product mixture
and/or maintaining the lives of the catalysts.
[0216] In some embodiments, contacting conditions are controlled
such that temperatures in one or more contacting zones may be
different. Operating at different temperatures allows for selective
change in crude feed properties while maintaining the stability of
the crude feed/total product mixture. The crude feed enters a first
contacting zone at the start of a process. A first contacting
temperature is the temperature in the first contacting zone. Other
contacting temperatures (for example, second temperature, third
temperature, fourth temperature, et cetera) are the temperatures in
contacting zones that are positioned after the first contacting
zone. A first contacting temperature may be in a range from about
100.degree. C. to about 420.degree. C. and a second contacting
temperature may be in a range that is about 20.degree. C. to about
100.degree. C., about 30.degree. C. to about 90.degree. C., or
about 40.degree. C. to about 60.degree. C. different than the first
contacting temperature. In some embodiments, the second contacting
temperature is greater than the first contacting temperature.
Having different contacting temperatures may reduce TAN and/or
C.sub.5 asphaltenes content in a crude product relative to the TAN
and/or the C.sub.5 asphaltenes content of the crude feed to a
greater extent than the amount of TAN and/or C.sub.5 asphaltene
reduction, if any, when the first and second contacting
temperatures are the same as or within 10.degree. C. of each
other.
EXAMPLES
[0217] Non-limiting examples of support preparations, catalyst
preparations, and systems with selected arrangement of catalysts
and controlled contacting conditions are set forth below.
Example 1
Preparation of a Catalyst Support
[0218] An alumina/silica support was prepared by mulling 550 grams
of an alumina/silica mixture, 26 grams of calcined alumina fines,
585 grams of water, and 8 grams of 16M nitric acid for 35 minutes.
The alumina/silica mixture was prepared by combining at least 0.98
grams of alumina/silica mixture (Criterion Catalysts and
Technologies LP) per gram of support with up to 0.02 grams of
silica (Criterion Catalysts and Technologies LP) per gram of
alumina/silica mixture. The mulled mixture was extruded through
1.94 mm and 3.28 mm diameter die plates, and then heat-treated at a
temperature in a range from 93.degree. C. (200.degree. F.) to
121.degree. C. (250.degree. F.) until a loss on ignition in a range
of 27 wt % to 30 wt %, based on initial extrudate weight, was
obtained. Loss on ignition was performed by heating the extrudates
to 540.degree. C. for 15 minutes to 50 minutes, and then
determining the relative amount of weight lost by the extrudates.
The extrudates were further heat-treated at 918.degree. C.
(1685.degree. F.) for 1 hour. The support had an average pore
diameter of 125 .ANG., a surface area of 281 m 2/g, a pore volume
of 0.875 cm.sup.3/g, and pores with a diameter of at least 350
.ANG., which provided 0.9% of the total pore volume of the support.
Example 1 demonstrates preparation of a support that has an average
pore diameter of at least 90 .ANG. and pores having a pore diameter
of at least 350 .ANG. provide at most 15% of the pore volume of the
support.
Example 2
Preparation of a Catalyst having a Median Pore Diameter of 115
.ANG. and a Selected Pore Volume Distribution
[0219] A catalyst was prepared as follows. An alumina/silica
support prepared as described in Example 1 was impregnated with a
molybdenum/nickel/phosphorus impregnation solution prepared as
follows. A first solution was made by combining 62.34 grams of
(NH.sub.4).sub.2Mo.sub.2O.sub.7, 17.49 grams of MoO.sub.3, 12.22
grams of 30% H.sub.2O.sub.2, and 50.47 grams of deionized water to
form a slurry. MEA (3.0 grams) was added to the slurry at a rate
sufficient to control the exotherm of dissolution. The slurry was
heated to 64.degree. C. (147.degree. F.) until the solids
dissolved, and then cooled to room temperature. The pH of the first
solution was 5.34.
[0220] A second solution was made by combining 8.2 grams of
Ni(NO.sub.3).sub.2-6H.sub.2O and 5.47 grams of NiCO.sub.3 with
30.46 grams of deionized water, and then adding 29.69 grams of 85
wt % H.sub.3PO.sub.4. The pH of the second solution was 0.29. The
first solution and second solution were combined, and sufficient
deionized water was added to bring the combined solution volume up
to 218.75 mL to yield the molybdenum/nickel/phosphorus impregnation
solution. The pH of the impregnation solution was 2.02.
[0221] The support (200.0 grams) was combined with the impregnation
solution and aged for several hours with occasional agitation. The
resulting support/metal mixture was heat-treated at 125.degree. C.
for several hours, and then heat-treated at 482.degree. C.
(900.degree. F.) for 2 hours. The resulting catalyst contained, per
gram of catalyst, 0.13 grams of molybdenum, 0.03 grams of nickel,
and 0.03 grams of phosphorus with the balance being support. The
catalyst had a pore size distribution with a median pore diameter
of 115 .ANG. with 66.7% of the total number of pores having a pore
diameter within 28 .ANG. of the median pore diameter. The surface
area of the catalyst was 179 m.sup.2/g. The pore volume of the
catalyst was 0.5 cm.sup.3/g. The pore volume distribution is
summarized in Table 1. TABLE-US-00001 TABLE 1 % of pore volume
Range, .ANG. Catalyst <70 3.07 70-100 16.21 100-130 69.36
130-150 7.81 150-180 0.86 180-200 0.37 200-240 0.47 240-300 0.39
300-350 0.23 350-450 0.27 450-600 0.23 600-1000 0.27 1000-3000 0.22
3000-5000 0.72 >5000 0
[0222] As shown in Table 1, the pores of the catalyst having a pore
diameter of at least of 350 .ANG. provided 1.71% of the total pore
volume of the catalyst.
[0223] Example 2 demonstrates preparation of a Column 6 metal
catalyst having a pore size distribution with a median pore
diameter of greater than 110 .ANG., and a pore volume in which
pores having a pore diameter of at least 350 .ANG. provide at most
10% of the total pore volume. This example also demonstrates
preparation of a Column 6 metal catalyst from a support having an
average pore diameter of at least 90 .ANG., and a pore volume in
which pores having a pore diameter of at least 350 .ANG. provide at
most 15% of the total pore volume.
Example 3
Contact of a Crude Feed with Two Catalysts
[0224] A tubular reactor with a centrally positioned thermowell was
equipped with thermocouples to measure temperatures throughout a
catalyst bed. The catalyst bed was formed by filling the space
between the thermowell and an inner wall of the reactor with
catalysts and silicon carbide (20-grid, Stanford Materials; Aliso
Viejo, Calif.). Such silicon carbide is believed to have low, if
any, catalytic properties under the process conditions described
herein. All catalysts were mixed with silicon carbide in a volume
ratio of 2 parts silicon carbide to 1 part catalyst before placing
the mixture into the contacting zone portions of the reactor.
[0225] The crude feed flow to the reactor was from the top of the
reactor to the bottom of the reactor. Silicon carbide was
positioned at the bottom of the reactor to serve as a bottom
support. A bottom catalyst/silicon carbide mixture (81 cm.sup.3)
was positioned on top of the silicon carbide to form a bottom
contacting zone. The bottom catalyst was prepared as described in
Example 2.
[0226] A top catalyst/silicon carbide mixture (9 cm.sup.3) was
positioned on top of the bottom contacting zone to form a top
contacting zone. The top catalyst was a molybdenum/vanadium
catalyst on a theta alumina support prepared as follows. A support
was prepared by mulling 576 grams of alumina (Criterion Catalysts
and Technologies LP, Michigan City, Michigan, U.S.A.) with 585
grams of water and 8 grams of glacial nitric acid for 35 minutes.
The resulting mulled mixture was extruded through a 1.3 mm die
plate, heat-treated between 90.degree. C. and about 125.degree. C.,
and further heat-treated at 918.degree. C., which resulted in 650
grams of a support with a median pore diameter of 182 .ANG.. The
heat-treated support was placed in a Lindberg furnace. The furnace
temperature was raised to about 1000.degree. C. to about
1100.degree. C. over 1.5 hours, and then held in this range for 2
hours to produce the support. The support was impregnated with a
molybdenum/vanadium impregnation solution prepared as follows. A
first solution was made by combining 2.14 grams of
(NH.sub.4).sub.2Mo.sub.2O.sub.7, 3.21 grams of MoO.sub.3, 0.56
grams of 30% H.sub.2O.sub.2, 0.14 grams of monoethanolamine, and
3.28 grams of deionized water to form a slurry. The slurry was
heated to 65.degree. C. until solids dissolved, and then cooled to
room temperature. A second solution was made by combining 3.57
grams of VOSO.sub.4.xH.sub.2O (x=3 to 5) with 40 grams of deionized
water. The first solution and second solution were combined and
sufficient deionized water was added to bring the combined solution
volume up to 82 mL to yield the molybdenum/vanadium impregnation
solution. The support was impregnated with the molybdenum/vanadium
impregnation solution and aged for 2 hours with occasional
agitation. The resulting support/metal mixture was heat-treated at
125.degree. C. for several hours, and then heat-treated at
480.degree. C. for 2 hours. The resulting catalyst contained, per
gram of catalyst, 0.02 grams of vanadium and 0.02 grams of
molybdenum, with the balance being support.
[0227] Silicon carbide was positioned on top of the top contacting
zone to fill dead space and to serve as a preheat zone. The
catalyst bed was loaded into a Lindberg furnace that included four
heating zones corresponding to the preheat zone, the top and bottom
contacting zones, and the bottom support.
[0228] The catalysts were sulfided by introducing a gaseous mixture
of 5 vol % hydrogen sulfide and 95 vol % hydrogen gas into the
contacting zones at a rate of about 1.5 liter of gaseous mixture
per volume (mL) of total catalyst (silicon carbide was not counted
as part of the volume of catalyst) for the time periods set forth
below. The reactor pressure was about 1.9 MPa (279.7 psi).
Temperatures of the contacting zones were increased from ambient to
204.degree. C. (400.degree. F.) over 1 hour, and then held at
204.degree. C. for 2 hours. After holding at 204.degree. C., the
contacting zones were increased incrementally to 316.degree. C.
(600.degree. F.) at a rate of about 10.degree. C. (about 50.degree.
F.) per hour. The contacting zones were maintained at 316.degree.
C. for an hour, incrementally raised to 370.degree. C. (700.degree.
F.) over 1 hour, and then held at 370.degree. C. for two hours. The
contacting zones were then allowed to cool to ambient
temperature.
[0229] After sulfiding, the contacting zones were then heated to
204.degree. C. over 2 hours and crude feed (BC-10, Brazil) was fed
to the top of the reactor. The crude feed flowed through the
preheat zone, top contacting zone, bottom contacting zone, and
bottom support of the reactor. The crude feed was contacted with
each of the catalysts in the presence of hydrogen gas. Contacting
conditions were as follows: ratio of hydrogen gas to the crude feed
provided to the reactor was 656 Nm.sup.3/m.sup.3 (4000 SCFB), LHSV
was 0.5 h.sup.-1, and pressure was 13.8 MPa (2014.7 psi). The two
contacting zones were incrementally heated from 204.degree. C. to
390.degree. C. at a rate in a range from 0.1.degree. C. per hour to
10.degree. C. per hour, and then maintained at 390.degree. C. for
311 hours. Temperatures of the catalyst bed was incrementally
raised to 400.degree. C., and maintained at 400.degree. C. for 352
hours.
[0230] The total product (that is, the crude product and gas)
exited the catalyst bed. The total product was introduced into a
gas-liquid phase separator. In the gas-liquid separator, the total
product was separated into the crude product and gas. Gas input to
the system was measured by a mass flow controller. Gas exiting the
system was cooled to a temperature sufficient to remove any liquid
components having a carbon number of at least 5 from the gas. The
separated gas was measured using a wet test meter. The crude
product was periodically analyzed to determine a weight percentage
of components of the crude product. Crude product and crude feed
properties are summarized in Table 2. TABLE-US-00002 TABLE 2 Crude
Property Crude Feed Product TAN 3.6 .ltoreq.0.05 API Gravity 15.1
20 Density at 15.56.degree. C. (60.degree. F.), 0.9651 0.9306
g/cm.sup.3 Hydrogen, wt % 11.4 12.1 Carbon, wt % 87.1 87.4 Sulfur,
wt % 0.433 0.05 Oxygen, wt % 0.42 0.01 Nitrogen, wt % 0.52 0.24
Basic Nitrogen, wt % 0.16 0.08 Calcium, wtppm 3.5 0.6 Potassium,
wtppm 1.8 1.3 Sodium, wtppm 5.3 0.6 Nickel, wtppm 12.4 7.3
Vanadium, wtppm 19.2 6.4 Iron, wtppm 10 0.4 Micro-Carbon Residue,
wt % 8.5 4.6 C.sub.5 Asphaltenes, wt % 7.5 4.3 Naphtha, wt % 0 4.1
Distillate, wt % 17.5 26.6 VGO, wt % 39.2 40.9 Residue, wt % 43.3
28.4 P-Value 5 3.6 Viscosity at 37.8.degree. C. 1705 156
(100.degree. F.), cSt
[0231] As shown in Table 2 the crude product had, per gram of crude
product, a nitrogen content of 0.0024 grams, a MCR content of 0.046
grams, and a C.sub.5 asphaltenes content of 0.043 grams. The crude
product also had a calcium content of 0.6 wtppm, a potassium
content of 1.3 wtppm, and a sodium content of 0.6 wtppm.
[0232] Example 3 demonstrates that contacting the crude feed with
one or more catalysts at controlled contacting conditions produced
a total product that included the crude product. At least one of
the catalysts was a Column 6 metal catalyst that: (a) included
Column 6 metal(s); (b) had a pore size distribution with a median
pore diameter of greater than 110 .ANG.; and (c) had a pore volume
in which pores having a pore diameter of at least 350 .ANG.
provided at most 10% of the pore volume. As measured by P-value,
crude feed/total product mixture stability was maintained. The
crude product had reduced MCR, a reduced alkali metal and
alkaline-earth metal salts in organic acids, reduced Ni/V/Fe
content, reduced sulfur content, reduced nitrogen content, reduced
C.sub.5 asphaltenes, and reduced oxygen content relative to the
crude feed.
Example 4
Preparation of a Catalyst Support
[0233] An alumina support was prepared by mulling 550 grams of
alumina powder (Criterion Catalysts and Technologies LP), 26 grams
of calcined alumina fines, 585 grams of water, and 8 grams of 16M
nitric acid for 35 minutes. The mulled mixture was extruded through
1.94 mm and 3.28 mm diameter die plates, heat-treated at 93.degree.
C. (200.degree. F.), 107.degree. C. (225.degree. F.), and then
heat-treated at 121.degree. C. (250.degree. F.) until a loss on
ignition in a range of 27 wt % to 30 wt %, based on initial
extrudate weight, was obtained. Loss on ignition was performed as
described in Example 1. The extrudates were further heat-treated at
918.degree. C. (1685.degree. F.) for 1 hour. The support had an
average pore diameter of 186.4 .ANG., a pore volume of 0.868
cm.sup.3/mL, and pores with a diameter of at least 350 .ANG., which
provided 13.3% of the total pore volume of the support. Example 4
demonstrates preparation of a support that has an average pore
diameter of at least 90 .ANG. and a pore volume in which pores
having a pore diameter of at least 350 .ANG. provide at most 15% of
the pore volume of the support.
Example 5
Preparation of a Catalyst having a Median Pore Diameter of 250
.ANG. and a Selected Pore Volume Distribution
[0234] The alumina support prepared as described in Example 4 was
impregnated with a molybdenum/cobalt/phosphorus impregnation
solution prepared as follows. MoO.sub.3 (22.95 grams) was combined
with 85 wt % H.sub.3PO.sub.4 (12.67 grams), and heated to
82.degree. C. (180.degree. F.) to form a molybdenum/phosphorous
solution. Co(OH).sub.2 (29.83 grams) was added to the
molybdenum/phosphorus solution and the resulting
molybdenum/cobalt/phosphorus solution was heated to 100.degree. C.
Citric acid monohydrate (21.5 grams) was added to the
molybdenum/cobalt/phosphorus solution, heated to 100.degree. C.,
and maintained at 100.degree. C. for 1 hour. The resulting solution
was reduced in volume to 252 mL to produce the
molybdenum/cobalt/phosphorus impregnation solution. The
impregnation solution had a pH of 3.22.
[0235] The alumina support (300.0 grams) was combined with the
impregnation solution and aged for several hours with occasional
agitation. The resulting support/metal mixture was heat-treated at
120.degree. C. for several hours, and then heat-treated at
426.degree. C. (800.degree. F.) for 2 hours. The resulting catalyst
was further heat-treated at 593.degree. C. (1100.degree. F.) for 2
hours. The catalyst contained, per gram of catalyst, 0.153 grams of
molybdenum, 0.043 grams of cobalt, and 0.008 grams of phosphorus,
with the balance being support. The catalyst had a pore size
distribution with a median pore diameter of 250 .ANG., with 67% of
the total number of pores having a pore diameter within 58 .ANG. of
the median pore diameter. The surface area of the catalyst was 98
m.sup.2/g. The pore volume distribution is summarized in Table 3.
TABLE-US-00003 TABLE 3 % of pore volume Range, .ANG. Catalyst
<70 0 70-100 0 100-130 0.15 130-150 0.5 150-180 2.5 180-200 4.25
200-240 22.66 240-300 63.77 300-350 3.36 350-450 0.98 450-600 0.46
600-1000 0.44 1000-3000 0.46 3000-5000 0.46 >5000 0
[0236] As shown in Table 3, pores having a pore diameter of at
least 350 .ANG. provided 2.8% of the total pore volume of the
catalyst.
[0237] Example 5 demonstrates the preparation of the Column 6 metal
catalyst having a pore size distribution with a median pore
diameter of greater than 110 .ANG., and a pore volume in which
pores of at least 350 .ANG. provide at most 10% of the total pore
volume. This example also demonstrates the preparation of the
Column 6 metal catalyst from a support having an average pore
diameter of at least 90 .ANG., and a pore volume in which pores
having a pore diameter of at least 350 .ANG. provide at least 15%
of the total pore volume.
Example 6
Contact of a Crude Feed with Two Catalysts
[0238] The reactor apparatus (except for content of contacting
zones), the crude feed, catalyst sulfiding method, total product
separation method, contacting conditions, contacting time, and
crude product analysis were the same as described in Example 3.
[0239] The crude feed flowed from the top of the reactor to the
bottom of the reactor. A molybdenum/cobalt/phosphorus catalyst
prepared as described in Example 5 was mixed with silicon carbide
and the mixture (81 cm.sup.3) was positioned in the bottom
contacting zone. The molybdenum/vanadium catalyst on a theta
alumina support, prepared as described in Example 3 was mixed with
silicon carbide. The molybdenum-vanadium catalyst/silicon carbide
mixture (9 cm.sup.3) was positioned in the top contacting zone.
[0240] Crude product properties are summarized in Table 4.
TABLE-US-00004 TABLE 4 Crude Property Crude Feed Product TAN 3.6
.ltoreq.0.05 API Gravity 15.1 19.2 Density at 15.56.degree. C.
0.9651 0.9554 (60.degree. F.), g/cm.sup.3 Hydrogen, wt % 11.4 11.6
Carbon, wt % 87.1 87.6 Sulfur, wt % 0.43 0.16 Oxygen, wt % 0.42
0.11 Nitrogen, wt % 0.52 0.47 Calcium, wtppm 5.4 0.5 Potassium,
wtppm 46 1.5 Sodium, wtppm 117 0.6 Nickel, wtppm 12.4 7.5 Vanadium,
wtppm 19.2 6.2 Iron, wtppm 10.4 0.9 Micro-Carbon Residue, wt % 8.5
7.2 C.sub.5 Asphaltenes, wt % 7.5 5.0 Naphtha, wt % 0 2.3
Distillate, wt % 17.5 20.3 VGO, wt % 39.2 42.0 Residue, wt % 43.3
35.4 P-Value 5 4.2 Viscosity at 37.8.degree. C. 1705 698
(100.degree. F.), cSt
[0241] As shown in Table 4, the crude product had a nitrogen
content of 0.0047 grams, a MCR content of 0.072 grams and a C.sub.5
asphaltenes content of 0.05 grams, per gram of crude product. The
crude product also had 0.5 wtppm of calcium, 1.5 wtppm of
potassium, and 0.6 wtppm of sodium.
[0242] Example 6 demonstrates that contacting the crude feed with
one or more catalysts under controlled contacting conditions
produced a total product that included the crude product. At least
one of the catalysts was a Columns 6 metal catalyst that: (a)
included Column 6 metal(s); (b) had a pore size distribution with a
median pore diameter of greater than 110 .ANG.; and (c) had a pore
volume in which pores having a pore diameter of at least 350 .ANG.
provided at most 10% of the pore volume. The crude product had
reduced MCR, reduced alkali metal and alkaline-earth metal salts of
organic acids, reduced Ni/V/Fe content, reduced sulfur content,
reduced nitrogen content, reduced C.sub.5 asphaltenes, and reduced
oxygen content relative to the crude feed.
[0243] In this patent, certain U.S. patents and U.S. patent
applications have been incorporated by reference. The text of such
U.S. patents and U.S. patent applications is, however, only
incorporated by reference to the extent that no conflict exists
between such text and the other statements and drawings set forth
herein. In the event of such conflict, then any such conflicting
text in such incorporated by reference U.S. patents and U.S. patent
applications is specifically not incorporated by reference in this
patent.
[0244] Further modifications and alternative embodiments of various
aspects of the invention will be apparent to those skilled in the
art in view of this description. Accordingly, this description is
to be construed as illustrative only and is for the purpose of
teaching those skilled in the art the general manner of carrying
out the invention. It is to be understood that the forms of the
invention shown and described herein are to be taken as examples of
embodiments. Elements and materials may be substituted for those
illustrated and described herein, parts and processes may be
reversed and certain features of the invention may be utilized
independently, all as would be apparent to one skilled in the art
after having the benefit of this description of the invention.
Changes may be made in the elements described herein without
departing from the spirit and scope of the invention as described
in the following claims.
* * * * *