Canadian Patents Database / Patent 2549088 Summary

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(12) Patent: (11) CA 2549088
(54) English Title: SYSTEMS, METHODS, AND CATALYSTS FOR PRODUCING A CRUDE PRODUCT
(54) French Title: SYSTEMES, PROCEDES, ET CATALYSEURS POUR LA PRODUCTION D'UN PRODUIT BRUT
(51) International Patent Classification (IPC):
  • C10G 29/04 (2006.01)
  • B01J 23/24 (2006.01)
  • B01J 35/00 (2006.01)
  • C10G 45/00 (2006.01)
(72) Inventors :
  • BHAN, OPINDER KISHAN (United States of America)
  • WELLINGTON, SCOTT LEE (United States of America)
(73) Owners :
  • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. (Not Available)
(71) Applicants :
  • SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. (Netherlands)
(74) Agent: NORTON ROSE FULBRIGHT CANADA LLP/S.E.N.C.R.L., S.R.L.
(74) Associate agent:
(45) Issued: 2013-06-04
(86) PCT Filing Date: 2004-12-16
(87) Open to Public Inspection: 2005-07-14
Examination requested: 2009-11-26
(30) Availability of licence: N/A
(30) Language of filing: English

(30) Application Priority Data:
Application No. Country/Territory Date
60/531,506 United States of America 2003-12-19
60/618,892 United States of America 2004-10-14

English Abstract




Contact of a crude feed with one or more catalysts produces a total product
that include a crude product. The crude product is a liquid mixture at 25~C
and 0.101 MPa. 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.


French Abstract

La présente invention a trait à un procédé comprenant la mise en contact d'une charge brute avec un ou des catalyseurs menant à la production d'un produit total comportant un produit brut. Le produit brut est un mélange liquide à 25 ·C et 0,101 MPa. Une ou des propriété(s) du produit brut peut/peuvent être modifiée(s) par au moins 10 % par rapport aux propriétés respectives de la charge brute.


Note: Claims are shown in the official language in which they were submitted.

CLAIMS:
1. A method of producing a catalyst, comprising:
combining a support with one or more metals to form a support/metal mixture,
wherein the support comprises theta alumina and has an alpha alumina content
of at most 0.1
grams of alpha alumina per gram of support, and the one or more metals
comprise one or
more metals from Column 6 of the Periodic Table, one or more compounds of one
or more
metals from Column 6 of the Periodic Table, or mixtures thereof, and in
addition one or more
metals from Column 5 of the Periodic Table, one or more compounds of one or
more Column
metals or mixtures thereof;
heat treating the theta alumina support/metal mixture at a temperature of at
least 400
°C to produce the catalyst, and wherein the catalyst has a pore size
distribution with a median
pore diameter of at least 230 .ANG., as determined by ASTM Method D4284.
2. The method as claimed in claim 1, wherein the median pore diameter of the
pore size
distribution is at most 500 .ANG..
3. The method as claimed in claim 1 or 2, wherein the pore volume of the
pores in the
pore size distribution is at least 0.3 cm3/g or at least 0.7 cm3/g.
4. The method as claimed in any one of claims 1-3, wherein the surface area
of the
catalyst is at least 60 m2/g or at least 90 m2/g.
5. The method as claimed in any one of claims 1-4, wherein the one or more
metals
comprise in addition vanadium, cobalt, nickel, or mixtures thereof.
6. The method as claimed in any one of claims 1-5, wherein the one or more
metals
comprise in addition at least one of: (a) one or more elements from Column 15
of the
Periodic Table; and (b) one or more compounds of one or more elements from
Column 15 of
the Periodic Table with the support.


83

7. The method as claimed in any one of claims 1-6, wherein the theta alumina
content of
the support is at least 0.1 grams, at least 0.3 grams, or at least 0.5 grams
of theta alumina per
gram of support.
8. The method as claimed in any one of claims 1-7, wherein the support
comprises in
addition at least one of: delta alumina and gamma alumina as determined by x-
ray diffraction.
9. A catalyst, comprising:
(a) one or more metals from Column 6 of the Periodic Table, one or more
compounds
of one or more metals from Column 6 of the Periodic Table, or mixtures
thereof, in addition
one or more metals from Column 5 of the Periodic Table, one or more compounds
of one or
more Column 5 metals, or mixtures thereof;
(b) a support material having theta alumina content of at least 0.1 grams of
theta
alumina per gram of support material, as determined by x-ray diffraction, an
alpha alumina
content of at most 0.1 grams of alpha alumina per gram of support; and
wherein the catalyst has a pore size distribution with a median pore diameter
of at
least 230 .ANG., as determined by ASTM Method D4284.
10. The catalyst as claimed in claim 9, wherein the one or more Column 5
metals is
vanadium.
11. The catalyst as claimed in claim 9 or 10, wherein the one or more Column 6
metals is
at least one of molybdenum and tungsten.
12. A method of producing a crude product, comprising:
contacting a crude feed with one or more catalysts as defined in any one of
claims 9-
11 to produce a total product that includes the crude product, wherein the
crude product is a
liquid mixture at 25 °C and 0.101 MPa, the crude feed has a total acid
number (TAN) of at
least 0.3; and



84

controlling contacting conditions at a temperature in the range of from 50-500
°C, a
pressure in the range from 0.1-20 MPa and a LHSV in the range from 0.1-30 h-1
such that the
crude product has a TAN of at most 90% of the TAN of the crude feed, wherein
TAN is as
determined by ASTM Method D664.
13. The method as claimed in claim 12, wherein the TAN of the crude product is
at most
50%, at most 30%, or at most 10% of the TAN of the crude feed.
14. The method as claimed in claim 12, wherein the TAN of the crude product is
in a
range from 1-80%, 20-70%, 30-60%, or 40-50% of the TAN of the crude feed.
15. The method as claimed in any one of claims 12-14, wherein the TAN of the
crude
product is in a range from 0.001 to 0.5, from 0.01 to 0.2, or from 0.05 to
0.1.
16. The method as claimed in any one of claims 12-15, wherein the TAN of the
crude
feed is in a range from 0.3 to 20, from 0.4 to 10, or from 0.5 to 5.
17. The method as claimed in any one of claims 12-16, wherein the crude feed
is
contacted in a contacting zone that is on or coupled to an offshore facility.
18. The method as claimed in any one of claims 12-17, wherein contacting
comprises
contacting in the presence of a hydrogen source.
19. The method as claimed in any one of claims 12-18, 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.
20. A method as claimed in any one of claims 12-19 further comprising the step
of
processing the crude product or blend to produce transportation fuel, heating
fuel, lubricants,
or chemicals.
21. The method as claimed in claim 20, wherein the processing comprises
distilling the
crude product or the blend into one or more distillate fractions.
22. The method as claimed in claim 20 or 21, wherein the processing comprises
hydrotreating.

85

Note: Descriptions are shown in the official language in which they were submitted.

CA 02549088 2006-06-09
WO 2005/063933 PCT/US2004/042640



SYSTEMS, METHODS, AND CATALYSTS FOR PRODUCING A CRUDE
PRODUCT
FIELD OF THE INVENTION
The present invention generally relates to systems, methods, and catalysts for

treating crude feed, and to compositions that can be produced using such
systems,
methods, and catalysts. 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 C
and 0.101 I\4Pa
and has one or more properties that are changed relative to the respective
property of the
crude feed.
DESCRIPTION OF RELATED ART
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".
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.
Disadvantaged crudes often contain relatively high levels of residue. Such
high
levels of residue tend to be difficult and expensive to transport and/or
process using
conventional facilities.
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.

WO 2005/063933 CA 02549088 2006-06-09 PCT/US2004/042640
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.
Coke 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. High temperatures used during regeneration may also
diminish
the activity of the catalyst and/or cause the catalyst to deteriorate.
Disadvantaged crudes may include metals in metal salts of organic acids (for
example, calcium, potassium and/or sodium). Metals in metal salts of organic
acids are
not typically separated from disadvantaged crudes by conventional processes,
for example,
desalting and/or acid washing.
Processes are often encountered in conventional processes 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 catalyst bed. Moreover, the
metals in metal
salts of organic acids may cause rapid deactivation of catalysts.
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.
Disadvantaged crudes may include hydrogen deficient hydrocarbons. When
processing of 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
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CA 02549088 2006-06-09
WO 2005/063933 PCT/US2004/042640

from forming coke. Hydrogen is costly to produce and/or costly to transport to
treatment
facilities.
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).
Conventional processes often lack the ability to change a selected property in
a
disadvantaged crude without also significantly changing other properties in
the
disadvantaged crude. For example, conventional processes often lack the
ability to
significantly reduce TAN in a disadvantaged crude while, at the same time,
only changing
by a desired amount the content of certain components (such as sulfur or metal

contaminants) in the disadvantaged crude.
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.
U.S. Patent Nos. 6,547,957 to Sudhakar et al.; 6,277,269 to Meyers et al.;
6,063,266 to Grande et al.; 5,928,502 to Bearden et al.; 5,914,030 to Bearden
et al.;
5,897,769 to Trachte et al.; 5,871,636 to Trachte et al.; and 5,851,381 to
Tanaka et al.,
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.
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). Other
undesirable
properties include relatively high amounts of undesirable components (for
example,
residue, organically bound heteroatoms, metal contaminants, metals in metal
salts of
organic acids, and/or organic oxygen compounds). Such properties 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


3

CA 02549088 2012-03-06

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 only selectively changing other properties in the disadvantaged
crude.
SUMMARY OF THE INVENTION
Inventions described herein generally relate to systems, methods and catalysts
for
conversion of a crude feed to a total product comprising a crude product and,
in some
embodiments, non-condensable gas. Inventions described herein also generally
relate to
compositions that have novel combinations of components therein. Such
compositions
can be obtained by using the systems and methods described herein.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.3, and at least one of the catalysts
having a pore
size distribution with a median pore diameter in a range from 90 A to 180 A,
with at least
60% of the total number of pores in the pore size distribution having a pore
diameter
within 45 A of the median pore diameter, wherein pore size distribution is as
determined
by ASTM Method D4284; and controlling contacting conditions such that the
crude
product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is
as
determined by ASTM Method D664.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.3, at least one of the catalysts
having a pore size
distribution with a median pore diameter of at least 90 A, as determined by
ASTM
Method D4284, and the catalyst having the pore size distribution having, per
gram of
catalyst, from 0.0001 grams to 0.08 grams of: molybdenum, one or more
molybdenum
compounds, calculated as weight of molybdenum, or mixtures thereof; and
controlling
contacting conditions such that the crude product has a TAN of at most 90% of
the TAN
of the crude feed, wherein TAN is as determined by ASTM Method D664.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.3, as determined by ASTM D664, at
least one of
the catalysts having a pore size distribution with a median pore diameter of
at least 180 A,
as determined by ASTM Method D4284, and the catalyst having the pore size
distribution
4

CA 02549088 2012-03-06

comprising one or more metals from Column 6 of the Periodic Table, one or more

compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
a TAN of at
most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM
Method D664.
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 C and
0.101 MPa,
the crude feed having TAN of at least 0.3, as determined by ASTM Method D664,
and at
least one of the catalysts comprises: (a) one or more metals from Column 6 of
the Periodic
Table, one or more compounds of one or more metals from Column 6 of the
Periodic
Table, or mixtures thereof; and (b) one or more metals from Column 10 of the
Periodic
Table, one or more compounds of one or more metals from Column 10 of the
Periodic
Table, or mixtures thereof; and wherein a molar ratio of total Column 10 metal
to total
Column 6 metal is in a range from 1 to 10; and controlling contacting
conditions such that
the crude product has a TAN of at most 90% of the TAN of the crude feed,
wherein TAN
is as determined by ASTM Method D664.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.3, and the one or more catalysts
comprising: (a)
a first catalyst, the first catalyst having, per gram of first catalyst, from
0.0001 to 0.06
grams of: one or more metals from Column 6 of the Periodic Table, one or more
compounds of one or more metals from Column 6 of the Periodic Table,
calculated as
weight of metal, or mixtures thereof; and (b) a second catalyst, the second
catalyst having,
per gram of second catalyst, at least 0.02 grams of: one or more metals from
Column 6 of
the Periodic Table, one or more compounds of one or more metals from Column 6
of the
Periodic Table, calculated as weight of metal, or mixtures thereof; and
controlling
contacting conditions such that the crude product has a TAN of at most 90% of
the TAN
of the crude feed, wherein TAN is as determined by ASTM Method D664.
The invention also provides a catalyst composition, comprising: (a) one or
more
metals from Column 5 of the Periodic Table, one or more compounds of one or
more
metals from Column 5 of the Periodic Table, or mixtures thereof; (b) a support
material
having a theta alumina content of at least 0.1 grams of theta alumina per gram
of support
material, as determined by x-ray diffraction; and wherein the catalyst has a
pore size
5

CA 02549088 2012-03-06



distribution with a median pore diameter of at least 230 A, as determined by
ASTM
Method D4284.
The invention also provides a catalyst composition, comprising: (a) one or
more
metals from Column 6 of the Periodic Table, one or more compounds of one or
more
metals from Column 6 of the Periodic Table, or mixtures thereof; (b) a support
material
having a theta alumina content of at least 0.1 grams of theta alumina per gram
of support
material, as determined by x-ray diffraction; and wherein the catalyst has a
pore size
distribution with a median pore diameter of at least 230 A, as determined by
ASTM
Method D4284.
The invention also provides a catalyst composition, comprising: (a) one or
more
metals from Column 5 of the Periodic Table, one or more compounds of one or
more
metals from Column 5 of the Periodic Table, one or more metals from Column 6
of the
Periodic Table, one or more compounds of one or more metals from Column 6 of
the
Periodic Table, or mixtures thereof; (b) a support material having a theta
alumina content
of at least 0.1 grams of theta alumina per gram of support material, as
determined by x-ray
diffraction; and wherein the catalyst has a pore size distribution with a
median pore
diameter of at least 230 A, as determined by ASTM Method D4284.
The invention also provides a method of producing a catalyst, comprising:
combining a support with one or more metals to form a support/metal mixture,
wherein
the support comprises theta alumina, and one or more of the metals comprising
one or
more metals from Column 5 of the Periodic Table, one or more compounds of one
or
more metals from Column 5 of the Periodic Table, or mixtures thereof; heat
treating the
theta alumina support/metal mixture at a temperature of at least 400 C; and
forming the
catalyst, wherein the catalyst has a pore size distribution with a median pore
diameter of
at least 230 A, as determined by ASTM Method D4284.
The invention also provides a method of producing a catalyst, comprising:
combining a support with one or more metals to form a support/metal mixture,
wherein
the support comprises theta alumina, and one or more of the metals comprising
one or
more metals from Column 6 of the Periodic Table, one or more compounds of one
or
more metals from Column 6 of the Periodic Table, or mixtures thereof; heat
treating the
theta alumina support metal mixture at a temperature of at least 400 C; and
forming the
catalyst, wherein the catalyst has a pore size distribution with a median pore
diameter of
at least 230 A, as determined by ASTM Method D4284.
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

6

CA 02549088 2012-03-06

the crude product, wherein the crude product is a liquid mixture at 25 C and
0.101 MPa,
the crude feed having a TAN of at least 0.3, at least one of the catalysts
having a pore size
distribution with a median pore diameter of at least 180 A, as determined by
ASTM
Method D4284, and the catalyst having the pore size distribution comprising
theta
alumina and one or more metals from Column 6 of the Periodic Table, one or
more
compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
a TAN of at
most 90% of the TAN of the crude feed, wherein TAN is as determined by ASTM
Method D664.
The invention also provides a method of producing a crude product, comprising:
contacting a crude feed with one or more catalysts in the presence of a
hydrogen source to
produce a total product that includes the crude product, wherein the crude
product is a
liquid mixture at 25 C and 0.101 MPa, the crude feed having a TAN of at least
0.3, the
crude feed having an oxygen content of at least 0.0001 grams of oxygen per
gram of
crude feed, and at least one of the catalysts having a pore size distribution
with a median
pore diameter of at least 90 A, as determined by ASTM Method D4284; and
controlling
contacting conditions to reduce TAN such that the crude product has a TAN of
at most
90% of the TAN of the crude feed, and to reduce a content of organic oxygen
containing
compounds such that the crude product has an oxygen content of at most 90% of
the
oxygen content of the crude feed, wherein TAN is as determined by ASTM Method
D664, and oxygen content is as determined by ASTM Method E385.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.1, and at least one of the catalysts
having, per
gram of catalyst, at least 0.001 grams of: one or more metals from Column 6 of
the
Periodic Table, one or more compounds of one or more metals from Column 6 of
the
Periodic Table, calculated as weight of metal, or mixtures thereof; and
controlling
contacting conditions such that a liquid hourly space velocity in a contacting
zone is over
10 h"1, and the crude product has a TAN of at most 90% of the TAN of the crude
feed,
wherein TAN is as determined by ASTM Method D664.



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CA 02549088 2006-06-09
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PCT/US2004/042640

The invention also provides a method of producing a crude product, comprising:

contacting a crude feed with one or more catalysts in the presence of a
hydrogen source to
produce a total product that includes the crude product, wherein the crude
product is a
liquid mixture at 25 C and 0.101 MPa, the crude feed having a TAN of at least
0.1, the
crude feed having a sulfur content of at least 0.0001 grams of sulfur per gram
of crude
feed, and at least one of the catalysts comprising one or more metals from
Column 6 of the
Periodic Table, one or more compounds of one or more metals from Column 6 of
the
Periodic Table, or mixtures thereof; and controlling contacting conditions
such that, during
contacting, the crude feed uptakes molecular hydrogen at a selected rate to
inhibit phase
separation of the crude feed during contacting, liquid hourly space velocity
in one or more
contacting zones is over 10 If% the crude product having a TAN of at most 90%
of the
TAN of the crude feed, and the crude product having a sulfur content of 70-
130% of the
sulfur content of the crude feed, wherein TAN is as determined by ASTM Method
D664,
and sulfur content is as determined by ASTM Method D4294.
The invention also provides a method of producing a crude product, comprising:
contacting a crude feed with one or more catalysts in the presence of a
gaseous hydrogen -
source to produce a total product that includes the crude product, wherein the
crude
product is a liquid mixture at 25 C and 0.101 MPa; and controlling contacting
conditions
such that the crude feed, during contact, uptakes hydrogen at a selected rate
to inhibit
phase separation of the crude feed during contact.
The invention also provides a method of producing a crude product, comprising:

contacting a crude feed with hydrogen in the presence of one or more catalysts
to produce
a total product that includes the crude product, wherein the crude product is
a liquid
mixture at 25 C and 0.101 MPA; and controlling contacting conditions such
that the crude
feed is contacted with hydrogen at a first hydrogen uptake condition and then
at a second
hydrogen uptake condition, the first hydrogen uptake condition being different
from the
second hydrogen uptake condition, and net hydrogen uptake in the first
hydrogen uptake
condition is controlled to inhibit P-value of a crude feed/total product
mixture from
decreasing below 1.5, and one or more properties of the crude product change
by at most
90% relative to the respective one or more properties of the crude feed.
The invention also provides a method of producing a crude product, comprising:

contacting a crude feed with one or more catalysts at a first temperature
followed by
contacting at a second temperature to produce a total product that includes
the crude
product, wherein the crude product is a liquid mixture at 25 C at 0.101 MPa,
the crude

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feed having a TAN of at least 0.3; and controlling contacting conditions such
that the first
contacting temperature is at least 30 C lower than the second contacting
temperature, and
the crude product has a TAN of at most 90% relative to the TAN of the crude
feed,
wherein TAN is as determined by ASTM Method D664.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.3, the crude feed having a sulfur
content of at
least 0.0001 grams of sulfur per gram of crude feed, and at least one of the
catalysts
comprising one or more metals from Column 6 of the Periodic Table, one or more
compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
a TAN of at
most 90% of the TAN of the crude feed, and the crude product has a sulfur
content of 70-
130% of the sulfur content of the crude feed, wherein TAN is as determined by
ASTM
Method D664, and sulfur content is as determined by ASTM Method D4294.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.1, the crude feed having a residue
content of at
least 0.1 grams of residue per gram of crude feed, and at least one of the
catalysts
comprising one or more metals from Column 6 of the Periodic Table, one or more
compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
a TAN of at
most 90% of the TAN of the crude feed, the crude product has a residue content
of 70-
130% of the residue content of the crude feed, and wherein TAN is as
determined by
ASTM Method D664, and residue content is as determined by ASTM Method D5307.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.1, the crude feed having a VG0
content of at
least 0.1 grams of VG0 per gram of crude feed, and at least one of the
catalysts
comprising one or more metals from Column 6 of the Periodic Table, one or more

compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
a TAN of at

9

CA 02549088 2006-06-09
WO 2005/063933 PCT/US2004/042640

most 90% of the TAN of the crude feed, the crude product has a VGO content of
70-130%
of the VGO content of the crude feed, and wherein VGO content is as determined
by
ASTM Method D5307.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.3, and at least one of the catalysts
is obtainable
by: combining a support with one or more metals from Column 6 of the Periodic
Table,
one or more compounds of one or more metals from Column 6 of the Periodic
Table, or
mixtures thereof, to produce a catalyst precursor; and forming the catalyst by
heating the
catalyst precursor in the presence of one or more sulfur containing compounds
at a
temperature below 500 C; and controlling contacting conditions such that the
crude
product has a TAN of at most 90% of the TAN of the crude feed.
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 C and
0.101 MPa,
the crude feed having a viscosity of at least 10 cSt at 37.8 C (100 F), the
crude feed
having an API gravity of at least 10, and at least one of the catalysts
comprising one or
more metals from Column 6 of the Periodic Table, one or more compounds of one
or more
metals from Column 6 of the Periodic Table, or mixtures thereof; and
controlling
contacting conditions such that the crude product has a viscosity at 37.8 C
of at most 90%
of the viscosity of the crude feed at 37.8 C, and the crude product having an
API gravity
of 70-130% of the API gravity of the crude feed, wherein API gravity is as
determined by
ASTM Method D6822, and viscosity is as determined by ASTM Method D2669.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.1, and the one or more catalysts
comprising: at
least one catalyst comprising vanadium, one or more compounds of vanadium, or
mixtures
thereof; and an additional catalyst, wherein the additional catalyst comprises
one or more
Column 6 metals, one or more compounds of one or more Column 6 metals, or
combinations thereof; and controlling contacting conditions such that the
crude product
has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is as
determined
by ASTM Method D664.


10

CA 02549088 2006-06-09
WO 2005/063933 PCT/US2004/042640

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 C and
0.101 MPa,
and the crude feed has a TAN of at least 0.1; generating hydrogen during the
contacting;
and controlling contacting conditions such that the crude product has a TAN of
at most
90% of the TAN of the crude feed, wherein TAN is as determined by ASTM Method
D664.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.1, and at least one of the catalysts
comprising
vanadium, one or more compounds of vanadium, or mixtures thereof; and
controlling
contacting conditions such that a contacting temperature is at least 200 C,
and the crude
product has a TAN of at most 90% of the TAN of the crude feed, wherein TAN is
as
determined by ASTM Method D664.
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 C and
0.101 MPa,
the crude feed having a TAN of at least 0.1, and at least one of the catalysts
comprising
vanadium, one or more compounds of vanadium, or mixtures thereof; providing a
gas
comprising a hydrogen source during contacting, the gas flow being provided in
a
direction that is counter to the flow of the crude feed; and controlling
contacting conditions
such that the crude product has a TAN of at most 90% of the TAN of the crude
feed,
wherein TAN is as determined by ASTM Method D664.
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 C and
0.101 MPa,
the crude feed having, per gram of crude feed, a total NiN/Fe content of at
least 0.00002
grams, at least one of the catalysts comprising vanadium, one or more
compounds of
vanadium, or mixtures thereof, and the vanadium catalyst having a pore size
distribution
with a median pore diameter of least 180 A; and controlling contacting
conditions such
that the crude product has a total NiN/Fe content of at most 90% of the
Ni/V/Fe content of
the crude feed, wherein NiN/Fe content is as determined by ASTM Method D5708.



11

WO 2005/063933 CA 02549088 2006-06-09 PCT/US2004/042640
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 C and
0.101 MPa,
at least one of the catalysts comprising vanadium, one or more compounds of
vanadium, or
mixtures thereof, the crude feed comprising one or more alkali metal salts of
one or more
organic acids, one or more alkaline-earth metal salts of one or more organic
acids, or
mixtures thereof, and the crude feed having, 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 controlling contacting conditions such that the crude product has a
total content
of alkali metal, and alkaline-earth metal, in the 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 determined by ASTM Method D1318.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, the
crude feed having, 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 having a pore size distribution with a median pore diameter in a
range from 90 A
to 180 A, with at least 60% of the total number of pores in the pore size
distribution having
a pore diameter within 45 A of the median pore diameter, wherein pore size
distribution is
as determined by ASTM Method D4282; 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 of the crude feed, wherein content of alkali
metal, and alkaline-
earth metal, in metal salts of organic acids is as determined by ASTM Method
D1318.
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 C and
0.101 MPa,
the crude feed having, per gram of crude feed, a total NiN/Fe content of at
least 0.00002
grams, and at least one of the catalysts having a pore size distribution with
a median pore
diameter in a range from 90 A to 180 A, with at least 60% of the total number
of pores in
12

CA 02549088 2012-03-06

the pore size distribution having a pore diameter within 45 A of the median
pore diameter,
wherein pore size distribution is as determined by ASTM Method D4284; and
controlling
contacting conditions such that the crude product has a total Ni/V/Fe content
of at most
90% of the Ni/V/Fe content of the crude feed, wherein Ni/V/Fe content is as
determined
by ASTM Method D5708.
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 C and
0.101 MPa,
the crude feed having a total content of alkali metals, and alkaline-earth
metals, in metal
salts of organic acids of at least 0.00001 grams per gram of crude feed, at
least one the
catalysts having a pore size distribution with a median pore diameter of at
least 180 A, as
determined by ASTM Method D4284, and the catalyst having the pore size
distribution
comprising one or more metals from Column 6 of the Periodic Table, one or more

compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; 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 D1318.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, and
the crude feed having, per gram of crude feed, a total content of alkali
metals, and
alkaline-earth metals in metal salts of organic acids of at least 0.00001
grams, at least one
of the catalysts having a pore size distribution with a median pore diameter
of at least 230
A, as determined by ASTM Method D4284, and the catalyst having a pore size
distribution comprising one or more metals from Column 6 of the Periodic
Table, one or
more compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; 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 D1318.
13

CA 02549088 2012-03-06

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 C and
0.101 MPa,
the crude feed having a total Ni/V/Fe content of at least 0.00002 grams of
Ni/V/Fe per
gram of crude feed, at least one of the catalysts having a pore size
distribution with a
median pore diameter of at least 230 A, as determined by ASTM Method D4284,
and the
catalyst having a pore size distribution comprising one or more metals from
Column 6 of
the Periodic Table, one or more compounds of one or more metals from Column 6
of the
Periodic Table, or mixtures thereof; and controlling contacting conditions
such that the
crude product has a total Ni/V/Fe content of at most 90% of the Ni/V/Fe
content of the
crude feed, wherein Ni/V/Fe content is as determined by ASTM Method D5708.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, the
crude feed having a total content, per gram of crude feed, of alkali metal,
and alkaline-
earth metal, in metal salts of organic acids of at least 0.00001 grams, at
least one of the
catalysts having a pore size distribution with a median pore diameter of at
least 90 A, as
determined by ASTM Method D4284, and the catalyst having the pore size
distribution
has a total molybdenum content, per gram of catalyst, from 0.0001 grams to 0.3
grams of:
molybdenum, one or more molybdenum compounds, calculated as weight of
molybdenum, or mixtures thereof; 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
D1318.
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 C and
0.101 MPa,
the crude feed having TAN of at least 0.3 and the crude feed having, per gram
of crude
feed, a total Ni/V/Fe content of at least 0.00002 grams, at least one of the
catalysts having
a pore size distribution with a median pore diameter of at least 90 A, as
determined by
ASTM Method D4284, and the catalyst having a total molybdenum content, per
gram of
14

CA 02549088 2012-03-06

catalyst, from 0.0001 grams to 0.3 grams of: molybdenum, one or more compounds
of
molybdenum, calculated as weight of molybdenum, or mixtures thereof; and
controlling
contacting conditions such that the crude product has a TAN of at most 90% of
the TAN
of the crude feed and the crude product has a total Ni/V/Fe content of at most
90% of the
Ni/V/Fe content of the crude feed, wherein Ni/V/Fe content is as determined by
ASTM
Method D5708, and TAN is as determined by ASTM Method D644.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, and
the crude feed having a total content, per gram of crude feed, 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 comprising: (a) one or more metals from Column 6 of the Periodic
Table,
one or more compounds of one or more metals from Column 6 of the Periodic
Table, or
mixtures thereof; and (b) one or more metals from Column 10 of the Periodic
Table, one
or more compounds of one or more metals from Column 10 of the Periodic Table,
or
mixtures thereof, wherein a molar ratio of total Column 10 metal to total
Column 6 metal
is in a range from 1 to 10; 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 D
1318.
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 C and
0.101 MPa,
the crude feed having a total Ni/V/Fe content of at least 0.00002 grams of
Ni/V/Fe per
gram of crude feed, and at least one of the catalysts comprises: (a) one or
more metals
from Column 6 of the Periodic Table, one or more compounds of one or more
metals
from Column 6 of the Periodic Table, or mixtures thereof; and (b) one or more
metals
from Column 10 of the Periodic Table, one or more compounds of one or more
metals
from Column 10 of the Periodic Table, or mixtures thereof, wherein a molar
ratio of total


15

CA 02549088 2006-06-09
WO 2005/063933 PCT/US2004/042640

Column 10 metal to total Column 6 metal is in a range from 1 to 10; and
controlling
contacting conditions such that the crude product has a total NiN/Fe content
of at most
90% of the NiN/Fe content of the crude feed, wherein NiN/Fe content is as
determined
by ASTM Method D5708.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, the
crude feed having, 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
the one or more
catalysts comprising: (a) a first catalyst, the first catalyst having, per
gram of first catalyst,
from 0.0001 to 0.06 grams, of: one or more metals from Column 6 of the
Periodic Table,
one or more compounds of one or more metals from Column 6 of the Periodic
Table,
calculated as weight of metal, or mixtures thereof; and (b) a second catalyst,
the second
catalyst having, per gram of second catalyst, at least 0.02 grams of: one or
more metals
from Column 6 of the Periodic Table; one or more compounds of one or more
metals from
Column 6 of the Periodic Table, calculated as weight of metal, or mixtures
thereof; 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 D1318.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, the
crude feed having, 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 having, per gram of catalyst, at least 0.001 grams of: one or more
metals from
Column 6 of the Periodic Table, one or more compounds of one or more metals
from
Column 6 of the Periodic Table, calculated as weight of metal, or mixtures
thereof; and
controlling contacting conditions such that liquid hourly space velocity in a
contacting

16

CA 02549088 2006-06-09
WO 2005/063933 PCT/US2004/042640

zone is over 10 If% and 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 D1318.
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 C and
0.101 MPa,
the crude feed having, per gram of crude feed, a total NiN/Fe content of at
least 0.00002
grams, at least one of the catalysts has, per gram of catalyst, at least 0.001
grams of: one or
more metals from Column 6 of the Periodic Table, one or more compounds of one
or more
metals from Column 6 of the Periodic Table, calculated as weight of metal, or
mixtures
thereof; and controlling contacting conditions such that liquid hourly space
velocity in a
contacting zone is over 10 If% and the crude product has a total NiN/Fe
content of at most
90% of the NiN/Fe content of the crude feed, wherein NiN/Fe content is as
determined
by ASTM Method D5708.
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 C and
0.101 MPa,
the crude feed having, per gram of crude feed: an oxygen content of at least
0.0001 grams
of oxygen, and a sulfur content of at least 0.0001 grams of sulfur, and at
least one of the
catalysts comprising one or more metals from Column 6 of the Periodic Table,
one or
more compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
an oxygen
content of at most 90% of the oxygen content of the crude feed, and the crude
product has
a sulfur content of 70-130% of the sulfur content of the crude feed, wherein
oxygen
content is as determined by ASTM Method E385, and sulfur content is as
determined by
ASTM Method D4294.
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 C and
0.101 MPa,
the crude feed having, per gram of crude feed, a total NiN/Fe content of at
least 0.00002
grams, and a sulfur content of at least 0.0001 grams of sulfur, and at least
one of the
catalysts comprising one or more metals from Column 6 of the Periodic Table,
one or

17

WO 2005/063933 CA 02549088 2006-06-09
PCT/US2004/042640
more compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
a total
NiN/Fe content of at most 90% of the NiN/Fe content of the crude feed, and the
crude
product has a sulfur content of 70-130% of the sulfur content of the crude
feed, wherein
NiN/Fe content is as determined by ASTM Method D5708, and sulfur content is as
determined by ASTM Method D4294.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, the
crude feed having, 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 a
residue content
of at least 0.1 grams of residue, and at least one of the catalysts comprising
one or more
metals from Column 6 of the Periodic Table, one or more compounds of one or
more
Metals from Column 6 of the Periodic Table, or mixtures thereof; 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, the crude
product has a residue content of 70-130% of the residue content of the crude
feed, and
wherein content of alkali metal, and alkaline-earth metal, in metal salts of
organic acids is
as determined by ASTM Method D1318, and residue content is as determined by
ASTM
Method D5307.
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 C and
0.101 MPa,
the crude feed having, per gram of crude feed, a residue content of at least
0.1 grams of
residue, and a total NiN/Fe content of at least 0.00002 grams, and at least
one of the
catalysts comprising one or more metals from Column 6 of the Periodic Table,
one or
more compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; and controlling contacting conditions such that the crude product has
a total
NiN/Fe content of at most 90% of the NiN/Fe content of the crude feed and the
crude
product has a residue content of 70-130% of the residue content of the crude
feed, wherein

18

WO 2005/063933 CA 02549088 2006-06-09PCT/US2004/042640
NiN/Fe content is as determined by ASTM Method D5708, and residue content is
as
determined by ASTM Method D5307.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, the
crude feed having, per gram of crude feed, a vacuum gas oil ("VGO") content of
at least
0.1 grams, and a total content of alkali metal, and alkaline-earth metal, in
metal salts of
organic acids of 0.0001 grams, and at least one of the catalysts comprises one
or more
metals from Column 6 of the Periodic Table, one or more compounds of one or
more
metals from Column 6 of the Periodic Table, or mixtures thereof; 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, and the
crude product has a VGO content of 70-130% of the VGO content of the crude
feed,
wherein VGO content is as determined by ASTM Method D5307, and content of
alkali
metal, and alkaline-earth metal, in metal salts of organic acids is as
determined by ASTM
Method D1318.
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 C and
0.101 MPa,
the crude feed having, per gram of crude feed, a total NiN/Fe content of at
least 0.00002
grams, and a VGO content of at least 0.1 grams, and at least one of the
catalysts comprises
one or more metals from Column 6 of the Periodic Table, one or more compounds
of one
or more metals from Column 6 of the Periodic Table, or mixtures thereof; and
controlling
contacting conditions such that the crude product has a total NiN/Fe content
of at most
90% of the Ni/V/Fe content of the crude feed, and the crude product has a VGO
content of
70-130% of the VGO content of the crude feed, wherein VGO content is as
determined by
ASTM Method D5307, and NiN/Fe content is as determined by ASTM Method D5708.
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 C and
0.101 MPa,
the crude feed comprising one or more alkali metal salts of one or more
organic acids, one
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or more alkaline-earth metal salts of one or more organic acids, or mixtures
thereof, and
the crude feed having, 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 obtainable by: combining a support with one or more metals from
Column 6 of
the Periodic Table, one or more compounds of one or more metals from Column 6
of the
Periodic Table, or mixtures thereof to produce a catalyst precursor, and
forming the
catalyst by heating a precursor of the catalyst in the presence of one or more
sulfur
containing compounds at a temperature below 400 C; 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
determined by
ASTM Method D1318.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 C and
0.101 MPa,
the crude feed having, per gram of crude feed, a total NiN/Fe content of at
least 0.00002
grams, and at least one of the catalysts is obtainable by: combining a support
with one or
more metals from Column 6 of the Periodic Table, one or more compounds of one
or more
metals from Column 6 of the Periodic Table, or mixtures thereof to produce a
catalyst
precursor; and forming the catalyst by heating the catalyst precursor in the
presence of one
or more sulfur containing compounds at a temperature below 400 C; and
controlling
contacting conditions such that the crude product has a total NiN/Fe content
of at most
90% of the NiN/Fe content of the crude feed, wherein NiN/Fe content is as
determined
by ASTM Method D5708.
The invention also provides a crude composition having, per gram of crude
composition: at least 0.001 grams of hydrocarbons with a boiling range
distribution
between 95 C and 260 C at 0.101 MPa; at least 0.001 grams of hydrocarbons
with a
boiling range distribution between 260 C and 320 C at 0.101 MPa; at least
0.001 grams
of hydrocarbons with a boiling range distribution between 320 C and 650 C at
0.101
MPa; and greater than 0 grams, but less than 0.01 grams of one or more
catalysts per gram
of crude product.
The invention also provides a crude composition having, per gram of
composition:
at least 0.01 grams of sulfur, as determined by ASTM Method D4294; at least
0.2 grams of
20

CA 02549088 2012-03-06



residue, as determined by ASTM Method D5307, and the composition has a weight
ratio
of MCR content to C5 asphaltenes content of at least 1.5, wherein MCR content
is as
determined by ASTM Method D4530, and C asphaltenes content is as determined by

ASTM Method D2007.
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 condensable at 25 C and 0.101
MPa, the
crude feed a MCR content of at least 0.001 grams per gram of crude feed, and
at least one
of the catalysts is obtainable by: combining a support with one or more metals
from
Column 6 of the Periodic Table, one or more compounds of one or more metals
from
Column 6 of the Periodic Table, or mixtures thereof, to produce a catalyst
precursor; and
forming the catalyst by heating the catalyst precursor in the presence of one
or more
sulfur containing compounds at a temperature below 500 C; 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.
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 condensable at 25 C and 0.101
MPa, the
crude feed a MCR content of at least 0.001 grams per gram of crude feed, and
at least one
of the catalysts having a pore size distribution with a median pore diameter
in a range
from 70 A to 180 A, with at least 60% of the total number of pores in the pore
size
distribution having a pore diameter within 45 A of the median pore diameter,
wherein
pore size distribution is as determined by ASTM Method D4284; and controlling
contacting conditions such that the crude product has a MCR of at most 90% of
the MCR
of the crude feed, wherein MCR is as determined by ASTM Method D4530.
The invention also provides a crude composition having, per gram of
composition:
at most 0.004 grams of oxygen, as determined by ASTM Method E385; at most
0.003
grams of sulfur, as determined by ASTM Method D4294; and at least 0.3 grams of
residue, as determined by ASTM Method D5307.
The invention also provides a crude composition having, per gram of
composition:
at most 0.004 grams of oxygen, as determined by ASTM Method E385; at most
0.003
grams of sulfur, as determined by ASTM Method D4294; at most 0.04 grams of
basic
nitrogen, as determined by ASTM Method D2896; at least 0.2 grams of residue,
as

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WO 2005/063933 CA 02549088 2006-06-09PCT/US2004/042640
determined by ASTM Method D5307; and the composition has a TAN of at most 0.5,
as
determined by ASTM Method D664.
The invention also provides a crude composition having, per gram of
composition:
at least 0.001 grams of sulfur, as determined by ASTM Method D4294; at least
0.2 grams
of residue, as determined by ASTM Method D5307; and the composition having a
weight
ratio of MCR content to C5 asphaltenes content of at least 1.5, and the
composition having
a TAN of at most 0.5, wherein TAN is as determined by ASTM Method D664, weight
of
MCR is as determined by ASTM Method D4530, and weight of C5 asphaltenes is as
determined by ASTM Method D2007.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, crude feed
that: (a) has
not been treated in a refinery, distilled, and/or fractionally distilled; (b)
has components
having a carbon number above 4, and the crude feed has at least 0.5 grams of
such
components per gram of crude feed; (c) comprises hydrocarbons, a portion of
which have:
a boiling range distribution below 100 C at 0.101 MPa, a boiling range
distribution
between 100 C and 200 C at 0.101 MPa, a boiling range distribution between
200 C and
300 C at 0.101 MPa, a boiling range distribution between 300 C and 400 C at
0.101
MPa, and a boiling range distribution between 400 C and 650 C at 0.101 MPa;
(d) has,
per gram of crude feed, at least: 0.001 grams of hydrocarbons having a boiling
range
distribution below 100 C at 0.101 MPa, 0.001 grams of hydrocarbons having a
boiling
range distribution between 100 C and 200 C at 0.101 MPa, 0.001 grams of
hydrocarbons
having a boiling range distribution between 200 C and 300 C at 0.101 MPa,
0.001 grams
of hydrocarbons having a boiling range distribution between 300 C and 400 C
at 0.101
MPa, and 0.001 grams of hydrocarbons having a boiling range distribution
between 400 C
and 650 C at 0.101 MPa; (e) has a TAN of at least 0.1, at least 0.3, or in a
range from 0.3
to 20, 0.4 to 10, or 0.5 to 5; (f) has an initial boiling point of at least
200 C at 0.101 MPa;
(g) comprises nickel, vanadium and iron; (h) has at least 0.00002 grams of
total NiN/Fe
per gram of crude feed; (i) comprises sulfur; (j) has at least 0.0001 grams or
0.05 grams of
sulfur per gram of crude feed; (k) has at least 0.001 grams of VG0 per gram of
crude feed;
(1) has at least 0.1 grams of residue per gram of crude feed; (m) comprises
oxygen
containing hydrocarbons; (n) one or more alkali metal salts of one or more
organic acids,
one or more alkaline-earth metal salts of one or more organic acids, or
mixtures thereof;
(o) comprises at least one zinc salt of an organic acid; and/or (p) comprises
at least one
arsenic salt of an organic acid:
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WO 2005/063933 CA 02549088 2006-06-09
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In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, crude feed
that is
obtainable by removing naphtha and compounds more volatile than naphtha from a
crude.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method of
contacting a
crude feed with one or more catalysts to produce a total product that includes
the crude
product in which the crude feed and crude product both have a C5 asphaltenes
content and
a MCR content, and: (a) a sum of a crude feed C5 asphaltenes content and crude
feed MCR
content is S, a sum of a crude product C5 asphaltenes content and a crude
product MCR
content is S', and contacting conditions are controlled such that S' is at
most 99% of S;
and/or (b) the contacting conditions are controlled such that a weight ratio
of a MCR
content of the crude product to a C5 asphaltenes content of the crude product
is in a range
from 1.2 to 2.0, or 1.3 to 1.9.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a hydrogen
source, in
which the hydrogen source is: (a) gaseous; (b) hydrogen gas; (c) methane; (d)
light
hydrocarbons; (e) inert gas; and/or(f) mixtures thereof.
In some embodiments, the invention also provides, in combination with one or ,
more of the methods or compositions according to the invention, a method of
contacting a
crude feed with one or more catalysts to produce a total product that includes
the crude
product wherein the crude feed is contacted in a contacting zone that is on or
coupled to an
offshore facility.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method that
comprises
contacting a crude feed with one or more catalysts in the presence of a gas
and/or a
hydrogen source and controlling contacting conditions such that: (a) a ratio
of a gaseous
hydrogen source to the crude feed is in a range from 5-800 normal cubic meters
of gaseous
hydrogen source per cubic meter of crude feed contacted with one or more of
the catalysts;
(b) the selected rate of net hydrogen uptake is controlled by varying a
partial pressure of
the hydrogen source; (c) the rate of hydrogen uptake is such that the crude
product has
TAN of less than 0.3, but the hydrogen uptake is less than an amount of
hydrogen uptake
that will cause substantial phase separation between the crude feed and the
total product
during contact; (d) the selected rate of hydrogen uptake is in a range from 1-
30 or 1-80
normal cubic meters of the hydrogen source per cubic meter of crude feed; (e)
the liquid
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hourly space velocity of gas and/or the hydrogen source is at least 11 h4, at
least 15 If% or
at most 20114; (f) a partial pressure of the gas and/or the hydrogen source is
controlled
during contacting; (g) a contacting temperature is in a range from 50-500 C,
a total liquid
hourly space velocity of the gas and/or the hydrogen source is in a range from
0.1-30 If%
and total pressure of the gas and/or the hydrogen source is in a range from
1.0-20 MPa; (h)
a flow of the gas and/or the hydrogen source is in a direction that is counter
to a flow of
the crude feed; (i) the crude product has a H/C of 70-130% of a H/C of the
crude feed; (i)
hydrogen uptake by the crude feed is at most 80 and/or in a range from 1- 80
or 1-50
normal cubic meters of hydrogen per cubic meter of crude feed; (k) the crude
product has a
total NiN/Fe content of at most 90%, at most 50%, or at most 10% of the NiN/Fe
content
of the crude feed; (1) the crude product has a sulfur content of 70-130% or 80-
120% of the
sulfur content of the crude feed; (m) the crude product has a VGO content of
70-130% or
90-110% of the VGO content of the crude feed; (n) the crude product has a
residue content
of 70-130% or 90-110% of the residue content of the crude feed; (o) the crude
product has
an oxygen content of most 90%, at most 70%, at most 50%, at most 40%, or at
most 10%
Of the oxygen content of the crude feed; (p) 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
50%, or at most 10% of the content of alkali metal, and alkaline-earth metal,
in metal salts
of organic acids in the crude feed; (q) a P-value of the crude feed, during
contacting, is at
least 1.5; (r) the crude product has a viscosity at 37.8 C of at most 90%, at
most 50%, or
at most 10% of the viscosity of the crude feed at 37.8 C; (s) the crude
product has an API
gravity of 70-130% of an API gravity of the crude feed; and/or (t) the crude
product has a
TAN of at most 90%, at most 50%, at most 30%, at most 20%, or at most 10%, of
the
TAN of the crude feed and/or in a range from 0.001 to 0.5, 0.01 to 0.2, or
0.05 to 0.1.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method that
comprises
contacting a crude feed with one or more catalysts and controlling contacting
conditions to
reduce a content of organic oxygen containing compounds in which: (a) a
content of
selected organic oxygen compounds is reduced such that the crude product has
an oxygen
content of at most 90% of the oxygen content of the crude feed; (b) at least
one compound
of the organic oxygen containing compounds comprises a metal salt of a
carboxylic acid;
(c) at least one compound of the organic oxygen containing compounds comprises
an
alkali metal salt of a carboxylic acid; (d) at least one compound of the
organic oxygen
containing compounds comprises an alkaline-earth metal salt of a carboxylic
acid; (e) at

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least one compound of the organic oxygen containing compounds comprises a
metal salt of
a carboxylic acid, wherein the metal comprises one or more metals from Column
12 of the
Periodic Table; (f) the crude product has a content of non-carboxylic
containing organic
compounds of at most 90% of the content of non-carboxylic containing organic
compounds in the crude feed; and/or (g) at least one of the oxygen containing
compounds
in the crude feed originates from naphthenic acid or non-carboxylic containing
organic
oxygen compounds.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method that
comprises
contacting a crude feed with one or more catalysts in which: (a) the crude
feed is contacted
with at least one of the catalysts at a first temperature followed by
contacting at a second
temperature, and the contacting conditions are controlled such that the first
contacting
temperature is at least 30 C lower than the second contacting temperature;
(b) the crude
feed is contacted with hydrogen at a first hydrogen uptake condition and then
at a second
hydrogen uptake condition, and the temperature of the first uptake condition
is at least 30
C lower than the temperature of the second uptake condition; (c) the crude
feed is
contacted with at least one of the catalysts at a first temperature followed
by contacting at a
second temperature, and the contacting conditions are controlled such that the
first
contacting temperature is at most 200 C lower than the second contacting
temperature; (d) ,
hydrogen gas is generated during contacting; (e) hydrogen gas is generated
during
contacting, and the contacting conditions are also controlled such that the
crude feed
uptakes at least a portion of the generated hydrogen; (f) the crude feed is
contacted with a
first and second catalyst, and contacting of the crude feed and the first
catalyst forms an
initial crude product, and wherein the initial crude product has a TAN of at
most 90% of
the TAN of the crude feed; and contacting of the initial crude product and the
second
catalyst forms a crude product, and wherein the crude product has a TAN of at
most 90%
of the TAN of the initial crude product; (g) contacting is performed in a
stacked bed
reactor; (h) contacting is performed in an ebullating bed reactor; (i) the
crude feed is
contacted with an additional catalyst subsequent to contact with the one or
more catalysts;
(j) one or more of the catalysts is a vanadium catalyst and the crude feed is
contacted with
an additional catalyst in the presence of a hydrogen source subsequent to
contact with the
vanadium catalyst; (k) hydrogen is generated at a rate in a range from 1-20
normal cubic
meters per cubic meter of crude feed; (1) hydrogen is generated during the
contacting, the
crude feed is contacted with an additional catalyst in the presence of a gas
and at least a

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WO 2005/063933 CA 02549088 2006-06-09PCT/US2004/042640
portion of the generated hydrogen, and the contacting conditions are also
controlled such
that a flow of the gas is in a direction that is counter to the flow of the
crude feed and a
flow of the generated hydrogen; (m) the crude feed is contacted with a
vanadium catalyst
at a first temperature and subsequently with an additional catalyst at a
second temperature,
and the contacting conditions are controlled such that the first temperature
is at least 30 C
lower than the second temperature; (n) hydrogen gas is generated during
contacting, the
crude feed is contacted with an additional catalyst, and the contacting
conditions are
controlled such that the additional catalyst uptakes at least a portion of the
generated
hydrogen; and/or (o) the crude feed is subsequently contacted with an
additional catalyst at
a second temperature, and the contacting conditions are controlled such that
the second
temperature is at least 180 C.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method that
comprises
contacting a crude feed with one or more catalysts in which: (a) the catalyst
is a supported
catalyst and the support comprises alumina, silica, silica-alumina, titanium
oxide,
zirconium oxide, magnesium oxide, or mixtures thereof; (b) the catalyst is a
supported
catalyst and the support is porous; (c) the method further comprises an
additional catalyst
that has been heat treated at a temperature above 400 C prior to
sulfurization; (d) a life of
at least one of the catalysts is at least 0.5 year; and/or (e) at least one of
the catalysts is in a
fixed bed or slurried in the crude feed.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method that
comprises
contacting a crude feed with one or more catalysts, at least one of the
catalyst is a
supported catalyst or a bulk metal catalyst and the supported catalyst or bulk
metal
catalyst: (a) comprises one or more metals from Columns 5-10 of the Periodic
Table, one
or more compounds of one or more metals from Columns 5-10 of the Periodic
Table, or
mixtures thereof; (b) has, per gram of catalyst, at least 0.0001 grams, from
0.0001-0.6
grams, or from 0.001-0.3 grams of: one or more metals from Columns 5-10 of the
Periodic
Table, one or more compounds of one or more metals from Columns 5-10 of the
Periodic
Table, or mixtures thereof; (c) comprises one or more metals from Columns 6-10
of the
Periodic Table, one or more compounds of one or more metals from Columns 6-10
of the
Periodic Table, or mixtures thereof; (d) comprises one or more metals from
Columns 7-10
of the Periodic Table, one or more compounds of one or more metals from
Columns 7-10
of the Periodic Table, or mixtures thereof; (e) has, per gram of catalyst,
from 0.0001-0.6
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WO 2005/063933 CA 02549088 2006-06-09 PCT/US2004/042640
grams or 0.001-0.3 grams of: one or more metals from Columns 7-10 of the
Periodic
Table, one or more compounds of one or more metals from Columns 7-10 of the
Periodic
Table, or mixtures thereof; (f) comprises one or more metals from Columns 5-6
of the
Periodic Table; one or more compounds of one or more metals from Columns 5-6
of the
Periodic Table, or mixtures thereof; (g) comprises one or more metals from
Column 5 of
the Periodic Table, one or more compounds of one or more metals from Column 5
of the
Periodic Table, or mixtures thereof; (h) has, per gram of catalyst, at least
0.0001 grams,
from 0.0001-0.6 grams, 0.001-0.3 grams, 0.005-0.1 grams, or 0.01-0.08 grams
of: one or
more metals from Column 5 of the Periodic Table, one or more compounds of one
or more
metals from Column 5 of the Periodic Table, or mixtures thereof; (i) comprises
one or
more metals from Column 6 of the Periodic Table, one or more compounds of one
or more
metals from Column 6 of the Periodic Table, or mixtures thereof; (j) has, per
gram of
catalyst, from 0.0001-0.6 grams, 0.001-0.3 grams, 0.005-0.1 grams, 0.01-0.08
grams of
one or more metals from Column 6 of the Periodic Table, one or more compounds
of one
or more metals from Column 6 of the Periodic Table, or mixtures thereof; (k)
comprises
- one or more metals from Column 10 of the Periodic Table, one or more
compounds of one
or more metals from Column 10 of the Periodic Table, or mixtures thereof; (1)
has, per
gram of catalyst, from 0.0001-0.6 grams or 0.001-0.3 grams of: one or more
metals from
Column 10 of the Periodic Table, one or more compounds of one or more metals
from
Column 10 of the Periodic Table, or mixtures thereof; (m) comprises vanadium,
one or
more compounds of vanadium, or mixtures thereof; (n) comprises nickel, one or
mdre
compounds of nickel, or mixtures thereof; (o) comprises cobalt, one or more
compounds of
cobalt, or mixtures thereof; (p) comprises molybdenum, one or more compounds
of
molybdenum, or mixtures thereof; (q) has, per gram of catalyst, from 0.001-0.3
grams or
from 0.005-0.1 grams of: molybdenum, one or more molybdenum compounds, or
mixtures
thereof; (r) comprises tungsten, one or more compounds of tungsten, or
mixtures thereof;
(s) has, per gram of catalyst, from 0.001-0.3 grams of: tungsten, one or more
tungsten
compounds, or mixtures thereof; (t) comprises one or more metals from Column 6
of the
Periodic Table and one or more metals from Column 10 of the Periodic Table,
wherein the
molar ratio of the Column 10 metal to the Column 6 metal is from 1 to 5; (u)
comprises
one or more elements from Column 15 of the Periodic Table, one or more
compounds of
one or more elements from Column 15 of the Periodic Table, or mixtures
thereof; (v) has,
per gram of catalyst, from 0.00001-0.06 grams of: one or more elements from
Column 15
of the Periodic Table, one or more compounds of one or more elements from
Column 15
27

WO 2005/063933 CA 02549088 2006-06-09
PCT/US2004/042640
of the Periodic Table, or mixtures thereof; (w) phosphorus, one or more
compounds of
phosphorus, or mixtures thereof; (x) has at most 0.1 grams of alpha alumina
per gram of
catalyst; and/or (y) has at least 0.5 grams of theta alumina per gram of
catalyst.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method of
forming a
catalyst comprising combining a support with one or more metals to form a
support/metal
mixture, wherein the support comprises theta alumina, and heat treating the
theta alumina
support/metal mixture at a temperature of at least 400 C, and further
comprising: (a)
combining the support/metal mixture with water to form a paste, and extruding
the paste;
(b) obtaining theta alumina by heat treating alumina at a temperature of at
least 800 C;
and/or (c) sulfurizing the catalyst.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method that
comprises
contacting a crude feed with one or more catalysts, in which the pore size
distribution of at
least one of the catalysts has: (a) a median pore diameter of at least 60 A,
at least 90 A, at
, least 180 A, at least 200 A, at least 230 A, at least 300 A, at most
230 A, at most 500 A, or ,
in a range from 90-180 A, 100-140 A, 120-130 A, 230-250 A; 180-500 A, 230-500
A; or = ,
60-300 A; (b) at least 60% of the total number of pores have a pore diameter
within 45 A,.
35 A, or 25 A, of the median pore diameter; (c) a surface area of at least 60
m2/g, at least
90 m2/g, at least 100 m2/g, at least 120 m2/g, at least 150 m2/g, at least 200
m2/g, or at least
220 m2/g; and/or (d) a total volume of all of the pores of at least 0.3 cm3/g,
at least 0.4
cm3/g, at least 0.5 cm3/g, or at least 0.7 cm3/g.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a method that
comprises
contacting a crude feed with one or more supported catalysts, in which the
support: (a)
comprises alumina, silica, silica-alumina, titanium oxide, zirconium oxide,
magnesium
oxide, or mixtures thereof, and/or zeolite; (b) comprises gamma alumina and/or
delta
alumina; (c) has, per gram of support, at least 0.5 grams of gamma alumina;
(d) has, per
gram of support, at least 0.3 grams or at least 0.5 grams of theta alumina;
(e) comprises
alpha alumina, gamma alumina, delta alumina, theta alumina, or mixture
thereof; (f) has at
most 0.1 grams of alpha alumina per gram of support.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a vanadium
catalyst that:
(a) has a pore size distribution with a median pore diameter of at least 60 A;
(b) comprises

WO 2005/063933 CA 02549088 2006-06-09PCT/US2004/042640
a support, the support comprising theta alumina, and the vanadium catalyst has
a pore size
distribution with a median pore diameter of at least 60 A; (c) comprises one
or more
metals from Column 6 of the Periodic Table, one or more compounds of one or
more
metals from Column 6 of the Periodic Table, or mixtures thereof; and/or (d)
has, per gram
of catalyst, at least 0.001 grams of: one or more metals from Column 6 of the
Periodic
Table, one or more compounds of one or more metals from Column 6 of the
Periodic
Table, or mixtures thereof.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a crude
product that has:
(a) a TAN from at most 0.1, from 0.001 to 0.5, from 0.01 to 0.2; or from 0.05
to 0.1; (b) at
most 0.000009 grams of the alkali metal, and alkaline-earth metal, in metal
salts of organic
acids per gram of crude product; (c) at most 0.00002 grams of NiN/Fe per gram
of crude
product; and/or (d) greater than 0 grams, but less than 0.01 grams, of at
least one of the
catalysts per gram of crude product.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, one or more
alkali metal
salts of one or more organic acids, one or more alkaline-earth metal salts of
one or more
organic acids, or mixtures thereof in which: (a) at least one of the alkali
metals is lithium,
sodium, or potassium; and/or (b) at least one of the alkaline-earth metals is
magnesium or
calcium.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, 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: (a) combining the crude
product with a
crude that is the same or different from the crude feed to form a blend
suitable for
transporting; (b) combining the crude product with a crude that is the same or
different
from the crude feed to form a blend suitable for treatment facilities; (c)
fractionating the
crude product; and/or (d) fractionating the crude product into one or more
distillate
fractions, and producing transportation fuel from at least one of the
distillate fractions.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a supported
catalyst
composition that: (a) has at least 0.3 grams or at least 0.5 grams of theta
alumina per gram
of support; (b) comprises delta alumina in the support; (c) has at most 0.1
grams of alpha
alumina per gram of support; (d) has a pore size distribution with a median
pore diameter
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WO 2005/063933 CA 02549088 2006-06-09 PCT/US2004/042640
of at least 230 A; (e) has a pore volume of the pores of the pore size
distribution of at least
0.3 cm3/g or at least 0.7 cm3/g; (f) has a surface area of at least 60 m2/g or
at least 90 m2/g;
(g) comprises one or more metals from Columns 7-10 of the Periodic Table, one
or more
compounds of one or more metals from Columns 7-10 of the Periodic Table, or
mixtures
thereof; (h) comprises one or more metals from Column 5 of the Periodic Table,
one or
more compounds of one or more metals from Column 5 of the Periodic Table, or
mixtures
thereof; (i) has, per gram of catalyst, from 0.0001-0.6 grams or from 0.001-
0.3 grams of:
one or more Column 5 metals, one or more Column 5 metal compounds, or mixtures

thereof; (j) comprises one or more metals from Column 6 of the Periodic Table,
one or
more compounds of one or more metals from Column 6 of the Periodic Table, or
mixtures
thereof; (k) has, per gram of catalyst, from 0.0001-0.6 grams or from 0.001-
0.3 grams of:
one or more Column 6 metals, one or more Column 6 metal compounds, or mixtures

thereof; (1) comprises vanadium, one or more compounds of vanadium, or
mixtures
thereof; (m) comprises molybdenum, one or more compounds of molybdenum, or
mixtures
thereof; (n) comprises tungsten, one or more compounds of tungsten, or
mixtures thereof;
(o) comprises cobalt, one or more compounds of cobalt, or mixtures thereof;
and/or (p)
comprises nickel, one or more compounds of nickel, or mixtures thereof.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a crude
composition that:
(a) has a TAN of at most 1, at most 0.5, at most 0.3, or at most 0.1; (b) has,
per gram of
composition, at least 0.001 grams of hydrocarbons with a boiling range
distribution
between 95 C and 260 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 260
C and 320
C at 0.101 MPa; and at least 0.001 grams of hydrocarbons with a boiling range
distribution between 320 C and 650 C at 0.101 MPa; (c) has at least 0.0005
grams of
basic nitrogen per gram of composition; (d) has, per gram of composition, at
least 0.001
grams or at least 0.01 grams of total nitrogen; and/or (e) has at most 0.00005
grams of total
nickel and vanadium per gram of composition.
In some embodiments, the invention also provides, in combination with one or
more of the methods or compositions according to the invention, a crude
composition that
includes one or more catalysts, and at least one of the catalysts: (a) has a
pore size
distribution with the median pore diameter of, at least 180 A, at most 500 A,
and/or in a
range from 90-180 A, 100-140 A, 120-130 A; (b) has a median pore diameter of
at least 90
A, with greater than 60% of the total number of pores in the pore size
distribution having a
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WO 2005/063933 CA 02549088 2006-06-09PCT/US2004/042640
pore diameter within 45 A, 35 A, or 25 A of the median pore diameter; (c) has
a surface
area of at least 100 m2/g, at least 120 m2/g, or at least 220 m2/g; (d)
comprises a support;
and the support comprises alumina, silica, silica-alumina, titanium oxide,
zirconium oxide,
magnesium oxide, zeolite, and/or mixtures thereof; (e) comprises one or more
metals from
Columns 5-10 of the Periodic Table, one or more compounds of one or more
metals form
Columns 5-10 of the Periodic Table, or mixtures thereof; (f) comprises one or
more metals
from Column 5 of the Periodic Table, one or more compounds of one or more
metals from
Column 5 of the Periodic Table, or mixtures thereof; (g) has, per gram of
catalyst, at least
0.0001 grams of: one or more Column 5 metals, one or more Column 5 metal
compounds,
or mixtures thereof; (h) comprises one or more metals from Column 6 of the
Periodic
Table, one or more compounds of one or more metals from Column 6 of the
Periodic
Table, or mixtures therof; (i) has, per gram of catalyst at least 0.0001 grams
of: one or
more Column 6 metals, one or more Column 6 metal compounds, or mixtures
thereof; (j)
comprises one or more metals from Column 10 of the Periodic Table, one or more
compounds of one or more metals from Column 10 of the Periodic Table, of
mixtures
thereof; and/or (k) comprises one or more elements from Column 15 of the
Periodic Table;
one or more compounds of one or more elements from Column 15 of the Periodic
Table, ,
or mixtures thereof.
In further embodiments, features from specific embodiments of the invention
may
be combined with features from other embodiments of the invention. For
example,
features from one embodiment of the invention may be combined with features
from any
of the other embodiments.
In further embodiments, crude products are obtainable by any of the methods
and
systems described herein.
In further embodiments, additional features may be added to the specific
embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
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:
FIG. 1 is a schematic of an embodiment of a contacting system.
FIGS. 2A and 2B are schematics of embodiments of contacting systems that
include two contacting zones.

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FIGS. 3A and 3B are schematics of embodiments of contacting systems that
include three contacting zones.
FIG. 4 is a schematic of an embodiment of a separation zone in combination
with a
contacting system.
FIG. 5 is a schematic of an embodiment of a blending zone in combination with
a
contacting system.
FIG. 6 is a schematic of an embodiment of a combination of a separation zone,
a
contacting system, and a blending zone.
FIG. 7 is a tabulation of representative properties of crude feed and crude
product
for an embodiment of contacting the crude feed with three catalysts.
FIG. 8 is a graphical representation of weighted average bed temperature
versus
length of run for an embodiment of contacting the crude feed with one or more
catalysts.
FIG. 9 is a tabulation of representative properties of crude feed and crude
product
for an embodiment of contacting the crude feed with two catalysts.
FIG. 10 is another tabulation of representative properties of crude feed and
crude
, product for an embodiment of contacting the crude feed with two catalysts.
FIG. 11 is a tabulation of crude feed and crude products for embodiments of
contacting crude feeds with four different catalyst systems.
FIG. 12 is a graphical representation of P-value of crude products versus run
time
for embodiments of contacting crude feeds with four different catalyst
systems.
FIG. 13 is a graphical representation of net hydrogen uptake by crude feeds
versus
run time for embodiments of contacting crude feeds with four different
catalyst systems.
FIG. 14 is a graphical representation of residue content, expressed in weight
percentage, of crude products versus run time for embodiments of contacting
crude feeds
with four different catalyst systems.
FIG. 15 is a graphical representation of change in API gravity of crude
products
versus run time for embodiments of contacting the crude feed with four
different catalyst
systems.
FIG. 16 is a graphical representation of oxygen content, expressed in weight
percentage, of crude products versus run time for embodiments of contacting
crude feeds
with four different catalyst systems.
FIG. 17 is a tabulation of representative properties of crude feed and crude
products for embodiments of contacting the crude feed with catalyst systems
that include
various amounts of a molybdenum catalyst and a vanadium catalyst, with a
catalyst system

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that include a vanadium catalyst and a molybdenum/vanadium catalyst, and with
glass
beads.
FIG. 18 is a tabulation of properties of crude feed and crude products for
embodiments of contacting crude feeds with one or more catalysts at various
liquid hourly
space velocities.
FIG. 19 is a tabulation of properties of crude feeds and crude products for
embodiments of contacting crude feeds at various contacting temperatures.
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
Certain embodiments of the inventions are described herein in more detail.
Terms
used herein are defined as follows.
"ASTM" refers to American Standard Testing and Materials.
"API gravity" refers to API gravity at 15.5 'V (60 F). API gravity is as
determined by ASTM Method D6822.
Atomic hydrogen percentage and atomic carbon percentage of the crude feed and
the crude product are as determined by ASTM Method D5291.
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.
"C5 asphaltenes" refers to asphaltenes that are insoluble in pentane. C5
asphaltenes
content is as determined by ASTM Method D2007.
"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.
"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
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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.
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 Mo03 is
used per
gram of catalyst, the calculated weight of the molybdenum metal in the
catalyst is 0.067
grams per gram of catalyst.
"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.
"Crude feed/total product mixture" refers to the mixture that contacts the
catalyst
during processing.
"Distillate" refers to hydrocarbons with a boiling range distribution between
204
C (400 F) and 343 C (650 F) at 0.101 MPa. Distillate content is as
determined by
ASTM Method D5307.
"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.
"Hydrogen source" refers to hydrogen, and/or a compound and/or compounds that
when in the presence of a crude feed and the 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, C1 to C4 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.
"Flat plate crush strength" refers to compressive force needed to crush a
catalyst.
Flat plate crush strength is as determined by ASTM Method D4179.
"LHSV" refers to a volumetric liquid feed rate per total volume of catalyst,
and is
expressed in hours (114). Total volume of catalyst is calculated by summation
of all
catalyst volumes in the contacting zones, as described herein.
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"Liquid mixture" refers to a composition that includes one or more compounds
that
are liquid at standard temperature and pressure (25 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.
"Periodic Table" refers to the Periodic Table as specified by the
International
Union of Pure and Applied Chemistry (IUPAC), November 2003.
"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.
"Micro-Carbon Residue" ("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.
"Naphtha" refers to hydrocarbon components with a boiling range distribution
between 38 C (100 F) and 200 C (392 F) at 0.101 MPa. Naphtha content is as
determined by ASTM Method D5307.
"NiN/Fe" refers to nickel, vanadium, iron, or combinations thereof.
"NiN/Fe content" refers to the content of nickel, vanadium, iron, or
combinations
thereof. The NiN/Fe content is as determined by ASTM Method D5708.
"Nm3/m3" refers to normal cubic meters of gas per cubic meter of crude feed.
"Non-carboxylic containing organic oxygen compounds" refers to organic oxygen
compounds that do not have a carboxylic (-0O2-) 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.
"Non-condensable gas" refers to components and/or mixtures of components that
are gases at STP.
"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.
"Pore diameter", "median pore diameter", and "pore volume" refer to pore
diameter, median pore diameter, and pore volume, as determined by ASTM Method
D4284 (mercury porosimetry at a contact angle equal to 140 ). A micromeritics
A9220



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PCT/US2004/042640

instrument (Micromeritics Inc., Norcross, Georgia, U.S.A.) may be used to
determine
these values.
"Residue" refers to components that have a boiling range distribution above
538 C
(1000 F), as determined by ASTM Method D5307.
"SCFB" refers to standard cubic feet of gas per barrel of crude feed.
"Surface area" of a catalyst is as determined by ASTM Method D3663.
"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.
"VGO" refers to hydrocarbons with a boiling range distribution between 343 C
(650 F) and 538 C (1 000 F) at 0.101 MPa. VG0 content is as determined by
ASTM
Method D5307.
"Viscosity" refers to kinematic viscosity at 37.8 C (100 F). Viscosity is as
detellnined using ASTM Method D445.
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.
Crudes may be produced and/or retorted from hydrocarbon containing formations
.
and then stabilized. Crudes may include crude oil. Crudes are generally solid,
semi-solid,
and/or liquid. Stabilization may include, but is not limited to, removal of
non-condensable
gases, water, salts, 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.
Stabilized crudes typically 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, VG0, 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 components per
gram of
crude. Examples of stabilized crudes include whole crudes, topped crudes,
desalted
crudes, desalted topped crudes, or combinations thereof. "Topped" refers to a
crude that
has been treated such that at least some of the components that have a boiling
point below
C at 0.101 MPa (95 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.



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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 that is deemed too costly to produce, transport, and/or
treat.
Properties of disadvantaged crudes may include, but are not limited to: a) TAN
of
at least 0.1, at least 0.3; b) viscosity of at least 10 cSt; c) API gravity at
most 19; d) a total
NiN/Fe content of at least 0.00002 grams or at least 0.0001 grams of NiN/Fe
per gram of
crude; e) a total heteroatoms content of at least 0.005 grams of heteroatoms
per gram of
crude; f) a residue content of at least 0.01 grams of residue per gram of
crude; g) a C5
asphaltenes content of at least 0.04 grams of C5 asphaltenes per gram of
crude; h) a MCR
content of at least 0.002 grams of MCR per gram of crude; i) a content of
metals in metal
salts of organic acids of at least 0.00001 grams of metals per gram of crude;
or j)
combinations thereof. In some embodiments, disadvantaged crude may include,
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,
the
disadvantaged crude may have a TAN in a range from 0.1 or 0.3 to 20, 0.3 or
0.5 to 10, or
0.4 or 0.5 to 5. In certain embodiments, disadvantaged crudes, per gram of
disadvantaged
crude, may have a sulfur content of at least 0.005 grams, at least 0.01 grams,
or at least
0.02 grams.
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 C5 asphaltenes content of at least 0.04 grams of
C5 asphaltenes
per gram of crude feed; d) a higher than desired viscosity (for example, > 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 metals per gram of crude; or f)
combinations thereof.
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 95 C and 200 C at 0.101 MPa; at least 0.01 grams, at
least 0.005
grams, or at least 0.001 grams of hydrocarbons with a boiling range
distribution between
200 C and 300 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 300 C
and 400 C
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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 400 C and 650 C at
0.101 MPa.
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 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
100 C and
200 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 200 C and 300 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 300 C and 400 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 400 C and 650 C at 0.101 MPa.
Some disadvantaged eludes 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 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.
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 least 200 C at 0.101 MPa.
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 least 650 C.
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 and southern California, Canada Tar sands, Brazilian
Santos and
Campos basins, Egyptian Gulf of Suez, Chad, United Kingdom North Sea, Angola
Offshore, Chinese Bohai Bay, 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
product
resulting from treatment of the crude feed, as described herein, is generally
suitable for

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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 or no pre-treatment, thereby enhancing refining
efficiencies. Pre-
treatment may include desulfurization, demetallization and/or atmospheric
distillation to
remove impurities.
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.
N FIG. 1 is a schematic of contacting system 100 that includes contacting
zone 102A
crude feed enters contacting zone 102 via 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.
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 TAN of the crude feed. Subsequent contact of the reduced
TAN
crude feed with the second catalyst decreases heteroatoms content and
increases API
gravity. 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.
In certain embodiments, a volume of catalyst in the contacting zone is in a
range
from 10-60 vol%, from 20-50 vol%, or from 30-40 vol% of a total volume of
crude feed in
the contacting zone. In some embodiments, a slurry of catalyst and crude feed
may

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include from 0.001-10 grams, 0.005-5 grams, or 0.01-3 grams of catalyst per
100 grams of
crude feed in the contacting zone.
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 50-
500 C,
60-440 C, 70-430 C, or 80-420 C. Pressure in a contacting zone may range
from 0.1-20
MPa, 1-12 MPa, 4-10 MPa, or 6-8 MPa. LHSV of the crude feed will generally
range
from 0.1-30111, 0.5-25 111, 1-20 h.% 1.5-15 h', or 2-10 11-1. In some
embodiments, LHSV
is at least 5 h-1, at least 11 h-1, at least 15 If', or at least 20
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 0.1-100,000 Nm3/m3, 0.5-10,000 Nm3/m3, 1-8,000 Nm3/m3, 2-5,000 Nm3/m3, 5-
3,000
Nm3/m3, or 10-800 Nm3/m3 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 .
zones(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.
The hydrogen source may enter contacting zone 102 co-currently with the crude
feed in conduit 104 or separately via conduit 106. In 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
contacting
zone 102 and enter separation zone 108 via conduit 110.
In 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 separation zone 108 via 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.
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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).
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
contacting zones 102 and 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 contacting zone 102 via conduit
104.
In some embodiments, the carrier gas is combined with the hydrogen source in
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
conduit 106
and/or in a direction counter to the flow of the crude feed via, for example,
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.
Contact of the crude feed with catalyst(s) in contacting zone 102 forms a feed

stream. The feed stream flows from contacting zone 102 to contacting zone 114.
In FIGS.
3A and 3B, the feed stream flows from contacting zone 114 to contacting zone
116.
Contacting zones 102, 114, 116 may include one or more catalysts. As shown in
FIG. 2B, the feed stream exits contacting zone 102 via conduit 118 and enters
contacting
zone 114. As shown in FIG. 3B, the feed stream exits contacting zone 114 via
conduit 118
and enters contacting zone 116.
The feed stream may be contacted with additional catalyst(s) in contacting
zone
114 and/or contacting zone 116 to form the total product. The total product
exits
contacting zone 114 and/or contacting zone 11 6 and enters separation zone 108
via conduit
110. The crude product and/or gas is (are) separated from the total product.
The crude
product exits separation zone 108 via conduit 1 12.
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
separation zone 120 via conduit 122. In 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) to produce the crude feed. For
example, water
may be at least partially separated from the disadvantaged crude. In another
example,
components that have a boiling range distribution below 95 C or below 100 C
may be at
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least partially separated from the disadvantaged crude 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 separation zone 120 via conduit 124.
The crude feed obtained from separation zone 120, in some embodiments,
includes
a mixture of components with a boiling range distribution of at least 100 C
or, in some
embodiments, a boiling range distribution of at least 120 C. Typically, the
separated
crude feed includes a mixture of components with a boiling range distribution
between
100-1000 C, 120-900 C, or 200-800 C. At least a portion of the crude feed
exits
separation zone 120 and enters contacting system 100 (see, for example, the
contacting
zones in FIGS. 1-3) via conduit 126 to be further processed to form a crude
product. In
some embodiments, separation zone 120 may be positioned upstream or downstream
of a
desalting unit. After processing, the crude product exits contacting system
100 via conduit
112.
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 that is
different,
thereby producing a product that has a TAN that is between the TAN of the
crude product
and the crude. The blended product may be suitable for transportation and/or
treatment.
As shown in FIG. 5, in certain embodiments, crude feed enters contacting
system
100 via 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 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
conduit 134 to be transported or processed.
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In FIG. 6, the disadvantaged crude enters separation zone 120 through 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 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 conduit 128. Other process streams and/or crudes enter blending
zone 130
directly or via conduit 132 and are combined with the crude product to form a
blended
product. The blended product exits blending zone 130 via conduit 134.
In some embodiments, the crude product and/or the blended product are
transported to a refinery and/or a treatment facility. The crude product
and/or the blended
product may be processed to produce commercial products such as transportation
fuel,
heating fuel, lubricants, or chemicals. Processing may include distilling
and/or fractionally
distilling the crude product and/or blended product to produce one or more
distillate
fractions. In some embodiments, the crude product, the blended product, and/or
the one or
more distillate fractions may be hydrotreated.
In some embodiments, 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 some embodiments,
crude
product has a TAN in a range of 1-80%, 20-70%, 30-60%, or 40-50% 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 0.001 to 0.5, 0.01 to 0.2, or
0.05 to 0.1.
In some embodiments, the crude product has a total Ni/V/Fe content of at most
90%, at most 50%, at most 10%, at most 5%, or at most 3% of the Ni/V/Fe
content of the
crude feed. The crude product, in some embodiments, has a total Ni/V/Fe
content in a
range of 1-80%, 10-70%, 20-60%, or 30-50% 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 1 x 1 e grams to 5 x 10-5 grams, 3 x 10-7 grams to 2 x
1 e grams,
or 1 x 10-6 grams to 1 x 1 e grams. In certain embodiments, the crude has at
most 2 x 10-5
grams of Ni/V/Fe. In some embodiments, the total Ni/V/Fe content of the crude
product is
70-130%, 80-120%, or 90-110% of the Ni/V/Fe content of the crude feed.
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 10%, or at most 5% of
the total
content of metals in metal salts of organic acids in the crude feed. In
certain embodiments,
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the crude product has a total content of metals in metal salts of organic
acids in a range of
1-80%o, 10-70%, 20-60%, or 30-50% of the total content of metals in metal
salts of
organic acids in 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.
In certain embodiments, the crude product has a total content of metals in
metal
salts of organic acids, per gram of crude product, in a range from 0.0000001
grams to
0.00005 grams, from 0.0000003 grams to 0.00002 grams, or from 0.000001 grams
to
0.00001 grams of metals in metal salts of organic acids per gram of crude
product. In
some embodiments, a total content of metals in metal salts of organic acids of
the crude
product is 70-130%, 80-120%, or 90-110% of the total content of metals in
metal salts of
organic acids in the crude feed.
In certain embodiments, API gravity of the crude product produced from contact

of the crude feed with catalyst, at the contacting conditions, is 70-130%, 80-
120%, 90-
110%, or 100-130%) of the API gravity of the crude feed. In certain
embodiments, API
gravity of the crude product is from 14-40, 15-30, or 16-25.
In certain embodiments, the crude product has a viscosity of at most 90%, at
most
80%, or at most 70% of the viscosity of the crude feed. In some embodiments,
the crude
product has a viscosity in a range of 10-60%, 20-50%, or 30-40% 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 70-
130%, 80-
120%, or 90-110% of the API gravity the crude feed.
In some embodiments, the crude product has a total heteroatoms content of at
most
90%, at most 50%, 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.
In some embodiments, the sulfur content of the crude product may be at most
90%, at
most 50%, 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
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WO 2005/063933 CA 02549088 2006-06-09PCT/US2004/042640
least 80%, or at least 99% of the sulfur content of the crude feed. In some
embodiments,
the sulfur content of the crude product is 70-130%, 80-120%, or 90-110% of the
sulfur
content of the crude feed.
In some embodiments, total nitrogen content of the crude product may be at
most
90%, at most 80%, 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 some embodiments, basic nitrogen content of the crude product may at most
95%, at most 90%, at most 50%, 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.
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 crude product has an oxygen content of
at least
1%, at least 30%, at least 80%, or at least 99% of the oxygen content of the
crude feed. In
some embodiments, the oxygen content of the crude product is in a range from 1-
80%, 10-
70%, 20-60%, or 30-50% 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 10%, at most 5% of the content of the carboxylic acid
compounds in
the crude feed. In certain embodiments, the crude product has a total content
of carboxylic
acid compounds of 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.
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).
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%, or at most
40% of
the TAN of the crude feed. In certain embodiments, the crude product has an
oxygen
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content of 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.
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 containing organic oxygen
compounds
within 70-130%, 80-120%, or 90-110% of the non-carboxylic containing organic
oxygen
compounds of the crude feed.
In some embodiments, the crude product includes, in its molecular structures,
from
0.05-0.15 grams or from 0.09-0.13 grams of hydrogen per gram of crude product.
The
crude product may include, in its molecular structure, from 0.8-0.9 grams or
from 0.82-
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 70-130%, 80-120%, or 90-110%
of the
atomic H/C ratio of the crude feed. A crude product atomic H/C ratio within 10-
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_
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 0.001 to 0.5 grams of hydrocarbons with a boiling range
distribution of at
most 100 C at 0.101 MPa; at least 0.001 grams, or from 0.001-0.5 grams of
hydrocarbons
with a boiling range distribution between 100 C and 200 C at 0.101 MPa; at
least 0.001
grams, or from 0.001-0.5 grams of hydrocarbons with a boiling range
distribution between
200 C and 300 C at 0.101 MPa; at least 0.001 grams, or from 0.001-0.5 grams
of
hydrocarbons with a boiling range distribution between 300 C and 400 C at
0.101 MPa;
and at least 0.001 grams, or from 0.001 to 0.5 grams of hydrocarbons with a
boiling range
distribution between 400 C and 538 C at 0.101 MPa.
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 C at
0.101 MPa and/or at least 0.001 grams of hydrocarbons with a boiling range
distribution
between 100 C and 200 C at 0.101 MPa.
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.
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In some embodiments, the crude product has a distillate content of 70-130%, 80-

120%, or 90-110% of the distillate content of the crude feed. The distillate
content of the
crude product may be, per gram of crude product, in a range from 0.00001-0.5
grams,
0.001-0.3 grams, or 0.002-0.2 grams.
In certain embodiments, the crude product has a VGO content of 70-130%, 80-
120%, or 90-110% of the VGO content of the crude feed. In some embodiments,
the crude
product has, per gram of crude product, a VGO content in a range from 0.00001-
0.8
grams, 0.001-0.5 grams, 0.002-0.4 grams, or 0.001-0.3 grams.
In some embodiments, the crude product has a residue content of 70-130%, 80-
120%, or 90-110% 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 0.00001-0.8
grams, 0.0001-
0.5 grams, 0.0005-0.4 grams, 0.001-0.3 grams, 0.005-0.2 grams, or 0.01-0.1
grams.
In certain embodiments, the crude product has a MCR content of 70-130%, 80-
120%, or 90-110% of the MCR content of the crude feed, while the crude product
has a C5
asphaltenes content of at most 90%, at most 80%, or at most 50% of the C5
asphaltenes
content of the crude feed. In certain embodiments, the C5 asphaltenes content
of the crude
feed is at least 10%, at least 60%, or at least 70% of the C5 asphaltenes
content of the crude
feed while the MCR content of the crude product is within 10-30% of the MCR
content of
the crude feed. In some embodiments, decreasing the C5 asphaltenes content of
the crude
feed while maintaining a relatively stable MCR content may increase the
stability of the
crude feed/total product mixture.
In some embodiments, the C5 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 C5 asphaltenes content and a crude feed MCR
content may
be represented by S. A sum of a crude product C5 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 1-99%, 10-90%, or 20-80% of S. In some embodiments, a ratio
of
MCR content of the crude product to C5 asphaltenes content is in a range from
1.0-3.0,
1.2-2.0, or 1.3-1.9.
In certain embodiments, the crude product has a MCR content that is at most
90%,
at most 80%, at most 50%, 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 of 1-80%, 10-70%,
20-


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60%, or 30-50% of the MCR content of the crude feed. The crude product has, in
some
embodiments, from 0.0001-0.1 grams, 0.005-0.08 grams, or 0.01-0.05 grams of
MCR per
gram of crude product.
In some embodiments, the crude product includes from greater than 0 grams, but
less than 0.01 grams, 0.000001-0.001 grams, or 0.00001-0.0001 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.
The crude product produced from contacting system 100 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 NiN/Fe content; d) reduced
content
of sulfur, oxygen, nitrogen, or combinations thereof; e) reduced residue
content; f) reduced
C5 asphaltenes content; g) reduced MCR content; h) increased API gravity; i) a
reduced
content of metals in metal salts of organic acids; or j) combinations thereof.
In some
embodiments, one or more properties of the crude product, relative to the
crude feed, may
be selectively changed while other properties are not changed as much, or do
not
substantially change. For example, it may be desirable to only selectively
reduce TAN in a
crude feed without also significantly changing the amount of other components
(for
example, sulfur, residue, NiN/Fe, or VGO). In this manner, hydrogen uptake
during
contacting may be "concentrated" on TAN reduction, and not on reduction of
other
components. Thus, the TAN of the crude feed can be reduced, while using less
hydrogen,
since less of such hydrogen is also being used to reduce other components in
the crude
feed. If, for example, a disadvantaged crude has a high TAN, but a sulfur
content that is
acceptable to meet treatment and/or transportation specifications, then such
crude feed may
be more efficiently treated to reduce TAN without also reducing sulfur.
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
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are contemplated to be used as described herein include HDS3; HDS22; HDN60;
C234;
C311; C344; C411; C424; C344; C444; C447; C454; C448; C524; C534; DN110;
DN120;
DN130; DN140; DN190; DN200; DN800; DN2118; DN2318; DN3100; DN3110;
DN3300; DN3310; RC400; RC410; RN412; RN400; 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,
Texas,
U.S.A.).
In some embodiments, catalysts used to change properties of the crude feed
include
one or more Columns 5-10 metals 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 The catalyst may have, per gram of catalyst, a total
Columns 5-10
metal(s) content of at least 0.0001 grams, at least 0.001 grams, at least 0.01
grams or in a
range from 0.0001-0.6 grams, 0.005-0.3 grams, 0.001-0.1 grams, or 0.01-0.08
grams. In
some embodiments, the catalyst includes Column 15 element(s) in addition to
the Columns
5-10 metal(s). Examples of Column 15 elements include phosphorus. The catalyst
may
have a total Column 15 element content, per gram of catalyst, in range from
0.000001-0.1
grams, 0.00001-0.06 grams, 0.00005-0.03 grams, or 0.0001-0.001 grams.
In certain embodiments, a catalyst includes Column 6 metal(s). The catalyst
may
have, per gram of catalyst, a total Column 6 metal(s) content of at least
0.0001 grams, at
least 0.01 grams, at least 0.02 grams and/or in a range from 0.0001-0.6 grams,
0.001-0.3
grams, 0.005-0.1 grams, or 0.01-0.08 grams. In some embodiments, the catalyst
includes
from 0.0001-0.06 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).
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 0.1-20, 1-10, or 2-5. A molar
ratio of
Column 6 metal to Columns 7-10 metal may be in a range from 0.1-20, 1-10, or 2-
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 1-10, or from 2-5. In certain embodiments, the catalyst
includes

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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 1-10, or from
2-5.
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, Texas, 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, Pennsylvania, U.S.A.).
,=
The support, in some embodiments, is prepared such that the support has an
average pore diameter of at least 150 A, at least 170 A, or at least 180 A. In
certain=
embodiments, a support is prepared by forming an aqueous paste of the support
material.
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.
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 5-260 C or from 85-235 C for a
period of time
(for example, for 0.5-8 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 800-1200 C or 900-1100 C) to form the support
having an
average pore diameter of at least 150 A.
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 therof, per gram of catalyst support,
may be in a
range from 0.0001-0.99 grams, 0.001-0.5 grams, 0.01-0.1 grams, or at most 0.1
grams as

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determined by x-ray diffraction. In some 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 0.1-0.99 grams, 0.5-0.9 grams, or 0.6-0.8 grams, as determined by
x-ray
diffraction. In some embodiments, the support may have 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.
Supported catalysts may be prepared using generally known catalyst preparation

techniques. Examples of catalyst preparations are described in U.S. Patent
Nos. 6,21 8,333
to Gabrielov et al.; 6,290,841 to Gabrielov et al.; and 5,744,025 to Boon et
al., and U.S.
Patent Application Publication No. 20030111391 to Bhan.
In some embodiments, the support may be impregnated with metal to form a
catalyst. In certain embodiments, the support is heat treated at temperatures
in a range
from 400-1200 C, 450-1000 C, or 600-900 C prior to impregnation with a
metal. In
some embodiments, impregnation aids may be used during preparation of the
catalyst.
Examples of impregnation aids include a citric acid component,
ethylenediaminetetraacetic
acid (EDTA), ammonia, or mixtures thereof.
In certain embodiments, a catalyst may be formed by adding or incorporating
the
Columns 5-10 metal(s) to heat treated shaped mixtures of support
("overlaying").
Overlaying a metal on top of the heat treated shaped support having a
substantially or
relatively uniform concentration of metal often provides beneficial catalytic
properties of
the catalyst. Heat treating of a shaped 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. 20030111391 to Bhan.
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. The Columns 5-10
metal(s)/support mixture may be mixed using suitable mixing equipment.
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 generally known device, that will suitably provide the Columns
5-1 0
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.
In some embodiments, the catalyst is heat treated at temperatures from 150-750
C,
from 200-740 C, or from 400-730 C after combining the support with the
metal.

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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 400 C and 1000 C
to remove
volatile matter such that at least a portion of the Columns 5-10 metals are
converted to the
corresponding metal oxide.
In other embodiments, however, the catalyst may be heat treated in the
presence of
air at temperatures in a range from 35-500 C (for example, below 300 C,
below 400 C
or below 500 C) for a period of time in a range from 1-3 hours to remove a
majority of
the volatile components without converting the Columns 5-10 metals to the
metal oxide.
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 in the support. Preparations of
such catalysts
are described in U.S. Patent Nos. 6,218,333 to Gabrielov et al., and 6,290,841
to Gabrielov
etal.
In certain embodiments, a theta alumina support may be combined with Columns
5-10 metals to form a theta alumina support/Columns 5-10 metals mixture. The
theta
alumina support/Columns 5-10 metals mixture may be heat treated at a
temperature of at
least 400 C to form the catalyst having a pore size distribution with a
median pore
diameter of at least 230 A. Typically, such heat treating is conducted at
temperatures of at
most 1200 C.
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
metal(s). For example, the supported catalyst and/or the bulk metal catalyst
may be
crushed into a powder with an average particle size from 1-50 microns, 2-45
microns, or 5-
40 microns. The powder may be combined with 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 80-200 A or 90-180 A, or 120-130 A.
Combining the catalyst with the support allows, in some embodiments, at least
a
portion of the metal to reside under the surface of the embedded metal
catalyst (for
example, embedded in the support), 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.
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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.
Intercalation and/or mixing of the components of the catalysts changes, in
some
embodiments, the structured order of the Column 6 metal in the Column 6 oxide
crystal
structure to a substantially random order of Column 6 metal in the crystal
structure of the
embedded catalyst. The order of the Column 6 metal may be determined using
powder x-
ray diffraction methods. The order of elemental metal in the catalyst relative
to the order
of elemental metal in the metal oxide may be determined by comparing the order
of the
Column 6 metal peak in an x-ray diffraction spectrum of the Column 6 oxide to
the order
of the Column 6 metal peak in an x-ray diffraction spectrum of the catalyst.
From
broadening and/or absence of patterns associated with Column 6 metal in an x-
ray
diffraction spectrum, it is possible to estimate that the Column 6 metal(s)
are substantially
randomly ordered in the crystal structure.
For example, molybdenum trioxide and the alumina support having a median pore
diameter of at least 180 A may be combined to form an alumina/molybdenum
trioxide
mixture. The molybdenum trioxide has a definite pattern (for example, definite
D001, D002
and/or D003 peaks). The alumina/Column 6 trioxide mixture may be heat treated
at a
temperature of at least 538 C (1000 F) to produce a catalyst that does not
exhibit a
pattern for molybdenum dioxide in an x-ray diffraction spectrum (for example,
an absence
of the D001 peak).
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 sizes versus pore diameters. The median pore diameter of the
pore size
distribution may be in a range from 30-1000 A, 50-500 A, or 60-300 A. 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 60-200
A; 90-180 A, 100-140 A, or 120-130 A. 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 180-500 A, 200-300 A, or 230-250 A. In
some
embodiments, the median pore diameter of the pore size distribution is at
least 120 A, at
least 150 A, at least 180 A, at least 200 A, at least 220 A, at least 230 A,
or at least 300 A.
Such median pore diameters are typically at most 1000 A.



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The catalyst may have a pore size distribution with a median pore diameter of
at
least 60 A or at least 90 A. In some embodiments, the catalyst has a pore size
distribution
with a median pore diameter in a range from 90-180 A 100-140 A, or 120-130 A,
with at
least 60% of a total number of pores in the pore size distribution having a
pore diameter
within 45 A, 35 A, or 25 A of the median pore diameter. In certain
embodiments, the
catalyst has a pore size distribution with a median pore diameter in a range
from 70-180 A,
with at least 60% of a total number of pores in the pore size distribution
having a pore
diameter within 45 A, 35 A, or 25 A of the median pore diameter.
In embodiments in which the median pore diameter of the pore size distribution
is
at least 180 A, at least 200 A, or at least 230A, greater that 60% of a total
number of pores
in the pore size distribution have a pore diameter within 50 A, 70 A, or 90 A
of the median
pore diameter. In some embodiments, the catalyst has a pore size distribution
with a
median pore diameter in a range from 180-500 A, 200-400 A, or 230-300 A, with
at least
60% of a total number of pores in the pore size distribution having a pore
diameter within
50 A, 70 A, or 90 A of the median pore diameter.
In some embodiments, pore volume of pores may be at least 0.3 cm3/g, at least
0.7
cm3/g or at least 0.9 cm3/g. In certain embodiments, pore volume of pores may
range from
0.3-0.99 cm3/g, 0.4-0.8 cm3/g, or 0.5-0.7 cm3/g.
The catalyst having a pore size distribution with a median pore diameter in a
range
from 90-180 A may, in some embodiments, have a surface area of at least 100
m2/g, at
least 120 m2/g, at least 170 m2/g, at least 220 or at least 270 m2/g. Such
surface area may
be in a range from 100-300 m2/g, 120-270 m2/g, 130-250 m2/g, or 170-220 m2/g.
In certain embodiments, the catalyst having a pore size distribution with a
median
pore diameter in a range from 180-300 A may have a surface area of at least 60
m2/g, at
least 90 m2/g, least 100 m2/g, at least 120 m2/g, or at least 270 m2/g. Such
surface area
may be in a range from 60-300 m2/g, 90-280 m2/g, 100-270 m2/g, or 120-250
m2/g.
In certain embodiments, the catalyst exists in shaped forms, for example,
pellets,
cylinders, and/or extrudates. The catalyst typically has a flat plate crush
strength in a
range from 50-500 N/cm, 60-400 N/cm, 100-350 N/cm, 200-300 N/cm, or 220-280
N/cm.
In some embodiments, the catalyst and/or the catalyst precursor is sulfided to
form
metal sulfides (prior to use) using techniques known in the art (for example,
ACTICATTm
process, CRI International, Inc.). In some embodiments, the catalyst may be
dried then
sulfided. Alternatively, the catalyst may be sulfided in situ by contact of
the catalyst with
a crude feed that includes sulfur-containing compounds. In-situ sulfurization
may utilize
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WO 2005/063933 CA 02549088 2006-06-09PCT/US2004/042640
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. Patent Nos.
5,468,372 to
Seamans et al., and 5,688,736 to Seamans et al.
In certain embodiments, a first type of catalyst ("first catalyst") includes
Columns
5-10 metal(s) in combination with a support, and has a pore size distribution
with a median
pore diameter in a range from 150-250 A. The first catalyst may have a surface
area of at
least 100 m2/g. The pore volume of the first catalyst may be at least 0.5
cm3/g. The first
catalyst may have a gamma alumina content of at least 0.5 grams of gamma
alumina, and
typically at most 0.9999 grams of gamma alumina, per gram of first catalyst.
The first
catalyst has, in some embodiments, a total content of Column 6 metal(s), per
gram of
catalyst, in a range from 0.0001 to 0.1 grams. The first catalyst is capable
of removing a
portion of the NiN/Fe from a crude feed, removing a portion of the components
that
contribute to TAN of a crude feed, removing at least a portion of the C5
asphaltenes from a
crude feed, removing at least a portion of the metals in metal salts of
organic acids in the
crude feed, or combinations thereof Other properties (for example, sulfur
content, VG0
content, API gravity, residue content, or combinations thereof) may exhibit
relatively
small changes when the crude feed is contacted with the first catalyst. Being
able to
selectively change properties of a crude feed while only changing other
properties in
relatively small amounts may allow the crude feed to be more efficiently
treated. In some
embodiments, one or more first catalysts may be used in any order.
In certain embodiments, the second type of catalyst ("second catalyst")
includes
Columns 5-10 metal(s) in combination with a support, and has a pore size
distribution with
a median pore diameter in a range from 90 A to 180 A. At least 60% of the
total number
of pores in the pore size distribution of the second catalyst have a pore
diameter within 45
A of the median pore diameter. Contact of the crude feed with the second
catalyst under
suitable contacting conditions may produce a crude product that has selected
properties
(for example, TAN) significantly changed relative to the same properties of
the crude feed
while other properties are only changed by a small amount. A hydrogen source,
in some
embodiments, may be present during contacting.
The second catalyst may reduce at least a portion of the components that
contribute
to the TAN of the crude feed, at least a portion of the components that
contribute to
relatively high viscosities, and reduce at least a portion of the NiN/Fe
content of the crude
product. Additionally, contact of crude feeds with the second catalyst may
produce a
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crude product with a relatively small change in the sulfur content relative to
the sulfur
content of the crude feed. For example, the crude product may have a sulfur
content of

70%-130% of the sulfur content of the crude feed. The crude product may also
exhibit
relatively small changes in distillate content, VG0 content, and residue
content relative to
the crude feed.
In some embodiments, the crude feed may have a relatively low content of
NiN/Fe
(for example, at most 50 wtppm), but a relatively high TAN, asphaltenes
content, or
content of metals in metal salts of organic acids. A relatively high TAN (for
example,
TAN of at least 0.3) may render the crude feed unacceptable for transportation
and/or
refining. A disadvantaged crude with a relatively high C5 asphaltenes content
may exhibit
less stability during processing relative to other crudes with relatively low
C5 asphaltenes
content. Contact of the crude feed with the second catalysts, may remove
acidic
components and/or C5 asphaltenes contributing to TAN from the crude feed. In
some
embodiments, reduction of C5 asphaltenes and/or components contributing to TAN
may
reduce the viscosity of the crude feed/total product mixture relative to the
viscosity of the
crude feed. In certain embodiments, one or more combinations of second
catalysts may
= enhance stability of the total prodUct/crude product mixture, increase
catalyst life, allow
minimal net hydrogen uptake by the crude feed, or combinations thereof, when
used to
treat crude feed as described herein.
In some embodiments, a third type of catalyst ("third catalyst") may be
obtainable
by combining a support with Column 6 metal(s) to produce a catalyst precursor.
The
catalyst precursor may be heated in the presence of one or more sulfur
containing
compounds at a temperature below 500 C (for example, below 482 C) for a
relatively
short period of time to form the uncalcined third catalyst. Typically, the
catalyst precursor
is heated to at least 100 C for 2 hours. In certain embodiments, the third
catalyst may, per
gram of catalyst, have a Column 15 element content in a range from 0.001-0.03
grams,
0.005-0.02 grams, or 0.008-0.01 grams. The third catalyst 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 C in the presence
of one or
more sulfur compounds.
The third catalyst may reduce at least a portion of the components that
contribute to
the TAN of the crude feed, reduce at least a portion of the metals in metal
salts of organic

acids, reduce a NiN/Fe content of the crude product, and reduce the viscosity
of the crude
product. Additionally, contact of crude feeds with the third catalyst may
produce a crude


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product with a relatively small change in the sulfur content relative to the
sulfur content of
the crude feed and with relatively minimal net hydrogen uptake by the crude
feed. For
example, a crude product may have a sulfur content of 70%430% of the sulfur
content of
the crude feed. The crude product produced using the third catalyst may also
exhibit
relatively small changes in API gravity, distillate content, VG0 content, and
residue
content relative to the crude feed. The ability to reduce the TAN, the metals
in metal salts
of organic salts, the NiN/Fe content, and the viscosity of the crude product
while also only
changing by a small amount the API gravity, distillate content, VGO content,
and residue
contents relative to the crude feed, may allow the crude product to be used by
a variety of
treatment facilities.
The third catalyst, in some embodiments, may reduce at least a portion of the
MCR
content of the crude feed, while maintaining crude feed/total product
stability. In certain
embodiments, the third catalyst may have a Column 6 metal(s) content in a
range from
0.0001-0.1 grams, 0.005-0.05 grams, or 0.001-0.01 grams and a Column 10
metal(s)
content in a range from 0.0001-0.05 grams, 0.005-0.03 grams, or 0.001-0.01
grams per
gram of catalyst. A Columns 6 and 10 metal(s) catalyst 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 300-500 C or 350-450 C and pressures in a range from 0.1-10 MPa,
1-8
MPa, or 2-5 MPa.
In certain embodiments, a fourth type of catalyst ("fourth catalyst") includes

Column 5 metal(s) in combination with a theta alumina support. The fourth
catalyst has a
pore size distribution with a median pore diameter of at least 180 A. In some
embodiments, the median pore diameter of the fourth catalyst may be at least
220 A, at
least 230 A, at least 250 A, or at least 300 A. The support may include at
least 0.1 grams,
at least 0.5 grams, at least 0.8 grams, or at least 0.9 grams of theta alumina
per gram of
support. The fourth catalyst may include, in some embodiments, at most 0.1
grams of
Column 5 metal(s) per gram of catalyst, and at least 0.0001 grams of Column 5
metal(s)
per gram of catalyst. In certain embodiments, the Column 5 metal is vanadium.
In some embodiments, the crude feed may be contacted with an additional
catalyst
subsequent to contact with the fourth catalyst. The additional catalyst may be
one or more
of the following: the first catalyst, the second catalyst, the third catalyst,
the fifth catalyst,
the sixth catalyst, the seventh catalyst, commercial catalysts described
herein, or
combinations thereof.



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In some embodiments, hydrogen may be generated during contacting of the crude
feed with the fourth catalyst at a temperature in a range from 300-400 C, 320-
380 C, or
330-370 C. The crude product produced from such contacting may have a TAN of
at
most 90%, at most 80%, at most 50%, or at most 10% of the TAN of the crude
feed.
Hydrogen generation may be in a range from 1-50 Nm3/m3, 10-40 Nm3/m3, or 15-25

Nm3/m3. The crude product may have a total NiN/Fe content of at most 90%, at
most
80%, at most 70%, at most 50%, at most 10%, or at least 1 % of total NiN/Fe
content of
the crude feed.
In certain embodiments, a fifth type of catalyst ("fifth catalyst") includes
Column 6
metal(s) in combination with a theta alumina support. The fifth catalyst has a
pore size
distribution with a median pore diameter of at least 180 A, at least 220 A, at
least 230 A, at
least 250 A, at least 300 A, or at most 500 A. The support may include at
least 0.1 grams,
at least 0.5 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 certain embodiments, net hydrogen uptake by the crude feed may be
relatively
low (for example, from 0.01-100 Nm3/m3, 1-80 Nm3/m3, 5-50 Nm3/m3, or 10-30
Nm3/m3)
when the crude feed is contacted with the fifth catalyst at a temperature in a
range from
310-400 C, from 320-370 C, or from 330-360 C. Net hydrogen uptake by the
crude
feed, in some embodiments, may be in a range from 1-20 Nm3/m3, 2-15 Nm3/m3, or
3-10
Nm3/m3. The crude product produced from contact of the crude feed with the
fifth catalyst
may have a TAN of at most 90%, at most 80%, at most 50%, or at most 10% of the
TAN
of the crude feed. TAN of the crude product may be in a range from 0.01-0.1,
0.03-0.05,
or 0.02-0.03.
In certain embodiments, a sixth type of catalyst ("sixth catalyst") includes
Column
5 metal(s) and Column 6 metal(s) in combination with the theta alumina
support. The
sixth catalyst has a pore size distribution with a median pore diameter of at
least 180 A. In
some embodiments, the median pore diameter of pore size distribution may be at
least 220
A, at least 230 A, at least 250 A, at least 300 A, or at most 500 A. The
support may
include at least 0.1 grams, at least 0.5 grams, at least 0.8 grams, at least
0.9 grams, or at
most 0.99 grams of theta alumina per gram of support. The catalyst may
include, in some
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embodiments, a total of Column 5 metal(s) and Column 6 metal(s) of at most 0.1
grams
per gram of catalyst, and at least 0.0001 grams of Column 5 metal(s) and
Column 6
metal(s) per gram of catalyst. In some embodiments, the molar ratio of total
Column 6
metal to total Column 5 metal may be in a range from 0.1-20, 1-10, or 2-5. In
certain
embodiments, the Column 5 metal is vanadium and the Column 6 metal(s) are
molybdenum and/or tungsten.
When the crude feed is contacted with the sixth catalyst at a temperature in a
range
from 310-400 C, from 320-370 C, or from 330-360 C, net hydrogen uptake by
the crude
feed may be in a range from -10 Nm3/m3 to 20 Nm3/m3, -7 Nm3/m3 to 10 Nm3/m3,
or -5
Nm3/m3 to 5 Nm3/m3. Negative net hydrogen uptake is one indication that
hydrogen is
being generated in situ. The crude product produced from contact of the crude
feed with
the sixth catalyst may have a TAN of at most 90%, at most 80%, at most 50%, at
most
10%, or at least 1% of the TAN of the crude feed. TAN of the crude product may
be in a
range from 0.01-0.1, 0.02-0.05, or 0.03-0.04.
Low net hydrogen uptake during contacting of the crude feed with the fourth,
fifth,
or sixth catalyst reduces the overall requirement of hydrogen during
processing while
producing a crude product that is acceptable for transportation and/or
treatment. Since
producing and/or transporting hydrogen is costly, minimizing the usage of
hydrogen in a
process decreases overall processing costs.
In certain embodiments, a seventh type of catalyst ("seventh catalyst") has a
total
content of Column 6 metal(s) in a range from 0.0001-0.06 grams of Column 6
metal(s) per
gram of catalyst. The Column 6 metal is molybdenum and/or tungsten. The
seventh
catalyst is beneficial in producing a crude product that has a TAN of at most
90% of the
TAN of the crude feed.
Other embodiments of the first, second, third, fourth, fifth, sixth, and
seventh
catalysts may also be made and/or used as is otherwise described herein.
Selecting the catalyst(s) of this application and controlling operating
conditions
may allow a crude product to be produced that has TAN and/or selected
properties
changed relative to the crude feed while other properties of the crude feed
are not
significantly changed. The resulting crude product may have enhanced
properties relative
to the crude feed and, thus, be more acceptable for transportation and/or
refining.
Arrangement of two or more catalysts in a selected sequence may control the
sequence of property improvements for the crude feed. For example, TAN, API
gravity, at
least a portion of the C5 asphaltenes, at least a portion of the iron, at
least a portion of the

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nickel, and/or at least a portion of the vanadium in the crude feed can be
reduced before at
least a portion of heteroatoms in the crude feed are reduced.
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.
Combinations of selected catalysts may allow reduction in at least a portion
of the
NiN/Fe, at least a portion of the C5 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, C5 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.
In some embodiments, the first catalyst (described above) may be positioned
upstream of a series of catalysts. Such positioning of the first catalyst may
allow removal
of high molecular weight contaminants, metal contaminants, and/or metals in
metal salts of
organic acids, while maintaining the stability of the crude feed/total product
mixture.
The first catalyst allows, in some embodiments, for removal of at least a
portion of
NiN/Fe, removal of acidic components, removal of components that contribute to
a
decrease in the life of other catalysts in the system, or combinations
thereof, from the
crude feed. For example, reducing at least a portion of C5 asphaltenes 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
NiN/Fe from the crude feed may, in some embodiments, increase a life of one or
more
catalysts positioned after the first catalyst.
The second catalyst(s) and/or the third catalyst(s) may be positioned
downstream of
the first catalyst. Further contact of the crude feed/total product mixture
with the second
catalyst(s) and/or third catalyst(s) may further reduce TAN, reduce the
content of NiN/Fe,

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reduce sulfur content, reduce oxygen content, and/or reduce the content of
metals in metal
salts of organic acids.
In some embodiments, contact of the crude feed with the second catalyst(s)
and/or
the third catalyst(s) may produce a crude feed/total product mixture that has
a reduced
TAN, a reduced sulfur content, a reduced oxygen content, a reduced content of
metals in
metal salts of organic acids, a reduced asphaltenes content, a reduced
viscosity, or
combinations thereof, relative to the respective properties of the crude feed
while
maintaining the stability of the crude feed/total product mixture during
processing. The
second catalyst may be positioned in series, either with the second catalyst
being upstream
of the third catalyst, or vice versa.
The ability to deliver hydrogen to specified contacting zones tends to
minimize
hydrogen usage during contacting. Combinations of catalysts that facility
generation of
hydrogen during contacting, and catalysts that uptake a relatively low amount
of hydrogen
during contacting, may be used to change selected properties of a crude
product relative to
the same properties of the crude feed. For example, the fourth catalyst may be
used in
combination with the first catalyst(s), second catalyst(s), third catalyst(s),
fifth catalyst(s),
sixth catalyst(s), and/or seventh catalyst(s) to change selected properties of
a crude feed,
= while only changing other properties of the crude feed by selected amounts,
and/or while
maintaining crude feed/total product stability. The order and/or number of
catalysts may
be selected to minimize net hydrogen uptake while maintaining the crude
feed/total
product stability. Minimal net hydrogen uptake allows residue content, VG0
content,
distillate content, API gravity, or combinations thereof of the crude feed to
be maintained
within 20% of the respective properties of the crude feed, while the TAN
and/or the
viscosity of the crude product is at most 90% of the TAN and/or the viscosity
of the crude
feed.
Reduction in net hydrogen uptake by the crude feed may produce a crude product

that has a boiling range distribution similar to the boiling point
distribution of the crude
feed, and a reduced TAN relative to the TAN of the crude feed. The atomic H/C
of the
crude product may also only change by relatively small amounts as compared to
the
atomic H/C of the crude feed.
Hydrogen generation in specific contacting zones may allow selective addition
of
hydrogen to other contacting zones and/or allow selective reduction of
properties of the
crude feed. In some embodiments, fourth catalyst(s) may be positioned
upstream,
downstream, or between additional catalyst(s) described herein. Hydrogen may
be

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generated during contacting of the crude feed with the fourth catalyst(s), and
hydrogen
may be delivered to the contacting zones that include the additional
catalyst(s). The
delivery of the hydrogen may be counter to the flow of the crude feed. In some

embodiments, the delivery of the hydrogen may be concurrent to the flow of the
crude
feed.For example, in a stacked configuration (see, for example, FIG. 2B),
hydrogen may
be generated during contacting in one contacting zone (for example, contacting
zone 102
in FIG. 2B), and hydrogen may be delivered to an additional contacting zone
(for example,
contacting zone 114 in FIG. 2B) in a direction that is counter to flow of the
crude feed. In
some embodiments, the hydrogen flow may be concurrent with the flow of the
crude feed.
Alternatively, in a stacked configuration (see, for example, FIG. 3B),
hydrogen may be
generated during contacting in one contacting zone (for example, contacting
zone 102 in
FIG. 3B). A hydrogen source may be delivered to a first additional contacting
zone in a
direction that is counter to flow of the crude feed (for example, adding
hydrogen through
conduit 106' to contacting zone 114 in FIG. 3B), and to a second additional
contacting
zone in a direction that is concurrent to the flow of the crude feed (for
example, adding
hydrogen through conduit 106' to contacting zone 116 in FIG. 3B).
In some embodiments, the fourth catalyst and the sixth catalyst are used in
series,
either with the fourth catalyst being upstream of the sixth catalyst, or vice
versa. The
combination of the fourth catalyst with an additional catalyst(s) may reduce
TAN, reduce
NiN/Fe content, and/or reduce a content of metals in metal salts of organic
acids, with low
net uptake of hydrogen by the crude feed. Low net hydrogen uptake may allow
other
properties of the crude product to be only changed by small amounts relative
to the same
properties of the crude feed.
In some embodiments, two different seventh catalysts may be used in
combination.
The seventh catalyst used upstream from the downstream seventh catalyst may
have a total
content of Column 6 metal(s), per gram of catalyst, in a range from 0.0001-
0.06 grams.
The downstream seventh catalyst may have a total content of Column 6
metals(s), per
gram of downstream seventh catalyst, that is equal to or larger than the total
content of
Column 6 metal(s) in the upstream seventh catalyst, or at least 0.02 grams of
Column 6
metal(s) per gram of catalyst. In some embodiments, the position of the
upstream seventh
catalyst and the downstream seventh catalyst may be reversed. The ability to
use a
relatively small amount of catalytic active metal in the downstream seventh
catalyst may
allow other properties of the crude product to be only changed by small
amounts relative to
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the same properties of the crude feed (for example, a relatively small change
in heteroatom
content, API gravity, residue content, VGO content, or combinations thereof).
Contact of the crude feed with the upstream and downstream seventh catalysts
may
produce a crude product that has a TAN of at most 90%, at most 80%, at most
50%, at
most 10%, or at least 1% of the TAN of the crude feed. In some embodiments,
the TAN
of the crude feed may be incrementally reduced by contact with the upstream
and
downstream seventh catalysts (for example, contact of the crude feed with a
catalyst to
form an initial crude product with changed properties relative to the crude
feed, and then
contact of the initial crude product with an additional catalyst to produce
the crude product
with changed properties relative to the initial crude product). The ability to
reduce TAN
incrementally may assist in maintaining the stability of the crude feed/total
product
mixture during processing.
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.
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, C5 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
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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.
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.
In some embodiments, contacting temperatures are controlled such that C5
asphaltenes and/or other asphaltenes are removed while maintaining the MCR
content of =
the crude feed. Reduction of the MCR content through hydrogen uptake and/or
higher
contacting temperatures may result in formation of two phases that may reduce
the
stability of the crude feed/total product mixture and/or life of one or more
of the catalysts.
Control of contacting temperature and hydrogen uptake in combination with the
catalysts
described herein allows the C5 asphaltenes to be reduced while the MCR content
of the
crude feed only changes by a relatively small amount.
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
100-420 C
and a second contacting temperature may be in a range that is 20-100 C, 30-90
C, or 40-
60 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 C5 asphaltenes content in a
crude product
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relative to the TAN and/or the C5 asphaltenes content of the crude feed to a
greater extent
than the amount of TAN and/or C5 asphaltene reduction, if any, when the first
and second
contacting temperatures are the same as or within 10 C of each other.
For example, a first contacting zone may include a first catalyst(s) and/or a
fourth
catalyst(s) and a second contacting zone may include other catalyst(s)
described herein.
The first contacting temperature may be 350 C and the second contacting
temperature
may be 300 C. Contact of the crude feed in the first contacting zone with the
first catalyst
and/or fourth catalyst at the higher temperature prior to contact with the
other catalyst(s) in
the second contacting zone may result in greater than TAN and/or C5
asphaltenes reduction
in the crude feed relative to the TAN and/or C5 asphaltenes reduction in the
same crude
feed when the first and second contacting temperatures are within 10 C.

EXAMPLES
Non-limiting examples of support preparation, catalyst preparations, and
systems
with selected arrangement of catalysts and controlled contacting conditions
are set forth
below.
Example 1. Preparation of a Catalyst Support. 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 TrilobeTm die plate, dried
between 90-
125 C, and then calcined at 918 C, which resulted in 650 grams of a calcined
support
with a median pore diameter of 182 A. The calcined support was placed in a
Lindberg
furnace. The furnace temperature was raised to 1000-1100 C over 1.5 hours,
and then
held in this range for 2 hours to produce the support. The support included,
per gram of
support, 0.0003 grams of gamma alumina, 0.0008 grams of alpha alumina, 0.0208
grams
of delta alumina, and 0.9781 grams of theta alumina, as determined by x-ray
diffraction.
The support had a surface area of 110 m2/g and a total pore volume of 0.821
cm3/g. The
support had a pore size distribution with a median pore diameter of 232 A,
with 66.7% of
the total number of pores in the pore size distribution having a pore diameter
within 85 A
of the median pore diameter.
This example demonstrates how to prepare a support that has a pore size
distribution of at least 180 A and includes at least 0.1 grams of theta
alumina.


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Example 2. Preparation of a Vanadium Catalyst Haying a Pore Size Distribution
With a Median Pore Diameter of At Least 230 A. The vanadium catalyst was
prepared
in the following manner. The alumina support, prepared by the method described
in
Example 1, was impregnated with a vanadium impregnation solution prepared by
combining 7.69 grams of VOSO4 with 82 grams of deionized water. A pH of the
solution
was 2.27.
The alumina support (100 g) was impregnated with the vanadium impregnation
solution, aged for 2 hours with occasional agitation, dried at 125 C for
several hours, and
then calcined at 480 C for 2 hours. The resulting catalyst contained 0.04
grams of
vanadium, per gram of catalyst, with the balance being support. The vanadium
catalyst
had a pore size distribution with a median pore diameter of 350 A, a pore
volume of 0.69
cm3/g, and a surface area of 110 m2/g. Additionally, 66.7% of the total number
of pores in
the pore size distribution of the vanadium catalyst had a pore diameter within
70 A of the
median pore diameter.
This example demonstrates the preparation of a Column 5 catalyst having a pore

size distribution with a median pore diameter of at least 230 A.
Example 3. Preparation of a Molybdenum Catalyst haying a Pore Size
Distribution
With a Median Pore Diameter of At Least 230 A. The molybdenum catalyst was
prepared in the following manner. The alumina support prepared by the method
described
in Example 1 was impregnated with a molybdenum impregnation solution. The
molybdenum impregnation solution was prepared by combining 4.26 grams of
(NH4)21\40207, 6.38 grams of Mo03, 1.12 grams of 30% H202, 0.27 grams of
monoethanolamine (MEA), and 6.51 grams of deionized water to form a slurry.
The slurry
was heated to 65 C until dissolution of the solids. The heated solution was
cooled to
room temperature. The pH of the solution was 5.36. The solution volume was
adjusted to
82 mL with deionized water.
The alumina support (100 grams) was impregnated with the molybdenum
impregnation solution, aged for 2 hours with occasional agitation, dried at
125 C for
several hours, and then calcined at 480 C for 2 hours. The resulting catalyst
contained
0.04 grams of molybdenum per gram of catalyst, with the balance being support.
The
molybdenum catalyst had a pore size distribution with a median pore diameter
of 250 A, a
pore volume of 0.77 cm3/g, and a surface area of 116 m2/g. Additionally, 67.7%
of the


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total number of pores in the pore size distribution of the molybdenum catalyst
had a pore
diameter within 86 A of the median pore diameter.
This example demonstrates the preparation of a Column 6 metal catalyst having
a
pore size distribution with a median pore diameter of at least 230 A.
Example 4. Preparation of a Molybdenum/Vanadium Catalyst haying a Pore Size
Distribution With a Median Pore Diameter of At Least 230 A. The
molybdenum/vanadium catalyst was prepared in the following manner. The alumina

support, prepared by the method described in Example 1, was impregnated with a

molybdenum/vanadium impregnation solution prepared as follows. A first
solution was
made by combining 2.14 grams of (NH4)2Mo207, 3.21 grams of Mo03, 0.56 grams of
30%
hydrogen peroxide (H202), 0.14 grams of monoethanolamine (MEA), and 3.28 grams
of
deionized water to form a slurry. The slurry was heated to 65 C until
dissolution of the
solids. The heated solution was cooled to room temperature.
A second solution was made by combining 3.57 grams of VOSO4 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 alumina was impregnated with
the
molybdenum/vanadium impregnation solution, aged for 2 hours with occasional
agitation,
dried at 125 C for several hours, and then calcined at 480 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. The molybdenum/vanadium catalyst
had a
pore size distribution with a median pore diameter of 300 A.
This example demonstrates the preparation of a Column 6 metal and a Column 5
metal catalyst having a pore size distribution with a median pore diameter of
at least 230
A.
Example 5. Contact of a Crude Feed With Three Catalysts. 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, CA). Such silicon carbide is
believed to have
low, if any, catalytic properties under the process conditions described
herein. All
catalysts were blended with an equal volume amount of silicon carbide before
placing the
mixture into the contacting zone portions of the reactor.

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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 (42 cm3) was
positioned on top
of the silicon carbide to form a bottom contacting zone. The bottom catalyst
had a pore
size distribution with a median pore diameter of 77 A, with 66.7% of the total
number of
pores in the pore size distribution having a pore diameter within 20 A of the
median pore
diameter. The bottom catalyst contained 0.095 grams of molybdenum and 0.025
grams of
nickel per gram of catalyst, with the balance being an alumina support.
A middle catalyst/silicone carbide mixture (56 cm3) was positioned on top of
the
bottom contacting zone to form a middle contacting zone. The middle catalyst
had a pore
size distribution with a median pore diameter of 98 A, with 66.7% of the total
number of
pores in the pore size distribution having a pore diameter within 24 A of the
median pore
diameter. The middle catalyst contained 0.02 grams of nickel and 0.08 grams of

molybdenum per gram of catalyst, with the balance being an alumina support.
A top catalyst/silicone carbide mixture (42 cm3) was positioned on top of the
middle contacting zone to form a top contacting zone. The top catalyst had a
pore size
distribution with a median pore diameter of 192 A and contained 0.04 grams of
molybdenum per gram of catalyst, with the balance being primarily a gamma
alumina
support.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 five heating zones corresponding to the preheat zone, the top,
middle, and bottom
contacting zones, and the bottom support.
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 1.5
liter of gaseous
mixture per volume (mL) of total catalyst (silicon carbide was not counted as
part of the
volume of catalyst). Temperatures of the contacting zones were increased to
204 C (400
F) over 1 hour and held at 204 C for 2 hours. After holding at 204 C, the
contacting
zones were increased incrementally to 316 C (600 F) at a rate of 10 C (50
F) per hour.
The contacting zones were maintained at 316 C for an hour, then incrementally
raised to
370 C (700 F) over 1 hour and held at 370 C for two hours. The contacting
zones were
allowed to cool to ambient temperature.
Crude from the Mars platform in the Gulf of Mexico was filtered, then heated
in an
oven at a temperature of 93 C (200 F) for 12-24 hours to form the crude feed
having the

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properties summarized in Table 1, FIG. 7. The crude feed was fed to the top of
the reactor.
The crude feed flowed through the preheat zone, top contacting zone, middle
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 328 Nm3/m3 (2000 SCFB), LHSV was 1 If% and pressure was 6.9 MPa (1014.7
psi).
The three contacting zones were heated to 370 C (700 F) and maintained at
370 C for
500 hours. Temperatures of the three contacting zones were then increased and
maintained
in the following sequence: 379 C (715 F) for 500 hours, and then 388 C (730
F) for 500
hours, then 390 C (734 F) for 1800 hours, and then 394 C (742 F) for 2400
hours.
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 measured by
a wet
test meter. The crude product was periodically analyzed to determine a weight
percentage
of components of the crude product. The results listed are averages of the
determined
weight percentages of components. Crude product properties are summarized in
Table 1
of FIG. 7.
As shown in Table 1, the crude product had, per gram of crude product, a
sulfur
content of 0.0075 grams, a residue content of 0.255 grams, an oxygen content
of 0.0007
grams. The crude product had a ratio of MCR content to C5 asphaltenes content
of 1.9 and
a TAN of 0.09. The total of nickel and vanadium was 22.4 wtppm.
The lives of the catalysts were determined by measuring a weighted average bed

temperature ("WABT") versus run length of the crude feed. The catalysts lives
may be
correlated to the temperature of the catalyst bed. It is believed that as
catalyst life
decreases, a WABT increases. FIG. 8 is a graphical representation of WABT
versus time
("t") for improvement of the crude feed in the contacting zones described in
this example.
Plot 136 represents the average WABT of the three contacting zones versus
hours of run
time for contacting a crude feed with the top, middle, and bottom catalysts.
Over a
majority of the run time, the WABT of the contacting zones only changed
approximately
20 C. From the relatively stable WABT, it was possible to estimate that the
catalytic
activity of the catalyst had not been affected. Typically, a pilot unit run
time of 3000-3500
hours correlates to 1 year of commercial operation.



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This example demonstrates that contacting the crude feed with one catalyst
having
a pore size distribution with a median pore diameter of at least 180 A and
additional
catalysts having a pore size distribution with a median pore diameter in a
range between
90-180 A, with at least 60% of the total number of pores in the pore size
distribution
having a pore diameter within 45 A of the median pore diameter, with
controlled
contacting conditions, produced a total product that included the crude
product. As
measured by P-value, crude feed/total product mixture stability was
maintained. The
crude product had reduced TAN, reduced NiN/Fe content, reduced sulfur content,
and
reduced oxygen content relative to the crude feed, while the residue content
and the VGO
content of the crude product was 90% -110% of those properties of the crude
feed.
Example 6. Contact of a Crude Feed With Two Catalysts That Have a Pore Size
Distribution with a Median Pore Diameter in a Range Between 90-180 A. The
reactor
apparatus (except for the number and content of contacting zones), catalyst
sulfiding
method, method of separating the total product and method of analyzing the
crude product
were the same as described in Example 5. Each catalyst was mixed with an equal
volume
of silicon carbide.
The crude feed flow to the reactor was from the top of the reactor to the
bottom of
the reactor. The reactor was filled from bottom to top in the following
manner. Silicon
carbide was positioned at the bottom of the reactor to serve as a bottom
support. A bottom
catalyst/silicon carbide mixture (80 cm3) was positioned on top of the silicon
carbide to
form a bottom contacting zone. The bottom catalyst had a pore size
distribution with a
median pore diameter of 127 A, with 66.7% of the total number pores in the
pore size
distribution having a pore diameter within 32 A of the median pore diameter.
The bottom
catalyst included 0.11 grams of molybdenum and 0.02 grams of nickel per gram
of
catalyst, with the balance being support.
A top catalyst/silicone carbide mixture (80 cm3) was positioned on top of the
bottom contacting zone to form the top contacting zone. The top catalyst had a
pore size
distribution with a median pore diameter of 100 A, with 66.7% of the total
number of
pores in the pore size distribution having a pore diameter within 20 A of the
median pore
diameter. The top catalyst included 0.03 grams of nickel and 0.12 grams of
molybdenum
per gram of catalyst, with the balance being alumina. Silicon carbide was
positioned on
top of the first 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 two contacting zones, and the bottom
support.
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BS-4 crude (Venezuela) having the properties summarized in Table 2, FIG. 9,
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.
The
contacting conditions were as follows: ratio of hydrogen gas to the crude feed
provided to
the reactor was 160 Nm3/m3 (1000 SCFB), LHSV was 1 h-1, and pressure was 6.9
MPa
(1014.7 psi). The two contacting zones were heated to 260 C (500 F) and
maintained at
260 C (500 F) for 287 hours. Temperatures of the two contacting zones were
then
increased and maintained in the following sequence: 270 C (525 1) for 190
hours, then
288 C (550 F) for 216 hours, then 315 C (600 F) for 360 hours, and then 343
C (650
F) for 120 hours for a total run time of 1173 hours.
The total product exited the reactor and was separated as described in Example
5.
The crude product had an average TAN of 0.42 and an average API gravity of
12.5 during
processing. The crude product had, per gram of crude product, 0.0023 grams of
sulfur,
0.0034 grams of oxygen, 0.441 grams of VG0, and 0.378 grams of residue.
Additional
properties of the crude product are listed in TABLE 2 in FIG. 9.
This example demonstrates that contacting the crude feed with the catalysts
having
pore size distributions with a median pore diameter in a range between 90-180
A produced
a crude product that had a reduced TAN, a reduced Ni/V/Fe content, and a
reduced oxygen
content, relative to the properties of the crude feed, while residue content
and VGO
content of the crude product were 99% and 100% of the respective properties of
the crude
feed.
Example 7. Contact of a Crude Feed With Two Catalysts. The reactor apparatus
(except for number and content of contacting zones), catalysts, the total
product separation
method, crude product analysis, and catalyst sulfiding method were the same as
described
in Example 6.
A crude feed (BC-10 crude) having the properties summarized in Table 3, FIG.
10,
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
contacting conditions were as follows: ratio of hydrogen gas to the crude feed
provided to
the reactor was 80 Nm3/m3 (500 SCFB), LHSV was 2 h-1, and pressure was 6.9 MPa

(1014.7 psi). The two contacting zones were heated incrementally to 343 C
(650 F). A
total run time was 1007 hours.



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The crude product had an average TAN of 0.16 and an average API gravity of
16.2
during processing. The crude product had 1.9 wtppm of calcium, 6 wtppm of
sodium, 0.6
wtppm of zinc, and 3 wtppm of potassium. The crude product had, per gram of
crude
product, 0.003 3 grams of sulfur, 0.002 grams of oxygen, 0.376 grams of VG0,
and 0.401
grams of residue. Additional properties of the crude product are listed in
Table 3 in FIG.
10.
This example demonstrates that contacting of the crude feed with the selected
catalysts with pore size distributions in a range of 90-180 A produced a crude
product that
had a reduced TAN, a reduced total calcium, sodium, zinc, and potassium
content while
sulfur content, VG0 content, and residue content of the crude product were
76%, 94%,
and 103% of the respective properties of the crude feed.
Examples 8-11. Contact of a Crude Feed With Four Catalyst Systems and At
Various Contacting Conditions. Each reactor apparatus (except for the number
and
content of contacting zones), each catalyst sulfiding method, each total
product separation
method, and each crude product analysis were the same as described in Example
5. All
catalysts were mixed with silicon carbide in a volume ratio of 2 parts silicon
carbide to 1
part catalyst unless otherwise indicated. The crude feed flow through each
reactor was
from the top of the reactor to the bottom of the reactor. Silicon carbide was
positioned at
the bottom of each reactor to serve as a bottom support. Each reactor had a
bottom
contacting zone and a top contacting zone. After the catalyst/silicone carbide
mixtures
were placed in the contacting zones of each reactor, silicone carbide was
positioned on top
of the top contacting zone to fill dead space and to serve as a preheat zone
in each reactor.
Each reactor was loaded into a Lindberg furnace that included four heating
zones
corresponding to the preheat zone, the two contacting zones, and the bottom
support.
In Example 8, an uncalcined molybdenum/nickel catalyst/silicon carbide mixture

(48 cm3) was positioned in the bottom contacting zone. The catalyst included,
per gram of
catalyst, 0.146 grams of molybdenum, 0.047 grams of nickel, and 0.021 grams of

phosphorus, with the balance being alumina support.
A molybdenum catalyst/silicon carbide mixture (12 cm3) with the catalyst
having a
pore size distribution with a median pore diameter of 180 A was positioned in
the top
contacting zone. The molybdenum catalyst had a total content of 0.04 grams of
molybdenum per gram of catalyst, with the balance being support that included
at least
0.50 grams of gamma alumina per gram of support.



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In Example 9, an uncalcined molybdenum/cobalt catalyst/silicon carbide mixture

(48 cm3) was positioned in the both contacting zones. The uncalcined
molybdenum/cobalt
catalyst included 0.143 grams of molybdenum, 0.043 grams of cobalt, and 0.021
grams of
phosphorus with the balance being alumina support.
A molybdenum catalyst/silicon carbide mixture (12 cm3) was positioned in the
top
contacting zone. The molybdenum catalyst was the same as in the top contacting
zone of
Example 8.
In Example 10, the molybdenum catalyst as described in the top contacting zone
of
Example 8 was mixed with silicon carbide and positioned in the both contacting
zones (60
cm3).
In Example 11, an uncalcined molybdenum/nickel catalyst/silicone carbide
mixture
(48 cm3) was positioned in the bottom contacting zone. The uncalcined
molybdenum/nickel catalyst included, per gram of catalyst, 0.09 grams of
molybdenum,
0.025 grams of nickel, and 0.01 grams of phosphorus, with the balance being
alumina
support_
A molybdenum catalyst/silicon carbide mixture (12 cm3) was positioned in the
top
contacting zone. The molybdenum catalyst was the same as in the top contacting
zone of
Example 8.
Crude from the Mars platform (Gulf of Mexico) was filtered, then heated in an
oven at a temperature of 93 C (200 F) for 12-24 hours to form the crude feed
for
Examples 8-11 having the properties summarized in Table 4, FIG. 11. The crude
feed was
fed to the top of the reactor in these examples. 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 for each example were as follows: ratio of hydrogen gas
to crude
feed during contacting was 160 Nm3/m3 (1000 SCFB), and the total pressure of
each
system was 6.9 MPa (1014.7 psi). LHSV was 2.0 If' during the first 200 hours
of
contacting, and then lowered to 1.0 for the remaining contacting times.
Temperatures
in all contacting zones were 343 C (650 F) for 500 hours of contacting.
After 500 hours,
the temperatures in all contacting zones were controlled as follows: the
temperature in the
contacting zones were raised to 354 C (670 F), held at 354 C for 200 hours;
raised to
366 C (690 F), held at 366 C for 200 hours; raised to 371 C (700 F), held
at 371 C for
1000 hours; raised to 385 C (725 C), held at 385 C for 200 hours; then
raised to a final



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temperature of 399 C (750 C) and held at 399 C for 200 hours, for a total
contacting
time of 2300 hours.
The crude products were periodically analyzed to determine TAN, hydrogen
uptake
by the crude feed, P-value, VG0 content, residue content, and oxygen content.
Average
values for properties of the crude products produced in Examples 8-11 are
listed in Table 5
in FIG. 11.
FIG. 12 is a graphical representation of P-value of the crude product ("P")
versus
run time ("t") for each of the catalyst systems of Examples 8-11. The crude
feed had a P-
value of at least 1.5. Plots 140, 142, 144, and 146 represent the P-value of
the crude
product obtained by contacting the crude feed with the four catalyst systems
of Examples
8-11 respectively. For 2300 hours, the P-value of the crude product remained
of at least
1.5 for catalyst systems of Examples 8-10. In Example 11, the P-value was
above 1.5 for
most of the run time. At the end of the run (2300 hours) for Example 11, the P-
value was
1.4. From the P-value of the crude product for each trial, it may be inferred
that the crude
feed in each trial remained relatively stable during contacting (for example,
the crude feed
. did not phase separate). As shown in FIG. 12, the P-value of the crude
product remained
relatively constant during significant portions of each trial, except in
Example 10, in which
the P-value increased.
FIG. 13 is a graphical representation of net hydrogen uptake by crude feed
("H2")
versus run time ("t") for four catalyst systems in the presence of hydrogen
gas. Plots 148,
150 152, 154 represent net hydrogen uptake obtained by contacting the crude
feed with
each of the catalyst systems of Examples 8-11, respectively. Net hydrogen
uptake by a
crude feed over a run time period of 2300 hours was in a range between 7-48
Nm3/m3
(43.8-300 SCFB). As shown in FIG. 13, the net hydrogen uptake of the crude
feed was
relatively constant during each trial.
FIG. 14 is a graphical representation of residue content, expressed in weight
percentage, of crude product ("R") versus run time ("t") for each of the
catalyst systems of
Examples 8-11. In each of the four trials, the crude product had a residue
content of 88-
90% of the residue content of the crude feed. Plots 156, 158, 160, 162
represent residue
content of the crude product obtained by contacting the crude feed with the
catalyst
systems of Examples 8-11, respectively. As shown in FIG. 14, the residue
content of the
crude product remained relatively constant during significant portions of each
trial.
FIG. 15 is a graphical representation of change in API gravity of the crude
product
("A API") versus run time ("t") for each of the catalyst systems of Examples 8-
11. Plots
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164, 166, 168, 170 represent API gravity of the crude product obtained by
contacting the
crude feed with the catalyst systems of Examples 8-11, respectively. In each
of the four
trials, each crude product had a viscosity in a range from 58.3-72.7 cSt. The
API gravity
of each crude products increased by 1.5 to 4.1 degrees. The increased API
gravity
corresponds to an API gravity of the crude products in a range from 21.7-
22.95. API
gravity in this range is 110-117% of the API gravity of the crude feed.
FIG. 16 is a graphical representation of oxygen content, expressed in weight
percentage, of the crude product ("02") versus run time ("t") for each of the
catalyst
systems of Examples 8-11. Plots 172, 174, 176, 178 represent oxygen content of
the crude
product obtained by contacting the crude feed with the catalyst systems of
Examples 8-11,
respectively. Each crude product had an oxygen content of at most 16% of the
crude feed.
Each crude product had an oxygen content in a range from 0.0014-0.0015 grams
per gram
of crude product during each trial. As shown in FIG. 16, the oxygen content of
the crude
product remained relatively constant after 200 hours of contacting time. The
relatively
constant oxygen content of the crude product demonstrates that selected
organic oxygen
compounds are reduced during the contacting. Since TAN was also reduced in
these
examples, it may be inferred that at least a portion of the carboxylic
containing organic
oxygen compounds are reduced selectively over the non-carboxylic containing
organic
oxygen compounds.
In Example 11, at reaction conditions of: 371 C (700 F), a pressure of 6.9
MPa
(1014.7 psi), and a ratio of hydrogen to crude feed of 160 Nm3/m3 (1000 SCFB),
the
reduction of crude feed MCR content was 17.5 wt%, based on the weight of the
crude
feed. At a temperature of 399 C (750 F), at the same pressure and ratio of
hydrogen to
crude feed, the reduction of crude feed MCR content was 25.4 wt%, based on the
weight
of the crude feed.
In Example 9, at reaction conditions of: 371 C (700 F), a pressure of 6.9
MPa
(1014.7 psi), and a ratio of hydrogen to crude feed of 160 Nm3/m3 (1000 SCFB),
the
reduction of crude feed MCR content was 17.5 wt%, based on the weight of the
crude
feed. At a temperature of 399 C (750 F), at the same pressure and ratio of
hydrogen to
crude feed, the reduction of crude feed MCR content was 19 wt%, based on the
weight of
the crude feed.
This increased reduction in crude feed MCR content demonstrates that the
uncalcined Columns 6 and 10 metals catalyst facilitates MCR content reduction
at higher
temperatures than the uncalcined Columns 6 and 9 metals catalyst.

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These examples demonstrate that contact of a crude feed with a relatively high

TAN (TAN of 0.8) with one or more catalysts produces the crude product, while
maintaining the crude feed/total product mixture stability and with relatively
small net
hydrogen uptake. Selected crude product properties were at most 70% of the
same
properties of the crude feed, while selected properties of the crude product
were within 20-
30% of the same properties of the crude feed.
Specifically, as shown in Table 4, each of the crude products was produced
with a
net hydrogen uptake by the crude feeds of at most 44 Nm3/m3 (275 SCFB). Such
products
had an average TAN of at most 4% of the crude feed, and an average total NiN
content of
at most 61% of the total NiN content of the crude feed, while maintaining a P-
value for
the crude feed of above 3. The average residue content of each crude product
was 88-90%
of the residue content of the crude feed. The average VGO content of each
crude product
was 115-117% of the VG0 content of the crude feed. The average API gravity of
each
crude product was 110-117% of the API gravity of the crude feed, while the
viscosity of
each crude product was at most 45% of the viscosity of the crude feed.
Examples 12-14: Contact ,of a Crude Feed With Catalysts Haying a Pore Size =
Distribution With a Median Pore Diameter of At Least 180 A With Minimal
Hydrogen Consumption. In Examples 12,14, each reactor apparatus (except for
number
and content of contacting zones), each catalyst sulfiding method, each total
product
separation method and each crude product analysis were the same as described
in Example
5. All catalysts were mixed with an equal volume of silicon carbide. The crude
feed flow
to each reactor was from the top of the reactor to the bottom of the reactor.
Silicon carbide
was positioned at the bottom of each reactor to serve as a bottom support.
Each reactor
contained one contacting zone. After the catalyst/silicone carbide mixtures
were placed in
the contacting zone of each reactor, silicone carbide was positioned on top of
the top
contacting zone to fill dead space and to serve as a preheat zone in each
reactor. Each
reactor was loaded into a Lindberg furnace that included three heating zones
corresponding
to the preheat zone, the contacting zone, and the bottom support. The crude
feed was
contacted with each of the catalysts in the presence of hydrogen gas.
A catalyst/silicon carbide mixture (40 cm3) was positioned on top of the
silicon
carbide to form the contacting zone. For Example 12, the catalyst was the
vanadium
catalyst as prepared in Example 2. For Example 13, the catalyst was the
molybdenum
catalyst as prepared in Example 3. For Example 14, the catalyst was the
molybdenum/vanadium catalyst as prepared in Example 4.


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The contacting conditions for Examples 12-14 were as follows: ratio of
hydrogen
to the crude feed provided to the reactor was 160 Nm3/m3 (1000 SCFB), LHSV was
1 If',
and pressure was 6.9 MPa (1014.7 psi). The contacting zones were heated
incrementally
to 343 C (650 F) over a period of time and maintained at 343 C for 120
hours for a total
run time of 360 hours.
Total products exited the contacting zones and were separated as described in
Example 5. Net hydrogen uptake during contacting was determined for each
catalyst
system. In Example 12, net hydrogen uptake was -10.7 Nm3/m3 (-65 SCFB), and
the crude
product had a TAN of 6.75. In Example 13, net hydrogen uptake was in a range
from 2.2-
3.0 Nm3/m3 (13.9-18.7 SCFB), and the crude product had a TAN in a range from
0.3-0.5.
In Example 14, during contacting of the crude feed with the
molybdenum/vanadium
catalyst, net hydrogen uptake was in a range from -0.05 Nm3/m3 to 0.6 Nm3/m3 (-
0.36
SCFB to 4.0 SCFB), and the crude product had a TAN in a range from 0.2-0.5.
From the net hydrogen uptake values during contacting, it was estimated that
hydrogen was generated at the rate of 10.7 Nm3/m3 (65 SCFB) during contacting
of the
crude feed and the vanadium catalyst. Generation of hydrogen during contacting
allows ,1
= less hydrogen to be used in the process relative to an amount of
hydrogen used in
conventional processes to improve properties of disadvantaged crudes. The
requirement
for less hydrogen during contacting tends to decrease the costs of processing
a crude.
Additionally, contact of the crude feed with the molybdenum/vanadium catalyst
produced a crude product with a TAN that was lower than the TAN of the crude
product
produced from the individual molybdenum catalyst.
Examples 15-18. Contact of a Crude Feed With a Vanadium Catalyst and an
Additional Catalyst. Each reactor apparatus (except for number and content of
contacting
zones), each catalyst sulfiding method, each total product separation method,
and each
crude product analysis were the same as described in Example 5. All catalysts
were mixed
with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part
catalyst unless
otherwise indicated. The crude feed. flow to each reactor was from the top of
the reactor to
the bottom of the reactor. Silicon carbide was positioned at the bottom of
each reactor to
serve as a bottom support. Each reactor had a bottom contacting zone and a top
contacting
zone. After the catalyst/silicone carbide mixtures were placed in the
contacting zones of
each reactor, silicone carbide was positioned on top of the top contacting
zone to fill dead
space and to serve as a preheat zone in each reactor. Each reactor was loaded
into a


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Lindberg furnace that included four heating zones corresponding to the preheat
zone, the
two contacting zones, and the bottom support.
In each example, the vanadium catalyst was prepared as described in Example 2
and used with the additional catalyst.
In Example 15, an additional catalyst/silicon carbide mixture (45 cm3) was
positioned in the bottom contacting zone, with the additional catalyst being
the
molybdenum catalyst prepared by the method described in Example 3. The
vanadium
catalyst/silicone carbide mixture (15 cm3) was positioned in the top
contacting zone.
In Example 16, an additional catalyst/silicon carbide mixture (30 cm3) was
positioned in the bottom contacting zone, with the additional catalyst being
the
molybdenum catalyst prepared by the method described in Example 3. The
vanadium
catalyst/silicon carbide mixture (30 cm3) was positioned in the top contacting
zone.
In Example 17, an additional catalyst/silicone mixture (30 cm3) was positioned
in
the bottom contacting zone, with the additional catalyst being the
molybdenum/vanadium
catalyst as prepared in Example 4. The vanadium catalyst/silicon carbide
mixture (30 cm3)
was positioned in the top contacting zone.
In Example 18, Pyrex 41) (Glass Works Corporation, New York, U.S.A.) beads (30

cm3) were positioned in each contacting zone.
Crude (Santos Basin, Brazil) for Examples 15-18 having the properties
summarized
in Table 5, FIG. 17 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 for each example were as follows: ratio of
hydrogen
gas to the crude feed provided to the reactor was 160 Nm3/m3 (1000 SCFB) for
the first 86
hours and 80 Nm3/m3 (500 SCFB) for the remaining time period, LHSV was 111-1,
and
pressure was 6.9 MPa (1014.7 psi). The contacting zones were heated
incrementally to
343 C (650 F) over a period of time and maintained at 343 C for a total run
time of 1400
hours.
These examples demonstrate that contact of a crude feed with a Column 5 metal
catalyst having a pore size distribution with a median pore diameter of 350 A
in
combination with an additional catalyst having a pore size distribution with a
median pore
diameter in a range from 250-300 A, in the presence of a hydrogen source,
produces a
crude product with properties that are changed relative to the same properties
of crude
feed, while only changing by small amounts other properties of the crude
product relative
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to the same properties of the crude feed. Additionally, during processing,
relatively small
hydrogen uptake by the crude feed was observed.
Specifically, as shown in Table 5, FIG_ 17, the crude product has a TAN of at
most
15% of the TAN of the crude feed for Examples 15-17. The crude products
produced in
Examples 15-17 each had a total NiN/Fe content of at most 44%, an oxygen
content of at
most 50%, and viscosity of at most 75% relative to the same properties of the
crude feed.
Additionally, the crude products produced in Examples 15-17 each had an API
gravity of
100-103% of the API gravity of the crude feed.
In contrast, the crude product produced under non-catalytic conditions
(Example
18) produced a product with increased viscosity and decreased API gravity
relative to the
viscosity and API gravity of the crude feed. From the increased viscosity and
decreased
API gravity, it may be possible to infer that coking and/or polymerization of
the crude feed
was initiated.
Examples 19. Contact of a Crude Feed at Various LHSV. The contacting systems
and
the catalysts were the same as described in Example 6. The properties of the
crude feeds
are listed in Table 6 in FIG. 18. The contacting conditions were as follows: a
ratio of
hydrogen gas to the crude feed provided to the reactor was 160 Nm3/m3 (1000
SCFB),
pressure was 6.9 MPa (1014.7 psi), and temperature of the contacting zones was
371 C '
(700 F) for the total run time. In Example 19, the LHSV during contacting was
increased
over a period of time from 1 h-1 to 12 h-1, maintained at 12h-1 for 48 hours,
and then the
LHSV was increased to 20.7 h-1 and maintained at 20.711-1 for 96 hours.
In Example 19, the crude product was analyzed to determine TAN, viscosity,
density, VGO content, residue content, hetero atoms content, and content of
metals in metal
salts of organic acids during the time periods that the LHSV was at 12 h-1 and
at 20.7 h-1.
Average values for the properties of the crude products are shown in Table 6,
FIG. 18.
As shown in Table 6, FIG. 18, the crude product for Example 19 had a reduced
TAN and a reduced viscosity relative to the TAN and the viscosity of the crude
feed, while
the API gravity of the crude product was 104-110% of the API gravity of the
crude feed.
A weight ratio of MCR content to C5 asphaltenes content was at least 1.5. The
sum of the
MCR content and C5 asphaltenes content was reduced relative to the sum of the
MCR
content and C5 asphaltenes content of the crude feed. From the weight ratio of
MCR
content to C5 asphaltenes content and the reduced sum of the MCR content and
the C5
asphaltenes, it may be inferred that asphaltenes rather than components that
have a
tendency to form coke are being reduced. The crude product also had total
content of

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potassium, sodium, zinc, and calcium of at most 60% of the total content of
the same
metals of the crude feed. The sulfur content of the crude product was 80-90%
of the sulfur
content of the crude feed.
Examples 6 and 19 demonstrate that contacting conditions can be controlled
such
that a LHSV through the contacting zone is greater than 10h-1, as compared to
a process
that has a LHSV of 1 h-1, to produce crude products with similar properties.
The ability to
selectively change a property of a crude feed at liquid hourly space
velocities greater than
h-1 allows the contacting process to be performed in vessels of reduced size
relative to
commercially available vessels. A smaller vessel size may allow the treatment
of
10 disadvantaged crudes to be performed at production sites that have size
constraints (for
example, offshore facilities).
Example 20. Contact of a Crude Feed at Various Contacting Temperatures. The
contacting systems and the catalysts were the same as described in Example 6.
The crude
feed having the properties listed in Table 7 in FIG. 19 was added to the top
of the reactor
and contacted with the two catalysts in the two contacting zones in the
presence of
hydrogen to produce a crude product. The two contacting zones were operated at
different
temperatures.
Contacting conditions in the top contacting zone were as follows: LHSV was I
11-1; ,
temperature in the top contacting zone was 260 C (500 F); a ratio of hydrogen
to crude
feed was 160 Nm3/m3 (1000 SCFB); and pressure was 6.9 MPa (1014.7 psi).
Contacting conditions in the bottom contacting zone were as follows: LHSV was
1
h-1; temperature in the bottom contacting zone was 315 C (600 F); a ratio of
hydrogen to
crude feed was 160 Nm3/m3 (1000 SCFB); and pressure was 6.9 MPa (1014.7 psi).
The total product exited the bottom contacting zone and was introduced into
the
gas-liquid phase separator. In the gas-liquid phase separator, the total
product was
separated into the crude product and gas. The crude product was periodically
analyzed to
determine TAN and C5 asphaltenes content.
Average values for the properties of crude product obtained during the run are
listed in Table 7, FIG. 19. The crude feed had a TAN of 9.3 and a C5
asphaltenes content
of 0.055 grams of C5 asphaltenes per gram of crude feed. The crude product had
an
average TAN of 0.7 and an average C5 asphaltenes content of 0.039 grams of C5
asphaltenes per gram of crude product. The C5 asphaltenes content of the crude
product
was at most 71% of the C5 asphaltenes content of the crude product.

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The total content of potassium and sodium in the crude product was at most 53%
of
the total content of the same metals in the crude feed. The TAN of the crude
product was
at most 10% of the TAN of the crude feed. A P-value of 1.5 or higher was
maintained
during contacting.
As demonstrated in Examples 6 and 20, having a first (in this case, top)
contacting
temperature that is 50 C lower than the contacting temperature of the second
(in this case,
bottom) zone tends to enhance the reduction of C5 asphaltenes content in the
crude product
relative to the C5 asphaltenes content of the crude feed.
Additionally, reduction of the content of metals in metal salts of organic
acids was
enhanced using controlled temperature differentials. For example, reduction in
the total
potassium and sodium content of the crude product from Example 20 was enhanced

relative to the reduction of the total potassium and sodium content of the
crude product
from Example 6 with a relatively constant crude feed/total product mixture
stability for
each example, as measured by P-value.
Using a lower temperature of a first contacting zone allows removal of the
high
molecular weight compounds (for example, C5 asphaltenes and/or metals salts of
organic
acids) that have a tendency to form polymers and/or compounds having physical
properties
of softness and/or stickiness (for example, gums and/or tars). Removal of
these
compounds at lower temperature allow such compounds to be removed before they
plug
and coat the catalysts, thereby increasing the life of the catalysts operating
at higher
temperatures that are positioned after the first contacting zone.
Example 21. Contact of a Crude Feed and a Catalyst as a Slurry. A bulk metal
catalyst and/or a catalyst of the application (0.0001-5 grams or 0.02-4 grams
of catalyst per
100 grams of the crude feed) may, in some embodiments, be slurried with the
crude feed
and reacted under the following conditions: temperature in a range from 85-425
C (185-
797 F), pressure in a range from 0.5-10 MPa, and ratio of hydrogen source to
crude feed
of 16-1600 Nm3/m3 for a period of time. After sufficient reaction time to
produce the
crude product, the crude product is separated from the catalyst and/or
residual crude feed
using a separation apparatus, such as a filter and/or centrifuge. The crude
product may
have a changed TAN, iron, nickel, and/or vanadium content and a reduced C5
asphaltenes
content relative to the crude feed.
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
81

= CA 02549088 2012-03-06

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.



82

A single figure which represents the drawing illustrating the invention.

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Admin Status

Title Date
Forecasted Issue Date 2013-06-04
(86) PCT Filing Date 2004-12-16
(87) PCT Publication Date 2005-07-14
(85) National Entry 2006-06-09
Examination Requested 2009-11-26
(45) Issued 2013-06-04

Abandonment History

There is no abandonment history.

Maintenance Fee

Description Date Amount
Last Payment 2019-11-20 $450.00
Next Payment if small entity fee 2020-12-16 $225.00
Next Payment if standard fee 2020-12-16 $450.00

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Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Filing $400.00 2006-06-09
Maintenance Fee - Application - New Act 2 2006-12-18 $100.00 2006-06-09
Registration of Documents $100.00 2006-09-15
Maintenance Fee - Application - New Act 3 2007-12-17 $100.00 2007-11-02
Maintenance Fee - Application - New Act 4 2008-12-16 $100.00 2008-11-21
Maintenance Fee - Application - New Act 5 2009-12-16 $200.00 2009-11-09
Request for Examination $800.00 2009-11-26
Maintenance Fee - Application - New Act 6 2010-12-16 $200.00 2010-09-28
Maintenance Fee - Application - New Act 7 2011-12-16 $200.00 2011-11-08
Maintenance Fee - Application - New Act 8 2012-12-17 $200.00 2012-10-10
Final Fee $312.00 2013-03-19
Maintenance Fee - Patent - New Act 9 2013-12-16 $200.00 2013-11-13
Maintenance Fee - Patent - New Act 10 2014-12-16 $250.00 2014-11-26
Maintenance Fee - Patent - New Act 11 2015-12-16 $250.00 2015-11-25
Maintenance Fee - Patent - New Act 12 2016-12-16 $250.00 2016-11-23
Maintenance Fee - Patent - New Act 13 2017-12-18 $250.00 2017-11-22
Maintenance Fee - Patent - New Act 14 2018-12-17 $250.00 2018-11-21
Maintenance Fee - Patent - New Act 15 2019-12-16 $450.00 2019-11-20
Current owners on record shown in alphabetical order.
Current Owners on Record
SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Past owners on record shown in alphabetical order.
Past Owners on Record
BHAN, OPINDER KISHAN
WELLINGTON, SCOTT LEE
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.

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Abstract 2006-06-09 1 54
Claims 2006-06-09 3 162
Drawings 2006-06-09 17 373
Description 2006-06-09 82 5,565
Representative Drawing 2006-06-09 1 2
Cover Page 2006-08-23 1 32
Claims 2006-06-10 3 142
Description 2012-03-06 82 5,574
Claims 2012-03-06 3 121
Representative Drawing 2013-05-14 1 3
Cover Page 2013-05-14 1 33
PCT 2006-06-10 14 559
Assignment 2006-09-15 2 67
PCT 2006-06-09 5 146
Assignment 2006-06-09 4 142
Correspondence 2006-08-18 1 28
Correspondence 2006-10-19 1 23
Assignment 2006-12-19 2 61
Prosecution-Amendment 2009-11-26 2 67
Prosecution-Amendment 2009-11-26 9 263
Prosecution-Amendment 2011-09-09 4 181
Prosecution-Amendment 2012-03-06 18 987
Correspondence 2013-03-19 2 64