U.S. patent application number 11/425985 was filed with the patent office on 2007-01-04 for method and catalyst for producing a crude product having selected properties.
Invention is credited to Opinder Kishan Bhan, Scott Lee Wellington.
Application Number | 20070000808 11/425985 |
Document ID | / |
Family ID | 34753547 |
Filed Date | 2007-01-04 |
United States Patent
Application |
20070000808 |
Kind Code |
A1 |
Bhan; Opinder Kishan ; et
al. |
January 4, 2007 |
METHOD AND CATALYST FOR PRODUCING A CRUDE PRODUCT HAVING SELECTED
PROPERTIES
Abstract
A catalyst that one or more metals from Columns 6-10 of the
Periodic Table and/or one or more compounds of one or more metals
from Columns 6-10 of the Periodic Table is described. The catalyst
exhibits one or more bands in a range from 800 cm.sup.-1 to 900
cm.sup.-1, as determined by Raman Spectroscopy. Methods of
contacting a crude feed with hydrogen with the catalyst to produce
a crude product having selected properties are also described.
Inventors: |
Bhan; Opinder Kishan; (Katy,
TX) ; Wellington; Scott Lee; (Bellaire, TX) |
Correspondence
Address: |
SHELL OIL COMPANY
P O BOX 2463
HOUSTON
TX
772522463
US
|
Family ID: |
34753547 |
Appl. No.: |
11/425985 |
Filed: |
June 22, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11014335 |
Dec 16, 2004 |
|
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|
11425985 |
Jun 22, 2006 |
|
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60531506 |
Dec 19, 2003 |
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60618681 |
Oct 14, 2004 |
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Current U.S.
Class: |
208/58 |
Current CPC
Class: |
C10G 2300/107 20130101;
C10G 47/02 20130101; C10G 2300/1033 20130101; C10G 47/04 20130101;
C10G 45/04 20130101; C10G 47/14 20130101; C10G 47/26 20130101; C10G
11/08 20130101; C10G 45/16 20130101; C10G 2300/301 20130101; C10G
2300/302 20130101; C10G 47/12 20130101; C10G 11/04 20130101; C10G
45/08 20130101; C10G 45/10 20130101; C10G 29/06 20130101; C10G
11/02 20130101; C10G 2300/304 20130101; C10G 69/00 20130101 |
Class at
Publication: |
208/058 |
International
Class: |
C10G 69/00 20060101
C10G069/00 |
Claims
1. A catalyst composition, comprising one or more metals from
Columns 6-10 of the Periodic Table and/or one or more compounds of
one or more metals from Columns 6-10 of the Periodic Table, wherein
the catalyst exhibits one or more bands in a range from 800
cm.sup.-1 to 900 cm.sup.-1, as determined by Raman
Spectroscopy.
2. The catalyst of claim 1, wherein the catalyst has a pore size
distribution with a median pore diameter of at least 180 .ANG..
3. The catalyst of claim 1, wherein the catalyst has a pore size
distribution with a median pore diameter of at least 230 .ANG..
4. The catalyst of claim 1, wherein at least one of the Column 6-10
metals is molybdenum.
5. The catalyst of claim 1, wherein at least one of the bands is
near 810 cm.sup.-1.
6. The catalyst of claim 1, wherein at least one of the bands is
near 835 cm.sup.-1.
7. The catalyst of claim 1, wherein at least one of the bands is
near 880 cm.sup.-1.
8. The catalyst of claim 1, wherein the catalyst is a supported
catalyst, and wherein the support comprises alumina, silica,
silica-alumina, titanium oxide, zirconium oxide, magnesium oxide,
or mixtures thereof.
9. The catalyst of claim 1, wherein the catalyst is a supported
catalyst, and wherein the support comprises theta alumina, wherein
a content of the theta alumina is at least 0.5 grams per gram of
total catalyst.
10. The catalyst of claim 1, further comprising one or more
elements or one or more compounds of one or more elements from
Column 15 of the Periodic Table.
11. A method of producing a crude product, comprising: contacting a
crude feed with one or more catalysts to produce a total product
that includes the crude product, wherein the crude product is a
liquid mixture at 25.degree. C. and 0.101 MPa, the crude feed
having a residue content at least 0.1 grams of residue per gram of
crude feed, at least one of the catalysts exhibits one or more
bands between 800 cm.sup.-1 to 900 cm.sup.-1, as determined by
Raman Spectroscopy, and the catalyst exhibiting the bands
comprising one or more metals from Columns 6-10 of the Periodic
Table and/or one or more compounds of one or more metals from
Columns 6-10 of the Periodic Table; and controlling contacting
conditions such that the crude product has a residue content of at
most 90% of the residue content of the crude feed, wherein residue
content is as determined by ASTM Method D5307.
12. The method of claim 11, wherein the residue content of the
crude feed is at most 50% of the residue content of the crude
feed.
13. The method of claim 11, wherein the crude product has a residue
content ranging from about 0.00001 grams to about 0.3 grams per
gram of crude product.
14. The method of claim 11, wherein the crude product has a residue
content ranging from about 0.0001 grams to about 0.2 grams per gram
of crude product.
15. The method of claim 11, wherein one of the bands exhibited by
the catalyst is near 810 cm.sup.-1.
16. The method of claim 11, wherein one of the bands exhibited by
the catalyst is near 835 cm.sup.-1.
17. The method of claim 11, wherein one of the bands exhibited by
the catalyst is near 880 cm.sup.-1.
18. The method of claim 11, wherein the catalyst is a supported
catalyst, and wherein the support comprises alumina, silica,
silica-alumina, titanium oxide, zirconium oxide, magnesium oxide,
or mixtures thereof.
19. A method of producing a crude product, comprising: contacting a
crude feed with one or more catalysts to produce a total product
that includes the crude product, wherein the crude product is a
liquid mixture at 25.degree. C. and 0.101 MPa, the crude feed
having a TAN of at least 0.1, at least one of the catalysts
exhibits one or more bands between 800 cm.sup.-1 to 900 cm.sup.-1,
as determined by Raman Spectroscopy, and the catalyst exhibiting
the bands comprising one or more metals from Columns 6-10 of the
Periodic Table and/or one or more compounds of one or more metals
from Columns 6-10 of the Periodic Table; and 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
D664.
20. The method of claim 19, wherein the TAN of the crude feed is at
least 1.
21. The method of claim 19, wherein the crude product has a TAN
ranging from 0.001 to about 0.5.
22. The method of claim 19, wherein the crude product has a TAN
ranging from 0.005 to about 1.
23. The method of claim 19, wherein one of the bands exhibited by
the catalyst is near 810 cm.sup.-1.
24. The method of claim 19, wherein one of the bands exhibited by
the catalyst is near 835 cm.sup.-1.
25. The method of claim 19, wherein one of the bands exhibited by
the catalyst is near 880 cm.sup.-1.
26. The method of claim 19, wherein the catalyst is a supported
catalyst, and wherein the support comprises alumina, silica,
silica-alumina, titanium oxide, zirconium oxide, magnesium oxide,
or mixtures thereof.
27. The method of claim 19, wherein the crude feed has, per gram of
crude feed, a total content of alkali metal and alkaline-earth
metal in metal salts of organic acids of at least 0.00001 grams and
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.
28. The method of claim 27, wherein one or more of the metals is
calcium, potassium, sodium, magnesium, lithium, or combinations
thereof.
29. The method of claim 19, wherein the crude feed has a content of
Columns 5-12 metals in metal salts of organic acids, and the crude
product has a content of Columns 5-12 metals in metal salts of
organic acids of at most 90% of the content of Columns 5-12 metals
in metal salts of organic acids of the crude feed.
30. The method of claim 29, wherein one or more of the metals is
vanadium, molybdenum, chromium, iron, nickel, zinc, or combinations
thereof.
31. The method of claim 19, wherein the crude feed comprises
silicon, and the crude product has a content of silicon of at most
90% of the content of the silicon of the crude feed.
32. The method of claim 19, wherein the crude feed has a viscosity
of at least 10 cSt at 37.8.degree. C. (100.degree. F.) and the
contacting conditions are controlled such that the crude product
has a viscosity at 37.8.degree. C. of at most 90% of the viscosity
of the crude feed at 37.8.degree. C.
Description
PRIORITY
[0001] This application claims priority to U.S. patent application
Ser. No. 11/014,335 entitled "SYSTEMS, METHODS, AND CATALYSTS FOR
PRODUCING A CRUDE PRODUCT" filed on Dec. 16, 2004 which claims
priority to U.S. Provisional Patent Application No. 60/531,506
filed on Dec. 19, 2003 and to U.S. Provisional Patent Application
No. 60/618,681 filed on Oct. 14, 2004
FIELD OF THE INVENTION
[0002] 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.degree. C. and 0.101 MPa and has one
or more properties that are changed relative to the respective
property of the crude feed.
DESCRIPTION OF RELATED ART
[0003] Crudes that have one or more unsuitable properties that do
not allow the crudes to be economically transported, or processed
using conventional facilities, are commonly referred to as
"disadvantaged crudes".
[0004] Disadvantaged crudes may include acidic components that
contribute to the total acid number ("TAN") of the crude feed.
Disadvantaged crudes with a relatively high TAN may contribute to
corrosion of metal components during transporting and/or processing
of the disadvantaged crudes. Removal of acidic components from
disadvantaged crudes may involve chemically neutralizing acidic
components with various bases. Alternately, corrosion-resistant
metals may be used in transportation equipment and/or processing
equipment. The use of corrosion-resistant metal often involves
significant expense, and thus, the use of corrosion-resistant metal
in existing equipment may not be desirable. Another method to
inhibit corrosion may involve addition of corrosion inhibitors to
disadvantaged crudes before transporting and/or processing of the
disadvantaged crudes. The use of corrosion inhibitors may
negatively affect equipment used to process the crudes and/or the
quality of products produced from the crudes.
[0005] Disadvantaged crudes often contain relatively high levels of
residue. Such high levels of residue tend to be difficult and
expensive to transport and/or process using conventional
facilities.
[0006] Disadvantaged crudes often contain organically bound
heteroatoms (for example, sulfur, oxygen, and nitrogen).
Organically bound heteroatoms may, in some situations, have an
adverse effect on catalysts.
[0007] Disadvantaged crudes may include relatively high amounts of
metal contaminants, for example, nickel, vanadium, and/or iron.
During processing of such crudes, metal contaminants and/or
compounds of metal contaminants, may deposit on a surface of the
catalyst or in the void volume of the catalyst. Such deposits may
cause a decline in the activity of the catalyst.
[0008] 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.
[0009] 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.
[0010] 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.
[0011] Disadvantaged crudes may include organic oxygen compounds.
Treatment facilities that process disadvantaged crudes with an
oxygen content of at least 0.002 grams of oxygen per gram of
disadvantaged crude may encounter problems during processing.
Organic oxygen compounds, when heated during processing, may form
higher oxidation compounds (for example, ketones and/or acids
formed by oxidation of alcohols, and/or acids formed by oxidation
of ethers) that are difficult to remove from the treated crude
and/or may corrode/contaminate equipment during processing and
cause plugging in transportation lines.
[0012] Disadvantaged crudes may include hydrogen deficient
hydrocarbons. When processing 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 from forming coke.
Hydrogen is costly to produce and/or costly to transport to
treatment facilities.
[0013] Disadvantaged crudes also tend to exhibit instability during
processing in conventional facilities. Crude instability tends to
result in phase separation of components during processing and/or
formation of undesirable by-products (for example, hydrogen
sulfide, water, and carbon dioxide).
[0014] Conventional processes 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.
[0015] Some processes for improving the quality of crude include
adding a diluent to disadvantaged crudes to lower the weight
percent of components contributing to the disadvantaged properties.
Adding diluent, however, generally increases costs of treating
disadvantaged crudes due to the costs of diluent and/or increased
costs to handle the disadvantaged crudes. Addition of diluent to a
disadvantaged crude may, in some situations, decrease stability of
such crude.
[0016] U.S. Pat. No. 6,547,957 to Sudhakar et al.; U.S. Pat. No.
6,277,269 to Meyers et al.; U.S. Pat. No. 6,063,266 to Grande et
al.; U.S. Pat. No. 5,928,502 to Bearden et al.; U.S. Pat. No.
5,914,030 to Bearden et al.; U.S. Pat. No. 5,897,769 to Trachte et
al.; U.S. Pat. No. 5,871,636 to Trachte et al.; and U.S. Pat. No.
5,851,381 to Tanaka et al.; U.S. Published Patent Application Nos.
20050133414 through 20050133418 to Bhan et al.; 20050139518 through
20050139522 to Bhan et al.; 20050145543 to Bhan et al.; 20050150818
to Bhan et al.; 20050155908 to Bhan et al.; 20050167320 to Bhan et
al.; 20050167324 through 20050167332 to Bhan et al.; 20050173301
through 20050173303 to Bhan et al., 20060060510 to Bhan; and U.S.
patent application Ser. Nos. 11/400,542; 11/400,294; 11/399,843;
11/400,628; and 11/400,295, all entitled "Systems, Methods, and
Catalysts for Producing a Crude Product" and all filed Apr. 7,
2006, all of which are incorporated herein by reference, describe
various processes, systems, and catalysts for processing
crudes.
[0017] In sum, disadvantaged crudes generally have undesirable
properties (for example, relatively high TAN, a tendency to become
unstable during treatment, and/or a tendency to consume relatively
large amounts of hydrogen during treatment). 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 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
[0018] Inventions described herein generally relate to systems,
methods, and catalyst 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.
[0019] In some embodiments, the invention describes a method of
producing a crude product, comprising contacting a crude feed with
one or more catalysts for at least 500 hours at a liquid hourly
space velocity (LHSV) of at least 1 h.sup.-1 to produce a total
product that includes the crude product, wherein the one or more
catalysts are not replaced during treatment of the crude feed, and
wherein the crude product is a liquid mixture at 25.degree. C. and
0.101 MPa, and at least one of the catalysts has a pore size
distribution with a median pore diameter of at least 180 .ANG., as
determined by ASTM Method D4282, 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
wherein the TAN of the crude product remains at most 30% of the TAN
of the crude feed during contact of the crude feed with one or more
catalysts, wherein TAN is as determined by ASTM Method D664.
[0020] In some embodiments, the invention describes a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed having a total acid
number (TAN) of at least 0.1, at least one of the catalysts having
a pore size distribution with a median pore diameter of at least
180 .ANG., as determined by ASTM Method D4282, 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 TAN of at most 30% of the TAN of the crude feed after
500 hours of continuous use at a liquid hourly space velocity
(LHSV) of at least 1 h.sup.-1 of the one or more catalysts.
[0021] In some embodiments, the invention describes a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed having a total acid
number (TAN) of at least 1, at least one of the catalysts having a
pore size distribution with a median pore diameter of at least 180
.ANG., as determined by ASTM Method D4282, 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 TAN from about 0.001 to about 0.5 after 500 hours of
continuous use at a liquid hourly space velocity (LHSV) of at least
1 h.sup.-1 of the one or more catalysts, wherein TAN is as
determined by ASTM Method D664.
[0022] In some embodiments, the invention describes a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed having a total acid
number (TAN) of at least 0.1, at least one of the catalysts having
a pore size distribution with a median pore diameter of at least
180 .ANG., as determined by ASTM Method D4282, 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 of: a total hydrogen
partial pressure of at most 3.5 MPa, a temperature above
360.degree. C., and a liquid hourly space velocity (LHSV) of at
least 1 h.sup.-1; wherein the one or more catalysts are capable of
producing crude product with a TAN of at most 30% of the TAN of the
crude feed after at least 500 hours of continuous use of the one or
more catalysts.
[0023] In some embodiments, the invention describes a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed having a TAN of at
least 1, at least one of the catalysts comprising one or more
metals from Columns 6-10 of the Periodic Table and/or one or more
compounds of one or more metals from Columns 6-10 of the Periodic
Table; and controlling contacting conditions such that the crude
product has a TAN from about 0.001 to about 0.5, wherein TAN is as
determined by ASTM D664.
[0024] In some embodiments, the invention describes a catalyst
composition comprising one or more metals from Column 5 of the
Periodic Table and/or one or more compounds of one or more metals
from Column 5 of the Periodic Table, wherein the catalyst exhibits
one or more bands in a range from 650 cm.sup.-1 to 1000 cm.sup.-1,
as determined by Raman Spectroscopy.
[0025] In some embodiments, the invention describes a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, at least one of the catalysts exhibits
one or more bands in a range from 650 cm.sup.-1 to 1000 cm.sup.-1,
as determined by Raman Spectroscopy, and the catalyst exhibiting
the bands comprising one or more metals from Column 5 of the
Periodic Table and/or one or more compounds of one or more metals
from Column 5 of the Periodic Table; and controlling contacting
conditions such that an atomic hydrogen/carbon (H/C) of the crude
product is between 80% and 120% of the atomic H/C of the crude
feed.
[0026] In some embodiments, the invention describes a catalyst
composition, comprising one or more metals from Columns 6-10 of the
Periodic Table and/or one or more compounds of one or more metals
from Columns 6-10 of the Periodic Table, wherein the catalyst
exhibits one or more bands in a range between 800 cm.sup.-1 to 900
cm.sup.-1, as determined by Raman Spectroscopy.
[0027] In some embodiments, the invention describes a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed having a residue
content at least 0.1 grams of residue per gram of crude feed, at
least one of the catalysts exhibits one or more bands between 800
cm.sup.-1 to 900 cm.sup.-1, as determined by Raman Spectroscopy,
and the catalyst exhibiting the bands comprising one or more metals
from Columns 6-10 of the Periodic Table and/or one or more
compounds of one or more metals from Columns 6-10 of the Periodic
Table; and controlling contacting conditions such that the crude
product has a residue content of at most 90% of the residue content
of the crude feed, wherein residue content is as determined by ASTM
Method D5307.
[0028] In some embodiments, the invention describes a method of
producing a crude product, comprising: contacting a crude feed with
one or more catalysts to produce a total product that includes the
crude product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed having a TAN of at
least 0.1, at least one of the catalysts exhibits one or more bands
between 800 cm.sup.-1 to 900 cm.sup.-1, as determined by Raman
Spectroscopy, and the catalyst exhibiting the bands comprising one
or more metals from Columns 6-10 of the Periodic Table and/or one
or more compounds of one or more metals from Columns 6-10 of the
Periodic Table; and controlling contacting conditions such that the
crude product has a TAN of at most 90% of the TAN of the crude
feed.
[0029] In further embodiments, features from specific embodiments
may be combined with features from other embodiments. For example,
features from one embodiment may be combined with features from any
of the other embodiments.
[0030] In further embodiments, crude products are obtainable by any
of the methods and systems described herein.
[0031] In further embodiments, additional features may be added to
the specific embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] 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:
[0033] FIG. 1 is a schematic of an embodiment of a contacting
system.
[0034] FIGS. 2A and 2B are schematics of embodiments of contacting
systems that include two contacting zones.
[0035] FIGS. 3A and 3B are schematics of embodiments of contacting
systems that include three contacting zones.
[0036] FIG. 4 is a schematic of an embodiment of a separation zone
in combination with a contacting system.
[0037] FIG. 5 is a schematic of an embodiment of a blending zone in
combination with a contacting system.
[0038] FIG. 6 is a schematic of an embodiment of a combination of a
separation zone, a contacting system, and a blending zone.
[0039] FIG. 7 depicts a Raman spectrum of a vanadium catalyst and
various molybdenum catalysts.
[0040] FIG. 8 is a tabulation of representative properties of crude
feed and crude product for an embodiment of contacting the crude
feed with three catalysts.
[0041] FIG. 9 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.
[0042] FIG. 10 is a tabulation of representative properties of
crude feed and crude product for an embodiment of contacting the
crude feed with two catalysts.
[0043] FIG. 11 is another tabulation of representative properties
of crude feed and crude product for an embodiment of contacting the
crude feed with two catalysts.
[0044] FIG. 12 is a tabulation of crude feed and crude products for
embodiments of contacting crude feeds with four different catalyst
systems.
[0045] FIG. 13 is a graphical representation of P-value of crude
products versus run time for embodiments of contacting crude feeds
with four different catalyst systems.
[0046] FIG. 14 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.
[0047] FIG. 15 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.
[0048] FIG. 16 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.
[0049] FIG. 17 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.
[0050] FIG. 18 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
that include a vanadium catalyst and a molybdenum/vanadium
catalyst, and with glass beads.
[0051] FIG. 19 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.
[0052] FIG. 20 is a tabulation of properties of crude feeds and
crude products for embodiments of contacting crude feeds at various
contacting temperatures.
[0053] FIG. 21 is a tabulation of crude feed and crude products for
embodiments of contacting a crude feed for greater than 500
hours.
[0054] FIG. 22 is a tabulation of crude feed and crude products for
embodiments of contacting a crude feed with a molybdenum
catalyst.
[0055] 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
[0056] Certain embodiments of the inventions are described herein
in more detail. Terms used herein are defined as follows.
[0057] "ASTM" refers to American Standard Testing and
Materials.
[0058] "API gravity" refers to API gravity at 15.5.degree. C.
(60.degree. F.). API gravity is as determined by ASTM Method
D6822.
[0059] Atomic hydrogen percentage and atomic carbon percentage of
the crude feed and the crude product are as determined by ASTM
Method D5291.
[0060] 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.
[0061] "C.sub.5 asphaltenes" refers to asphaltenes that are
insoluble in n-pentane. C.sub.5 asphaltenes content is as
determined by ASTM Method D2007.
[0062] "C.sub.7 asphaltenes" refers to asphaltenes that are
insoluble in n-heptane. C.sub.7 asphaltenes content is as
determined by ASTM Method D3279.
[0063] "Column X metal(s)" refers to one or more metals of Column X
of the Periodic Table and/or one or more compounds of one or more
metals of Column X of the Periodic Table, in which X corresponds to
a column number (for example, 1-12) of the Periodic Table. For
example, "Column 6 metal(s)" refers to one or more metals from
Column 6 of the Periodic Table and/or one or more compounds of one
or more metals from Column 6 of the Periodic Table.
[0064] "Column X element(s)" refers to one or more elements of
Column X of the Periodic Table, and/or one or more compounds of one
or more elements of Column X of the Periodic Table, in which X
corresponds to a column number (for example, 13-18) of the Periodic
Table. For example, "Column 15 element(s)" refers to one or more
elements from Column 15 of the Periodic Table and/or one or more
compounds of one or more elements from Column 15 of the Periodic
Table.
[0065] In the scope of this application, weight of a metal from the
Periodic Table, weight of a compound of a metal from the Periodic
Table, weight of an element from the Periodic Table, or weight of a
compound of an element from the Periodic Table is calculated as the
weight of metal or the weight of element. For example, if 0.1 grams
of MoO.sub.3 is used per gram of catalyst, the calculated weight of
the molybdenum metal in the catalyst is 0.067 grams per gram of
catalyst.
[0066] "Content" refers to the weight of a component in a substrate
(for example, a crude feed, a total product, or a crude product)
expressed as weight fraction or weight percentage based on the
total weight of the substrate. "Wtppm" refers to parts per million
by weight.
[0067] "Crude feed/total product mixture" refers to the mixture
that contacts the catalyst during processing.
[0068] "Distillate" refers to hydrocarbons with a boiling range
distribution between 204.degree. C. (400.degree. F.) and
343.degree. C. (650.degree. F.) at 0.101 MPa. Distillate content is
as determined by ASTM Method D5307.
[0069] "Heteroatoms" refers to oxygen, nitrogen, and/or sulfur
contained in the molecular structure of a hydrocarbon. Heteroatoms
content is as determined by ASTM Methods E385 for oxygen, D5762 for
total nitrogen, and D4294 for sulfur. "Total basic nitrogen" refers
to nitrogen compounds that have a pKa of less than 40. Basic
nitrogen ("bn") is as determined by ASTM Method D2896.
[0070] "Hydrogen source" refers to hydrogen, and/or a compound
and/or compounds that when in the presence of a crude feed and 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, C.sub.1 to C.sub.4 hydrocarbons such as
methane, ethane, propane, butane), water, or mixtures thereof. A
mass balance may be conducted to assess the net amount of hydrogen
provided to the compound(s) in the crude feed.
[0071] "Flat plate crush strength" refers to compressive force
needed to crush a catalyst. Flat plate crush strength is as
determined by ASTM Method D4179.
[0072] "LHSV" refers to a volumetric liquid feed rate per total
volume of catalyst, and is expressed in hours (h.sup.-1). Total
volume of catalyst is calculated by summation of all catalyst
volumes in the contacting zones, as described herein.
[0073] "Liquid mixture" refers to a composition that includes one
or more compounds that are liquid at standard temperature and
pressure (25.degree. C., 0.101 MPa, hereinafter referred to as
"STP"), or a composition that includes a combination of one of more
compounds that are liquid at STP with one or more compounds that
are solids at STP.
[0074] "Periodic Table" refers to the Periodic Table as specified
by the International Union of Pure and Applied Chemistry (IUPAC),
November 2003.
[0075] "Metals in metal salts of organic acids" refer to alkali
metals, alkaline-earth metals, zinc, arsenic, chromium, or
combinations thereof. A content of metals in metal salts of organic
acids is as determined by ASTM Method D1318.
[0076] "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.
[0077] "Naphtha" refers to hydrocarbon components with a boiling
range distribution between 38.degree. C. (100.degree. F.) and
200.degree. C. (392.degree. F.) at 0.101 MPa. Naphtha content is as
determined by ASTM Method D5307.
[0078] "Ni/V/Fe" refers to nickel, vanadium, iron, or combinations
thereof.
[0079] "Ni/V/Fe content" refers to the content of nickel, vanadium,
iron, or combinations thereof. The Ni/V/Fe content is as determined
by ASTM Method D5708.
[0080] "Nm.sup.3/m.sup.3" refers to normal cubic meters of gas per
cubic meter of crude feed.
[0081] "Non-carboxylic containing organic oxygen compounds" refers
to organic oxygen compounds that do not have a carboxylic
(--CO.sub.2--) group. Non-carboxylic containing organic oxygen
compounds include, but are not limited to, ethers, cyclic ethers,
alcohols, aromatic alcohols, ketones, aldehydes, or combinations
thereof, which do not have a carboxylic group.
[0082] "Non-condensable gas" refers to components and/or mixtures
of components that are gases at STP.
[0083] "P (peptization) value" or "P-value" refers to a numeral
value, which represents the flocculation tendency of asphaltenes in
the crude feed. Determination of the P-value is described by J. J.
Heithaus in "Measurement and Significance of Asphaltene
Peptization", Journal of Institute of Petroleum, Vol. 48, Number
458, February 1962, pp. 45-53.
[0084] "Pore diameter", "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.degree.). A micromeritics.RTM. A9220 instrument
(Micromeritics Inc., Norcross, Ga., U.S.A.) may be used to
determine these values.
[0085] "Residue" refers to components that have a boiling range
distribution above 538.degree. C. (1000.degree. F.), as determined
by ASTM Method D5307.
[0086] "Sediment" refers to impurities and/or coke that are
insoluble in the crude feed/total product mixture. Sediment is as
determined by the Shell Hot Filtration Test ("SHFST") as described
by Van Kemoort et al. in the Journal of Institute of Petroleum,
1951, pages 596-604.
[0087] "SCFB" refers to standard cubic feet of gas per barrel of
crude feed.
[0088] "Surface area" of a catalyst is as determined by ASTM Method
D3663.
[0089] "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.
[0090] "VGO" refers to hydrocarbons with a boiling range
distribution between 343.degree. C. (650.degree. F.) and
538.degree. C. (1000.degree. F.) at 0.101 MPa. VGO content is as
determined by ASTM Method D5307.
[0091] "Viscosity" refers to kinematic viscosity at 37.8.degree. C.
(100.degree. F.). Viscosity is as determined using ASTM Method
D445.
[0092] All referenced methods are incorporated herein by reference.
In the context of this application, it is to be understood that if
the value obtained for a property of the substrate tested is
outside of limits of the test method, the test method may be
modified and/or recalibrated to test for such property.
[0093] Crudes may be produced and/or retorted from hydrocarbon
containing formations and then stabilized. Crudes are generally
solid, semi-solid, and/or liquid. Crudes may include crude oil.
Stabilization may include, but is not limited to, removal of
non-condensable gases, water, salts, 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.
[0094] 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, VGO, and/or lubricating oils). Distillation
includes, but is not limited to, atmospheric distillation methods
and/or vacuum distillation methods. Undistilled and/or
unfractionated stabilized crudes may include components that have a
carbon number above 4 in quantities of at least 0.5 grams of
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 35.degree. C. at 0.101 MPa (about
95.degree. F. at 1 atm) have been removed. Typically, topped crudes
will have a content of at most 0.1 grams, at most 0.05 grams, or at
most 0.02 grams of such components per gram of the topped
crude.
[0095] 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.
[0096] Properties of disadvantaged crudes may include, but are not
limited to: a) TAN of at least 0.1, at least 0.3; or at least 1 b)
viscosity of at least 10 cSt; c) API gravity at most 19; d) a total
Ni/V/Fe content of at least 0.00002 grams or at least 0.0001 grams
of Ni/V/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
C.sub.5 asphaltenes content of at least 0.04 grams of C.sub.5
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 about 0.1 or 0.3 to about 20, about 0.3 or 0.5 to about 10, or
about 0.4 or 0.5 to about 5. In certain embodiments, disadvantaged
crudes, per gram of disadvantaged crude, may have a sulfur content
of at least 0.005, at least 0.01, or at least 0.02 grams.
[0097] In some embodiments, disadvantaged crudes have properties
including, but not limited to: a) TAN of at least 0.5 or at least
1; b) an oxygen content of at least 0.005 grams of oxygen per gram
of crude feed; c) a C.sub.5 asphaltenes content of at least 0.04
grams of C.sub.5 asphaltenes per gram of crude feed; d) a higher
than desired viscosity (for example, >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.
[0098] Disadvantaged crudes may include, per gram of disadvantaged
crude: at least 0.001 grams, at least 0.005 grams, or at least 0.01
grams of hydrocarbons with a boiling range distribution between
about 95.degree. C. and about 200.degree. C. at 0.101 MPa; at least
0.01 grams, at least 0.005 grams, or at least 0.001 grams of
hydrocarbons with a boiling range distribution between about
200.degree. C. and about 300.degree. C. at 0.101 MPa; at least
0.001 grams, at least 0.005 grams, or at least 0.01 grams of
hydrocarbons with a boiling range distribution between about
300.degree. C. and about 400.degree. C. at 0.101 MPa; and at least
0.001 grams, at least 0.005 grams, or at least 0.01 grams of
hydrocarbons with a boiling range distribution between about
400.degree. C. and 650.degree. C. at 0.101 MPa.
[0099] Disadvantaged crudes may include, per gram of disadvantaged
crude: at least 0.001 grams, at least 0.005 grams, or at least 0.01
grams of hydrocarbons with a boiling range distribution of at most
100.degree. C. at 0.101 MPa; at least 0.001 grams, at least 0.005
grams, or at least 0.01 grams of hydrocarbons with a boiling range
distribution between about 100.degree. C. and about 200.degree. C.
at 0.101 MPa; at least 0.001 grams, at least 0.005 grams, or at
least 0.01 grams of hydrocarbons with a boiling range distribution
between about 200.degree. C. and about 300.degree. C. at 0.101 MPa;
at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams
of hydrocarbons with a boiling range distribution between about
300.degree. C. and about 400.degree. C. at 0.101 MPa; and at least
0.001 grams, at least 0.005 grams, or at least 0.01 grams of
hydrocarbons with a boiling range distribution between about
400.degree. C. and 650.degree. C. at 0.101 MPa.
[0100] Some disadvantaged crudes may include, per gram of
disadvantaged crude, at least 0.001 grams, at least 0.005 grams, or
at least 0.01 grams of hydrocarbons with a boiling range
distribution of at most 100.degree. C. at 0.101 MPa, in addition to
higher boiling components. Typically, the disadvantaged crude has,
per gram of disadvantaged crude, a content of such hydrocarbons of
at most 0.2 grams or at most 0.1 grams.
[0101] 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.degree. C. at 0.101 MPa.
[0102] Some disadvantaged crudes may include, per gram of
disadvantaged crude, at least 0.001 grams, at least 0.005 grams, or
at least 0.01 grams of hydrocarbons with a boiling range
distribution of at least 650.degree. C.
[0103] 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.
[0104] Treatment of disadvantaged crudes may enhance the properties
of the disadvantaged crudes such that the crudes are acceptable for
transportation and/or treatment.
[0105] 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 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.
[0106] Treatment of a crude feed in accordance with inventions
described herein may include contacting the crude feed with the
catalyst(s) in a contacting zone and/or combinations of two or more
contacting zones. In a contacting zone, at least one property of a
crude feed may be changed by contact of the crude feed with one or
more catalysts relative to the same property of the crude feed. In
some embodiments, contacting is performed in the presence of a
hydrogen source. In some embodiments, the hydrogen source is one or
more hydrocarbons that under certain contacting conditions react to
provide relatively small amounts of hydrogen to compound(s) in the
crude feed.
[0107] FIG. 1 is a schematic of contacting system 100 that includes
an upstream contacting zone 102. The crude feed enters upstream
contacting zone 102 via crude feed conduit 104. A contacting zone
may be a reactor, a portion of a reactor, multiple portions of a
reactor, or combinations thereof. Examples of a contacting zone
include a stacked bed reactor, a fixed bed reactor, an ebullating
bed reactor, a continuously stirred tank reactor ("CSTR"), a
fluidized bed reactor, a spray reactor, and a liquid/liquid
contactor. In certain embodiments, the contacting system is on or
coupled to an offshore facility. Contact of the crude feed with the
catalyst(s) in contacting system 100 may be a continuous process or
a batch process.
[0108] The contacting zone may include one or more catalysts (for
example, two catalysts). In some embodiments, contact of the crude
feed with a first catalyst of the two catalysts may reduce 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.
[0109] In certain embodiments, a volume of catalyst in the
contacting zone is in a range from about 10-60 vol %, about 20-50
vol %, or about 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 include from about 0.001-10 grams, about 0.005-5
grams, or about 0.01-3 grams of catalyst per 100 grams of crude
feed in the contacting zone.
[0110] Contacting conditions in the contacting zone may include,
but are not limited to, temperature, pressure, hydrogen source
flow, crude feed flow, or combinations thereof. Contacting
conditions in some embodiments are controlled to produce a crude
product with specific properties. Temperature in the contacting
zone may range from about 50-500.degree. C., about 60-440.degree.
C., about 70-430.degree. C., or about 80-420.degree. C. LHSV of the
crude feed will generally range from about 0.1-30 h.sup.-1, about
0.5-25 h.sup.-1, about 1-20 h.sup.-1, about 1.5-15 h.sup.-1, or
about 2-10 h.sup.-1. In some embodiments, LHSV is at least 5
h.sup.-1, at least 11 h.sup.-1, at least 15 h.sup.-1, or at least
20 h.sup.-1. A total hydrogen partial pressure in the contacting
zone may range from about 0.1-8 MPa, about 1-7 MPa, about 2-6 MPa,
or about 3-5 MPa. In some embodiments, a total partial pressure of
hydrogen may be at most 7 MPa, at most 6 MPa, at most 5 MPa, at
most 4 MPa, at most 3 MPa, or at most 3.5 MPa, or at most 2
MPa.
[0111] In embodiments in which the hydrogen source is supplied as a
gas (for example, hydrogen gas), a ratio of the gaseous hydrogen
source to the crude feed typically ranges from about 0.1-100,000
Nm.sup.3/m.sup.3, about 0.5-10,000 Nm.sup.3/m.sup.3, about 1-8,000
Nm.sup.3/m.sup.3, about 2-5,000 Nm.sup.3/m.sup.3, about 5-3,000
Nm.sup.3/m.sup.3, or about 10-800 Nm.sup.3/m.sup.3 contacted with
the catalyst(s). The hydrogen source, in some embodiments, is
combined with carrier gas(es) and recirculated through the
contacting zone. Carrier gas may be, for example, nitrogen, helium,
and/or argon. The carrier gas may facilitate flow of the crude feed
and/or flow of the hydrogen source in the contacting 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.
[0112] The hydrogen source may enter upstream contacting zone 102
co-currently with the crude feed in crude feed conduit 104 or
separately via gas conduit 106. In upstream contacting zone 102,
contact of the crude feed with a catalyst produces a total product
that includes a crude product, and, in some embodiments, gas. In
some embodiments, a carrier gas is combined with the crude feed
and/or the hydrogen source in conduit 106. The total product may
exit upstream contacting zone 102 and enter downstream separation
zone 108 via total product conduit 110.
[0113] In downstream separation zone 108, the crude product and gas
may be separated from the total product using generally known
separation techniques, for example, gas-liquid separation. The
crude product may exit downstream separation zone 108 via crude
product conduit 112, and then be transported to transportation
carriers, pipelines, storage vessels, refineries, other processing
zones, or a combination thereof. The gas may include gas formed
during processing (for example, hydrogen sulfide, carbon dioxide,
and/or carbon monoxide), excess gaseous hydrogen source, and/or
carrier gas. The excess gas may be recycled to contacting system
100, purified, transported to other processing zones, storage
vessels, or combinations thereof.
[0114] In some embodiments, contacting the crude feed with the
catalyst(s) to produce a total product is performed in two or more
contacting zones. The total product may be separated to form the
crude product and gas(es).
[0115] FIGS. 2-3 are schematics of embodiments of contacting system
100 that includes two or three contacting zones. In FIGS. 2A and
2B, contacting system 100 includes upstream contacting zone 102 and
downstream contacting zone 114. FIGS. 3A and 3B include contacting
zones 102, 114, 116. In FIGS. 2A and 3A, contacting zones 102, 114,
116 are depicted as separate contacting zones in one reactor. The
crude feed enters upstream contacting zone 102 via crude feed
conduit 104.
[0116] In some embodiments, the carrier gas is combined with the
hydrogen source in gas conduit 106 and is introduced into the
contacting zones as a mixture. In certain embodiments, as shown in
FIGS. 3A and 3B, the hydrogen source and/or the carrier gas may
enter the one or more contacting zones with the crude feed
separately via gas conduit 106 and/or in a direction counter to the
flow of the crude feed via, for example, gas conduit 106'. Addition
of the hydrogen source and/or the carrier gas counter to the flow
of the crude feed may enhance mixing and/or contact of the crude
feed with the catalyst.
[0117] Contact of the crude feed with catalyst(s) in upstream
contacting zone 102 forms a feed stream. The feed stream flows from
upstream contacting zone 102 to downstream contacting zone 114. In
FIGS. 3A and 3B, the feed stream flows from downstream contacting
zone 114 to additional downstream contacting zone 116.
[0118] Contacting zones 102, 114, 116 may include one or more
catalysts. As shown in FIG. 2B, the feed stream exits upstream
contacting zone 102 via feed stream conduit 118 and enters
downstream contacting zone 114. As shown in FIG. 3B, the feed
stream exits downstream contacting zone 114 via conduit 118 and
enters additional downstream contacting zone 116.
[0119] The feed stream may be contacted with additional catalyst(s)
in downstream contacting zone 114 and/or additional downstream
contacting zone 116 to form the total product. The total product
exits downstream contacting zone 114 and/or additional downstream
contacting zone 116 and enters downstream separation zone 108 via
total product conduit 110. The crude product and/or gas is (are)
separated from the total product. The crude product exits
downstream separation zone 108 via crude product conduit 112.
[0120] FIG. 4 is a schematic of an embodiment of a separation zone
upstream of contacting system 100. The disadvantaged crude (either
topped or untopped) enters upstream separation zone 120 via crude
conduit 122. In upstream separation zone 120, at least a portion of
the disadvantaged crude is separated using techniques known in the
art (for example, sparging, membrane separation, pressure
reduction) 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.degree. C. or below 100.degree. C. may be at 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 upstream separation zone 120 via conduit 124.
[0121] The crude feed obtained from upstream separation zone 120,
in some embodiments, includes a mixture of components with a
boiling range distribution of at least 100.degree. C. or, in some
embodiments, a boiling range distribution of at least 120.degree.
C. Typically, the separated crude feed includes a mixture of
components with a boiling range distribution between about
100-1000.degree. C., about 120-900.degree. C., or about
200-800.degree. C. At least a portion of the crude feed exits
upstream separation zone 120 and enters contacting system 100 (see,
for example, the contacting zones in FIGS. 1-3) via additional
crude feed conduit 126 to be further processed to form a crude
product. In some embodiments, upstream separation zone 120 may be
positioned upstream or downstream of a desalting unit. After
processing, the crude product exits contacting system 100 via crude
product conduit 112.
[0122] In some embodiments, the crude product is blended with a
crude that is the same as or different from the crude feed. For
example, the crude product may be combined with a crude having a
different viscosity thereby resulting in a blended product having a
viscosity that is between the viscosity of the crude product and
the viscosity of the crude. In another example, the crude product
may be blended with crude having a TAN 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.
[0123] As shown in FIG. 5, in certain embodiments, crude feed
enters contacting system 100 via crude feed conduit 104, and at
least a portion of the crude product exits contacting system 100
via conduit 128 and is introduced into blending zone 130. In
blending zone 130, at least a portion of the crude product is
combined with one or more process streams (for example, a
hydrocarbon stream such as naphtha produced from separation of one
or more crude feeds), a crude, a crude feed, or mixtures thereof,
to produce a blended product. The process streams, crude feed,
crude, or mixtures thereof are introduced directly into blending
zone 130 or upstream of such blending zone via stream conduit 132.
A mixing system may be located in or near blending zone 130. The
blended product may meet product specifications designated by
refineries and/or transportation carriers. Product specifications
include, but are not limited to, a range of or a limit of API
gravity, TAN, viscosity, or combinations thereof. The blended
product exits blending zone 130 via blend conduit 134 to be
transported or processed.
[0124] In FIG. 6, the disadvantaged crude enters upstream
separation zone 120 through crude conduit 122, and the
disadvantaged crude is separated as previously described to form
the crude feed. The crude feed then enters contacting system 100
through additional crude feed conduit 126. At least some components
from the disadvantaged crude exit separation zone 120 via conduit
124. At least a portion of the crude product exits contacting
system 100 and enters blending zone 130 through crude product
conduit 128. Other process streams and/or crudes enter blending
zone 130 directly or via stream conduit 132 and are combined with
the crude product to form a blended product. The blended product
exits blending zone 130 via blend conduit 134.
[0125] In some embodiments, the crude product and/or the blended
product are transported to a refinery and distilled and/or
fractionally distilled to produce one or more distillate fractions.
The distillate fractions may be processed to produce commercial
products such as transportation fuel, lubricants, or chemicals.
[0126] In some embodiments, after contact of the crude feed with
the catalyst, the crude product has a TAN of at most 90%, at most
50%, or at most 10% of the TAN of the crude feed. In certain
embodiments, the crude product has a TAN of at most 1, at most 0.5,
at most 0.3, at most 0.2, at most 0.1, or at most 0.05. TAN of the
crude product will frequently be at least 0.0001 and, more
frequently, at least 0.001. In some embodiments, TAN of the crude
product may be in a range from about 0.001 to about 0.5, about 0.01
to about 0.2, or about 0.05 to about 0.1. In some embodiments, TAN
of the crude product may range from about 0.001 to about 0.5, 0.004
to about 0.4, from about 0.01 to about 0.3, or from about 0.1 to
about 0.2.
[0127] 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. In certain
embodiments, the crude product has, per gram of crude product a
total Ni/V/Fe content in a range from about 1.times.10.sup.-7 grams
to about 5.times.10.sup.-5 grams, about 3.times.10.sup.-7 grams to
about 2.times.10.sup.-5 grams, or about 1.times.10.sup.-6 grams to
about 1.times.10.sup.-5 grams. In certain embodiments, the crude
product has at most 2.times.10.sup.-5 grams of Ni/V/Fe. In some
embodiments, a total Ni/V/Fe content of the crude product is about
70-130%, about 80-120%, or about 90-110% of the Ni/V/Fe content of
the crude feed.
[0128] In some embodiments, the crude product has a total content
of metals in metal salts of organic acids of at most 90%, at most
50%, at most 10%, or at most 5% 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.
[0129] 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 about 0.0000001 grams to about
0.00005 grams, about 0.0000003 grams to about 0.00002 grams, or
about 0.000001 grams to about 0.00001 grams of metals in metal salt
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 about 70-130%, about 80-120%, or about 90-110% of
the total content of metals in metal salts of organic acids in the
crude feed.
[0130] In certain embodiments, API gravity of the crude product
produced from contact of the crude feed with catalyst, at the
contacting conditions, is about 70-130%, about 80-120%, about
90-110%, or about 100-130% of the API gravity of the crude feed. In
certain embodiments, API gravity of the crude product is from about
14-40, about 15-30, or about 16-25.
[0131] 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 viscosity of the crude product
is at most 90% of the viscosity of the crude feed while the API
gravity of the crude product is about 70-130%, about 80-120%, or
about 90-110% of the API gravity the crude feed.
[0132] 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.
[0133] 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 product. In certain embodiments, the
crude product has a sulfur content of at least 1%, at least 30%, at
least 80%, or at least 99% of the sulfur content of the crude feed.
In some embodiments, the sulfur content of the crude product is
about 70-130%, about 80-120%, or about 90-110% of the sulfur
content of the crude feed.
[0134] 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.
[0135] 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.
[0136] 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 a 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 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.
[0137] 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).
[0138] 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 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.
[0139] 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 about 70-130%, about 80-120%, or about 90-110% of the
non-carboxylic containing organic oxygen compounds of the crude
feed.
[0140] In some embodiments, the crude product includes, in its
molecular structures, from about 0.05-0.15 grams or from about
0.09-0.13 grams of hydrogen per gram of crude product. The crude
product may include, in its molecular structure, from about 0.8-0.9
grams or from about 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 about 70-130%, about 80-120%, or about
90-110% of the atomic H/C ratio of the crude feed. A crude product
atomic H/C ratio within about 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.
[0141] The crude product includes components with a range of
boiling points. In some embodiments, the crude product includes,
per gram of the crude product: at least 0.001 grams, or from about
0.001-0.5 grams of hydrocarbons with a boiling range distribution
of at most 100.degree. C. at 0.101 MPa; at least 0.001 grams, or
from about 0.001-0.5 grams of hydrocarbons with a boiling range
distribution between about 100.degree. C. and about 200.degree. C.
at 0.101 MPa; at least 0.001 grams, or from about 0.001-0.5 grams
of hydrocarbons with a boiling range distribution between about
200.degree. C. and about 300.degree. C. at 0.101 MPa; at least
0.001 grams, or from about 0.001-0.5 grams of hydrocarbons with a
boiling range distribution between about 300.degree. C. and about
400.degree. C. at 0.101 MPa; and at least 0.001 grams, or from
about 0.001-0.5 grams of hydrocarbons with a boiling range
distribution between about 400.degree. C. and about 538.degree. C.
at 0.101 MPa.
[0142] In some embodiments the crude product includes, per gram of
crude product, at least 0.001 grams of hydrocarbons with a boiling
range distribution of at most 100.degree. C. at 0.101 MPa and/or at
least 0.001 grams of hydrocarbons with a boiling range distribution
between about 100.degree. C. and about 200.degree. C. at 0.101
MPa.
[0143] 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.
[0144] In some embodiments, the crude product has a distillate
content of about 70-130%, about 80-120%, or about 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
about 0.00001-0.5 grams, about 0.001-0.3 grams, or about 0.002-0.2
grams.
[0145] In certain embodiments, the crude product has a VGO content
of about 70-130%, about 80-120%, or about 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 about
0.00001-0.8 grams, about 0.001-0.5 grams, about 0.002-0.4 grams, or
about 0.001-0.3 grams.
[0146] In some embodiments, the crude product has a residue content
of about 70-130%, about 80-120%, or about 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 about 0.00001-0.8
grams, about 0.0001-0.5 grams, about 0.0005-0.4 grams, about
0.001-0.3 grams, about 0.005-0.2 grams, or about 0.01-0.1
grams.
[0147] In certain embodiments, the crude product has a residue
content of at least 90%, at least 80%, at least 50%, at least 30%,
at least 20%, or at least 10% of the residue content of the crude
feed. The residue content of the crude product may range from about
99% to about 0.5%, from about 80% to about 1%, from about 70% to
about 10% of the residue content of the crude feed. In some
embodiments, the crude product has, per gram of crude product, a
residue content from about 0.00001 to about 0.8 grams, about 0.0001
grams to about 0.5 grams, about 0.0005 grams to about 0.4 grams,
about 0.001 grams to about 0.3 grams, about 0.005 grams to about
0.2 grams, or about 0.01 grams to about 0.1 grams.
[0148] In certain embodiments, the crude product has a MCR content
of about 70-130%, about 80-120%, or about 90-110% of the MCR
content of the crude feed, while the crude product has a C.sub.5
asphaltenes content of at most 90%, at most 80%, or at most 50% of
the C.sub.5 asphaltenes content of the crude feed. In certain
embodiments, the C.sub.5 asphaltenes content of the crude feed is
at least 10%, at least 60%, or at least 70% of the C.sub.5
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 C.sub.5 asphaltenes
content of the crude feed while maintaining a relatively stable MCR
content may increase the stability of the crude feed/total product
mixture.
[0149] In some embodiments, the C.sub.5 asphaltenes content and MCR
content may be combined to produce a mathematical relationship
between the high viscosity components in the crude product relative
to the high viscosity components in the crude feed. For example, a
sum of a crude feed C.sub.5 asphaltenes content and a crude feed
MCR content may be represented by S. A sum of a crude product
C.sub.5 asphaltenes content and a crude product MCR content may be
represented by S'. The sums may be compared (S' to S) to assess the
net reduction in high viscosity components in the crude feed. S' of
the crude product may be in a range from about 1-99%, about 10-90%,
or about 20-80% of S. In some embodiments, a ratio of MCR content
of the crude product to C.sub.5 asphaltenes content is in a range
from about 1.0-3.0, about 1.2-2.0, or about 1.3-1.9.
[0150] In certain embodiments, the crude product has an 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. The crude product has, in some
embodiments, from about 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, about 0.000001-0.001 grams, or about
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.
[0151] 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 Ni/V/Fe content; d) reduced
content of sulfur, oxygen, nitrogen, or combinations thereof; e)
reduced residue content; f) reduced C.sub.5 asphaltenes content; g)
reduced MCR content; h) increased API gravity; i) a reduced content
of metals in metal salts of organic acids; 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, Ni/V/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.
[0152] Catalysts used in one or more embodiments of the inventions
may include one or more bulk metals and/or one or more metals on a
support. The metals may be in elemental form or in the form of a
compound of the metal. The catalysts described herein may be
introduced into the contacting zone as a precursor, and then become
active as a catalyst in the contacting zone (for example, when
sulfur and/or a crude feed containing sulfur is contacted with the
precursor). The catalyst or combination of catalysts used as
described herein may or may not be commercial catalysts. Examples
of commercial catalysts that are contemplated to be used as
described herein include 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, Tex., U.S.A.).
[0153] 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
in a range from at least 0.0001 grams, at least 0.001 grams, at
least 0.01 grams, or in a range about 0.0001-0.6 grams, about
0.001-0.3 grams, about 0.005-0.1 grams, or about 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 about
0.000001-0.1 grams, about 0.00001-0.06 grams, about 0.00005-0.03
grams, or about 0.0001-0.001 grams.
[0154] In certain embodiments, the catalyst includes Column 6
metal(s). The catalyst may have, per gram of catalyst, a total
Column 6 metal(s) content of at least 0.00001, at least 0.01 grams,
at least 0.02 grams and/or in a range from about 0.0001-0.6 grams,
about 0.001-0.3 grams, about 0.005-0.1 grams, or about 0.01-0.08
grams. In some embodiments, the catalyst includes from about
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).
[0155] In some embodiments, the catalyst includes a combination of
Column 6 metal(s) with one or more metals from Column 5 and/or
Columns 7-10. A molar ratio of Column 6 metal to Column 5 metal may
be in a range from about 0.1-20, about 1-10, or about 2-5. A molar
ratio of Column 6 metal to Columns 7-10 metal may be in a range
from about 0.1-20, about 1-10, or about 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 about 1-10, or from about 2-5. In certain
embodiments, the catalyst includes Column 5 metal(s) and Column 10
metal(s). A molar ratio of the total Column 10 metal to the total
Column 5 metal in the catalyst may be in a range from about 1-10,
or from about 2-5.
[0156] In some embodiments, Columns 5-10 metal(s) are incorporated
in, or deposited on, a support to form the catalyst. In certain
embodiments, Columns 5-10 metal(s) in combination with Column 15
element(s) are incorporated in, or deposited on, the support to
form the catalyst. In embodiments in which the metal(s) and/or
element(s) are supported, the weight of the catalyst includes all
support, all metal(s), and all element(s). The support may be
porous and may include refractory oxides, porous carbon based
materials, zeolites, or combinations thereof. Refractory oxides may
include, but are not limited to, alumina, silica, silica-alumina,
titanium oxide, zirconium oxide, magnesium oxide, or mixtures
thereof. Supports may be obtained from a commercial manufacturer
such as Criterion Catalysts and Technologies LP (Houston, Tex.,
U.S.A.). Porous carbon based materials include, but are not limited
to, activated carbon and/or porous graphite. Examples of zeolites
include Y-zeolites, beta zeolites, mordenite zeolites, ZSM-5
zeolites, and ferrierite zeolites. Zeolites may be obtained from a
commercial manufacturer such as Zeolyst (Valley Forge, Pa.,
U.S.A.).
[0157] The support, in some embodiments, is prepared such that the
support has an average pore diameter of at least 150 .ANG., at
least 170 .ANG., or at least 180 .ANG.. 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.
[0158] The paste may be extruded and cut using generally known
catalyst extrusion methods and catalyst cutting methods to form
extrudates. The extrudates may be heat treated at a temperature in
a range from about 65-260.degree. C. or from about 85-235.degree.
C. for a period of time (for example, for about 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 about 800-1200.degree. C. or about
900-1100.degree. C.) to form the support having an average pore
diameter of at least 150 .ANG..
[0159] In certain embodiments, the support includes gamma alumina,
theta alumina, delta alumina, alpha alumina, or combinations
thereof. The amount of gamma alumina, delta alumina, alpha alumina,
or combinations thereof, per gram of catalyst support, may be in a
range from about 0.0001-0.99 grams, about 0.001-0.5 grams, about
0.01-0.1 grams, or at most 0.1 grams as 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 about 0.1-0.99 grams,
about 0.5-0.9 grams, or about 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.
[0160] Supported catalysts may be prepared using generally known
catalyst preparation techniques. Examples of catalyst preparations
are described in U.S. Pat. No. 6,919,018 to Bhan; U.S. Pat. No.
6,759,364 to Bhan; U.S. Pat. No. 6,218,333 to Gabrielov et al.;
U.S. Pat. No. 6,290,841 to Gabrielov et al.; and U.S. Pat. No.
5,744,025 to Boon et al., all of which are incorporated herein by
reference.
[0161] 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 about 400-1200.degree.
C., about 450-1000.degree. C., or about 600-900.degree. 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.
[0162] 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. Pat. No. 6,759,364 to
Bhan.
[0163] 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 5-10 metal(s)/support
mixture. In certain embodiments, the materials are mixed until the
Columns 5-10 metal(s) is (are) substantially homogeneously
dispersed in the support.
[0164] In some embodiments, the catalyst is heat treated at
temperatures from about 150-750.degree. C., from about
200-740.degree. C., or from about 400-730.degree. C. after
combining the support with the metal.
[0165] 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.degree. C. and 1000.degree. C. to remove volatile
matter such that at least a portion of the Columns 5-10 metals are
converted to the corresponding metal oxide.
[0166] In other embodiments, however, the catalyst may be heat
treated in the presence of air at temperatures in a range from
about 35-500.degree. 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. Pat. No. 6,218,333 to Gabrielov et
al., and U.S. Pat. No. 6,290,841 to Gabrielov et al. 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.degree. C. to form
the catalyst having a pore size distribution with a median pore
diameter of at least 230 .ANG.. Typically, such heat treating is
conducted at temperatures of at most 1200.degree. C.
[0167] 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
about 1-50 microns, about 2-45 microns, or about 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 about 80-200 .ANG. or about 90-180 .ANG.,
or about 120-130 .ANG..
[0168] 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. 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.
[0169] 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.
[0170] For example, molybdenum trioxide and the alumina support
having a median pore diameter of at least 180 .ANG. may be combined
to form an alumina/molybdenum trioxide mixture. The molybdenum
trioxide has a definite pattern (for example, definite D.sub.001,
D.sub.002 and/or D.sub.003 peaks). The alumina/Column 6 trioxide
mixture may be heat treated at a temperature of at least
538.degree. C. (1000.degree. 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 D.sub.001
peak).
[0171] 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 about
30-1000 .ANG., about 50-500 .ANG., or about 60-300 .ANG.. In some
embodiments, catalysts that include at least 0.5 grams of gamma
alumina per gram of catalyst have a pore size distribution with a
median pore diameter in a range from about 60-200 .ANG.; about
90-180 .ANG., about 100-140 .ANG., or about 120-130 .ANG.. In other
embodiments, catalysts that include at least 0.1 grams of theta
alumina per gram of catalyst have a pore size distribution with a
median pore diameter in a range from about 180-500 .ANG., about
200-300 .ANG., or about 230-250 .ANG.. In some embodiments, the
median pore diameter of the pore size distribution is at least 120
.ANG., at least 150 .ANG., at least 180 .ANG., at least 200 .ANG.,
at least 220 .ANG., at least 230 .ANG., or at least 300 .ANG.. Such
median pore diameters are typically at most 1000 .ANG..
[0172] The catalyst may have a pore size distribution with a median
pore diameter of at least 60 .ANG. or at least 90 .ANG.. In some
embodiments, the catalyst has a pore size distribution with a
median pore diameter in a range from about 90-180 .ANG. about
100-140 .ANG., or about 120-130 .ANG., with at least 60% of a total
number of pores in the pore size distribution having a pore
diameter within about 45 .ANG., about 35 .ANG., or about 25 .ANG.
of the median pore diameter. In certain embodiments, the catalyst
has a pore size distribution with a median pore diameter in a range
from about 70-180 .ANG., with at least 60% of a total number of
pores in the pore size distribution having a pore diameter within
about 45 .ANG., about 35 .ANG., or about 25 .ANG. of the median
pore diameter.
[0173] In embodiments in which the median pore diameter of the pore
size distribution is at least 180 .ANG., at least 200 .ANG., or at
least 230 .ANG., greater that 60% of a total number of pores in the
pore size distribution have a pore diameter within about 50 .ANG.,
about 70 .ANG., or about 90 .ANG. of the median pore diameter. In
some embodiments, the catalyst has a pore size distribution with a
median pore diameter in a range from about 180-500 .ANG., about
200-400 .ANG., or about 230-300 .ANG., with at least 60% of a total
number of pores in the pore size distribution having a pore
diameter within about 50 .ANG., about 70 .ANG., or about 90 .ANG.
of the median pore diameter.
[0174] In some embodiments, pore volume of pores may be at least
0.3 cm.sup.3/g, at least 0.7 cm.sup.3/g, or at least 0.9
cm.sup.3/g. In certain embodiments, pore volume of pores may range
from about 0.3-0.99 cm.sup.3/g, about 0.4-0.8 cm.sup.3/g, or about
0.5-0.7 cm.sup.3/g.
[0175] The catalyst having a pore size distribution with a median
pore diameter in a range from about 90-180 .ANG. may, in some
embodiments, have a surface area of at least 100 m.sup.2/g, at
least 120 m.sup.2/g, at least 170 m.sup.2/g, at least 220, or at
least 270 m.sup.2/g. Such surface area may be in a range from about
100-300 m.sup.2/g, about 120-270 m.sup.2/g, about 130-250
m.sup.2/g, or about 170-220 m.sup.2/g.
[0176] In certain embodiments, the catalyst having a pore size
distribution with a median pore diameter in a range from about
180-300 .ANG. may have a surface area of at least 60 m.sup.2/g, at
least 90 m.sup.2/g, least 100 m.sup.2/g, at least 120 m.sup.2/g, or
at least 270 m.sup.2/g. Such surface area may be in a range from
about 60-300 m.sup.2/g, 90-280 m.sup.2/g, about 100-270 m.sup.2/g,
or about 120-250 m.sup.2/g.
[0177] In some embodiments, the catalyst is characterized using
Raman spectroscopy. The catalyst that includes metals from Columns
6-10 may exhibit bands in a region between 800 cm.sup.-1 and 900
cm.sup.-1. Bands observed in the 800 cm.sup.-1 to 900 cm.sup.-1
region may be attributed to Metal-Oxygen-Metal antisymmetric
stretching. In some embodiments, the catalyst that includes theta
alumina and Column 6 metals exhibits bands near 810 cm.sup.-1, near
835 cm.sup.-1, and 880 cm.sup.-1. In some embodiments, the Raman
shift of a molybdenum catalyst at these bands may indicate that the
catalyst includes a species intermediate between
Mo.sub.7O.sub.24.sup.6- and MO.sub.4.sup.2-. In some embodiments,
the intermediate species is crystalline.
[0178] In some embodiments, the catalyst that includes metals from
Columns 5 may exhibit bands in a region between 650 cm.sup.-1 and
1000 cm.sup.-1. Bands observed near 650 cm.sup.-1 and 1000
cm.sup.-1 may be attributed to V=O motions. In some embodiments,
the catalyst that includes theta alumina and Columns 5 and 6 metals
exhibits bands near 670 cm.sup.-1 and 990 cm.sup.-1.
[0179] 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 about
50-500 N/cm, about 60-400 N/cm, about 100-350 N/cm, about 200-300
N/cm, or about 220-280 N/cm.
[0180] 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, ACTICAT.TM. 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
either gaseous hydrogen sulfide in the presence of hydrogen, or
liquid-phase sulfurizing agents such as organosulfur compounds
(including alkylsulfides, polysulfides, thiols, and sulfoxides).
Ex-situ sulfurization processes are described in U.S. Pat. No.
5,468,372 to Seamans et al., and U.S. Pat. No. 5,688,736 to Seamans
et al., both of which are incorporated herein by reference.
[0181] 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 about 150-250 .ANG.. The first catalyst
may have a surface area of at least 100 m.sup.2/g. The pore volume
of the first catalyst may be at least 0.5 cm.sup.3/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 about 0.0001 to about 0.1 grams. The
first catalyst is capable of removing a portion of the Ni/V/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 C.sub.5
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, VGO 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.
[0182] 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 about 90 .ANG. to about 180 .ANG.. At
least 60% of the total number of pores in the pore size
distribution of the second catalyst have a pore diameter within
about 45 .ANG. 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.
[0183] 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 Ni/V/Fe content
of the crude product. Additionally, contact of crude feeds with the
second catalyst may produce a 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 about 70%-130% of the sulfur content of the crude feed.
The crude product may also exhibit relatively small changes in
distillate content, VGO content, and residue content relative to
the crude feed.
[0184] In some embodiments, the crude feed may have a relatively
low content of Ni/V/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 C.sub.5 asphaltenes content may exhibit less
stability during processing relative to other crudes with
relatively low C.sub.5 asphaltenes content. Contact of the crude
feed with the second catalysts, may remove acidic components and/or
C.sub.5 asphaltenes contributing to TAN from the crude feed. In
some embodiments, reduction of C.sub.5 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.
[0185] 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.degree. C. (for example, below
482.degree. C.) for a relatively short period of time to form the
uncalcined third catalyst. Typically, the catalyst precursor is
heated to at least 100.degree. C. for about 2 hours. In certain
embodiments, the third catalyst may, per gram of catalyst, have a
Column 15 element content in a range from about 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.degree. C. in the
presence of one or more sulfur compounds.
[0186] 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 Ni/V/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 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 about 70%-130% 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, VGO content, and residue content relative to
the crude feed. The ability to reduce the TAN, the metals in metal
salts of organic salts, the Ni/V/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.
[0187] 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
about 0.0001-0.1 grams, about 0.005-0.05 grams, or about 0.001-0.01
grams and a Column 10 metal(s) content in a range from about
0.0001-0.05 grams, about 0.005-0.03 grams, or about 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 about 300-500.degree. C. or about 350-450.degree. C. and
pressures in a range from about 0.1-10 MPa, about 1-8 MPa, or about
2-5 MPa.
[0188] 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 .ANG.. In some
embodiments, the median pore diameter of the fourth catalyst may be
at least 220 .ANG., at least 230 .ANG., at least 250 .ANG., or at
least 300 .ANG.. 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.
[0189] 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.
[0190] In some embodiments, hydrogen may be generated during
contacting of the crude feed with the fourth catalyst at a
temperature in a range from about 300-400.degree. C., about
320-380.degree. C., or about 330-370.degree. 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 about 1-50
Nm.sup.3/m.sup.3, about 10-40 Nm.sup.3/m.sup.3, or about 15-25
Nm.sup.3/m.sup.3. The crude product may have a total Ni/V/Fe
content of at most 90%, at most 80%, at most 70%, at most 50%, at
most 10%, or at least 1% of total Ni/V/Fe content of the crude
feed.
[0191] 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 .ANG., at least 220
.ANG., at least 230 .ANG., at least 250 .ANG., at least 300 .ANG.,
or at most 500 .ANG.. The support may include at least 0.1 grams,
at least 0.5 grams, or at 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.
[0192] In certain embodiments, net hydrogen uptake by the crude
feed may be relatively low (for example, from about 0.01-100
Nm.sup.3/m.sup.3) when the crude feed is contacted with the fifth
catalyst at a temperature in a range from about 310-400.degree. C.,
from about 320-370.degree. C., or from about 330-360.degree. C. Net
hydrogen uptake by the crude feed may be in a range from about 1-20
Nm.sup.3/m.sup.3, about 2-15 Nm.sup.3/m.sup.3, or about 3-10
Nm.sup.3/m.sup.3. 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 about
0.01-0.1, about 0.03-0.05, or about 0.02-0.03.
[0193] 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 .ANG.. In some embodiments, the median pore diameter of pore
size distribution may be at least 220 .ANG., at least 230 .ANG., at
least 250 .ANG., at least 300 .ANG., or at most 500 .ANG.. The
support may include at least 0.1 grams, at least 0.5 grams, 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
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 about 0.1-20, about 1-10, or
about 2-5. In certain embodiments, the Column 5 metal is vanadium
and the Column 6 metal(s) are molybdenum and/or tungsten.
[0194] When the crude feed is contacted with the sixth catalyst at
a temperature in a range from about 310-400.degree. C., from about
320-370.degree. C., or from about 330-360.degree. C., net hydrogen
uptake by the crude feed may be in a range from about -10
Nm.sup.3/m.sup.3 to about 20 Nm.sup.3/m.sup.3, about -7
Nm.sup.3/m.sup.3 to about 10 Nm.sup.3/m.sup.3, or about -5
Nm.sup.3/m.sup.3 to about 5 Nm.sup.3/m.sup.3. 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 about 0.01-0.1, about
0.02-0.05, or about 0.03-0.04.
[0195] 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.
[0196] In some embodiments, contact of crude feed with the fourth
catalyst, the fifth catalyst, the sixth catalyst or combinations
thereof at a temperature in a range from about 360.degree. C. to
about 500.degree. C., from about 380.degree. C. to about
480.degree. C., from about 400.degree. C. to about 470.degree. C.,
or from about 410.degree. C. to about 460.degree. C., produces the
crude product with a residue content of at least 90%, at least 80%,
at least 50%, at least 30% or at least 10% of the residue content
of the crude feed.
[0197] At elevated temperatures (for example greater than
360.degree. C.), impurities and/or coke may form during contact of
the crude feed with one or more catalysts. When contact is
performed in a continuously stirred reactor, formation of
impurities and/or coke may be determined by measuring an amount of
sediment produced during contacting. In some embodiments, the
content of sediment produced may be at most 0.002 grams or at most
0.001 grams, per gram of crude feed/total product. When the content
of sediment approaches 0.001 grams, adjustment of contacting
conditions may be necessary to prevent shutdown of the process
and/or to maintain a suitable flowrate of crude feed through the
contacting zone. The sediment content may range, per gram of crude
feed/total product, from about 0.00001 grams to about 0.03 grams,
from about 0.0001 grams to about 0.02 grams, from about 0.001 to
about 0.01 grams. Contact of the crude product with the fourth
catalyst, the fifth catalyst, the sixth catalyst, or combinations
thereof at elevated temperatures allows reduction of residue with
minimal formation of sediment.
[0198] In certain embodiments, a seventh type of catalyst ("seventh
catalyst") has a total content of Column 6 metal(s) in a range from
about 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.
[0199] 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.
[0200] 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.
[0201] 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
C.sub.5 asphaltenes, at least a portion of the iron, at least a
portion of the 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.
[0202] 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.
[0203] Combinations of selected catalysts may allow reduction in at
least a portion of the Ni/V/Fe, at least a portion of the C.sub.5
asphaltenes, at least a portion of the metals in metal salts of
organic acids, at least a portion of the components that contribute
to TAN, at least a portion of the residue, or combinations thereof,
from the crude feed before other properties of the crude feed are
changed, while maintaining the stability of the crude feed/total
product mixture during processing (for example, maintaining a crude
feed P-value of above 1.5). Alternatively, C.sub.5 asphaltenes,
TAN, and/or API gravity may be incrementally reduced by contact of
the crude feed with selected catalysts. The ability to
incrementally and/or selectively change properties of the crude
feed may allow the stability of the crude feed/total product
mixture to be maintained during processing.
[0204] 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.
[0205] The first catalyst allows, in some embodiments, for removal
of at least a portion of Ni/V/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 C.sub.5
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 Ni/V/Fe from the crude feed may, in
some embodiments, increase a life of one or more catalysts
positioned after the first catalyst.
[0206] 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
Ni/V/Fe, reduce sulfur content, reduce oxygen content, and/or
reduce the content of metals in metal salts of organic acids.
[0207] 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.
[0208] 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, VGO 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.
[0209] 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.
[0210] 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 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.
[0211] 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).
[0212] 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 Ni/V/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.
[0213] 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 about 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 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).
[0214] 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.
[0215] 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.
[0216] At certain times during the contacting period, the
concentration of crude feed and/or total product in the crude
feed/total product mixture may change. As the concentration of the
total product in the crude feed/total product mixture changes due
to formation of the crude product, solubility of the components of
the crude feed and/or components of the total product in the crude
feed/total product mixture tends to change. For example, the crude
feed may contain components that are soluble in the crude feed at
the beginning of processing. As properties of the crude feed change
(for example, TAN, MCR, C.sub.5 asphaltenes, P-value, or
combinations thereof), the components may tend to become less
soluble in the crude feed/total product mixture. In some instances,
the crude feed and the total product may form two phases and/or
become insoluble in one another. Solubility changes may also result
in the crude feed/total product mixture forming two or more phases.
Formation of two phases, through flocculation of asphaltenes,
change in concentration of crude feed and total product, and/or
precipitation of components, tends to reduce the life of one or
more of the catalysts. Additionally, the efficiency of the process
may be reduced. For example, repeated treatment of the crude
feed/total product mixture may be necessary to produce a crude
product with desired properties.
[0217] 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.
[0218] In some embodiments, contacting temperatures are controlled
such that C.sub.5 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 C.sub.5 asphaltenes to be reduced while the MCR
content of the crude feed only changes by a relatively small
amount.
[0219] In some embodiments, contacting conditions are controlled
such that temperatures in one or more contacting zones may be
different. Operating at different temperatures allows for selective
change in crude feed properties while maintaining the stability of
the crude feed/total product mixture. The crude feed enters a first
contacting zone at the start of a process. A first contacting
temperature is the temperature in the first contacting zone. Other
contacting temperatures (for example, second temperature, third
temperature, fourth temperature, et cetera) are the temperatures in
contacting zones that are positioned after the first contacting
zone. A first contacting temperature may be in a range from about
100-420.degree. C. and a second contacting temperature may be in a
range that is about 20-100.degree. C., about 30-90.degree. C., or
about 40-60.degree. C. different than the first contacting
temperature. In some embodiments, the second contacting temperature
is greater than the first contacting temperature. Having different
contacting temperatures may reduce TAN and/or C.sub.5 asphaltenes
content in a crude product relative to the TAN and/or the C.sub.5
asphaltenes content of the crude feed to a greater extent than the
amount of TAN and/or C.sub.5 asphaltene reduction, if any, when the
first and second contacting temperatures are the same as or within
10.degree. C. of each other.
[0220] 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 about 350.degree. C. and the second
contacting temperature may be about 300.degree. 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 C.sub.5 asphaltenes reduction in the
crude feed relative to the TAN and/or C.sub.5 asphaltenes reduction
in the same crude feed when the first and second contacting
temperatures are within 10.degree. C.
[0221] In some embodiments, contacting conditions are controlled
such that the total hydrogen partial pressure of the contacting
zone is maintained at a desired pressure, at a set flow rate and
elevated temperatures. The ability to operate at partial pressures
of hydrogen of at most 3.5 MPa allows an increase in LHSV (for
example an increase to at least 0.5 h.sup.-1, at least 1 h.sup.-1,
at least 2 h.sup.-1, at least 5 h.sup.-1, or at least 10 h.sup.-1)
with the same or longer catalyst life as contacting at hydrogen
partial pressures of at least 4 MPa. Operating at lower partial
pressures of hydrogen decreases the cost of the operation and
allows contacting to be performed where limited amounts of hydrogen
are available.
[0222] For example, a contacting zone may include a fourth catalyst
and/or a fifth catalyst. The contacting conditions may be:
temperature of above 360.degree. C., a LHSV of about 1 h.sup.-1, a
total hydrogen partial pressure of about 3.5 MPa. Contact of the
crude feed with the fourth and/or fifth catalyst at these
conditions may allow continuous use of a catalyst for at least 500
hours, while reducing selected properties of the crude feed.
EXAMPLES
[0223] 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
[0224] A support was prepared by mulling 576 grams of alumina
(Criterion Catalysts and Technologies LP, Michigan City, Mich.,
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 Trilobe.TM. die plate, dried between 90-125.degree. C., and
then calcined at 918.degree. C., which resulted in 650 grams of a
calcined support with a median pore diameter of 182 .ANG.. The
calcined support was placed in a Lindberg furnace. The furnace
temperature was raised to about 1000-1100.degree. 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 m.sup.2/g and a
total pore volume of 0.821 cm.sup.3/g. The support had a pore size
distribution with a median pore diameter of 232 .ANG., with 66.7%
of the total number of pores in the pore size distribution having a
pore diameter within 85 .ANG. of the median pore diameter.
[0225] This example demonstrates how to prepare a support that has
a pore size distribution of at least 180 .ANG. and includes at
least 0.1 grams of theta alumina.
Example 2
Preparation of a Vanadium Catalyst Having a Pore Size Distribution
with a Median Pore Diameter of at Least 230 .ANG.
[0226] 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 VOSO.sub.4 with 82 grams of deionized
water. A pH of the solution was about 2.27.
[0227] The alumina support (100 g) was impregnated with the
vanadium impregnation solution, aged for 2 hours with occasional
agitation, dried at 125.degree. C. for several hours, and then
calcined at 480.degree. 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 .ANG., a pore
volume of 0.69 cm.sup.3/g, and a surface area of 110 m.sup.2/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
.ANG. of the median pore diameter.
[0228] This example demonstrates the preparation of a Column 5
catalyst having a pore size distribution with a median pore
diameter of at least 230 .ANG.. T
Example 3
Preparation of a Molybdenum Catalyst having a Pore Size
Distribution with a Median Pore Diameter of at Least 230 .ANG.
[0229] 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 (NH.sub.4).sub.2Mo.sub.2O.sub.7, 6.38 grams of MoO.sub.3,
1.12 grams of 30% H.sub.2O.sub.2, 0.27 grams of monoethanolamine
(MEA), and 6.51 grams of deionized water to form a slurry. The
slurry was heated to 65.degree. 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.
[0230] The alumina support (100 grams) was impregnated with the
molybdenum impregnation solution, aged for 2 hours with occasional
agitation, dried at 125.degree. C. for several hours, and then
calcined at 480.degree. 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 .ANG., a pore
volume of 0.77 cm.sup.3/g, and a surface area of 116 m.sup.2/g.
Additionally, 67.7% of the total number of pores in the pore size
distribution of the molybdenum catalyst had a pore diameter within
86 .ANG. of the median pore diameter.
[0231] The molybdenum catalyst exhibited bands near 810 cm.sup.-1,
834 cm.sup.-1, and 880 cm.sup.-1 when analyzed by Raman
Spectroscopy. The Raman spectrum of the catalyst was obtained on a
Chromex Raman 200 spectrometer operated at four-wavenumber
resolution. The excitation wavelength was 785 nm at a power of
approximately 45 mW at the sample. The spectrometer wavenumber
scale was calibrated using the known bands of 4-acetominophenol.
The band positions of 4-actiominophenol were reproduced to within
.+-.cm.sup.-1. A molybdenum catalyst with a gamma alumina support
did not exhibit bands between 810 cm.sup.-1 and 900 cm.sup.-1 when
analyzed by Raman Spectroscopy. FIG. 7 depicts the spectrum of the
two catalysts. Plot 138 represents the molybdenum catalyst having a
pore size distribution with a median pore diameter of 250 .ANG..
Plot 140 represents a Column 6/Column 10 metal catalyst that
includes at least 0.5 grams of gamma alumina having a pore size
distribution with a median pore diameter of about 120 .ANG..
[0232] 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 .ANG.. This example also demonstrates
preparation of a Column 6 metal catalyst having bands near 810
cm.sup.-1, 834 cm.sup.-1, and 880 cm.sup.-1, as determined by Raman
Spectroscopy. The catalyst prepared by this method is different
than a gamma alumina catalyst having a pore size distribution with
a median pore diameter of at least 100 .ANG..
Example 4
Preparation of a Molybdenum/Vanadium Catalyst having a Pore Size
Distribution with a Median Pore Diameter of at Least 230 .ANG.
[0233] 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 (NH.sub.4).sub.2Mo.sub.2O.sub.7,
3.21 grams of MoO.sub.3, 0.56 grams of 30% hydrogen peroxide
(H.sub.2O.sub.2), 0.14 grams of monoethanolamine (MEA), and 3.28
grams of deionized water to form a slurry. The slurry was heated to
65.degree. C. until dissolution of the solids. The heated solution
was cooled to room temperature.
[0234] A second solution was made by combining 3.57 grams of
VOSO.sub.4 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.degree. C.
for several hours, and then calcined at 480.degree. C. for 2 hours.
The resulting catalyst contained, per gram of catalyst, 0.02 grams
of vanadium and 0.02 grams of molybdenum, with the balance being
support. The molybdenum/vanadium catalyst had a pore size
distribution with a median pore diameter of 300 .ANG..
[0235] 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 .ANG.. The
vanadium/molybdenum catalyst exhibited bands near 770 cm.sup.-1 and
990 cm.sup.-1 when analyzed by Raman Spectroscopy. FIG. 7 depicts
the spectrum of the vanadium catalyst. Plot 142 represents the
molybdenum catalyst having a pore size distribution with a median
pore diameter of 250 .ANG..
[0236] This example also demonstrates the preparation of a Column 5
catalyst having bands near 770 cm.sup.-1 and 990 cm.sup.-1 when
analyzed by Raman Spectroscopy.
Example 5
Contact of a Crude Feed with Three Catalysts
[0237] A tubular reactor with a centrally positioned thermowell was
equipped with thermocouples to measure temperatures throughout a
catalyst bed. The catalyst bed was formed by filling the space
between the thermowell and an inner wall of the reactor with
catalysts and silicon carbide (20-grid, Stanford Materials; Aliso
Viejo, Calif.). Such silicon carbide is believed to have low, if
any, catalytic properties under the process conditions described
herein. All catalysts were blended with an equal volume amount of
silicon carbide before placing the mixture into the contacting zone
portions of the reactor.
[0238] 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 cm.sup.3)
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 .ANG., with 66.7% of the total
number of pores in the pore size distribution having a pore
diameter within 20 .ANG. 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.
[0239] A middle catalyst/silicone carbide mixture (56 cm.sup.3) 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 .ANG., with 66.7% of the total
number of pores in the pore size distribution having a pore
diameter within 24 .ANG. 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.
[0240] A top catalyst/silicone carbide mixture (42 cm.sup.3) 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 .ANG. and contained 0.04 grams of
molybdenum per gram of catalyst, with the balance being primarily a
gamma alumina support.
[0241] 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.
[0242] The catalysts were sulfided by introducing a gaseous mixture
of 5 vol % hydrogen sulfide and 95 vol % hydrogen gas into the
contacting zones at a rate of about 1.5 liter of gaseous mixture
per volume (mL) of total catalyst (silicon carbide was not counted
as part of the volume of catalyst). Temperatures of the contacting
zones were increased to 204.degree. C. (400.degree. F.) over 1 hour
and held at 204.degree. C. for 2 hours. After holding at
204.degree. C., the contacting zones were increased incrementally
to 316.degree. C. (600.degree. F.) at a rate of about 10.degree. C.
(about 50.degree. F.) per hour. The contacting zones were
maintained at 316.degree. C. for an hour, then incrementally raised
to 370.degree. C. (700.degree. F.) over 1 hour and held at
370.degree. C. for two hours. The contacting zones were allowed to
cool to ambient temperature.
[0243] Crude from the Mars platform in the Gulf of Mexico was
filtered, then heated in an oven at a temperature of 93.degree. C.
(200.degree. F.) for 12-24 hours to form the crude feed having the
properties summarized in Table 1, FIG. 8. 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
Nm.sup.3/m.sup.3 (2000 SCFB), LHSV was 1 h.sup.-1, and pressure was
6.9 MPa (1014.7 psi). The three contacting zones were heated to
370.degree. C. (700.degree. F.) and maintained at 370.degree. C.
for 500 hours. Temperatures of the three contacting zones were then
increased and maintained in the following sequence: 379.degree. C.
(715.degree. F.) for 500 hours, and then 388.degree. C.
(730.degree. F.) for 500 hours, then 390.degree. C. (734.degree.
F.) for 1800 hours, and then 394.degree. C. (742.degree. F.) for
about 2400 hours.
[0244] 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. 8.
[0245] 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 C.sub.5 asphaltenes content
of 1.9 and a TAN of 0.09. The total of nickel and vanadium was 22.4
wtppm.
[0246] 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. 9 is a graphical
representation of WABT versus time for improvement of the crude
feed in the contacting zones described in this example. Plot 144
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.degree. 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
about 1 year of commercial operation.
[0247] 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 .ANG. and additional catalysts having
a pore size distribution with a median pore diameter in a range
between 90-180 .ANG., with at least 60% of the total number of
pores in the pore size distribution having a pore diameter within
45 .ANG. 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 Ni/V/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
.ANG.
[0248] 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.
[0249] 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 cm.sup.3)
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 .ANG., with 66.7% of the total
number pores in the pore size distribution having a pore diameter
within 32 .ANG. 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.
[0250] A top catalyst/silicone carbide mixture (80 cm.sup.3) 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 .ANG., with 66.7% of the total number
of pores in the pore size distribution having a pore diameter
within 20 .ANG. 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.
[0251] BS-4 crude (Venezuela) having the properties summarized in
Table 2, 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 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
Nm.sup.3/m.sup.3 (1000 SCFB), LHSV was 1 h.sup.-1, and pressure was
6.9 MPa (1014.7 psi). The two contacting zones were heated to
260.degree. C. (500.degree. F.) and maintained at 260.degree. C.
(500.degree. F.) for 287 hours. Temperatures of the two contacting
zones were then increased and maintained in the following sequence:
270.degree. C. (525.degree. F.) for 190 hours, then 288.degree. C.
(550.degree. F.) for 216 hours, then 315.degree. C. (600.degree.
F.) for 360 hours, and then 343.degree. C. (650.degree. F.) for 120
hours for a total run time of 1173 hours.
[0252] 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 VGO, and 0.378 grams
of residue. Additional properties of the crude product are listed
in TABLE 2 in FIG. 10.
[0253] 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 .ANG. 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 about 99% and 100% of the respective properties of the crude
feed.
Example 7
Contact of a Crude Feed with Two Catalysts
[0254] 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.
[0255] A crude feed (BC-10 crude) having the properties summarized
in Table 3, FIG. 11, 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 Nm.sup.3/m.sup.3 (500 SCFB), LHSV
was 2 h.sup.-1, and pressure was 6.9 MPa (about 1014.7 psi). The
two contacting zones were heated incrementally to 343.degree. C.
(650.degree. F.). A total run time was 1007 hours.
[0256] 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,
0.0033 grams of sulfur, 0.002 grams of oxygen, 0.376 grams of VGO,
and 0.401 grams of residue. Additional properties of the crude
product are listed in Table 3 in FIG. 11.
[0257] This example demonstrates that contacting of the crude feed
with the selected catalysts with pore size distributions in a range
of 90-180 .ANG. produced a crude product that had a reduced TAN, a
reduced total calcium, sodium, zinc, and potassium content while
sulfur content, VGO content, and residue content of the crude
product were about 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
[0258] 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.
[0259] In Example 8, an uncalcined molybdenum/nickel
catalyst/silicon carbide mixture (48 cm.sup.3) 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.
[0260] A molybdenum catalyst/silicon carbide mixture (12 cm.sup.3)
with the catalyst having a pore size distribution with a median
pore diameter of 180 .ANG. 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.
[0261] In Example 9, an uncalcined molybdenum/cobalt
catalyst/silicon carbide mixture (48 cm.sup.3) was positioned in
the both contacting zones. The uncalcined molybdenum/cobalt
catalyst included 0.143 grams of molybdenum, 0.043 grams of cobalt,
and about 0.021 grams of phosphorus with the balance being alumina
support.
[0262] A molybdenum catalyst/silicon carbide mixture (12 cm.sup.3)
was positioned in the top contacting zone. The molybdenum catalyst
was the same as in the top contacting zone of Example 8.
[0263] 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 cm.sup.3).
[0264] In Example 11, an uncalcined molybdenum/nickel
catalyst/silicone carbide mixture (48 cm.sup.3) was positioned in
the bottom contacting zone. The uncalcined molybdenum/nickel
catalyst included, per gram of catalyst, about 0.09 grams of
molybdenum, about 0.025 grams of nickel, and about 0.01 grams of
phosphorus, with the balance being alumina support.
[0265] A molybdenum catalyst/silicon carbide mixture (12 cm.sup.3)
was positioned in the top contacting zone. The molybdenum catalyst
was the same as in the top contacting zone of Example 8.
[0266] Crude from the Mars platform (Gulf of Mexico) was filtered,
then heated in an oven at a temperature of 93.degree. C.
(200.degree. F.) for 12-24 hours to form the crude feed for
Examples 8-11 having the properties summarized in Table 4, FIG. 12.
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 Nm.sup.3/m.sup.3 (1000 SCFB), and the total
pressure of each system was 6.9 MPa (1014.7 psi). LHSV was 2.0
h.sup.-1 during the first 200 hours of contacting, and then lowered
to 1.0 h.sup.-1 for the remaining contacting times. Temperatures in
all contacting zones were 343.degree. C. (650.degree. 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.degree. C. (670.degree. F.),
held at 354.degree. C. for 200 hours; raised to 366.degree. C.
(690.degree. F.), held at 366.degree. C. for 200 hours; raised to
371.degree. C. (700.degree. F.), held at 371.degree. C. for 1000
hours; raised to 385.degree. C. (725.degree. C.), held at about
385.degree. C. for 200 hours; then raised to a final temperature of
399.degree. C. (750.degree. C.) and held at 399.degree. C. for 200
hours, for a total contacting time of 2300 hours.
[0267] The crude products were periodically analyzed to determine
TAN, hydrogen uptake by the crude feed, P-value, VGO content,
residue content, and oxygen content. Average values for properties
of the crude products produced in Examples 8-11 are listed in Table
4 in FIG. 12.
[0268] FIG. 13 is a graphical representation of P-value of the
crude product versus run time for each of the catalyst systems of
Examples 8-11. The crude feed had a P-value of at least 1.5. Plots
150, 152, 154, and 156 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 about 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. 13, 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.
[0269] FIG. 14 is a graphical representation of net hydrogen uptake
by crude feed versus run time for four catalyst systems in the
presence of hydrogen gas. Plots 158, 160 162, 164 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 about 7-48 Nm.sup.3/m.sup.3 (43.8-300 SCFB). As
shown in FIG. 14, the net hydrogen uptake of the crude feed was
relatively constant during each trial.
[0270] FIG. 15 is a graphical representation of residue content,
expressed in weight percentage, of crude product versus run time
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 166, 168, 170, 172
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. 15, the residue content of the
crude product remained relatively constant during significant
portions of each trial.
[0271] FIG. 16 is a graphical representation of change in API
gravity of the crude product versus run time for each of the
catalyst systems of Examples 8-11. Plots 174, 176, 178, 180
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.
[0272] FIG. 17 is a graphical representation of oxygen content,
expressed in weight percentage, of the crude product versus run
time for each of the catalyst systems of Examples 8-11. Plots 182,
184, 186, 188 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. 17, 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.
[0273] In Example 11, at reaction conditions of: 371.degree. C.
(700.degree. F.), a pressure of 6.9 MPa (1014.7 psi), and a ratio
of hydrogen to crude feed of about 160 Nm.sup.3/m.sup.3 (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.degree. C.
(750.degree. 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.
[0274] In Example 9, at reaction conditions of: 371.degree. C.
(700.degree. F.), a pressure of 6.9 MPa (1014.7 psi), and a ratio
of hydrogen to crude feed of about 160 Nm.sup.3/m.sup.3 (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.degree. C.
(750.degree. 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.
[0275] 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.
[0276] 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.
[0277] 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 Nm.sup.3/m.sup.3 (275 SCFB). Such products had an
average TAN of at most 4% of the crude feed, and an average total
Ni/V content of at most 61% of the total Ni/V 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 VGO 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 Having a Pore Size
Distribution with a Median Pore Diameter of at Least 180 .ANG. With
Minimal Hydrogen Consumption
[0278] 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.
[0279] A catalyst/silicon carbide mixture (40 cm.sup.3) 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.
[0280] The contacting conditions for Examples 12-14 were as
follows: ratio of hydrogen to the crude feed provided to the
reactor was about 160 Nm.sup.3/m.sup.3 (1000 SCFB), LHSV was 1
h.sup.-1, and pressure was 6.9 MPa (about 1014.7 psi). The
contacting zones were heated incrementally to 343.degree. C.
(650.degree. F.) over a period of time and maintained at
343.degree. C. for 120 hours for a total run time of 360 hours.
[0281] 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 about -10.7 Nm.sup.3/m.sup.3 (-65 SCFB),
and the crude product had a TAN of 6.75. In Example 13, net
hydrogen uptake was in a range from about 2.2-3.0 Nm.sup.3/m.sup.3
(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 about -0.05 Nm.sup.3/m.sup.3 to about 0.6
Nm.sup.3/m.sup.3 (-0.36 SCFB to 4.0 SCFB), and the crude product
had a TAN in a range from 0.2-0.5.
[0282] From the net hydrogen uptake values during contacting, it
was estimated that hydrogen was generated at the rate of about 10.7
Nm.sup.3/m.sup.3 (65 SCFB) during contacting of the crude feed and
the vanadium catalyst. Generation of hydrogen during contacting
allows 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.
[0283] 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
[0284] 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
Lindberg furnace that included four heating zones corresponding to
the preheat zone, the two contacting zones, and the bottom
support.
[0285] In each example, the vanadium catalyst was prepared as
described in Example 2 and used with the additional catalyst.
[0286] In Example 15, an additional catalyst/silicon carbide
mixture (45 cm.sup.3) 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 cm.sup.3) was positioned in
the top contacting zone.
[0287] In Example 16, an additional catalyst/silicon carbide
mixture (30 cm.sup.3) 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 cm.sup.3) was positioned in the top contacting
zone.
[0288] In Example 17, an additional catalyst/silicone mixture (30
cm.sup.3) 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 cm.sup.3) was positioned in the top contacting
zone.
[0289] In Example 18, Pyrex.RTM. (Glass Works Corporation, New
York, U.S.A.) beads (30 cm.sup.3) were positioned in each
contacting zone.
[0290] Crude (Santos Basin, Brazil) for Examples 15-18 having the
properties summarized in Table 5, FIG. 18 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 about 160 Nm.sup.3/m.sup.3 (1000 SCFB)
for the first 86 hours and about 80 Nm.sup.3/m.sup.3 (500 SCFB) for
the remaining time period, LHSV was 1 h.sup.-1, and pressure was
6.9 MPa (about 1014.7 psi). The contacting zones were heated
incrementally to about 343.degree. C. (650.degree. F.) over a
period of time and maintained at 343.degree. C. for a total run
time of about 1400 hours.
[0291] 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 .ANG. in combination with an additional
catalyst having a pore size distribution with a median pore
diameter in a range from 250-300 .ANG., 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 to the same properties of the crude feed. Additionally,
during processing, relatively small hydrogen uptake by the crude
feed was observed.
[0292] Specifically, as shown in Table 5, FIG. 18, 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 Ni/V/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.
[0293] 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
[0294] Contact of a Crude Feed at Various LHSV
[0295] 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. 19. The contacting conditions were as
follows: a ratio of hydrogen gas to the crude feed provided to the
reactor was about 160 Nm.sup.3/m.sup.3 (1000 SCFB), pressure was
6.9 MPa (about 1014.7 psi), and temperature of the contacting zones
was 371.degree. C. (about 700.degree. F.) for the total run time.
In Example 19, the LHSV during contacting was increased over a
period of time from 1 h.sup.-1 to 12 h.sup.-1, maintained at 12
h.sup.-1 for 48 hours, and then the LHSV was increased to 20.7
h.sup.-1 and maintained at about 20.7 h.sup.-1 for 96 hours.
[0296] In Example 19, the crude product was analyzed to determine
TAN, viscosity, density, VGO content, residue content, heteroatoms
content, and content of metals in metal salts of organic acids
during the time periods that the LHSV was at 12 h.sup.-1 and at
20.7 h.sup.-1. Average values for the properties of the crude
products are shown in Table 6, FIG. 19.
[0297] As shown in Table 6, FIG. 19, 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 C.sub.5 asphaltenes content was at
least 1.5. The sum of the MCR content and C.sub.5 asphaltenes
content was reduced relative to the sum of the MCR content and
C.sub.5 asphaltenes content of the crude feed. From the weight
ratio of MCR content to C.sub.5 asphaltenes content and the reduced
sum of the MCR content and the C.sub.5 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 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.
[0298] Examples 6 and 19 demonstrate that contacting conditions can
be controlled such that a LHSV through the contacting zone is
greater than 10 h.sup.-1, as compared to a process that has a LHSV
of 1 h.sup.-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 10 h.sup.-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 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
[0299] 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. 20 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.
[0300] Contacting conditions in the top contacting zone were as
follows: LHSV was about 1 h.sup.-1; temperature in the top
contacting zone was 260.degree. C. (500.degree. F.); a ratio of
hydrogen to crude feed was about 160 Nm.sup.3/m.sup.3 (1000 SCFB);
and pressure was 6.9 MPa (1014.7 psi).
[0301] Contacting conditions in the bottom contacting zone were as
follows: LHSV was about 1 h.sup.-1; temperature in the bottom
contacting zone was 315.degree. C. (600.degree. F.); a ratio of
hydrogen to crude feed was 160 Nm.sup.3/m.sup.3 (1000 SCFB); and
pressure was 6.9 MPa (1014.7 psi).
[0302] 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 C.sub.5 asphaltenes content.
[0303] Average values for the properties of crude product obtained
during the run are listed in Table 7, FIG. 20. The crude feed had a
TAN of about 9.3 and a C.sub.5 asphaltenes content of about 0.055
grams of C.sub.5 asphaltenes per gram of crude feed. The crude
product had an average TAN of 0.7 and an average C.sub.5
asphaltenes content of about 0.039 grams of C.sub.5 asphaltenes per
gram of crude product. The C.sub.5 asphaltenes content of the crude
product was at most 71% of the C.sub.5 asphaltenes content of the
crude product.
[0304] 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 about 1.5 or higher was
maintained during contacting.
[0305] As demonstrated in Examples 6 and 20, having a first (in
this case, top) contacting temperature that is 50.degree. C. lower
than the contacting temperature of the second (in this case,
bottom) zone tends to enhance the reduction of C.sub.5 asphaltenes
content in the crude product relative to the C.sub.5 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.
[0306] Using a lower temperature of a first contacting zone allows
removal of the high molecular weight compounds (for example,
C.sub.5 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 to Produce a Crude Product
[0307] The reactor apparatus (except for number and content of
contacting zones), the total product separation method, crude
product analysis, the catalysts and catalyst sulfiding method were
the same as described in Example 5.
[0308] A molybdenum catalyst (11.25 cm.sup.3) prepared by the
method described in Example 3 and mixed with silicon carbide (22.50
cm.sup.3) to form a molybdenum catalyst/silicon carbide mixture
(37.75 cm.sup.3) was positioned in the bottom contacting zone. A
vanadium catalyst (3.75 cm.sup.3) prepared by the method described
in Example 4 was mixed with silicon carbide (7.5 cm.sup.3) to form
a vanadium catalyst/silicone carbide mixture (11.25 cm.sup.3) was
positioned in the top contacting zone.
[0309] A crude feed (BC-10 crude) having the properties summarized
in Table 8, FIG. 21, 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 160 Nm.sup.3/m.sup.3 (1000 SCFB), LHSV
was 2 h.sup.-1, and pressure was 3.4 MPa (about 500 psig). The two
contacting zones were heated incrementally to 343.degree. C.
(650.degree. F.).
[0310] After total run time of 1175 hours, the crude product had a
TAN of 0.44 and an API gravity of 15.9. The crude product had 0.6
wtppm of calcium, 0.8 wtppm of sodium, 0.9 wtppm of zinc, 1.5 wtppm
of potassium, 0.8 wt ppm silicon. The crude product had, per gram
of crude product, 0.0043 grams of sulfur, 0.003 grams of oxygen,
0.407 grams of VGO, and 0.371 grams of residue. Additional
properties of the crude product are listed in Table 8 in FIG.
21.
[0311] After total run time of 5207 hours with no catalyst
replacement, the crude product had a TAN of 0.27 and an API gravity
of 15.7. The crude product had 0.4 wtppm of calcium, 1.1 wtppm of
sodium, 0.9 wtppm of zinc, and 1.7 wtppm of potassium. The crude
product had, per gram of crude product, 0.00396 grams of sulfur,
0.407 grams of VGO, and 0.38 grams of residue. Additional
properties of the crude product are listed in Table 8 in FIG.
21.
[0312] This example demonstrates that contacting of the crude feed
with the selected catalysts and at least one of the catalysts
having a pore size distribution with a median pore diameter of
greater than 180 .ANG. produced a crude product that had a reduced
TAN, a reduced total calcium, sodium, zinc, potassium and silicon
content while sulfur content, VGO content, and residue content of
the crude product were about 100%, 102%, and 95.6% of the
respective properties of the crude feed. This example also
demonstrates that the TAN of the crude product is at least 30% of
the TAN of the crude feed after 500 hours without replacement of
the catalysts.
[0313] This example also demonstrates that contact of a crude feed
with hydrogen in the presence of at least one Column 6-10 metals
catalyst that exhibits bands in the range of 810 cm.sup.-1 to 870
cm.sup.-1 as determined by Raman Spectroscopy produces a total
product that includes a crude product with a residue content of at
least 90% of the residue content of the crude feed.
[0314] This example also demonstrates that contact of a crude feed
with hydrogen in the presence of at least one Columns 6-10 metals
catalyst that exhibits bands in the range of 810 cm.sup.-1 to 870
cm.sup.-1 as determined by Raman Spectroscopy produces a total
product that includes a crude product with a TAN that is at least
90% of the TAN of the crude feed.
[0315] This example also demonstrates that contact of a crude feed
with hydrogen in the presence of at least one Column 5 metal
catalyst that exhibits bands in the range of 650 cm.sup.-1 to 1000
cm.sup.-1 as determined by Raman Spectroscopy produces a total
product that includes crude product that has a atomic H/C between
80% and 120% of the atomic H/C of the crude feed.
Example 22
Contact of a Crude Feed and a Catalyst in an Continuously Stirred
Reactor (CSTR)
[0316] A molybdenum catalyst (25.5 grams, 50 cm.sup.-3) prepared as
in Example 3 was charged to a CSTR. Crude feed (BS-4) having the
properties listed in Table 9 in FIG. 22 was metered at a flow rate
of 24.1 g/hr to produce a LHSV of 0.5 h.sup.-1. A temperature
421.degree. C. (790.degree. F.), a total pressure of 14 MPa (about
2000 psig), and ratio of hydrogen source to crude feed of 320
Nm.sup.3/m.sup.3 (2000 SCFB) were maintained through out the run.
Total product was removed from the top of the reactor and separated
into crude product and process gases. During the run, an amount of
sediment was monitored to determine if the reaction vessel was
filling with impurities and/or coke. The amount of sediment, per
gram of crude feed, ranged between 0.0001 grams and 0.00013 grams
during the run.
[0317] Properties of the crude product after 286 hours are
tabulated in Table 9 of FIG. 22. The crude product had a TAN of
0.26 and an API gravity of 21.2. The crude product had 2.2 wtppm of
calcium, 0.2 wtppm of sodium, 6.4 wtppm of zinc, 0.7 wtppm of
silicon, 0.2 wtppm of potassium, 2.9 wtppm nickel, 0.6 wtppm
vanadium, and 2.3 wtppm iron. The crude product had, per gram of
crude product, 0.018 grams of sulfur, 0.386 of distillate, 0.41
grams of VGO, and 0.204 grams of residue.
[0318] This example demonstrates that contact of a crude feed with
hydrogen in the presence of at least one molybdenum catalyst that
exhibits bands in the range of 810 cm.sup.-1 to 870 cm.sup.-1 as
determined by Raman Spectroscopy produces a total product that
includes a crude product with a residue content of at least 90% of
the residue content of the crude feed. This example also
demonstrates that contact of a crude feed with hydrogen in the
presence of at least one Columns 6-10 metals catalyst that exhibits
bands in the range of 810 cm.sup.-1 to 870 cm.sup.-1 as determined
by Raman Spectroscopy produces a total product that includes a
crude product with a TAN that is at least 90% of the TAN of the
crude feed.
Comparative Example 23
Contact of a Crude Feed and a Catalyst in an Continuously Stirred
Reactor (CSTR)
[0319] The reactor apparatus, the total product separation method,
crude product analysis, and catalyst sulfiding method were the same
as described in Example 22. The catalyst had a pore size
distribution with a median pore diameter of 192 .ANG. and contained
0.04 grams of molybdenum per gram of catalyst, with the balance
being primarily a gamma alumina support. The catalyst did not
exhibit absorption in the range A810 cm.sup.-1 to A870 cm.sup.-1 as
determined by Raman Spectroscopy. The properties of the crude
product after 213 hours are tabulated in Table 9 of FIG. 22. At 213
hours a content of sediment, per gram of crude feed, was 0.0019
grams, per gram of crude feed/total product. After 765 hours the
sediment had increased to 0.00329 grams, per gram of crude
feed/total product. An increase in sediment relative to sediment
content of the crude feed/total product mixture when contacting the
crude feed with the molybdenum catalyst of Example 22 indicates
that impurities and/or coke are forming at an increased rate. An
increased rate of sediment formation decreases contacting time
and/or catalyst life, thus the catalyst of Example 22 has a longer
catalyst life than the catalyst of Example 23.
[0320] In this patent, certain U.S. patents have been incorporated
by reference. The text of such U.S. patents is, however, only
incorporated by reference to the extent that no conflict exists
between such text and the other statements and drawings set forth
herein. In the event of such conflict, then any such conflicting
text in such incorporated by reference U.S. patents is specifically
not incorporated by reference in this patent.
[0321] Further modifications and alternative embodiments of various
aspects of the invention will be apparent to those skilled in the
art in view of this description. Accordingly, this description is
to be construed as illustrative only and is for the purpose of
teaching those skilled in the art the general manner of carrying
out the invention. It is to be understood that the forms of the
invention shown and described herein are to be taken as examples of
embodiments. Elements and materials may be substituted for those
illustrated and described herein, parts and processes may be
reversed and certain features of the invention may be utilized
independently, all as would be apparent to one skilled in the art
after having the benefit of this description of the invention.
Changes may be made in the elements described herein without
departing from the spirit and scope of the invention as described
in the following claims.
* * * * *