U.S. patent application number 11/014281 was filed with the patent office on 2005-06-23 for systems and methods of producing a crude product.
Invention is credited to Brownscombe, Thomas Fairchild, Milam, Stanley Nemec, Wellington, Scott Lee.
Application Number | 20050133405 11/014281 |
Document ID | / |
Family ID | 34682023 |
Filed Date | 2005-06-23 |
United States Patent
Application |
20050133405 |
Kind Code |
A1 |
Wellington, Scott Lee ; et
al. |
June 23, 2005 |
Systems and methods of producing a crude product
Abstract
Contact of a crude feed with one or more catalysts produces a
total product that includes a crude product. The crude feed has a
residue content of at least 0.2 grams of residue per gram of crude
feed. At least a portion of the crude product may be produced as a
vapor. The crude product is a liquid mixture at 25.degree. C. and
0.101 MPa. One or more properties of the crude product may be
changed by at least 10% relative to the respective properties of
the crude feed.
Inventors: |
Wellington, Scott Lee;
(Bellaire, TX) ; Brownscombe, Thomas Fairchild;
(Houston, TX) ; Milam, Stanley Nemec; (Houston,
TX) |
Correspondence
Address: |
Richard F. Lemuth
Shell Oil Company
Legal - Intellectual Property
P. O. Box 2463
Houston
TX
77252-2463
US
|
Family ID: |
34682023 |
Appl. No.: |
11/014281 |
Filed: |
December 16, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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60531506 |
Dec 19, 2003 |
|
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60618814 |
Oct 14, 2004 |
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Current U.S.
Class: |
208/14 ; 208/143;
208/89 |
Current CPC
Class: |
C10G 65/04 20130101;
Y02P 20/142 20151101; Y02P 20/141 20151101; C10G 45/00 20130101;
C10L 1/04 20130101 |
Class at
Publication: |
208/014 ;
208/143; 208/089 |
International
Class: |
C10G 065/02; C10G
045/00; C10L 001/00 |
Claims
What is claimed is:
1. A method of producing a crude product, comprising: contacting a
crude feed with a hydrogen source in the presence of one or more
catalysts to produce a total product that includes the crude
product, wherein the crude product is a liquid mixture at
25.degree. C. and 0.101 MPa, the crude feed having at least 0.2
grams of residue per gram of crude feed, as determined by ASTM
Method D5307; producing at least a portion of the total product as
a vapor; condensing at least a portion of the vapor; and forming
the crude product, wherein the crude product has, per gram of crude
product: at least 0.001 grams of naphtha, the naphtha having an
octane number of at least 70; at least 0.001 grams of vacuum gas
oil (VGO), the VGO having at least 0.3 grams of aromatics per gram
of VGO, as determined by IP Method 368/90; and at most 0.05 grams
of residue, as determined by ASTM Method D5307.
2. The method of claim 1, wherein the vapor production is also
controlled such that the crude product comprises components with a
selected API gravity, as determined by ASTM Method D6822.
3. The method of claim 1, wherein the vapor production is also
controlled such that, during contacting, at most 0.5 grams of coke
is formed per gram of crude product.
4. The method of claim 1, wherein at least one of the catalysts
comprises an inorganic salt catalyst, and the inorganic salt
catalyst exhibits an emitted gas inflection of an emitted gas in a
temperature range between about 50.degree. C. and about 500.degree.
C., as determined by Temporal Analysis of Products.
5. The method of claim 1, wherein at least one of the catalysts
comprises an inorganic salt catalyst, and the inorganic salt
catalyst comprises one or more alkali metal carbonates, one or more
alkali metal hydroxides, one or more alkali metal hydrides, or
mixtures thereof.
6. The method of claim 1, wherein at least one of the catalysts
comprises an inorganic salt catalyst, and the inorganic salt
catalyst comprises one or more sulfides of one or more alkali
metals, one or more amides of one or more alkali metals, or
mixtures thereof.
7. The method of claim 1, wherein at least one of the catalysts
comprises an inorganic salt catalyst, and the inorganic salt
catalyst comprises a mixture of a potassium salt, a rubidium salt,
and a cesium salt.
8. The method of claim 7, wherein the potassium salt comprises
potassium carbonate, potassium hydroxide, potassium hydride, or
mixtures thereof; the rubidium salt comprises rubidium carbonate,
rubidium hydroxide, rubidium hydride, or mixtures thereof; and the
cesium salt comprises cesium carbonate, cesium hydroxide, cesium
hydride, or mixtures thereof.
9. The method of claim 1, wherein at least one of the catalysts
comprises an inorganic salt catalyst, and the inorganic salt
catalyst comprises a mixture of a sodium salt and a potassium
salt.
10. The method of claim 9, wherein the potassium salt comprises
potassium carbonate, potassium hydroxide, potassium hydride, or
mixtures thereof; and the sodium salt comprises sodium carbonate,
sodium hydroxide, sodium hydride, or mixtures thereof.
11. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides.
12. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides, and the transition
metal sulfides comprise a transition metal from Columns 6-10 of the
Periodic Table.
13. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides, and a transition
metal of at least one of the transition metal sulfides is iron.
14. The method of claim 1, wherein at least one of the catalysts
has a total of at least 0.4 grams of one or more transition metal
sulfides per gram of catalyst.
15. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides; and one or more
alkali metals, one or more compounds of one or more alkali metals,
or mixtures thereof.
16. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides; and one or more
alkaline-earth metals, one or more compounds of one or more
alkaline-earth metals, or mixtures thereof.
17. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides and zinc.
18. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides; and one or more
alkali metals, one or more compounds of one or more alkali metals,
or mixtures thereof, wherein an atomic ratio of transition metal to
sulfur in the catalyst is in a range from about 0.5 to about 2.5,
and an atomic ratio of the alkali metal to the transition metal is
in a range from above 0 to about 1.
19. The method of claim 1, wherein at least one of the catalysts
comprises one or more transition metal sulfides; and one or more
alkaline-earth metals, one or more compounds of one or more
alkaline-earth metals, or mixtures thereof; wherein an atomic ratio
of transition metal to sulfur in the catalyst is in a range from
about 0.5 to about 2.5, and an atomic ratio of the alkaline-earth
metal to the transition metal is in a range from above 0 to about
1.
20. The method of claim 1, wherein the crude product has from about
0.4 to about 0.9 grams of VGO per gram of crude product, and the
crude product also has from about 0.01 to about 0.4 grams of diesel
per gram of crude product.
21. The method of claim 1, wherein the crude product has from about
0.4 to about 0.9 grams of VGO per gram of crude product, and the
crude product also has from about 0.0001 to about 0.5 grams of
kerosene per gram of crude product.
22. The method of claim 1, wherein the crude product has from about
0.4 to about 0.9 grams of VGO per gram of crude product.
23. The method of claim 1, wherein the crude product has from about
0.6 to about 0.8 grams of VGO per gram of crude product.
24. The method of claim 1, wherein the crude product also has at
least 0.001 grams of kerosene per gram of crude product, at least
0.001 grams of diesel per gram of crude product, or mixtures
thereof.
25. The method of claim 1, wherein the method further comprises
combining the crude product with a crude that is the same as or
different from the crude feed to form a blend suitable for
transportation and/or treatment facilities.
26. The method of claim 1, wherein the method further comprises
processing the crude product to produce transportation fuel.
27. A crude product obtainable by a method, comprising: contacting
a crude feed with a hydrogen source in the presence of one or more
catalysts to produce a total product that includes the crude
product, the crude feed having at least 0.2 grams of residue per
gram of crude feed, as determined by ASTM Method D5307; producing
at least a portion of the total product as a vapor; condensing at
least a portion of the vapor; and forming the crude product,
wherein the crude product has, per gram of crude product: at least
0.001 grams of naphtha, the naphtha having an octane number of at
least 70; at least 0.001 grams of vacuum gas oil (VGO), the VGO
having at least 0.3 grams of aromatics per gram of VGO, as
determined by IP Method 368/90; and at most 0.5 grams of residue,
as determined by ASTM Method D5307.
28. A method of producing transportation fuel, comprising:
processing a crude product, wherein the crude product is obtainable
by: contacting a crude feed with a hydrogen source in the presence
of one or more catalysts to produce a total product that includes
the crude product, the crude feed having at least 0.2 grams of
residue per gram of crude feed, as determined by ASTM Method D5307;
producing at least a portion of the total product as a vapor;
condensing at least a portion of the vapor; and forming the crude
product, wherein the crude product has, per gram of crude product:
at least 0.001 grams of naphtha, the naphtha having an octane
number of at least 70; at least 0.001 grams of vacuum gas oil
(VGO), the VGO having at least 0.3 grams of aromatics per gram of
VGO, as determined by IP Method 368/90; and at most 0.5 grams of
residue, as determined by ASTM Method D5307.
29. The method of claim 28, wherein the processing comprises
distilling the crude product into one or more distillate
fractions.
30. The method of claim 28, wherein the processing comprises
hydrotreating.
Description
PRIORITY CLAIM
[0001] This application claims priority to Provisional patent
application No. 60/531,506 entitled "METHODS OF PREPARING IMPROVED
CRUDE FEED" filed on Dec. 19, 2003, and to Provisional patent
application No. 60/618,814 entitled "SYSTEMS AND METHODS OF
PRODUCING A CRUDE PRODUCT" filed on Oct. 14, 2004.
FIELD OF THE INVENTION
[0002] The present invention generally relates to systems and
methods for treating crude feed, and to compositions that are
produced, for example, using such systems and methods. More
particularly, embodiments described herein relate to systems and
methods for conversion of a crude feed that has a residue content
of at least 0.2 grams of residue per gram of crude feed to a crude
product that is (a) a liquid mixture at 25.degree. C. and 0.101
MPa, and (b) has one or more properties that are improved in
comparison to the same properties 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 often contain relatively high levels of
residue. Such crudes tend to be difficult and expensive to
transport and/or process using conventional facilities. High
residue crudes may be treated at high /temperatures to convert the
crude to coke. Alternatively, high residue crudes are typically
treated with water at high temperatures to produce less viscous
crudes and/or crude mixtures. During processing, water removal from
the less viscous crudes and/or crude mixtures may be difficult
using conventional means.
[0005] 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.
[0006] 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 by
coke. High temperatures used during regeneration may also diminish
the activity of the catalyst and/or cause the catalyst to
deteriorate.
[0007] 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.
[0008] Disadvantaged crudes may contain 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 the void volume of the catalyst. Such deposits may
cause a decline in the activity of the catalyst.
[0009] Disadvantaged crudes often include organically bound
heteroatoms (for example, sulfur, oxygen, and nitrogen).
Organically bound heteroatoms may, in some situations, have an
adverse effect on catalysts. Alkali metal salts and/or
alkaline-earth metal salts have been used in processes for
desulfurization of residue. These processes tend to result in poor
desulfurization efficiency, production of oil insoluble sludge,
poor demetallization efficiency, formation of substantially
inseparable salt-oil mixtures, utilization of large quantities of
hydrogen gas, and/or relatively high hydrogen pressures.
[0010] 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.
[0011] U.S. Pat. No. 3,136,714 to Gibson et al.; U.S. Pat. No.
3,558,747 to Gleim et al.; U.S. Pat. No. 3,847,797 to Pasternak et
al.; U.S. Pat. No. 3,948,759 to King et al.; U.S. Pat. No.
3,957,620 to Fukui et al.; U.S. Pat. No. 3,960,706 to McCollum et
al.; U.S. Pat. No. 3,960,708 to McCollum et al.; U.S. Pat. No.
4,119,528 to Baird, Jr. et al.; U.S. Pat. No. 4,127,470 to Baird,
Jr. et al.; U.S. Pat. No. 4,224,140 to Fujimori et al.; U.S. Pat.
No. 4,437,980 to Heredy et al.; U.S. Pat. No. 4,591,426 to Krasuk
et al.; U.S. Pat. No. 4,665,261 to Mazurek; U.S. Pat. No. 5,064,523
to Kretschmar et al.; U.S. Pat. No. 5,166,118 to Kretschmar et al.;
U.S. Pat. No. 5,288,681 to Gatsis; U.S. Pat. No. 6,547,957 to
Sudhakar et al.; and U.S. patent application Publication Nos.
20030000867 to Reynolds and 20030149317 to Rendina, all of which
are incorporated herein by reference, describe various processes
and systems used to treat crudes. The process, systems, and
catalysts described in these patents, however, have limited
applicability because of many of the technical problems set forth
above.
[0012] In sum, disadvantaged crudes generally have undesirable
properties (for example, relatively high residue, a tendency to
corrode equipment, 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, relatively high TAN, organically bound heteroatoms, and/or
metal contaminants). 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 properties that are more desirable.
SUMMARY OF THE INVENTION
[0013] Inventions described herein generally relate to systems and
methods for contacting a crude feed with one or more catalysts to
produce 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.
[0014] In certain embodiments, the invention provides a method of
preparing a crude product, comprising contacting a crude feed with
a hydrogen source in the presence of one or more catalysts
comprising a transition metal sulfide catalyst 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, and the
transition metal sulfide catalyst comprises
K.sub.3Fe.sub.10S.sub.14.
[0015] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, at least one of the catalysts comprising one or more
transition metal sulfides, and the crude feed having a residue
content of at least 0.2 grams of residue per gram of crude feed, as
determined by ASTM Method D5307; and controlling contacting
conditions such that the crude product has at most 0.05 grams of
coke per gram of crude product, the crude product has at least
0.001 grams of naphtha per gram of crude product, and the naphtha
has an octane number of at least 70.
[0016] In some embodiments, the invention provides a method of
preparing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, at least one of the catalysts comprising one or more
transition metal sulfides, and the crude feed having a residue
content of at least 0.2 grams of residue per gram of crude feed, as
determined by ASTM Method D5307; and controlling contacting
conditions such that the crude product comprises kerosene, the
kerosene having at least 0.2 grams of aromatics per gram of
kerosene, as determined by ASTM Method D5186, the kerosene having a
freezing point at a temperature of at most -30.degree. C., as
determined by ASTM Method D2386, and the crude product having at
most 0.05 grams of coke per gram of crude product.
[0017] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, at least one of the catalysts comprising one or more
transition metal sulfides, and the crude feed having a residue
content of at least 0.2 grams of residue per gram of crude feed;
and controlling contacting conditions such that the crude product
has at most 0.05 grams of coke per gram of crude product with a
weight ratio of atomic hydrogen to atomic carbon (H/C) in the crude
product of at most 1.75, as determined by ASTM Method D6730.
[0018] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, at least one of the catalysts comprising one or more
transition metal sulfides, and the crude feed having a residue
content of at least 0.2 grams of residue per gram of crude feed, as
determined by ASTM Method D5307, and a weight ratio of atomic
hydrogen to atomic carbon (H/C) in the crude feed is at least 1.5;
and controlling contacting conditions such that the crude product
has an atomic H/C ratio of about 80-120% of the atomic H/C ratio of
the crude feed, the crude product having a residue content of at
most 30% of the residue content of the crude feed, as determined by
ASTM Method D5307, the crude product having at least 0.001 grams of
naphtha per gram of crude product, and the naphtha having an octane
number of at least 70.
[0019] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts, to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, at least one of the catalysts comprising one or more
transition metal sulfides, and the crude feed has a residue content
of at least 0.2 rams of residue per gram of crude feed, as
determined by ASTM Method D5307; and controlling contacting
conditions such that the crude product has, per gram of crude
product: at least 0.001 grams of naphtha, the naphtha having an
octane number of at least 70; at least 0.001 grams of kerosene, the
kerosene comprising aromatics, the kerosene having at least 0.2
grams of aromatics per gram of kerosene, as determined by ASTM
Method D5186, and the kerosene having a freezing point at a
temperature of at most -30.degree. C., as determined by ASTM Method
D2386; at least 0.001 grams of vacuum gas oil (VGO), the VGO having
at least 0.3 grams of aromatics per gram of VGO, as determined by
IP Method 368/90; and at most 0.05 grams of residue, as determined
by ASTM Method D5307.
[0020] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts
comprising a transition metal sulfide catalyst 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 transition
metal sulfide catalyst having a total of at least 0.4 grams of one
or more transition metal sulfides per gram of total transition
metal sulfide catalyst, the crude feed having a residue content of
at least 0.2 grams of residue per gram of crude feed, as determined
by ASTM Method D5307; and controlling contacting conditions such
that the crude product has at most 0.05 grams of coke per gram of
crude product, and the crude product has a residue content of at
most 30% of the residue content of the crude feed, as determined by
ASTM Method D5307.
[0021] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts
comprising a transition metal sulfide catalyst 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 transition
metal sulfide catalyst having a total of least 0.4 grams of one or
more transition metal sulfides per gram of transition metal sulfide
catalyst, the crude feed having a nitrogen content of at least
0.001 grams of nitrogen per gram of crude feed, and the crude feed
having a residue content of at least 0.2 grams of residue per gram
of crude feed; and controlling contacting conditions such that the
crude product has a nitrogen content of at most 90% of the nitrogen
content of the crude feed, and the crude product has a residue
content of at most 30% of the residue content of the crude feed,
wherein nitrogen content is as determined by ASTM Method D5762 and
residue content is as determined by ASTM Method D5307.
[0022] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts
comprising a transition metal sulfide catalyst 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 transition
metal sulfide catalyst has a total of least 0.4 grams of one or
more transition metal sulfides per gram of total transition metal
sulfide catalyst, the crude feed has a total Ni/V/Fe content of at
least 0.0001 grams of Ni/V/Fe per gram of crude feed, and the crude
feed has a residue content of at least 0.2 grams of residue per
gram of crude feed; and controlling contacting conditions such that
the crude product has at most 0.05 grams of coke per gram of crude
product, the crude product has a total Ni/V/Fe content of at most
90% of the Ni/V/Fe content of the crude feed, the crude product has
a residue content of at most 30% of the residue content of the
crude feed, and wherein Ni/V/Fe content is as determined by ASTM
Method D5863, and residue content is as determined by ASTM Method
D5307.
[0023] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts
comprising a transition metal sulfide catalyst 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 transition
metal sulfide catalyst having a total of at least 0.4 grams of one
or more transition metal sulfides per gram of total transition
metal sulfide catalyst, the crude feed having a sulfur content of
at least 0.001 grams of sulfur per gram of crude feed, and the
crude feed having a residue content at least 0.2 grams of residue
per gram of crude feed; and controlling contacting conditions such
that the crude product has a sulfur content of at most 70% of the
sulfur content of the crude feed, and the crude product has a
residue content of at most 30% of the residue content of the crude
feed, wherein sulfur content is as determined by ASTM Method D4294
and residue content is as determined by ASTM Method D5307.
[0024] In certain embodiments, the invention provides a method of
producing a transition metal sulfide catalyst composition,
comprising: mixing a transition metal oxide and a metal salt to
form a transition metal oxide/metal salt mixture; reacting the
transition metal oxide/metal salt mixture with hydrogen to form an
intermediate; and reacting the intermediate with sulfur in the
presence of one or more hydrocarbons to produce the transition
metal sulfide catalyst.
[0025] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts
comprising a transition metal sulfide catalyst 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 transition
metal sulfide catalyst comprises a transition metal sulfide, the
crude feed having a residue content of at least 0.2 grams of
residue per gram of crude feed, as determined by ASTM Method D5307;
controlling contact conditions such that the crude product has a
residue content of at most 30% of the residue content of the crude
feed; and wherein the transition metal sulfide catalyst is
obtainable by: mixing a transition metal oxide and a metal salt to
form a transition metal oxide/metal salt mixture; reacting the
transition metal oxide/metal salt mixture with hydrogen to form an
intermediate; and reacting the intermediate with sulfur in the
presence of one or more hydrocarbons to produce the transition
metal sulfide catalyst.
[0026] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of one or more catalysts to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, and the crude feed having at least 0.2 grams of residue per
gram of crude feed, as determined by ASTM Method D5307; producing
at least a portion of the total product as a vapor; condensing at
least a portion of the vapor at 25.degree. C. and 0.101 MPa; and
forming the crude product, wherein the crude product has, per gram
of crude product: at least 0.001 grams of naphtha, the naphtha
having an octane number of at least 70; at least 0.001 grams of
vacuum gas oil (VGO), the VGO having at least 0.3 grams of
aromatics per gram of VGO, as determined by IP Method 368/90; and
at most 0.05 grams of residue, as determined by ASTM Method
D5307.
[0027] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, as determined by ASTM Method D5307,
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, and the crude product has, per gram of crude product: at least
0.001 grams of naphtha, the naphtha having at least 0.001 grams of
monocyclic ring aromatics per gram of naphtha, as determined by
ASTM Method D6730; at least 0.001 grams of distillate; and at most
0.05 grams of residue, as determined by ASTM Method D5307.
[0028] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, as determined by ASTM Method D5307,
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, and the crude product has, per gram of crude product: at least
0.001 grams of diesel, and the diesel has at east 0.3 grams of
aromatics per gram of diesel, as determined by IP Method 368/90; at
least 0.001 grams of vacuum as oil (VGO), and the VGO has at least
0.3 grams of aromatics per gram of VGO, as determined by IP Method
68/90; and at most 0.05 grams of residue, as determined by ASTM
Method D5307.
[0029] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product hat includes the crude product, wherein the
crude product is a liquid mixture at 25.degree. C. and 0.101 MPa,
the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, as determined by ASTM Method D5307,
and the crude feed has a monocyclic ring aromatics content of at
most 0.1 grams of monocyclic ring aromatics per gram of crude feed;
and controlling contacting conditions such that during the
contacting at most 0.2 grams of hydrocarbons that are not
condensable at 25.degree. C. and 0.101 MPa are formed per gram of
crude feed, as determined by mass balance, and such that the crude
product has a monocyclic ring aromatics content of at least 5%
greater than a monocyclic ring aromatics content of the crude feed,
wherein monocyclic ring aromatics content is as determined by ASTM
Method D6730.
[0030] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
a produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, as determined by ASTM Method D5307,
and the crude feed has an olefins content, expressed in grams of
olefins per gram of crude feed; and controlling contacting
conditions such that the crude product has an olefins content of at
least 5% greater than the olefins content of the crude feed,
wherein olefin content is as determined by ASTM Method D6730.
[0031] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst 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 of at least 0.2 grams
of residue per gram of crude feed, and the inorganic salt catalyst
exhibits an emitted gas inflection of an emitted gas in a
temperature range between about 50.degree. C. and about 500.degree.
C., as determined by Temporal Analysis of Products (TAP); and
controlling contacting conditions such that the crude product has a
residue content, expressed in grams of residue per gram of crude
product, of at most 30% of the residue content of the crude feed,
wherein residue content is as determined by ASTM Method D5307.
[0032] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, the inorganic salt catalyst
comprises at least two inorganic metal salts, and the inorganic
salt catalyst exhibits an emitted gas inflection of an emitted gas
in a temperature range, as determined by Temporal Analysis of
Products (TAP), wherein the emitted gas inflection temperature
range is between (a) a DSC temperature of at least one of the two
inorganic metal salts and (b) a DSC temperature of the inorganic
salt catalyst; and controlling contacting conditions such that the
crude product has a residue content, expressed in grams of residue
per gram of crude product, of at most 30% of the residue content of
the crude feed, wherein residue content is as determined by ASTM
Method D5307.
[0033] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, as determined by ASTM Method D5307,
and the inorganic salt catalyst exhibits an emitted gas inflection
of an emitted gas in a temperature range between about 50.degree.
C. and about 500.degree. C., as determined by Temporal Analysis of
Products (TAP); and producing the crude product such that a volume
of the crude product produced is at least 5% greater than the
volume of the crude feed, when the volumes are measured at
25.degree. C. and 0.101 MPa.
[0034] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, and the inorganic salt catalyst
exhibits an emitted gas inflection of an emitted gas in a
temperature range between about 50.degree. C. and about 500.degree.
C., as determined by Temporal Analysis of Products (TAP); and
controlling contacting conditions such that during the contacting
at most 0.2 grams of hydrocarbons that are not condensable at
25.degree. C. and 0.101 MPa are formed per gram of crude feed, as
determined by mass balance.
[0035] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst 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 of at least 0.2 grams
of residue per gram of crude feed, and the inorganic salt catalyst
has a heat transition in a temperature range between about
200.degree. C. and about 500.degree. C., as determined by
differential scanning calorimetry (DSC), at a rate of about
10.degree. C. per minute; and controlling contacting conditions
such that the crude product has a residue content, expressed in
grams of residue per gram of crude product, of at most 30% of the
residue content of the crude feed, wherein residue content is as
determined by ASTM Method D5307.
[0036] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst 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 of at least 0.2 grams
of residue per gram of crude feed, and the inorganic salt catalyst
has ionic conductivity that is at least the ionic conductivity of
at least one of the inorganic salts of the inorganic salt catalyst
at a temperature in a range from about 300.degree. C. and about
500.degree. C.; and controlling contacting conditions such that the
crude product has a residue content, expressed in grams of residue
per gram of crude product, of at most 30% of the residue content of
the crude feed, wherein residue content is as determined by ASTM
Method D5307.
[0037] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, the inorganic salt catalyst
comprises alkali metal salts, wherein at least one of the alkali
metal salts is an alkali metal carbonate, and the alkali metals
have an atomic number of at least 11, and at least one atomic ratio
of an alkali metal having an atomic number of at least 11 to an
alkali metal having an atomic number greater than 11 is in a range
from about 0.1 to about 10; and controlling contacting conditions
such that the crude product has a residue content of at most 30% of
the residue content of the crude feed, wherein residue content is
as determined by ASTM Method D5307.
[0038] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product, wherein the crude feed has a residue
content of at least 0.2 grams of residue per gram of crude feed,
the inorganic salt catalyst comprises alkali metal salts, wherein
at least one of the alkali metal salts is an alkali metal
hydroxide, and the alkali metals have an atomic number of at least
11, and at least one atomic ratio of an alkali metal having an
atomic number of at least 11 to an alkali metal having an atomic
number greater than 11 is in a range from about 0.1 to about 10;
producing at least a portion of the total product as a vapor;
condensing at least a portion of the vapor at 25.degree. C. and
0.101 MPa; and forming the crude product, wherein the crude product
has a residue content of at most 30% of the residue content of the
crude feed.
[0039] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product, wherein the crude feed has a residue
content of at least 0.2 grams of residue per gram of crude feed,
the inorganic salt catalyst comprises alkali metal salts, wherein
at least one of the alkali metal salts is an alkali metal hydride,
and the alkali metals have an atomic number of at least 11, and at
least one atomic ratio of an alkali metal having an atomic number
of at least 11 to an alkali metal having an atomic number greater
than 11 is in a range from about 0.1 to about 10; producing at
least a portion of the total product as a vapor; condensing at
least a portion of the vapor at 25.degree. C. and 0.101 MPa; and
forming the crude product, wherein the crude product has a residue
content of at most 30% of the residue content of the crude
feed.
[0040] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, the inorganic salt catalyst
comprises one or more alkali metal salts, one or more
alkaline-earth metal salts, or mixtures thereof, wherein one of the
alkali metal salts is an alkali metal carbonate, wherein the alkali
metals have an atomic number of at least 11; and controlling
contacting conditions such that the crude product has a residue
content of at most 30% of the residue content of the crude feed,
wherein residue content is as determined by ASTM Method D5307.
[0041] In certain embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, the inorganic salt catalyst
comprises one or more alkali metal hydroxides, one or more
alkaline-earth metal salts, or mixtures thereof, wherein the alkali
metals have an atomic number of at least 11; and controlling
contacting conditions such that the crude product has a residue
content of at most 30% of the residue content of the crude feed,
wherein residue content is as determined by ASTM Method D5307.
[0042] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a crude feed with
a hydrogen source in the presence of an inorganic salt catalyst to
produce a total product that includes the crude product, wherein
the crude product is a liquid mixture at 25.degree. C. and 0.101
MPa, the crude feed has a residue content of at least 0.2 grams of
residue per gram of crude feed, the inorganic salt catalyst
comprises one or more alkali metal hydrides, one or more
alkaline-earth salts, or mixtures thereof, and wherein the alkali
metals have an atomic number of at least 11; and controlling
contacting conditions such that the crude product has a residue
content, expressed in grams of residue per gram of crude product,
of at most 30% of the residue content of the crude feed, wherein
residue content is as determined by ASTM Method D5307.
[0043] In certain embodiments, the invention provides a method of
producing hydrogen gas, comprising: contacting a crude feed with
one or more hydrocarbons in the presence of an inorganic salt
catalyst and water, the hydrocarbons have carbon numbers in a range
from 1 to 6, the crude feed has a residue content of at least 0.2
grams of residue per gram of crude feed, and the inorganic salt
catalyst exhibits an emitted gas inflection of an emitted gas in a
temperature range between about 50.degree. C. and about 500.degree.
C., as determined by Temporal Analysis of Products (TAP); and
producing hydrogen gas.
[0044] In some embodiments, the invention provides a method of
producing a crude product, comprising: contacting a first crude
feed with an inorganic salt catalyst in the presence of steam to
generate a gas stream, the gas stream comprising hydrogen, wherein
the first crude feed has a residue content of at least 0.2 grams of
residue per gram of first crude feed, as determined using ASTM
Method D5307, and the inorganic salt catalyst exhibits an emitted
gas inflection of an emitted gas in a temperature range between
about 50.degree. C. and about 500.degree. C., as determined by
Temporal Analysis of Products (TAP); contacting a second crude feed
with a second catalyst in the presence of at least a portion of the
generated gas stream 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; and controlling contacting conditions
such that one or more properties of the crude product change by at
least 10% relative to the respective one or more properties of the
second crude feed.
[0045] In certain embodiments, the invention provides a method of
generating a gas stream, comprising: contacting a crude feed with
an inorganic salt catalyst in the presence of steam, wherein the
crude feed has a residue content of at least 0.2 grams of residue
per gram of crude feed, as determined by ASTM Method 5307; and
generating a gas stream, the gas stream comprising hydrogen, carbon
monoxide, and carbon dioxide, and wherein a molar ratio of the
carbon monoxide to the carbon dioxide is at least 0.3.
[0046] In some embodiments, the invention provides a method of
producing a crude product comprising: conditioning an inorganic
salt catalyst; contacting a crude feed with a hydrogen source in
the presence of the conditioned inorganic salt catalyst 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 of at least 0.2 grams of
residue per gram of crude feed; and controlling contacting
conditions such that the crude product has a residue content,
expressed in grams of residue per gram of crude product, of at most
30% of the residue content of the crude feed, wherein residue
content is as determined by ASTM Method D5307.
[0047] In certain embodiments, the invention provides a crude
composition, comprising hydrocarbons that have a boiling range
distribution between about 30.degree. C. and about 538.degree. C.
(1,000.degree. F.) at 0.101 MPa, the hydrocarbons comprising
iso-paraffins and n-paraffins with a weight ratio of the
iso-paraffins to n-paraffins of at most 1.4, as determined by ASTM
Method D6730.
[0048] In some embodiments, the invention provides a crude
composition having, per gram of composition: at least 0.001 grams
of hydrocarbons with a boiling range distribution of at most
204.degree. C. (400.degree. F.) at 0.101 MPa, at least 0.001 grams
of hydrocarbons with a boiling range distribution between about
204.degree. C. and about 300.degree. C. at 0.101 MPa, at least
0.001 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 of hydrocarbons with a boiling range
distribution between about 400.degree. C. and about 538.degree. C.
(1,000.degree. F.) at 0.101 MPa, and wherein the hydrocarbons that
have a boiling range distribution of at most 204.degree. C.
comprise iso-paraffins and n-paraffins with a weight ratio of the
iso-paraffins to the n-paraffins of at most 1.4, as determined by
ASTM Method D6730.
[0049] In certain embodiments, the invention provides a crude
composition having, per gram of composition: at least 0.001 grams
of naphtha, the naphtha having an octane number of at least 70, and
the naphtha having at most 0.15 grams of olefins per gram of
naphtha, as determined by ASTM Method D6730; at least 0.001 grams
of kerosene, the kerosene having at least 0.2 grams of aromatics
per gram of kerosene, as determined by ASTM D5186, and the kerosene
having a freezing point at a temperature of at most -30.degree. C.,
as determined by ASTM Method D2386; and at most 0.05 grams of
residue, as determined by ASTM Method D5307.
[0050] In some embodiments, the invention provides a crude
composition having, per gram of composition: at most 0.15 grams of
hydrocarbon gas that is non-condensable at 25.degree. C. and 0.101
MPa, the non-condensable hydrocarbon gas having at most 0.3 grams
of hydrocarbons with a carbon number from 1 to 3 (C.sub.1 to
C.sub.3), per gram of non-condensable hydrocarbon gas; at least
0.001 grams of naphtha, the naphtha having an octane number of at
least 70; at least 0.001 grams of kerosene, the kerosene having a
freezing point at a temperature of at most -30.degree. C., as
determined by ASTM Method D2386, and the kerosene having at least
0.2 grams of aromatics per gram of kerosene, as determined by ASTM
Method D5186; and at most 0.05 grams of residue, as determined by
ASTM Method D5307.
[0051] In certain embodiments, the invention provides a crude
composition, having, per gram of composition: at most 0.05 grams of
residue, as determined by ASTM Method D5307; at least 0.001 grams
of hydrocarbons with a boiling range distribution of at most
204.degree. C. (400.degree. F.) at 0.101 MPa; at least 0.001 grams
of hydrocarbons with a boiling range distribution between about
204.degree. C. and about 300.degree. C. at 0.101 MPa; at least
0.001 grams of hydrocarbons with a boiling range distribution
between about 300.degree. C. and about 400.degree. C. at 0.101 MPa;
at least 0.001 grams of hydrocarbons with a boiling range
distribution between about 400.degree. C. and about 538.degree. C.
(1,000.degree. F.) at 0.101 MPa; and wherein the hydrocarbons in a
boiling range distribution between about 20.degree. C. and about
204.degree. C. comprise olefins having terminal double bonds and
olefins having internal double bonds with a molar ratio of olefins
having terminal double bonds to olefins having internal double
bonds of at least 0.4, as determined by ASTM Method D6730.
[0052] In some embodiments, the invention provides a crude
composition, having, per gram of composition: at most 0.05 grams of
residue, as determined by ASTM Method D5307; and at least 0.001
grams of a mixture of hydrocarbons that have a boiling range
distribution between about 20.degree. C. and about 538.degree. C.
(1,000.degree. F.), as determined by ASTM Method D5307, and the
hydrocarbon mixture has, per gram of hydrocarbon mixture: at least
0.001 grams of paraffins, as determined by ASTM Method D6730; at
least 0.001 grams of olefins, as determined by ASTM Method D6730,
and the olefins have at least 0.001 grams of terminal olefins per
gram of olefins, as determined by ASTM Method D6730; at least 0.001
grams of naphtha; at least 0.001 grams of kerosene, the kerosene
having at least 0.2 grams of aromatics per gram of kerosene, as
determined by ASTM Method D5186; at least 0.001 grams of diesel,
the diesel having at least 0.3 grams of aromatics per gram of
diesel, as determined by IP Method 368/90; and at least 0.001 grams
of vacuum gas oil (VGO), the VGO having at least 0.3 grams of
aromatics per gram of VGO, as determined by IP Method 368/90.
[0053] In certain embodiments, the invention provides a crude
composition having, per gram of composition: at most 0.05 grams of
residue, as determined by ASTM Method D5307; at least 0.001 grams
of hydrocarbons with a boiling range distribution of at most
204.degree. C. (400.degree. F.) at 0.101 MPa; at least 0.001 grams
of hydrocarbons with a boiling range distribution between about
204.degree. C. and about 300.degree. C. at 0.101 MPa; at least
0.001 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 of hydrocarbons with a boiling range
distribution between about 400.degree. C. and about 538.degree. C.
(1,000.degree. F.) at 0.101 MPa, as determined by ASTM Method
D2887; and wherein the hydrocarbons having a boiling range
distribution of at most 204.degree. C. have, per gram of
hydrocarbons having a boiling range distribution of at most
204.degree. C.: at least 0.001 grams of olefins, as determined by
ASTM Method D6730; and at least 0.001 grams of paraffins, the
paraffins comprising iso-paraffins and n-paraffins with a weight
ratio of iso-paraffins to n-paraffins of at most 1.4, as determined
by ASTM Method D6730.
[0054] In some embodiments, the invention provides a crude
composition having, per gram of composition: at most 0.05 grams of
residue, as determined by ASTM Method D5307; and at least 0.001
grams of hydrocarbons with a boiling range distribution of at most
204.degree. C. (400.degree. F.) at 0.101 MPa; at least 0.001 grams
of hydrocarbons with a boiling range distribution between about
204.degree. C. and about 300.degree. C. at 0.101 MPa; at least
0.001 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 of hydrocarbons with a boiling range
distribution between about 400.degree. C. and about 538.degree. C.
(1,000.degree. F.) at 0.101 MPa, as determined by ASTM Method
D2887; and wherein the hydrocarbons having a boiling range
distribution between about -10.degree. C. and about 204.degree. C.
comprise compounds with a carbon number of 4 (C.sub.4), the C.sub.4
compounds having at least 0.001 grams of butadiene per gram of
C.sub.4 compounds.
[0055] In certain embodiments, the invention provides a crude
composition having, per gram of composition: at most 0.05 grams of
residue; at least 0.001 grams of hydrocarbons with a boiling range
distribution of at most 204.degree. C. (400.degree. F.) at 0.101
MPa, at least 0.001 grams of hydrocarbons with a boiling range
distribution between about 204.degree. C. and about 300.degree. C.
at 0.101 MPa, at least 0.001 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 of
hydrocarbons with a boiling range distribution between about
400.degree. C. and about 538.degree. C. at 0.101 MPa; and greater
than 0 grams, but less than 0.01 grams of one or more catalyst,
wherein the catalyst has at least one or more alkali metals.
[0056] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a crude feed
that: (a) has not been treated in a refinery, distilled, and/or
fractionally distilled; (b) comprises components having a carbon
number above 4, and the crude feed has at least 0.5 grams of such
components per gram of crude feed; (c) comprises hydrocarbons of
which a portion has: a boiling range distribution below 100.degree.
C. at 0.101 MPa, a boiling range distribution between 100.degree.
C. and 200.degree. C. at 0.101 MPa, a boiling range distribution
between about 200.degree. C. and about 300.degree. C. at 0.101 MPa,
a boiling range distribution between about 300.degree. C. and about
400.degree. C. at 0.101 MPa, and a boiling range distribution
between about 400.degree. C. and about 700.degree. C. at 0.101 MPa;
(d) has, per gram of crude feed: at least 0.001 grams of
hydrocarbons having a boiling range distribution below 100.degree.
C. at 0.101 MPa, at least 0.001 grams of hydrocarbons having a
boiling range distribution between 100.degree. C. and 200.degree.
C. at 0.101 MPa, at least 0.001 grams of hydrocarbons having a
boiling range distribution between about 200.degree. C. and about
300.degree. C. at 0.101 MPa, at least 0.001 grams of hydrocarbons
having a boiling range distribution between about 300.degree. C.
and about 400.degree. C. at 0.101 MPa, and at least 0.001 grams of
hydrocarbons having a boiling range distribution between about
400.degree. C. and about 700.degree. C. at 0.101 MPa; (e) has a
TAN; (f) has from about 0.2-0.99 grams, about 0.3-0.8 grams, or
about 0.4-0.7 grams of residue per gram of crude feed; (g)
comprises nickel, vanadium, iron, or mixtures thereof; (h)
comprises sulfur; and/or (i) nitrogen containing hydrocarbons.
[0057] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, the hydrogen
source that: (a) is gaseous; (b) comprises molecular hydrogen; (c)
comprises light hydrocarbons; (d) comprises methane, ethane,
propane, or mixtures thereof; (e) comprises water; and/or (f)
mixtures thereof.
[0058] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
that includes conditioning the inorganic salt catalyst, wherein
conditions the inorganic catalyst comprises: (a) heating the
inorganic salt catalyst to a temperature of at least 300.degree.
C.; and/or (b) heating the inorganic salt catalyst to a temperature
of at least 300.degree. C. and cooling the inorganic salt catalyst
to a temperature of at most 500.degree. C.
[0059] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
that comprises contacting a crude feed with one or more catalysts
and controlling contacting conditions: (a) such that during the
contacting at most 0.2 grams, at most 0.15 grams, at most 0.1
grams, or at most 0.05 grams of hydrocarbons that are not
condensable at 25.degree. C. and 0.101 MPa are formed per gram of
crude feed, as determined by mass balance; (b) such that a
contacting temperature is in a range from about 250-750.degree. C.
or between about 260-550.degree. C.; (c) a pressure is in a range
from about 0.1-20 MPa; (d) such that a ratio of a gaseous hydrogen
source to the crude feed is in a range from about 1-16100 or about
5-320 normal cubic meters of the hydrogen source per cubic meter of
the crude feed; (e) to inhibit coke formation; (f) to inhibit
formation of coke in the total product or in the crude feed during
the contacting; (g) such that the crude product also has at most
0.05 grams, at most 0.03 grams, at most 0.01 grams, or at most
0.003 grams of coke per gram of crude product; (h) such that at
least a portion of the inorganic salt catalyst is semi-liquid or
liquid at such contacting conditions; (i) such that the crude
product has a TAN of at most 90% of the TAN of the crude feed; (j)
such that the crude product has a total Ni/V/Fe content of at most
90%, at most 50%, or at most 10% of the Ni/V/Fe content of the
crude feed; (k) such that the crude product has a sulfur content of
at most 90%, at most 60%, or at most 30% of the sulfur content of
the crude feed; (l) such that the crude product has a nitrogen
content of at most 90%, at most 70%, at most 50%, or at most 10% of
the nitrogen content of the crude feed; (m) such that the crude
product has a residue content of at most 30%, at most 10%, or at
most 5% of the residue content of the crude feed; (n) such that
ammonia is co-produced with the crude product; (o) such that the
crude product comprises methanol, and the method further comprises:
recovering the methanol from the crude product; combining the
recovered methanol with additional crude feed to form an additional
crude feed/methanol mixture; and heating the additional crude
feed/methanol mixture such that TAN of the additional crude feed is
reduced to below 1; (p) such that one or more properties of the
crude product change by at most 90% relative to the respective one
or more properties of the crude feed; (q) such that an amount of
catalyst in the contacting zone ranges from about 1-60 grams of
total catalyst per 100 grams of crude feed; and/or (r) such that a
hydrogen source is added to the crude feed prior to or during the
contacting.
[0060] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, contacting
conditions that comprise: (a) mixing the inorganic salt catalyst
with the crude feed at a temperature below 500.degree. C., wherein
the inorganic salt catalyst is substantially insoluble in the crude
feed; (b) agitating the inorganic catalyst in the crude feed;
and/or (c) contacting the crude feed with the inorganic salt
catalyst in the presence of water and/or steam to produce a total
product that includes the crude product that is a liquid mixture at
STP.
[0061] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
that comprises contacting a crude feed with an inorganic salt
catalyst and that further comprises: (a) providing steam to a
contacting zone prior to or during contacting; (b) forming an
emulsion of the crude feed with water prior to contacting the crude
feed with the inorganic salt catalyst and the hydrogen source; (c)
spraying the crude feed into the contacting zone; and/or (d)
contacting steam with the inorganic salt catalyst to at least
partially remove coke from the surface of the inorganic salt
catalyst.
[0062] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
that comprises contacting a crude feed with an inorganic salt
catalyst to produce a total product wherein at least a portion of
the total product is produced as a vapor, and the method further
comprises condensing at least a portion of the vapor at 25.degree.
C. and 0.101 MPa to form the crude product, the contacting
conditions are controlled such that: (a) the crude product further
comprises components with a selected boiling range distribution;
and/or (b) the crude product comprises components having a selected
API gravity.
[0063] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
that comprises contacting a crude feed with an one or more
catalysts and that the one or more catalysts are nonacidic.
[0064] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a
K.sub.3Fe.sub.10S.sub.14 catalyst or a transition metal sulfide
catalyst that: (a) has a total of at least 0.4 grams, at least 0.6
grams, or at least 0.8 grams of at least one of transition metal
sulfides per gram of the K.sub.3Fe.sub.10S.sub.14 catalyst or the
transition metal sulfide catalyst; (b) has an atomic ratio of
transition metal to sulfur in the K.sub.3Fe.sub.10S.sub.14 catalyst
or the transition metal sulfide catalyst in a range from about 0.2
to about 20; (c) further comprises one or more alkali metals, one
or more compounds of one or more alkali metals, or mixtures
thereof; (d) further comprises one or more alkaline-earth metals,
one or more compounds of one or more alkaline-earth metals, or
mixtures thereof; (e) further comprises one or more alkali metals,
one or more compounds of one or more alkali metals, or mixtures
thereof, wherein an atomic ratio of transition metal to sulfur in
the K.sub.3Fe.sub.10GS.sub.14 catalyst or the transition metal
sulfide catalyst is in a range from about 0.5-2.5 and an atomic
ratio of the alkali metals to the transition metal is in a range
from above 0 to about 1; (f) further comprises one or more
alkaline-earth metals, one or more compounds of one or more
alkaline-earth metals, or mixtures thereof, an atomic ratio of
transition metal to sulfur in the K.sub.3Fe.sub.10S.sub.14 catalyst
or the transition metal sulfide catalyst is in a range from about
0.5-2.5; and an atomic ratio of the alkaline-earth metal to the
transition metal is in a range from above 0 to about 1; (g) further
comprises zinc; (h) further comprises K.sub.3Fe.sub.2S.sub.3; (i)
further comprises KFeS.sub.2; and/or (j) is nonacidic.
[0065] In some embodiments, the transition metal sulfide catalyst
comprises a mixture of one or more transition metal sulfides, one
or more alkali metals, one or more compounds of one or more alkali
metals, or mixtures thereof, and during contacting a portion of the
transition metal sulfides are convert to
K.sub.3Fe.sub.10S.sub.14.
[0066] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, one or more
of the transition metal sulfides that or in which: (a) comprise one
or more transition metals from Columns 6-10 of the Periodic Table,
one or more compounds of one or more transition metals from Columns
6-10, or mixtures thereof; (b) comprise one or more iron sulfides;
(c) comprises FeS; (d) comprises FeS.sub.2; (e) comprise a mixture
of iron sulfides, wherein the iron sulfides are represented by the
formula Fe.sub.(1-b)S, where b is in a range from above 0 to about
0.17; (f) further comprises K.sub.3Fe.sub.10S.sub.14 after contact
with the crude feed; (g) at least one of the transition metals of
the one or more transition metal sulfides is iron; and/or (h) are
deposited on a support, and the transition metal sulfide catalyst
has at most 0.25 grams of total support per 100 grams of
catalyst.
[0067] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method of
forming a transition metal sulfide catalyst composition the method
comprising mixing a transition metal oxide and a metal salt to form
a transition metal oxide/metal salt mixture; reacting the
transition metal oxide/metal salt mixture with hydrogen to form an
intermediate; and reacting the intermediate with sulfur in the
presence of one or more hydrocarbons to produce the transition
metal sulfide catalyst: (a) in which the transition metal
oxide/metal salt mixture comprises a hydrate; (b) the metal salt
comprises an alkali metal carbonate; (c) that further comprises
dispersing the intermediate in the one or more liquid hydrocarbons
while it is reacted with the sulfur; (d) in which one or more of
the hydrocarbons have a boiling point of at least 100.degree. C.;
(e) in which one or more of the hydrocarbons is VGO, xylene, or
mixtures thereof; (f) in which mixing the transition metal oxide
and the metal salt comprises: mixing the transition metal oxide and
the metal salt in the presence of de-ionized water to from a wet
paste; drying the wet paste at a temperature in a range from about
150-250.degree. C.; and calcining the dried paste at a temperature
in a range from about 300-600.degree. C.; (g) in which reacting the
intermediate with sulfur comprises heating the intermediate in the
presence of at least one of the hydrocarbons to a temperature in
the range from about 240-350.degree. C.; and/or (h) that further
comprises contacting the catalyst composition with a crude feed
that comprises sulfur and a hydrogen source.
[0068] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst that comprises: (a) one or more alkali metal
carbonates, one or more alkaline-earth metal carbonates, or
mixtures thereof; (b) one or more alkali metal hydroxides, one or
more alkaline-earth metal hydroxides, or mixtures thereof; (c) one
or more alkali metal hydrides, one or more alkaline-earth metal
hydrides, or mixtures thereof; (d) one or more sulfides of one or
more alkali metals, one or more sulfides of one or more
alkaline-earth metals, or mixtures thereof; (e) one or more amides
of one or more alkali metals, one or more amides of one or more
alkaline-earth metals, or mixtures thereof; (f) one or more metals
from Columns 6-10 of the Periodic Table, one or more compounds of
one or more metals from Columns 6-10 of the Periodic Table, or
mixtures thereof; (g) one or more inorganic metal salts, and
wherein at least one of the inorganic metal salts generates hydride
during use of the catalyst; (h) sodium, potassium, rubidium,
cesium, or mixtures thereof; (i) calcium and/or magnesium; (j) a
mixture of a sodium salt and a potassium salt and the potassium
salt comprises potassium carbonate, potassium hydroxide, potassium
hydride, or mixtures thereof, and the sodium salt comprises sodium
carbonate, sodium hydroxide, sodium hydride, or mixtures thereof;
and/or (k) mixtures thereof.
[0069] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst that includes alkali metals in which: (a) the atomic
ratio of an alkali metal having an atomic number of at least 11 to
an alkali metal having an atomic number greater than 11 is in a
range from about 0.1 to about 4; (b) at least two of the alkali
metals are sodium and potassium and an atomic ratio of sodium to
potassium is in a range from about 0.1 to about 4; (c) at least
three of the alkali metals are sodium, potassium, and rubidium, and
each of the atomic ratios of sodium to potassium, sodium to
rubidium, and potassium to rubidium is in a range from about 0.1 to
about 5; (d) at least three of the alkali metals are sodium,
potassium, and cesium, and each of the atomic ratios of sodium to
potassium, sodium to cesium, and potassium to cesium is in a range
from about 0.1 to about 5; (e) at least three of the alkali metals
are potassium, cesium, rubidium, and each of the atomic ratios of
potassium to cesium, potassium to rubidium, and cesium to rubidium
is in a range from about 0.1 to about 5.
[0070] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst comprising a support material, and: (a) the support
material comprises zirconium oxide, calcium oxide, magnesium oxide,
titanium oxide, hydrotalcite, alumina, germania, iron oxide, nickel
oxide, zinc oxide, cadmium oxide, antimony oxide, or mixtures
thereof; and/or (b) incorporated in the support material are: one
or more metals from Columns 6-10 of the Periodic Table, one or more
compounds of one or more metals from Columns 6-10 of the Periodic
Table; one or more alkali metal carbonates, one or more alkali
metal hydroxides, one or more alkali metal hydrides, one or more
alkaline-earth metal carbonates, one or more alkaline-earth metal
hydroxides, one or more alkaline-earth metal hydrides, and/or
mixtures thereof.
[0071] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
comprises contacting a crude feed with an inorganic salt catalyst
that: (a) the catalytic activity of the inorganic salt catalyst is
substantially unchanged in the presence of sulfur; and/or (b) the
inorganic salt catalyst is continuously added to the crude
feed.
[0072] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst that exhibits: (a) an emitted gas inflection in a TAP
temperature range, and the emitted gas comprises water vapor and/or
carbon dioxide; (b) a heat transition in a temperature range
between about 200-500.degree. C., about 250-450.degree. C., or
about 300-400.degree. C., as determined by differential scanning
calorimetry, at a heating rate of about 10.degree. C. per minute;
(c) a DSC temperature in a range between about 200-500.degree. C.,
or about 250-450.degree. C.; (d) at a temperature of at least
100.degree. C., an x-ray diffraction pattern that is broader than
an x-ray diffraction pattern of the inorganic salt catalyst below
100.degree. C.; and/or (e) after conditioning, ionic conductivity,
at 300.degree. C., that is less than ionic conductivity of the
inorganic salt catalyst before conditioning.
[0073] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst that exhibits an emitted inflection in a temperature
range, as determined by TAP, and the contacting conditions are also
controlled such that a contacting temperature is: (a) above
T.sub.1, wherein T.sub.1 is 30.degree. C., 20.degree. C., or
10.degree. C. below the TAP temperature of the inorganic salt
catalyst; (b) at or above a TAP temperature; and/or (c) at least
the TAP temperature of the inorganic salt catalyst.
[0074] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst that or in which: (a) is liquid or semi-liquid at
least at the TAP temperature of the inorganic salt catalyst, and
the inorganic salt catalyst is substantially insoluble in the crude
feed at least at the TAP temperature, wherein the TAP temperature
is the minimum temperature at which the inorganic salt catalyst
exhibits an emitted gas inflection; (b) is a mixture of a liquid
phase and a solid phase at a temperature in a range from about
50.degree. C. to about 500.degree. C.; and/or (c) at least one of
the two inorganic salts has a DSC temperature above 500.degree.
C.
[0075] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst that when tested in the form of particles that can
pass through a 1000 micron filter, self-deforms under gravity
and/or under a pressure of at least 0.007 MPa when heated to a
temperature of at least 300.degree. C., such that the inorganic
salt catalyst transforms from a first form to a second form, and
the second form is incapable of returning to the first form upon
cooling of the inorganic salt catalyst to about 20.degree. C.
[0076] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, an inorganic
salt catalyst that has, per gram of inorganic salt catalyst: (a) at
most 0.01 grams of lithium, or compounds of lithium, calculated as
the weight of lithium; (b) at most 0.001 grams of halide,
calculated as the weight of halogen; and/or (c) at most 0.001 grams
of glassy oxide compounds.
[0077] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, the total
product that has at least 0.8 grams of crude product per gram of
total product.
[0078] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a crude
product that: (a) has at most 0.003 grams, at most 0.02 grams, at
most 0.01 grams, at most 0.05 grams, most 0.001 grams, from about
0.000001-0.1 grams, about 0.00001-0.05 grams, or about 0.0001-0.03
grams of residue per gram of crude product; (b) has from about 0
grams to about 0.05 grams, about 0.00001-0.03 grams, or about
0.0001-0.01 grams of coke per gram of crude product; (c) has an
olefins content of at least 10% greater than the olefins content of
the crude feed; (d) has greater than 0 grams, but less than 0.01
grams of total inorganic salt catalyst per gram of crude product,
as determined by mass balance; (e) has at least 0.1 grams, from
about 0.00001-0.99 grams, from 0.04-0.9 grams from about 0.6-0.8
grams of VGO per gram of crude product; (f) comprises VGO and the
VGO has at least 0.3 grams of aromatics per gram of VGO; (g) has
0.001 grams or from about 0.1-0.5 grams of distillate; (h) an
atomic H/C of at most 1.4; (i) has an atomic H/C of about 90-110%
of the H/C of the crude feed; (j) has a monocyclic ring aromatic
content of at least 10% greater than the monocyclic ring aromatic
content of the crude feed; (k) has monocyclic ring aromatics that
comprise xylenes, ethylbenzene or compounds of ethylbenzene; (I)
has, per gram of crude product, at most 0.1 grams of benzene, from
about 0.05-0.15 grams of toluene, from about 0.3-0.9 grams of
meta-xylene, from about 0.5-0.15 grams of ortho-xylene, and from
about 0.2-0.6 grams of para-xylene; (m) has at least 0.0001 grams
or from about 0.01-0.5 grams of diesel; (n) comprises diesel, and
the diesel has at least 0.3 grams of aromatics per gram of diesel;
(o) has at least 0.001 grams, from above 0 to about 0.7 grams, or
from about 0.001-0.5 grams of kerosene; (p) comprises kerosene, and
the kerosene has at least 0.2 grams or at least 0.5 grams of
aromatics per gram of kerosene, and/or a freezing point at a
temperature of at most -30.degree. C., at most 40.degree. C., or at
most -50.degree. C.; (q) has at least 0.001 grams or at least 0.5
grams of naphtha; (r) comprises naphtha, and the naphtha has at
most 0.01 grams, at most 0.05 grams, or at most 0.002 grams of
benzene per gram of naphtha, an octane number of at least 70, at
least 80, or at least 90, and/or iso-paraffins and normal paraffins
with a weight ratio of iso-paraffins to normal paraffins in the
naphtha of at most 1.4; and/or (s) has a volume that is at least
10% greater than the volume of the crude feed.
[0079] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a method
that comprises contacting a crude feed with a catalyst to form a
total product that comprises a crude product, further comprising:
(a) combining the crude product with a crude that is the same or
different from the crude feed to form a blend suitable for
transporting; (b) combining the crude product with a crude that is
the same or different from the crude feed to form a blend suitable
for treatment facilities; (c) fractionating the crude product; (d)
fractionating the crude product into one or more distillate
fractions, and producing transportation fuel from at least one of
the distillate fractions; and/or (e) when the catalyst is a
transition metal sulfide catalyst, treating the transition metal
sulfide catalyst to recover metals from the transition metal
sulfide catalyst.
[0080] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a crude
composition that has, per gram of composition: (a) at least 0.001
grams of VGO, and the VGO has at least 0.3 grams of aromatics per
gram of VGO; (b) at least 0.001 grams of diesel, and the diesel has
at least 0.3 grams of aromatics per gram of diesel; (c) at least
0.001 grams of naphtha, and the naphtha: having at most 0.5 grams
of benzene per gram of naphtha, an octane number of at least 70,
and/or iso-paraffins and n-paraffins with a weight ratio of the
iso-paraffins to the n-paraffins of at most 1.4; (d) a total of at
least 0.001 grams of a mixture of components that have a boiling
range distribution of at most 204.degree. C. (about 400.degree.
F.), and the mixture having at most 0.15 grams of olefins per gram
of mixture; (e) a weight ratio of atomic hydrogen to atomic carbon
in the composition of at most 1.75, or at most 1.8; (f) at least
0.001 grams of kerosene, and the kerosene has: at least 0.5 grams
of aromatics per gram of kerosene and/or has a freezing point at a
temperature of at most -30.degree. C.; (g) from about 0.09-0.13
grams of atomic hydrogen per gram of composition; (h)
non-condensable hydrocarbon gases and naphtha, which, when
combined, have at most 0.15 grams of olefins per gram of the
combined non-condensable hydrocarbon gases and naphtha; (i)
non-condensable hydrocarbon gases and naphtha, which, when
combined, comprise iso-paraffins and n-paraffins with a weight
ratio of the iso-paraffins to the n-paraffins in the combined
naphtha and non-condensable hydrocarbon gases of at most 1.4; (j)
the hydrocarbons with a carbon number of up to 3 comprising:
olefins and paraffins with carbon numbers of 2 (C.sub.2) and 3
(C.sub.3), and a weight ratio of the combined C.sub.2 and C.sub.3
olefins to the combined C.sub.2 and C.sub.3 paraffins is at most
0.3; olefins and paraffins with a carbon number of 2 (C.sub.2),
wherein a weight ratio of the C.sub.2 olefins to the C.sub.2
paraffins is at most 0.2; and/or olefins and paraffins with a
carbon number of 3 (C.sub.3), wherein a weight ratio of the C.sub.3
olefins to the C.sub.3 paraffins is at most 0.3; (k) has butadiene
content of at least 0.005 grams; (l) has an API graving in a range
from about 15 to about 30 at 15.5.degree. C.; (m) has at most
0.00001 grams of total Ni/V/Fe per gram of composition; (n) a
paraffins content of the hydrocarbons having a boiling range
distribution of at most 204.degree. C. in a range from about
0.7-0.98 grams; (o) hydrocarbons with a boiling range distribution
of at most 204.degree. C. that have, per gram of olefins
hydrocarbons having a boiling range distribution of at most
204.degree. C., from about 0.001-0.5 grams of olefins (p)
hydrocarbons with a boiling range distribution of at most
204.degree. C. that comprise olefins, and the olefins have at least
0.001 grams of terminal olefins per gram of olefins; (q)
hydrocarbons with a boiling range distribution of at most
204.degree. C. that comprise olefins, and the olefins have a molar
ratio of terminal olefins to internal olefins of at least 0.4;
and/or (r) from about 0.001-0.5 grams of olefins per gram of
hydrocarbons in a boiling range distribution between about
20.degree. C. and about 204.degree. C.
[0081] In some embodiments, the invention also provides, in
combination with one or more of the above embodiments, a crude
composition that has at least one of the catalysts comprising one
or more alkali metals, in which: (a) at least one of the alkali
metals is potassium, rubidium; or cesium, or mixtures thereof;
and/or (b) at least one of the catalysts further comprises a
transition metal, a transition metal sulfide and/or bartonite.
[0082] In further embodiments, features from specific embodiments
may be combined with features from other embodiments. For example,
features from the any one of the series of embodiments may be
combined with features from any of the other series of
embodiments.
[0083] In further embodiments, crude products are obtainable by any
of the methods and systems described herein.
[0084] In further embodiments, additional features may be added to
the specific embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0085] 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:
[0086] FIG. 1 is a schematic of an embodiment of a contacting
system for contacting the crude feed with a hydrogen source in the
presence of one or more catalysts to produce the total product.
[0087] FIG. 2 is a schematic of another embodiment of a contacting
system for contacting the crude feed with a hydrogen source in the
presence of one or more catalysts to produce the total product.
[0088] FIG. 3 is a schematic of an embodiment of a separation zone
in combination with a contacting system.
[0089] FIG. 4 is a schematic of an embodiment of a blending zone in
combination with a contacting system.
[0090] FIG. 5 is a schematic of an embodiment of a separation zone,
a contacting system, and a blending zone.
[0091] FIG. 6 is a schematic of an embodiment of multiple
contacting systems.
[0092] FIG. 7 is a schematic of an embodiment of an ionic
conductivity measurement system.
[0093] FIG. 8 is a tabulation of properties of the crude feed and
properties of crude products obtained from embodiments of
contacting the crude feed with the transition metal sulfide
catalyst.
[0094] FIG. 9 is a tabulation of compositions of the crude feed and
compositions of non-condensable hydrocarbons obtained from
embodiments of contacting the crude feed with the transition metal
sulfide catalyst.
[0095] FIG. 10 is a tabulation of properties and compositions of
crude products obtained from embodiments of contacting the crude
feed with the transition metal sulfide catalyst.
[0096] FIG. 11 is a graphical representation of log 10 plots of ion
currents of emitted gases of an inorganic salt catalyst versus
temperature, as determined by TAP.
[0097] FIG. 12 is a graphic representation of log plots of the
resistance of inorganic salt catalysts and an inorganic salt
relative to the resistance of potassium carbonate versus
temperature.
[0098] FIG. 13 is a graphic representation of log plots of the
resistance of a Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3
catalyst relative to resistance of the potassium carbonate versus
temperature.
[0099] FIG. 14 is a graphical representation of weight percent of
coke, liquid hydrocarbons, and gas versus various hydrogen sources
produced from embodiments of contacting the crude feed with the
inorganic salt catalyst.
[0100] FIG. 15 is a graphical representation of weight percentage
versus carbon number of crude products produced from embodiments of
contacting the crude feed with the inorganic salt catalyst.
[0101] FIG. 16 is a tabulation of components produced from
embodiments of contacting the crude feed with inorganic salt
catalysts, a metal salt, or silicon carbide.
[0102] While the invention is susceptible to various modifications
and alternative forms, specific embodiments thereof are shown by
way of example in the drawings and will herein be described in
detail. 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.
DETAILED DESCRIPTION OF THE INVENTION
[0103] Certain embodiments of the inventions are described herein
in more detail. Terms used herein are defined as follows.
[0104] "Alkali metal(s)" refer to one or more metals from Column 1
of the Periodic Table, one or more compounds of one or more metals
from Column 1 of the Periodic Table, or mixtures thereof.
[0105] "Alkaline-earth metal(s)" refer to one or more metals from
Column 2 of the Periodic Table, one or more compounds of one or
more metals from Column 2 of the Periodic Table, or mixtures
thereof.
[0106] "AMU" refers to atomic mass unit.
[0107] "ASTM" refers to American Standard Testing and
Materials.
[0108] "C.sub.5 asphaltenes" refer to asphaltenes that are
insoluble in pentane. C.sub.5 asphaltenes content is as determined
by ASTM Method D2007.
[0109] Atomic hydrogen percentage and atomic carbon percentage of
crude feed, crude product, naphtha, kerosene, diesel, and VGO are
as determined by ASTM Method D5291.
[0110] "API gravity" refers to API gravity at 15.5.degree. C. API
gravity is as determined by ASTM Method D6822.
[0111] "Bitumen" refers to one type of crude produced and/or
retorted from a hydrocarbon formation.
[0112] Boiling range distributions for the crude feed and/or total
product are as determined by ASTM Methods D5307, unless otherwise
mentioned. Content of hydrocarbon components, for example,
paraffins, iso-paraffins, olefins, naphthenes and aromatics in
naphtha are as determined by ASTM Method D6730. Content of
aromatics in diesel and VGO is as determined by IP Method 368/90.
Content of aromatics in kerosene is as determined by ASTM Method
D5186.
[0113] "Br.o slashed.nsted-Lowry acid" refers to a molecular entity
with the ability to donate a proton to another molecular
entity.
[0114] "Br.o slashed.nsted-Lowry base" refers to a molecular entity
that is capable of accepting protons from another molecular entity.
Examples of Br.o slashed.nsted-Lowry bases include hydroxide
(OH.sup.-), water (H.sub.2O), carboxylate (RCO.sub.2.sup.-), halide
(Br.sup.-, Cr.sup.-, F.sup.-, I.sup.-), bisulfate
(HSO.sub.4.sup.-), and sulfate (SO.sub.4.sup.2-).
[0115] "Carbon number" refers to the total number of carbon atoms
in a molecule.
[0116] "Coke" refers to solids containing carbonaceous solids that
are not vaporized under process conditions. The content of coke is
as determined by mass balance. The weight of coke is the total
weight of solid minus the total weight of input catalysts.
[0117] "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.
[0118] "Diesel" refers to hydrocarbons with a boiling range
distribution between 260.degree. C. and 343.degree. C.
(500-650.degree. F.) at 0.101 MPa. Diesel content is as determined
by ASTM Method D2887.
[0119] "Distillate" refers to hydrocarbons with a boiling range
distribution between 204.degree. C. and 343.degree. C.
(400-650.degree. F.) at 0.101 MPa. Distillate content is as
determined by ASTM Method D2887. Distillate may include kerosene
and diesel.
[0120] "DSC" refers to differential scanning calorimetry.
[0121] "Freeze point" and "freezing point" refer to the temperature
at which formation of crystalline particles occurs in a liquid. A
freezing point is as determined by ASTM D2386.
[0122] "GC/MS" refers to gas chromatography in combination with
mass spectrometry.
[0123] "Hard base" refers to anions as described by Pearson in
Journal of American Chemical Society, 1963, 85, p. 3533, which is
incorporated by reference herein.
[0124] "H/C" refers to a weight ratio of atomic hydrogen to atomic
carbon. H/C is as determined from the values measured for weight
percentage of hydrogen and weight percentage of carbon by ASTM
Method D5291.
[0125] "Heteroatoms" refer 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
nitrogen, and D4294 for sulfur.
[0126] "Hydrogen source" refers to hydrogen, and/or a compound
and/or compounds when in the presence of a crude feed and the
catalyst react to provide hydrogen to one or more compounds in the
crude feed. A hydrogen source may include, but is not limited to,
hydrocarbons (for example, C.sub.1 to C.sub.6 hydrocarbons such as
methane, ethane, propane, butane, pentane, naphtha), water, or
mixtures thereof. A mass balance is conducted to assess the net
amount of hydrogen provided to one or more compounds in the crude
feed.
[0127] "Inorganic salt" refers to a compound that is composed of a
metal cation and an anion.
[0128] "IP" refers to the Institute of Petroleum, now the Energy
Institute of London, United Kingdom.
[0129] "Iso-paraffins" refer to branched-chain saturated
hydrocarbons.
[0130] "Kerosene" refers to hydrocarbons with a boiling range
distribution between about 204.degree. C. and about 260.degree. C.
(400-500.degree. F.) at 0.101 MPa. Kerosene content is as
determined by ASTM Method D2887.
[0131] "Lewis acid" refers to a compound or a material with the
ability to accept one or more electrons from another compound.
[0132] "Lewis base" refers to a compound and/or material with the
ability to donate one or more electrons to another compound.
[0133] "Light Hydrocarbons" refer to hydrocarbons having carbon
numbers in a range from 1 to 6.
[0134] "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 or more
compounds that are liquid at STP with one or more compounds that
are solid at STP.
[0135] "Micro-Carbon Residue" ("MCR") refers to a quantity of
carbon residue remaining after evaporation and pyrolysis of a
substance. MCR content is as determined by ASTM Method D4530.
[0136] "Naphtha" refers to hydrocarbon components with a boiling
range distribution between 38.degree. C. and 204.degree. C.
(100-400.degree. F.) at 0.101 MPa. Naphtha content is as determined
by ASTM Method D2887.
[0137] "Ni/V/Fe" refers to nickel, vanadium, iron, or combinations
thereof.
[0138] "Ni/V/Fe content" refers to Ni/V/Fe content in a substrate.
Ni/V/Fe content is as determined by ASTM Method D5863.
[0139] "Nm.sup.3/m.sup.3" refers to normal cubic meters of gas per
cubic meter of crude feed.
[0140] "Nonacidic" refers to Lewis base and/or Br.o
slashed.nsted-Lowry base properties.
[0141] "Non-condensable gas" refers to components and/or a mixture
of components that are gases at standard temperature and pressure
(25.degree. C., 0.101 MPa, hereinafter referred to as "STP").
[0142] "In-Paraffins" refer to normal (straight chain) saturated
hydrocarbons.
[0143] "Octane number" refers to a calculated numerical
representation of the antiknock properties of a motor fuel compared
to a standard reference fuel. A calculated octane number of naphtha
is as determined by ASTM Method D6730.
[0144] "Olefins" refer to compounds with non-aromatic carbon-carbon
double bonds. Types of olefins include, but are not limited to,
cis, trans, terminal, internal, branched, and linear.
[0145] "Periodic Table" refers to the Periodic Table as specified
by the International Union of Pure and Applied Chemistry (IUPAC),
November 2003.
[0146] "Polyaromatic compounds" refer to compounds that include two
or more aromatic rings. Examples of polyaromatic compounds include,
but are not limited to, indene, naphthalene, anthracene,
phenanthrene, benzothiophene, and dibenzothiophene.
[0147] "Residue" refers to components that have a boiling range
distribution above 538.degree. C. (1000.degree. F.) at 0.101 MPa,
as determined by ASTM Method D5307.
[0148] "Semiliquid" refers to a phase of a substance that has
properties of a liquid phase and a solid phase of the substance.
Examples of semiliquid inorganic salt catalysts include a slurry
and/or a phase that has a consistency of, for example, taffy,
dough, or toothpaste.
[0149] "SCFB" refers to standard cubic feet of gas per barrel of
crude feed.
[0150] "Superbase" refers to a material that can deprotonate
hydrocarbons such as paraffins and olefins under reaction
conditions.
[0151] "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.
[0152] "TAP" refers to temporal-analysis-of-products.
[0153] "TMS" refers to transition metal sulfide.
[0154] "VGO" refers to components with a boiling range distribution
between about 343.degree. C. and about 538.degree. C.
(650-1000.degree. F.) at 0.101 MPa. VGO content is as determined by
ASTM Method D2887.
[0155] 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 composition tested is
outside of the limits of the test method, the test method may be
recalibrated to test for such property. It should be understood
that other standardized testing methods that are considered
equivalent to the referenced testing methods may be used.
[0156] 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.
[0157] 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 are removed.
Typically, topped crudes 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.
[0158] 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.
[0159] Properties of disadvantaged crudes may include, but are not
limited to: a) TAN of at least 0.5; b) viscosity of at least about
0.2 Pa.s; c) API gravity of at most 19; d) a total Ni/V/Fe content
of at least 0.00005 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) an asphaltenes
content of at least 0.04 grams of asphaltenes per gram of crude; h)
a MCR content of at least 0.02 grams of MCR per gram of crude; or
i) 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 certain embodiments,
disadvantaged crude has about 0.2-0.99 grams, about 0.3-0.9 grams,
or about 0.4-0.7 grams of residue per gram of disadvantaged crude.
In certain embodiments, disadvantaged crudes, per gram of
disadvantaged crude, may have a sulfur content of at least 0.001
grams, at least 0.005 grams, at least 0.01 grams, or at least 0.02
grams.
[0160] Disadvantaged crudes may include a mixture of hydrocarbons
having a range of boiling points. 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 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 0.001 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 about 700.degree. C. at 0.101 MPa,
or combinations thereof.
[0161] In some embodiments, disadvantaged crudes may also 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 200.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 0.001 grams.
[0162] In certain embodiments, disadvantaged crudes may include,
per gram of disadvantaged crude, up to 0.9 grams, or up to 0.99
grams of hydrocarbons with a boiling range distribution of at least
300.degree. C. In certain embodiments, disadvantaged crudes may
also include, per gram of disadvantaged crude, at least 0.001 grams
of hydrocarbons with a boiling range distribution of at least
650.degree. C. In certain embodiments, disadvantaged crudes may
include, per gram of disadvantaged crude, up to about 0.9 grams, or
up to about 0.99 grams of hydrocarbons with a boiling range
distribution between about 300.degree. C. and about 1000.degree.
C.
[0163] Examples of disadvantaged crudes that can be treated using
the processes described herein include, but are not limited to,
crudes from the following countries and regions of those countries:
Canadian Alberta, Venezuelan Orinoco, U.S. southern Californian and
north slope Alaska, Mexico Bay of Campeche, Argentinean San Jorge
basin, Brazilian Santos and Campos basins, China Bohai Gulf, China
Karamay, Iraq Zagros, Kazakhstan Caspian, Nigeria Offshore, United
Kingdom North Sea, Madagascar northwest, Oman, and Netherlands
Schoonebek.
[0164] Treatment of disadvantaged crudes may enhance the properties
of the disadvantaged crudes such that the crudes are acceptable for
transportation and/or treatment. A crude and/or disadvantaged crude
that is to be treated may be referred to as "crude feed". The crude
feed may be topped as described herein. The crude product resulting
from treatment of the crude feed, using methods described herein,
is suitable for transporting and/or refining. Properties of the
crude product 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, and
thereby have enhanced economic value relative to 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 from the crude
product.
[0165] Methods of contacting a crude feed in accordance with
inventions are described herein. Additionally, embodiments to
produce products with various concentrations of naphtha, kerosene,
diesel, and/or VGO, which are not generally produced in
conventional types of processes, are described.
[0166] The crude feed may be contacted with a hydrogen source in
the presence of one or more of the catalysts in a contacting zone
and/or in combinations of two or more contacting zones.
[0167] In some embodiments, the hydrogen source is generated in
situ. In situ generation of the hydrogen source may include the
reaction of at least a portion of the crude feed with the inorganic
salt catalyst at temperatures in a range from about 200-500.degree.
C. or about 300-400.degree. C. to form hydrogen and/or light
hydrocarbons. In situ generation of hydrogen may include the
reaction of at least a portion of the inorganic salt catalyst that
includes, for example, alkali metal formate.
[0168] The total product generally includes gas, vapor, liquids, or
mixtures thereof produced during the contacting. The total product
includes the crude product that is a liquid mixture at STP and, in
some embodiments, hydrocarbons that are not condensable at STP. In
some embodiments, the total product and/or the crude product may
include solids (such as inorganic solids and/or coke). In certain
embodiments, the solids may be entrained in the liquid and/or vapor
produced during contacting.
[0169] A contacting zone typically includes a reactor, a portion of
a reactor, multiple portions of a reactor, or multiple reactors.
Examples of reactors that may be used to contact a crude feed with
a hydrogen source in the presence of catalyst include a stacked bed
reactor, a fixed bed reactor, a continuously stirred tank reactor
(CSTR), a spray reactor, a plug-flow reactor, and a liquid/liquid
contactor. Examples of a CSTR include a fluidized bed reactor and
an ebullating bed reactor.
[0170] Contacting conditions typically include temperature,
pressure, crude feed flow, total product flow, residence time,
hydrogen source flow, or combinations thereof. Contacting
conditions may be controlled to produce a crude product with
specified properties.
[0171] Contacting temperatures may range from about 200-800.degree.
C., about 300-700.degree. C., or about 400-600.degree. C. In
embodiments in which the hydrogen source is supplied as a gas (for
example, hydrogen gas, methane, or ethane), a ratio of the gas to
the crude feed will generally range from about 1-16,100
Nm.sup.3/m.sup.3, about 2-8000 Nm.sup.3/m.sup.3, about 3-4000
Nm.sup.3/m.sup.3, or about 5-320 Nm.sup.3/m.sup.3. Contacting
typically takes place in a pressure range between about 0.1-20 MPa,
about 1-16 MPa, about 2-10 MPa, or about 4-8 MPa. In some
embodiments in which steam is added, a ratio of steam to crude feed
is in a range from about 0.01-3 kilograms, about 0.03-2.5
kilograms, or about 0.1-1 kilogram of steam, per kilogram of crude
feed. A flow rate of crude feed may be sufficient to maintain the
volume of crude feed in the contacting zone of at least 10%, at
least 50%, or at least 90% of the total volume of the contacting
zone. Typically, the volume of crude feed in the contacting zone is
about 40%, about 60%, or about 80% of the total volume of the
contacting zone. In some embodiments, contacting may be done in the
presence of an additional gas, for example, argon, nitrogen,
methane, ethane, propanes, butanes, propenes, butenes, or
combinations thereof
[0172] FIG. 1 is a schematic of an embodiment of contacting system
100 used to produce the total product as a vapor. The crude feed
exits crude feed supply 101 and enters contacting zone 102 via
conduit 104. A quantity of the catalyst used in the contacting zone
may range from about 1-100 grams, about 2-80 grams, about 3-70
grams, or about 4-60 grams, per 100 grams of crude feed in the
contacting zone. In certain embodiments, a diluent may be added to
the crude feed to lower the viscosity of the crude feed. In some
embodiments, the crude feed enters a bottom portion of contacting
zone 102 via conduit 104. In certain embodiments, the crude feed
may be heated to a temperature of at least 100.degree. C. or at
least 300.degree. C. prior to and/or during introduction of the
crude feed to contacting zone 102. Typically, the crude feed may be
heated to a temperature in a range from about 100-500.degree. C. or
about 200-400.degree. C.
[0173] In some embodiments, the catalyst is combined with the crude
feed and transferred to contacting zone 102. The crude
feed/catalyst mixture may be heated to a temperature of at least
100.degree. C. or at least 300.degree. C. prior to introduction
into contacting zone 102. Typically, the crude feed may be heated
to a temperature in a range from about 200-500.degree. C. or about
300-400.degree. C. In some embodiments, the crude feed/catalyst
mixture is a slurry. In certain embodiments, TAN of the crude feed
may be reduced prior to introduction of the crude feed into the
contacting zone. For example, when the crude feed/catalyst mixture
is heated at a temperature in a range from about 100-400.degree. C.
or about 200-300.degree. C., alkali salts of acidic components in
the crude feed may be formed. The formation of these alkali salts
may remove some acidic components from the crude feed to reduce the
TAN of the crude feed.
[0174] In some embodiments, the crude feed is added continuously to
contacting zone 102. Mixing in contacting zone 102 may be
sufficient to inhibit separation of the catalyst from the crude
feed/catalyst mixture. In certain embodiments, at least a portion
of the catalyst may be removed from contacting zone 102, and in
some embodiments, such catalyst is regenerated and re-used. In
certain embodiments, fresh catalyst may be added to contacting zone
102 during the reaction process.
[0175] In some embodiments, the crude feed and/or a mixture of
crude feed with the inorganic salt catalyst is introduced into the
contacting zone as an emulsion. The emulsion may be prepared by
combining an inorganic salt catalyst/water mixture with a crude
feed/surfactant mixture. In some embodiments, a stabilizer is added
to the emulsion. The emulsion may remain stable for at least 2
days, at least 4 days, or at least 7 days. Typically, the emulsion
may remain stable for 30 days, 10 days, 5 days, or 3 days.
Surfactants include, but are not limited to, organic polycarboxylic
acids (Tenax 2010; MeadWestvaco Specialty Product Group;
Charleston, S.C., U.S.A.), C.sub.2, dicarboxylic fatty acid (DIACID
1550; MeadWestvaco Specialty Product Group), petroleum sulfonates
(Hostapur SAS 30; Clarient Corporation, Charlotte, N.C., U.S.A.),
Tergital NP-40 Surfactant (Union Carbide; Danbury, Conn., U.S.A.),
or mixtures thereof. Stabilizers include, but are not limited to,
diethyleneamine (Aldrich Chemical Co.; Milwaukee, Wis., U.S.A.)
and/or monoethanolamine (J. T. Baker; Phillipsburg, N.J.,
U.S.A.).
[0176] Recycle conduit 106 may couple conduit 108 and conduit 104.
In some embodiments, recycle conduit 106 may directly enter and/or
exit contacting zone 102. Recycle conduit 106 may include flow
control valve 110. Flow control valve 110 may allow at least a
portion of the material from conduit 108 to be recycled to conduit
104 and/or contacting zone 102. In some embodiments, a condensing
unit may be positioned in conduit 108 to allow at least a portion
of the material to be condensed and recycled to contacting zone
102. In certain embodiments, recycle conduit 106 may be a gas
recycle line. Flow control valves 110 and 110' may be used to
control flow to and from contacting zone 102 such that a constant
volume of liquid in the contacting zone is maintained. In some
embodiments, a substantially selected volume range of liquid can be
maintained in the contacting zone 102. A volume of feed in
contacting zone 102 may be monitored using standard
instrumentation. Gas inlet port 112 may be used to allow addition
of the hydrogen source and/or additional gases to the crude feed as
the crude feed enters contacting zone 102. In some embodiments,
steam inlet port 114 may be used to allow addition of steam to
contacting zone 102. In certain embodiments, an aqueous stream is
introduced into contacting zone 102 through steam inlet port
114.
[0177] In some embodiments, at least a portion of the total product
is produced as vapor from contacting zone 102. In certain
embodiments, the total product is produced as vapor and/or a vapor
containing small amounts of liquids and solids from the top of
contacting zone 102. The vapor is transported to separation zone
116 via conduit 108. The ratio of a hydrogen source to crude feed
in contacting zone 102 and/or the pressure in the contacting zone
may be changed to control the vapor and/or liquid phase produced
from the top of contacting zone 102. In some embodiments, the vapor
produced from the top of contacting zone 102 includes at least 0.5
grams, at least 0.8 grams, at least 0.9 grams, or at least 0.97
grams of crude product per gram of crude feed. In certain
embodiments, the vapor produced from the top of contacting zone 102
includes from about 0.8-0.99 grams, or about 0.9-0.98 grams of
crude product per gram of crude feed.
[0178] Used catalyst and/or solids may remain in contacting zone
102 as by-products of the contacting process. The solids and/or
used catalyst may include residual crude feed and/or coke.
[0179] In separation unit 116, the vapor is cooled and separated to
form the crude product and gases using standard separation
techniques. The crude product exits separation unit 116 and enters
crude product receiver 119 via conduit 118. The resulting crude
product may be suitable for transportation and/or treatment. Crude
product receiver 119 may include one or more pipelines, one or more
storage units, one or more transportation vessels, or combinations
thereof. In some embodiments, the separated gas (for example,
hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, or
methane) is transported to other processing units (for example, for
use in a fuel cell or a sulfur recovery plant) and/or recycled to
contacting zone 102 via conduit 120. In certain embodiments,
entrained solids and/or liquids in the crude product may be removed
using standard physical separation methods (for example,
filtration, centrifugation, or membrane separation).
[0180] FIG. 2 depicts contacting system 122 for treating crude feed
with one or more catalysts to produce a total product that may be a
liquid, or a liquid mixed with gas or solids. The crude feed may
enter contacting zone 102 via conduit 104. In some embodiments, the
crude feed is received from the crude feed supply. Conduit 104 may
include gas inlet port 112. In some embodiments, gas inlet port 112
may directly enter contacting zone 102. In certain embodiments,
steam inlet port 114 may be used to allow addition of the steam to
contacting zone 102. The crude feed may be contacted with the
catalyst in contacting zone 102 to produce a total product. In some
embodiments, conduit 106 allows at least a portion of the total
product to be recycled to contacting zone 102. A mixture that
includes the total product and/or solids and/or unreacted crude
feed exits contacting zone 102 and enters separation zone 124 via
conduit 108. In some embodiments, a condensing unit may be
positioned (for example, in conduit 106) to allow at least a
portion of the mixture in the conduit to be condensed and recycled
to contacting zone 102 for further processing. In certain
embodiments, recycle conduit 106 may be a gas recycle line. In some
embodiments, conduit 108 may include a filter for removing
particles from the total product.
[0181] In separation zone 124, at least a portion of the crude
product may be separated from the total product and/or catalyst. In
embodiments in which the total product includes solids, the solids
may be separated from the total product using standard solid
separation techniques (for example, centrifugation, filtration,
decantation, membrane separation). Solids include, for example, a
combination of catalyst, used catalyst, and/or coke. In some
embodiments, a portion of the gases is separated from the total
product. In some embodiments, at least a portion of the total
product and/or solids may be recycled to conduit 104 and/or, in
some embodiments, to contacting zone 102 via conduit 126. The
recycled portion may, for example, be combined with the crude feed
and enter contacting zone 102 for further processing. The crude
product may exit separation zone 124 via conduit 128. In certain
embodiments, the crude product may be transported to the crude
product receiver.
[0182] In some embodiments, the total product and/or crude product
may include at least a portion of the catalyst. Gases entrained in
the total product and/or crude product may be separated using
standard gas/liquid separation techniques, for example, sparging,
membrane separation, and pressure reduction. In some embodiments,
the separated gas is transported to other processing units (for
example, for use in a fuel cell, a sulfur recovery plant, other
processing units, or combinations thereof) and/or recycled to the
contacting zone.
[0183] In some embodiments, separation of at least a portion of a
crude feed is performed before the crude feed enters the contacting
zone. FIG. 3 is a schematic of an embodiment of a separation zone
in combination with a contacting system. Contacting system 130 may
be contacting system 100 and/or contacting system 122 (shown in
FIGS. 1 and 2). The crude feed enters separation zone 132 via
conduit 104. In separation zone 132, at least a portion of the
crude feed is separated using standard separation techniques to
produce a separated crude feed and hydrocarbons. The separated
crude feed, in some embodiments, includes a mixture of components
with a boiling range distribution of at least 100.degree. C., at
least 120.degree. C. or, in some embodiments, a boiling range
distribution of at least 200.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. The hydrocarbons
separated from the crude feed exit separation zone 132 via conduit
134 to be transported to other processing units, treatment
facilities, storage facilities, or combinations thereof.
[0184] At least a portion of the separated crude feed exits
separation zone 132 and enters contacting system 130 via conduit
136 to be further processed to form the crude product, which exits
contacting system 130 via conduit 138.
[0185] In some embodiments, the crude product produced from a crude
feed by any method described herein 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. The resulting blended product may be
suitable for transportation and/or treatment.
[0186] FIG. 4 is a schematic of an embodiment of a combination of
blending zone 140 and contacting system 130. In certain
embodiments, at least a portion of the crude product exits
contacting system 130 via conduit 138 and enters blending zone 140.
In blending zone 140, at least a portion of the crude product is
combined with one or more process streams (for example, a
hydrocarbon stream produced from separation of one or more crude
feeds, or naphtha), 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 140
or upstream of the blending zone via conduit 142. A mixing system
may be located in or near blending zone 140. The blended product
may meet specific product specifications. Specific 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 140 via conduit 144 to be
transported and/or processed.
[0187] In some embodiments, methanol is generated during the
contacting process using the catalyst. For example, hydrogen and
carbon monoxide may react to form methanol. The recovered methanol
may contain dissolved salts, for example, potassium hydroxide. The
recovered methanol may be combined with additional crude feed to
form a crude feed/methanol mixture. Combining methanol with the
crude feed tends to lower the viscosity of the crude feed. Heating
the crude feed/methanol mixture to at most 500.degree. C. may
reduce TAN of the crude feed to less than 1.
[0188] FIG. 5 is a schematic of an embodiment of a separation zone
in combination with a contacting system in combination with a
blending zone. The crude feed enters separation zone 132 through
conduit 104. The crude feed is separated as previously described to
form a separated crude feed. The separated crude feed enters
contacting system 130 through conduit 136. The crude product exits
contacting system 130 and enters blending zone 140 through conduit
138. In blending zone 140, other process stream and/or crudes
introduced via conduit 142 are combined with the crude product to
form a blended product. The blended product exits blending zone 140
via conduit 144.
[0189] FIG. 6 is a schematic of multiple contacting system 146.
Contacting system 100 (shown in FIG. 1) may be positioned before
contacting system 148. In an alternate embodiment, the positions of
the contacting systems can be reversed. Contacting system 100
includes an inorganic salt catalyst. Contacting system 148 may
include one or more catalysts. The catalyst in contacting system
148 may be an additional inorganic salt catalyst, the transition
metal sulfide catalyst, commercial catalysts, or mixtures thereof.
The crude feed enters contacting system 100 via conduit 104 and is
contacted with a hydrogen source in the presence of the inorganic
salt catalyst to produce the total product. The total product
includes hydrogen and, in some embodiments, a crude product. The
total product may exit contacting system 100 via conduit 108. The
hydrogen generated from contact of the inorganic salt catalyst with
the crude feed may be used as a hydrogen source for contacting
system 148. At least a portion of the generated hydrogen is
transferred to contacting system 148 from contacting system 100 via
conduit 150.
[0190] In an alternate embodiment, such generated hydrogen may be
separated and/or treated, and then transferred to contacting system
148 via conduit 150. In certain embodiments, contacting system 148
may be a part of contacting system 100 such that the generated
hydrogen flows directly from contacting system 100 to contacting
system 148. In some embodiments, a vapor stream produced from
contacting system 100 is directly mixed with the crude feed
entering contacting system 148.
[0191] A second crude feed enters contacting system 148 via conduit
152. In contacting system 148, contact of the crude feed with at
least a portion of the generated hydrogen and the catalyst produces
a product. The product is, in some embodiments, the total product.
The product exits contacting system 148 via conduit 154.
[0192] In certain embodiments, a system that includes contacting
systems, contacting zones, separation zones, and/or blending zones,
as shown in FIGS. 1-6, may be located at or proximate to a
production site that produces disadvantaged crude feed. After
processing through the catalytic system, the crude feed may be
considered suitable for transportation and/or for use in a refinery
process.
[0193] In some embodiments, the crude product and/or the blended
product are transported to a refinery and/or a treatment facility.
The crude product and/or the blended product may be processed to
produce commercial products such as transportation fuel, heating
fuel, lubricants, or chemicals. Processing may include distilling
and/or fractionally distilling the crude product and/or blended
product to produce one or more distillate fractions. In some
embodiments, the crude product, the blended product, and/or the one
or more distillate fractions may be hydrotreated.
[0194] The total product includes, in some embodiments, at most
0.05 grams, at most 0.03 grams, or at most 0.01 grams of coke per
gram of total product. In certain embodiments, the total product is
substantially free of coke (that is, coke is not detectable). In
some embodiments, the crude product may include at most 0.05 grams,
at most 0.03 grams, at most 0.01 grams, at most 0.005 grams, or at
most 0.003 grams of coke per gram of crude product. In certain
embodiments, the crude product has a coke content in a range from
above 0 to about 0.05, about 0.00001-0.03 grams, about 0.0001-0.01
grams, or about 0.001-0.005 grams per gram of crude product, or is
not detectable.
[0195] In certain embodiments, the crude product has an MCR content
that is at most 90%, at most 80%, at most 50%, at most 30%, or at
most 10% of the MCR content of the crude feed. In some embodiments,
the crude product has a negligible MCR content. In some
embodiments, the crude product has, per gram of crude product, at
most 0.05 grams, at most 0.03 grams, at most 0.01 grams, or at most
0.001 grams of MCR. Typically, the crude product has from about 0
grams to about 0.04 grams, about 0.000001-0.03 grams, or about
0.00001-0.01 grams of MCR per gram of crude product.
[0196] In some embodiments, the total product includes
non-condensable gas. The non-condensable gas typically includes,
but is not limited to, carbon dioxide, ammonia, hydrogen sulfide,
hydrogen, carbon monoxide, methane, other hydrocarbons that are not
condensable at STP, or a mixture thereof.
[0197] In certain embodiments, hydrogen gas, carbon dioxide, carbon
monoxide, or combinations thereof can be formed in situ by contact
of steam and light hydrocarbons with the inorganic salt catalyst.
Typically, under thermodynamic conditions a molar ratio of carbon
monoxide to carbon dioxide is about 0.07. A molar ratio of the
generated carbon monoxide to the generated carbon dioxide, in some
embodiments, is at least 0.3, at least 0.5, or at least 0.7. In
some embodiments, a molar ratio of the generated carbon monoxide to
the generated carbon dioxide is in a range from about 0.3-1.0,
about 0.4-0.9, or about 0.5-0.8. The ability to generate carbon
monoxide preferentially to carbon dioxide in situ may be beneficial
to other processes located in a proximate area or upstream of the
process. For example, the generated carbon monoxide may be used as
a reducing agent in treating hydrocarbon formations or used in
other processes, for example, syngas processes.
[0198] In some embodiments, the total product as produced herein
may include a mixture of compounds that have a boiling range
distribution between about -10.degree. C. and about 538.degree. C.
The mixture may include hydrocarbons that have carbon numbers in a
range from 1 to 4. The mixture may include from about 0.001-0.8
grams, about 0.003-0.1 grams, or about 0.005-0.01 grams, of C.sub.4
hydrocarbons per gram of such mixture. The C.sub.4 hydrocarbons may
include from about 0.001-0.8 grams, about 0.003-0.1 grams, or about
0.005-0.01 grams of butadiene per gram of C.sub.4 hydrocarbons. In
some embodiments, iso-paraffins are produced relative to
n-paraffins at a weight ratio of at most 1.5, at most 1.4, at most
1.0, at most 0.8, at most 0.3, or at most 0.1. In certain
embodiments, iso-paraffins are produce relative to n-paraffins at a
weight ratio in a range from about 0.00001-1.5, about 0.0001-1.0,
or about 0.001-0.1. The paraffins may include iso-paraffins and/or
n-paraffins.
[0199] In some embodiments, the total product and/or crude product
may include olefins and/or paraffins in ratios or amounts that are
not generally found in crudes produced and/or retorted from a
formation. The olefins include a mixture of olefins with a terminal
double bond ("alpha olefins") and olefins with internal double
bonds. In certain embodiments, the olefin content of the crude
product is greater than the olefin content of the crude feed by a
factor of about 2, about 10, about 50, about 100, or at least 200.
In some embodiments, the olefin content of the crude product is
greater than the olefin content of the crude feed by a factor of at
most 1,000, at most 500, at most 300, or at most 250.
[0200] In certain embodiments, the hydrocarbons with a boiling
range distribution between 20-400.degree. C. have an olefins
content in a range from about 0.00001-0.1 grams, about 0.0001-0.05
grams, or about 0.01-0.04 grams per gram of hydrocarbons having a
boiling range distribution in a range between 20-400.degree. C.
[0201] In some embodiments, at least 0.001 grams, at least 0.005
grams, or at least 0.01 grams of alpha olefins per gram of crude
product may be produced. In certain embodiments, the crude product
has from about 0.0001-0.5 grams, about 0.001-0.2 grams, or about
0.01-0.1 grams of alpha olefins per gram of crude product. In
certain embodiments, the hydrocarbons with a boiling range
distribution between about 20-400.degree. C. have an alpha olefins
content in a range from about 0.0001-0.08 grams, about 0.001-0.05
grams, or about 0.01-0.04 grams per gram of hydrocarbons with a
boiling range distribution between about 20-400.degree. C.
[0202] In some embodiments, the hydrocarbons with a boiling range
distribution between 20-204.degree. C. have a weight ratio of alpha
olefins to internal double bond olefins of at least 0.7, at least
0.8, at least 0.9, at least 1.0, at least 1.4, or at least 1.5. In
some embodiments, the hydrocarbons with a boiling range
distribution between 20-204.degree. C. have a weight ratio of alpha
olefins to internal double bond olefins in a range from about
0.7-10, about 0.8-5, about 0.9-3, or about 1-2. A weight ratio of
alpha olefins to internal double bond olefins of the crudes and
commercial products is typically at most 0.5. The ability to
produce an increased amount of alpha olefins to olefins with
internal double bonds may facilitate the conversion of the crude
product to commercial products.
[0203] In some embodiments, contact of a crude feed with a hydrogen
source in the presence of an inorganic salt catalyst may produce
hydrocarbons with a boiling range distribution between
20-204.degree. C. that include linear olefins. The linear olefins
have cis and trans double bonds. A weight ratio of linear olefins
with trans double bonds to linear olefins with cis double bonds is
at most 0.4, at most 1.0, or at most 1.4. In certain embodiments,
the weight ratio of linear olefins with trans double bonds to
linear olefins with cis double bonds is in a range from about
0.001-1.4, about 0.01-1.0, or about 0.1-0.4.
[0204] In certain embodiments, hydrocarbons having a boiling range
distribution in a range between 20-204.degree. C. have a
n-paraffins content of at least 0.1 grams, at least 0.15 grams, at
least 0.20 grams, or at least 0.30 grams per gram of hydrocarbons
having a boiling range distribution in a range between
20-400.degree. C. The n-paraffins content of such hydrocarbons, per
gram of hydrocarbons, may be in a range from about 0.001-0.9 grams,
about 0.1-0.8 grams, or about 0.2-0.5 grams. In some embodiments,
such hydrocarbons have a weight ratio of the iso-paraffins to the
n-paraffins of at most 1.5, at most 1.4, at most 1.0, at most 0.8,
or at most 0.3. From the n-paraffins content in such hydrocarbons,
the n-paraffins content of the crude product may be estimated to be
in a range from about 0.001-0.9 grams, about 0.01-0.8 grams, or
about 0.1-0.5 grams per gram of crude product.
[0205] 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 a Ni/V/Fe content of the crude feed. In certain
embodiments, the crude product includes, per gram of crude product,
at most 0.0001 grams, at most 1.times.10.sup.-5 grams, or at most
1.times.10.sup.-6 grams of Ni/V/Fe. 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.
[0206] In some embodiments, the crude product has a TAN of at most
90%, at most 50%, or at most 10% of the TAN of the crude feed. The
crude product may, in certain embodiments, have a TAN of at most 1,
at most 0.5, at most 0.1, or at most 0.05. 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.
[0207] In certain embodiments, the API gravity of the crude product
is at least 10% higher, at least 50% higher, or at least 90% higher
than the API gravity of the crude feed. In certain embodiments, API
gravity of the crude product is between about 13-50, about 15-30,
or about 16-20.
[0208] In some embodiments, the crude product has a total
heteroatoms content of at most 70%, at most 50%, or at most 30% of
the total heteroatoms content of the crude feed. In certain
embodiments, the crude product has a total heteroatoms content of
at least 10%, at least 40%, or at least 60% of the total
heteroatoms content of the crude feed.
[0209] The crude product may have a sulfur content of at most 90%,
at most 70%, or at most 60% of a sulfur content of the crude feed.
The sulfur content of the crude product, per gram of crude product,
may be at most 0.02 grams, at most 0.008 grams, at most 0.005
grams, at most 0.004 grams, at most 0.003 grams, or at most 0.001
grams. In certain embodiments, the crude product has, per gram of
crude product, a sulfur content in a range from about 0.0001-0.02
grams or about 0.005-0.01 grams.
[0210] In certain embodiments, the crude product may have a
nitrogen content of at most 90% or at most 80% of a nitrogen
content of the crude feed. The nitrogen content of the crude
product, per gram of crude product, may be at most 0.004 grams, at
most 0.003 grams, or at most 0.001 grams. In some embodiments, the
crude product has, per gram of crude product, a nitrogen content in
a range from about 0.0001-0.005 grams, or about 0.001-0.003
grams.
[0211] In some embodiments, the crude product has, per gram of
crude product, from about 0.05-0.2 grams, or about 0.09-0.15 grams
of hydrogen. The H/C of the crude product may be at most 1.8, at
most 1.7, at most 1.6, at most 1.5, or at most 1.4. In some
embodiments, the H/C of the crude product is about 80-120%, or
about 90-110% of the H/C of the crude feed. In other embodiments,
the H/C of the crude product is about 100-120% of the H/C of the
crude feed. A crude product H/C within 20% of the crude feed H/C
indicates that uptake and/or consumption of hydrogen in the process
is minimal.
[0212] The crude product includes components with a range of
boiling points. In some embodiments, the crude product includes: at
least 0.001 grams, or from about 0.001 to about 0.5 grams of
hydrocarbons with a boiling range distribution of at most
200.degree. C. or at most 204.degree. C. at 0.101 MPa; at least
0.001 grams, or from about 0.001 to about 0.5 grams of hydrocarbons
with a boiling range distribution between about 200.degree. C. and
about 300.degree. C. at 0.101 MPa; at least 0.001 grams, or from
about 0.001 to about 0.5 grams of hydrocarbons with a boiling range
distribution between about 300.degree. C. and about 400.degree. C.
at 0.101 MPa; and at least 0.001 grams, or from about 0.001 to
about 0.5 grams of hydrocarbons with a boiling range distribution
between about 400.degree. C. and about 538.degree. C. at 0.101
MPa.
[0213] In some embodiments, the crude product has, per gram of
crude product, a naphtha content from about 0.00001-0.2 grams,
about 0.0001-0.1 grams, or about 0.001-0.05 grams. In certain
embodiments, the crude product has from 0.001-0.2 grams or
0.01-0.05 grams of naphtha. In some embodiments, the naphtha has at
most 0.15 grams, at most 0.1 grams, or at most 0.05 grams of
olefins per gram of naphtha. The crude product has, in certain
embodiments, from 0.00001-0.15 grams, 0.0001-0.1 grams, or
0.001-0.05 grams of olefins per gram of crude product. In some
embodiments, the naphtha has, per gram of naphtha, a benzene
content of at most 0.01 grams, at most 0.005 grams, or at most
0.002 grams. In certain embodiments, the naphtha has a benzene
content that is non-detectable, or in a range from about
1.times.10.sup.-7 grams to about 1.times.10.sup.-2 grams, about
1.times.10.sup.-6 grams to about 1.times.10.sup.-5 grams, about
5.times.10.sup.-6 grams to about 1.times.10.sup.-4 grams.
Compositions that contain benzene may be considered hazardous to
handle, thus a crude product that has a relatively low benzene
content may not require special handling.
[0214] In certain embodiments, naphtha may include aromatic
compounds. Aromatic compounds may include monocyclic ring compounds
and/or polycyclic ring compounds. The monocyclic ring compounds may
include, but are not limited to, benzene, toluene, ortho-xylene,
meta-xylene, para-xylene, ethyl benzene, 1-ethyl-3-methyl benzene;
1-ethyl-2-methyl benzene; 1,2,3-trimethyl benzene; 1,3,5-trimethyl
benzene; 1-methyl-3-propyl benzene; 1-methyl-2-propyl benzene;
2-ethyl-1,4-dimethyl benzene; 2-ethyl-2,4-dimethyl benzene;
1,2,3,4-tetra-methyl benzene; ethyl, pentylmethyl benzene; 1,3
diethyl-2,4,5,6-tetramethyl benzene; tri-isopropyl-ortho-xylene;
substituted congeners of benzene, toluene, ortho-xylene,
meta-xylene, para-xylene, or mixtures thereof. Monocyclic aromatics
are used in a variety of commercial products and/or sold as
individual components. The crude product produced as described
herein typically has an enhanced content of monocyclic
aromatics.
[0215] In certain embodiments, the crude product has, per gram of
crude product, a toluene content from about 0.001-0.2 grams, about
0.05-0.15 grams, or about 0.01-0.1 grams. The crude product has,
per gram of crude product, a meta-xylene content from about
0.001-0.1 grams, about 0.005-0.09 grams, or about 0.05-0.08 grams.
The crude product has, per gram of crude product, an ortho-xylene
content from about 0.001-0.2 grams, about 0.005-0.1 grams, or about
0.01-0.05 grams. The crude product has, per gram of crude product,
a para-xylene content from about 0.001-0.09 grams, about 0.005-0.08
grams, or about 0.001-0.06 grams.
[0216] An increase in the aromatics content of naphtha tends to
increase the octane number of the naphtha. Crudes may be valued
based on an estimation of a gasoline potential of the crudes.
Gasoline potential may include, but is not limited to, a calculated
octane number for the naphtha portion of the crudes. Crudes
typically have calculated octane numbers in a range of about 35-60.
The octane number of gasoline tends to reduce the requirement for
additives that increase the octane number of the gasoline. In
certain embodiments, the crude product includes naphtha that has an
octane number of at least 60, at least 70, at least 80, or at least
90. Typically, the octane number of the naphtha is in a range from
about 60-99, about 70-98, or about 80-95.
[0217] In some embodiments, the crude product has a higher total
aromatics content in hydrocarbons having a boiling range
distribution between 204.degree. C. and 500.degree. C. (total
"naphtha and kerosene") relative to the total aromatics content in
the total naphtha and kerosene of the crude feed by at least 5%, at
least 10%, at least 50%, or at least 99%. Typically, the total
aromatics content in the total naphtha and kerosene of crude feed
is about 8%, about 20%, about 75%, or about 100% greater than the
total aromatics content in the total naphtha and kerosene of the
crude feed.
[0218] In some embodiments, the kerosene and naphtha may have a
total polyaromatic compounds content in a range from about
0.00001-0.5 grams, about 0.0001-0.2 grams, or about 0.001-0.1 grams
per gram of total kerosene and naphtha.
[0219] The crude product has, per gram of crude product, a
distillate content in a range from about 0.0001-0.9 grams, from
about 0.001-0.5 grams, from about 0.005-0.3 grams, or from about
0.01-0.2 grams. In some embodiments, a weight ratio of kerosene to
diesel in the distillate, is in a range from about 1:4 to about
4:1, about 1:3 to about 3:1, or about 2:5 to about 5:2.
[0220] In some embodiments, crude product has, per gram of crude
product, at least 0.001 grams, from above 0 to about 0.7 grams,
about 0.001-0.5 grams, or about 0.01-0.1 grams of kerosene. In
certain embodiments, the crude product has from 0.001-0.5 grams or
0.01-0.3 grams of kerosene. In some embodiments, the kerosene has,
per gram of kerosene, an aromatics content of at least 0.2 grams,
at least 0.3 grams, or at least 0.4 grams. In certain embodiments,
the kerosene has, per gram of kerosene, an aromatics content in a
range from about 0.1-0.5 grams, or from about 0.2-0.4 grams.
[0221] In certain embodiments, a freezing point of the kerosene may
be below -30.degree. C., below 40.degree. C., or below -50.degree.
C. An increase in the content of aromatics of the kerosene portion
of the crude product tends to increase the density and reduce the
freezing point of the kerosene portion of the crude product. A
crude product with a kerosene portion having a high density and low
freezing point may be refined to produce aviation turbine fuel with
the desirable properties of high density and low freezing
point.
[0222] In certain embodiments, the crude product has, per gram of
crude product, a diesel content in a range from about 0.001-0.8
grams or from about 0.01-0.4 grams. In certain embodiments, the
diesel has, per gram of diesel, an aromatics content of at least
0.1 grams, at least 0.3 grams, or at least 0.5 grams. In some
embodiments, the diesel has, per gram of diesel, an aromatics
content in a range from about 0.1-1 grams, about 0.3-0.8 grams, or
about 0.2-0.5 grams.
[0223] In some embodiments, the crude product has, per gram of
crude product, a VGO content in a range from about 0.0001-0.99
grams, from about 0.001-0.8 grams, or from about 0.1-0.3 grams. In
certain embodiments, the VGO content in the crude product is in a
range from 0.4-0.9 grams, or about 0.6-0.8 grams per gram of crude
product. In certain embodiments, the VGO has, per gram of VGO, an
aromatics content in a range from about 0.1-0.99 grams, about
0.3-0.8 grams, or about 0.5-0.6 grams.
[0224] In some embodiments, the crude product has a residue content
of at most 70%, at most 50%, at most 30%, at most 10%, or at most
1% of the crude feed. In certain embodiments, the crude product
has, per gram of crude product, a residue content of at most 0.1
grams, at most 0.05 grams, at most 0.03 grams, at most 0.02 grams,
at most 0.01 grams, at most 0.005 grams, or at most 0.001 grams. In
some embodiments, the crude product has, per gram of crude product,
a residue content in a range from about 0.000001-0.1 grams, about
0.00001-0.05 grams, about 0.001-0.03 grams, or about 0.005-0.04
grams.
[0225] In some embodiments, the crude product may include at least
a portion of the catalyst. In some embodiments, a 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 catalyst per
gram of crude product. The catalyst may assist in stabilizing the
crude product during transportation and/or treatment in processing
facilities. The catalyst may inhibit corrosion, inhibit friction,
and/or increase water separation abilities of the crude product. A
crude product that includes at least a portion of the catalyst may
be further processed to produce lubricants and/or other commercial
products.
[0226] The catalyst used for treatment of a crude feed in the
presence of a hydrogen source to produce the total product may be a
single catalyst or a plurality of catalysts. The catalysts of the
application may first be a catalyst precursor that is converted to
the catalyst in the contacting zone when hydrogen and/or a crude
feed containing sulfur is contacted with the catalyst
precursor.
[0227] The catalysts used in contacting the crude feed with a
hydrogen source to produce the total product may assist in the
reduction of the molecular weight of the crude feed. Not to be
bound by theory, the catalyst in combination with the hydrogen
source may reduce a molecular weight of components in the crude
feed through the action of basic (Lewis basic or Br.o
slashed.nsted-Lowry basic) and/or superbasic components in the
catalyst. Examples of catalysts that may have Lewis base and/or
Br.o slashed.nsted-Lowry base properties include catalysts
described herein.
[0228] In some embodiments, the catalyst is a TMS catalyst. The TMS
catalyst includes a compound that contains a transition metal
sulfide. For the purposes of this application, weight of the
transition metal sulfide in the TMS catalyst is determined by
adding the total weight of the transition metal(s) to the total
weight of sulfur in the catalyst. An atomic ratio of the transition
metal to sulfur is typically in a range from about 0.2-20, about
0.5-10, or about 1-5. Examples of transition metal sulfides may be
found in "Inorganic Sulfur Chemistry"; Edited by G. Nickless;
Elsevier Publishing Company; Amsterdam--London--New York; Copyright
1968; Chapter 19, which is incorporated herein by reference.
[0229] In certain embodiments, the TMS catalyst may include a total
of at least 0.4 grams, at least 0.5 grams, at least 0.8 grams, or
at least 0.99 grams of one or more transition metal sulfides per
gram of catalyst. In certain embodiments, the TMS catalyst has, per
gram of catalyst, a total content of one or more transition metal
sulfides in a range from about 0.4-0.999 grams, about 0.5-0.9
grams, or about 0.6-0.8 grams.
[0230] The TMS catalyst includes one or more transition metal
sulfides. Examples of transition metal sulfides include pentlandite
(Fe.sub.4.5Ni.sub.4.5S.sub.8), smythite
(Fe.sub.6.75Ni.sub.2.25S.sub.11), bravoite
(Fe.sub.0.7Ni.sub.0.2Co.sub.0.1S.sub.2), mackinawite
(Fe.sub.0.75Ni.sub.0.25SO.sub.9), argentopentlandite
(AgFe.sub.6Ni.sub.2S.sub.8), isocubanite (CuFe.sub.2S.sub.3),
isocalcopyrite (Cu.sup.8Fe.sub.9.sub.S.sub.16), sphalerite
(Zn.sub.0.95Fe.sub.0.05S), mooihoekite (Cu.sub.9Fe.sub.9S.sub.16),
chatkalite (Cu.sub.6FeSn.sub.2S.sub.8), sternbergite
(AgFe.sub.2S.sub.3), chalcopyrite (CuFeS.sub.2), troilite (FeS),
pyrite (FeS.sub.2), pyrrhotite (Fe.sub.(1-x)S (x=0 to 0.17)),
heazlewoodite (Ni.sub.3S.sub.2) or vaesite (NiS.sub.2).
[0231] In some embodiments, the TMS catalyst includes one or more
transition metal sulfides in combination with alkali metal(s),
alkaline-earth metal(s), zinc, compounds of zinc, or mixtures
thereof. The TMS catalyst is, in some embodiments, represented by
the general chemical formula A.sub.c[M.sub.aS.sub.b].sub.d, in
which A represents alkali metal, alkaline-earth metal or zinc; M
represents a transition metal from Columns 6-10 of the Periodic
Table; and S is sulfur. An atomic ratio of a to b is in a range
from about 0.5 to about 2.5, or from about 1 to about 2. An atomic
ratio of c to a s in a range from 0.0001 to about 1, from about 0.1
to about 0.8, or from about 0.3 to about 0.5. In some embodiments,
the transition metal is iron.
[0232] In some embodiments, the TMS catalyst may include generally
known alkali and/or alkaline-earth metals/transition metal sulfides
(for example, bartonite (K.sub.3Fe.sub.10S.sub.14), rasvumite
(KFe.sub.2S.sub.3), djerfisherite
K.sub.6NaFe.sub.19Cu.sub.4NiS.sub.26Cl)- , chlorobartonite
(K.sub.6.1Fe.sub.24Cu.sub.0.2S.sub.26.1Cl.sub.0.7), and/or
coyoteite (NaFe.sub.3S.sub.5.(H.sub.2O).sub.2). In some
embodiments, the TMS catalyst includes bartonite prepared in situ.
Bartonite prepared in situ may be referred to as synthetic
bartonite. Natural and/or synthetic bartonite may be used as a TMS
catalyst in the methods described herein.
[0233] In some embodiments, the TMS catalyst may include at most 25
grams, at most 15 grams, or at most 1 gram of support material per
100 grams of the TMS catalyst. Typically, the TMS catalyst has from
0 to about 25 grams, about 0.00001 to about 20 grams, about 0.0001
grams to about 10 grams of support material per 100 grams of the
TMS catalyst. Examples of support materials that may be used with
the TMS catalyst include refractory oxides, porous carbon
materials, zeolites, or mixtures thereof. In some embodiments, the
TMS catalyst is substantially free, or free, of support
materials.
[0234] The TMS catalyst that includes alkali metal(s),
alkaline-earth metal(s), zinc, compounds of zinc, or mixtures
thereof may contain one or more transition metal sulfides,
bimetallic alkali metal-transition metal sulfides, higher valence
transition metal sulfides, transition metal oxides, or mixtures
thereof, as determined using x-ray diffraction. A portion of the
alkali metal(s) component, alkaline-earth metal(s) component, zinc
component and/or a portion of the transition metal sulfide
component of the TMS catalyst may, in some embodiments, be present
as an amorphous composition not detectable by x-ray diffraction
techniques.
[0235] In some embodiments, crystalline particles of the TMS
catalyst and/or mixtures of crystalline particles of the TMS
catalyst have a particle size of at most 10.sup.8 .ANG., at most
10.sup.3 .ANG., at most 100 .ANG., or at most 40 .ANG.. In normal
practice, the particle size of the crystalline particles of the TMS
catalyst will generally be at least 10 .ANG..
[0236] The TMS catalyst that includes alkali metal(s),
alkaline-earth metal(s), zinc, compounds of zinc, or mixtures
thereof may be prepared by mixing a sufficient amount of de-ionized
water, a desired amount of a transition metal oxide, and desired
amount of Columns 1-2 metal carbonate(s), Columns 1-2 metal
oxalate(s), Columns 1-2 metal acetate(s), zinc carbonate, zinc
acetate, zinc oxalate, or mixtures thereof to form a wet paste. The
wet paste may be dried at a temperature from about 100-300.degree.
C. or 150-250.degree. C. to form a transition metal oxide/salt
mixture. The transition metal oxide/salt mixture may be calcined at
a temperature ranging from about 300-1000.degree. C., about
500-800.degree. C., or about 600-700.degree. C. to form a
transition metal oxide/metal salt mixture. The transition metal
oxide/metal salt mixture may be reacted with hydrogen to form a
reduced intermediate solid. The addition of hydrogen may be
performed at a flow rate sufficient to provide an excess amount of
hydrogen to the transition metal oxide/metal salt mixture. Hydrogen
may be added over about 10-50 hours or about 20-40 hours to the
transition metal oxide/metal salt mixture to produce a reduced
intermediate solid that includes elemental transition metal.
Hydrogen addition may be performed at a temperature of about
35-500.degree. C., about 50-400.degree. C., or about
100-300.degree. C., and a total pressure of about 10-15 MPa, about
11-14 MPa, or about 12-13 MPa. It should be understood that
reduction time, reaction temperature, selection of reducing gas,
pressure of reducing gas, and/or flow rate of reducing gas used to
prepare the intermediate solid is often changed relative to the
absolute mass of the selected transition metal oxide. The reduced
intermediate solid may, in some embodiments, be passed through a
40-mesh sieve with minimal force.
[0237] The reduced intermediate solid may be incrementally added to
a hot (for example, about 100.degree. C.) diluent/elemental sulfur,
and/or one or more compounds of sulfur, mixture at a rate to
control the evolution of heat and production of gas. The diluent
may include any suitable diluent that provides a means to dissipate
the heat of sulfurization. The diluent may include solvents with a
boiling range distributions of at least 100.degree. C., at least
150.degree. C., least 200.degree. C., or at least 300.degree. C.
Typically the diluent has a boiling range distribution between
about 100-500.degree. C., about 150-400.degree. C., or about
200-300.degree. C. In some embodiments, the diluent is VGO and/or
xylenes. Sulfur compounds include, but are not limited to, hydrogen
sulfide and/or thiols. An amount of sulfur and/or sulfur compounds
may range from 1-100 mole %, 2-80 mole %, 5-50 mole %, 10-30 mole
%, based on the moles of Columns 1-2 metal or zinc in the Columns
1-2 metal salt or zinc salt. After addition of the reduced
intermediate solid to the diluent/elemental sulfur mixture, the
resulting mixture may be incrementally heated to a final
temperature of about 200-500.degree. C., about 250-450.degree. C.,
or about 300-400.degree. C. and maintained at the final temperature
for at least 1 hour, at least 2 hours, or at least 10 hours.
Typically, the final temperature is maintained for about 15 hours,
about 10 hours, about 5 hours, or about 1.5 hours. After heating to
the elevated sulfurizing reaction temperature, the diluent/catalyst
mixture may be cooled to a temperature in a range from about
0-100.degree. C., about 30-90.degree. C., or about 50-80.degree. C.
to facilitate recovery of the catalyst from the mixture. The
sulfurized catalyst may be isolated in an oxygen-free atmosphere
from the diluent using standard techniques and washed with at least
a portion of a low boiling solvent (for example, pentane, heptane,
or hexane) to produce the TMS catalyst. The TMS catalyst may be
powdered using standard techniques.
[0238] In some embodiments, the catalyst is an inorganic salt
catalyst. The anion of the inorganic salt catalyst may include an
inorganic compound, an organic compound, or mixtures thereof. The
inorganic salt catalyst includes alkali metal carbonates, alkali
metal hydroxides, alkali metal hydrides, alkali metal amides,
alkali metal sulfides, alkali metal acetates, alkali metal
oxalates, alkali metal formates, alkali metal pyruvates,
alkaline-earth metal carbonates, alkaline-earth metal hydroxides,
alkaline-earth metal hydrides, alkaline-earth metal amides,
alkaline-earth metal sulfides, alkaline-earth metal acetates,
alkaline-earth metal oxalates, alkaline-earth metal formates,
alkaline-earth metal pyruvates, or mixtures thereof.
[0239] Inorganic salt catalysts include, but are not limited to,
mixtures of: NaOH/RbOH/CsOH; KOH/RbOH/CsOH; NaOH/KOH/RbOH;
NaOH/KOH/CsOH; K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3;
Na.sub.2O/K.sub.2O/K.sub.2CO.sub.3;
NaHCO.sub.3/KHCO.sub.3/Rb.sub.2CO.sub- .3;
LiHCO.sub.3/KCO.sub.3/Rb.sub.2CO.sub.3; KOH/RbOH/CsOH mixed with a
mixture of K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3;
K.sub.2CO.sub.3/CaCO.sub.3; K.sub.2CO.sub.3/MgCO.sub.3;
Cs.sub.2CO.sub.3/CaO; Na.sub.2CO.sub.3/Ca(OH).sub.2; KH/CsCO.sub.3;
KOCHO/CaO; CsOCHO/CaCO.sub.3; CsOCHO/Ca(OCHO).sub.2;
NaNH.sub.2K.sub.2CO.sub.3/Rb.sub.2O;
K.sub.2CO.sub.3/CaCO.sub.3/Rb.sub.2C- O.sub.3;
K.sub.2CO.sub.3/CaCO.sub.3/Cs.sub.2CO.sub.3;
K.sub.2CO.sub.3/MgCO.sub.3/Rb.sub.2CO.sub.3;
K.sub.2CO.sub.3/MgCO.sub.3/C- s.sub.2CO.sub.3; or Ca(OH).sub.2
mixed with a mixture of
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3.
[0240] In some embodiments, the inorganic salt catalyst contains at
most 0.00001 grams, at most 0.001 grams, or at most 0.01 grams of
lithium, calculated as the weight of lithium, per gram of inorganic
salt catalyst. The inorganic salt catalyst has, in some
embodiments, from about 0 but less than 0.01 grams, about
0.0000001-0.001 grams, or about 0.00001-0.0001 grams of lithium,
calculated as the weight of lithium, per gram of inorganic salt
catalyst,
[0241] In certain embodiments, an inorganic salt catalyst includes
one or more alkali metal salts that include an alkali metal with an
atomic number of at least 11. An atomic ratio of an alkali metal
having an atomic number of at least 11 to an alkali metal having an
atomic number greater than 11, in some embodiments, is in a range
from about 0.1 to about 10, about 0.2 to about 6, or about 0.3 to
about 4 when the inorganic salt catalyst has two or more alkali
metals. For example, the inorganic salt catalyst may include salts
of sodium, potassium, and rubidium with the ratio of sodium to
potassium being in a range from about 0.1-6; the ratio of sodium to
rubidium being in a range from about 0.1-6; and the ratio of
potassium to rubidium being in a range from about 0.1-6. In another
example, the inorganic salt catalyst includes a sodium salt and a
potassium salt with the atomic ratio of sodium to potassium being
in a range from about 0.1 to about 4.
[0242] In some embodiments, an inorganic salt catalyst also
includes metals from Columns 8-10 of the Periodic Table, compounds
of metals from Columns 8-10 of the Periodic Table, metals from
Column 6 of the Periodic Table, compounds of metals from Column 6
of the Periodic Table, or mixtures thereof. Metals from Columns
8-10 include, but are not limited to, iron, ruthenium, cobalt, or
nickel. Metals from Column 6 include, but are not limited to,
chromium, molybdenum, or tungsten. In some embodiments, the
inorganic salt catalyst includes about 0.1-0.5 grams, or about
0.2-0.4 grams of Raney nickel per gram of inorganic salt
catalyst.
[0243] In certain embodiments, the inorganic salt catalyst also
includes metal oxides from Columns 1-2 and/or Column 13 of the
Periodic Table. Metals from Column 13 include, but are not limited
to, boron or aluminum. Non-limiting examples of metal oxides
include lithium oxide (Li.sub.2O), potassium oxide (K.sub.2O),
calcium oxide (CaO), or aluminum oxide (Al.sub.2O.sub.3).
[0244] The inorganic salt catalyst is, in certain embodiments, free
of or substantially free of Lewis acids (for example, BCl.sub.3,
AlCl.sub.3, and SO.sub.3), Br.O slashed.nsted-Lowry acids (for
example, H.sub.3P.sup.+, H.sub.2SO.sub.4, HCl, and HNO.sub.3),
glass-forming compositions (for example, borates and silicates),
and halides. The inorganic salt may contain, per gram of inorganic
salt catalyst: from about 0 grams to about 0.1 grams, about
0.000001-0.01 grams, or about 0.00001-0.005 grams of: a) halides;
b) compositions that form glasses at temperatures of at least
350.degree. C., or at most 1000.degree. C.; c) Lewis acids; d) Br.o
slashed.nsted-Lowry acids; or e) mixtures thereof.
[0245] The inorganic salt catalyst may be prepared using standard
techniques. For example, a desired amount of each component of the
catalyst may be combined using standard mixing techniques (for
example, milling and/or pulverizing). In other embodiments,
inorganic compositions are dissolved in a solvent (for example,
water or a suitable organic solvent) to form an inorganic
composition/solvent mixture. The solvent may be removed using
standard separation techniques to produce the inorganic salt
catalyst.
[0246] In some embodiments, inorganic salts of the inorganic salt
catalyst may be incorporated into a support to form a supported
inorganic salt catalyst. Examples of supports include, but are not
limited to, zirconium oxide, calcium oxide, magnesium oxide,
titanium oxide, hydrotalcite, alumina, germania, iron oxide, nickel
oxide, zinc oxide, cadmium oxide, antimony oxide, and mixtures
thereof. In some embodiments, an inorganic salt, a Columns 6-10
metal and/or a compound of a Columns 6-10 metal may be impregnated
in the support. Alternatively, inorganic salts may be melted or
softened with heat and forced in and/or onto a metal support or
metal oxide support to form a supported inorganic salt
catalyst.
[0247] A structure of the inorganic salt catalyst typically becomes
nonhomogenous, permeable, and/or mobile at a determined temperature
or in a temperature range when loss of order occurs in the catalyst
structure. The inorganic salt catalyst may become disordered
without a substantial change in composition (for example, without
decomposition of the salt). Not to be bound by theory, it is
believed that the inorganic salt catalyst becomes disordered
(mobile) when distances between ions in the lattice of the
inorganic salt catalyst increase. As the ionic distances increase,
a crude feed and/or a hydrogen source may permeate through the
inorganic salt catalyst instead of across the surface of the
inorganic salt catalyst. Permeation of the crude feed and/or
hydrogen source through the inorganic salt often results in an
increase in the contacting area between the inorganic salt catalyst
and the crude feed and/or the hydrogen source. An increase in
contacting area and/or reactivity area of the inorganic salt
catalyst may often increase the yield of crude product, limit
production of residue and/or coke, and/or facilitate a change in
properties in the crude product relative to the same properties of
the crude feed. Disorder of the inorganic salt catalyst (for
example, nonhomogeneity, permeability, and/or mobility) may be
determined using DSC methods, ionic conductivity measurement
methods, TAP methods, visual inspection, x-ray diffraction methods,
or combinations thereof.
[0248] The use of TAP to determine characteristics of catalysts is
described in U.S. Pat. No. 4,626,412 to Ebner et al.; U.S. Pat. No.
5,039,489 to Gleaves et al.; and U.S. Pat. No. 5,264,183 to Ebner
et al., all of which are incorporated herein by reference. A TAP
system may be obtained from Mithra Technologies (Foley, Mo.,
U.S.A.). The TAP analysis may be performed in a temperature range
from about 25-850.degree. C., about 50-500.degree. C., or about
60-400.degree. C., at a heating rate in a range from about
10-50.degree. C., or about 20-40.degree. C., and at a vacuum in a
range from about 1.times.10.sup.-13 to about 1.times.10.sup.-8
torr. The temperature may remain constant and/or increase as a
function of time. As the temperature of the inorganic salt catalyst
increases, gas emission from the inorganic salt catalyst is
measured. Examples of gases that evolve from the inorganic salt
catalyst include carbon monoxide, carbon dioxide, hydrogen, water,
or mixtures thereof. The temperature at which an inflection (sharp
increase) in gas evolution from the inorganic salt catalyst is
detected is considered to be the temperature at which the inorganic
salt catalyst becomes disordered.
[0249] In some embodiments, an inflection of emitted gas from the
inorganic salt catalyst may be detected over a range of
temperatures as determined using TAP. The temperature or the
temperature range is referred to as the "TAP temperature". The
initial temperature of the temperature range determined using TAP
is referred to as the "minimum TAP temperature".
[0250] The emitted gas inflection exhibited by inorganic salt
catalysts suitable for contact with a crude feed is in a TAP
temperature range from about 100-600.degree. C., about
200-500.degree. C., or about 300-400.degree. C. Typically, the TAP
temperature is in a range from about 300-500.degree. C. In some
embodiments, different compositions of suitable inorganic salt
catalysts also exhibit gas inflections, but at different TAP
temperatures.
[0251] The magnitude of the ionization inflection associated with
the emitted gas may be an indication of the order of the particles
in a crystal structure. In a highly ordered crystal structure, the
ion particles are generally tightly associated, and release of
ions, molecules, gases, or combinations thereof, from the structure
requires more energy (that is more heat). In a disordered crystal
structure, ions are not associated to each other as strongly as
ions in a highly ordered crystal structure. Due to the lower ion
association, less energy is generally required to release ions,
molecules, and/or gases from a disordered crystal structure, and
thus, a quantity of ions and/or gas released from a disordered
crystal structure is typically greater than a quantity of ions
and/or gas released from a highly ordered crystal structure at a
selected temperature.
[0252] In some embodiments, a heat of dissociation of the inorganic
salt catalyst may be observed in a range from about 50.degree. C.
to about 500.degree. C. at a heating rate or cooling rate of about
10.degree. C., as determined using a differential scanning
calorimeter. In a DSC method, a sample may be heated to a first
temperature, cooled to room temperature, and then heated a second
time. Transitions observed during the first heating generally are
representative of entrained water and/or solvent and may not be
representative of the heat of dissociations. For example, easily
observed heat of drying of a moist or hydrated sample may generally
occur below 250.degree. C., typically between 100-150.degree. C.
The transitions observed during the cooling cycle and the second
heating correspond to the heat of dissociation of the sample.
[0253] "Heat transition" refers to the process that occurs when
ordered molecules and/or atoms in a structure become disordered
when the temperature increases during the DSC analysis. "Cool
transition" refers to the process that occurs when molecules and/or
atoms in a structure become more homogeneous when the temperature
decreases during the DSC analysis. In some embodiments, the
heat/cool transition of the inorganic salt catalyst occurs over a
range of temperatures that are detected using DSC. The temperature
or temperature range at which the heat transition of the inorganic
salt catalyst occurs during a second heating cycle is referred to
as "DSC temperature". The lowest DSC temperature of the temperature
range during a second heating cycle is referred to as the "minimum
SC temperature". The inorganic salt catalyst may exhibit a heat
transition in a range between about 200-500.degree. C., bout
250-450.degree. C., or about 300-400.degree. C.
[0254] In an inorganic salt that contains inorganic salt particles
that are a relatively homogeneous mixture, a shape of the peak
associated with the heat absorbed during a second heating cycle may
be relatively narrow. In an inorganic salt catalyst that contains
inorganic salt particles in a relatively non-homogeneous mixture,
the shape of the peak associated with heat absorbed during a second
heating cycle may be relatively broad. An absence of peaks in a DSC
spectrum indicates that the salt does not absorb or release heat in
the scanned temperature range. Lack of a heat transition generally
indicates that the structure of the sample does not change upon
heating.
[0255] As homogeneity of the particles of an inorganic salt mixture
increases, the ability of the mixture to remain a solid and/or a
semiliquid during heating decreases. Homogeneity of an inorganic
mixture may be related to the ionic radius of the cations in the
mixtures. For cations with smaller ionic radii, the ability of a
cation to share electron density with a corresponding anion
increases and the acidity of the corresponding anion increases. For
a series of ions of similar charges, a smaller ionic radius results
in higher interionic attractive forces between the cation and the
anion if the anion is a hard base. The higher interionic attractive
forces tend to result in higher heat transition temperatures for
the salt and/or more homogeneous mixture of particles in the salt
(sharper peak and increased area under the DSC curve). Mixtures
that include cations with small ionic radii tend to be more acidic
than cations of larger ionic radii, and thus acidity of the
inorganic salt mixture increases with decreasing cationic radii.
For example, contact of a crude feed with a hydrogen source in the
presence of an inorganic mixture that includes lithium cations
tends to produce increased quantities of gas and/or coke relative
to contact of the crude feed with a hydrogen source in the presence
of an inorganic salt catalyst that includes cations with a larger
ionic radii than lithium. The ability to inhibit generation of gas
and/or coke increases the total liquid product yield of the
process.
[0256] In certain embodiments, the inorganic salt catalyst may
include two or more inorganic salts. A minimum DSC temperature for
each of the inorganic salts may be determined. The minimum DSC
temperature of the inorganic salt catalyst may be below the minimum
DSC temperature of at least one of the inorganic metal salts in the
inorganic salt catalyst. For example, the inorganic salt catalyst
may include potassium carbonate and cesium carbonate. Potassium
carbonate and cesium carbonate exhibit DSC temperatures greater
than 500.degree. C. A K.sub.2CO.sub.3/Rb.sub.2CO-
.sub.3/Cs.sub.2CO.sub.3 catalyst exhibits a DSC temperature in a
range from about 290-300.degree. C.
[0257] In some embodiments, the TAP temperature may be between the
DSC temperature of at least one of the inorganic salts and the DSC
temperature of the inorganic salt catalyst. For example, the TAP
temperature of the inorganic salt catalyst may be in a range from
about 350-500.degree. C. The DSC temperature of the same inorganic
salt catalyst may be in a range from about 200-300.degree. C., and
the DSC temperature of the individual salts may be at least
500.degree. C. or at most 1000.degree. C.
[0258] An inorganic salt catalyst that has a TAP and/or DSC
temperature between about 150-500.degree. C., about 200-450.degree.
C., or about 300-400.degree. C., and does not undergo decomposition
at these temperatures, in many embodiments, can be used to catalyze
conversion of high molecular weight and/or high viscosity
compositions (for example, crude feed) to liquid products.
[0259] In certain embodiments, the inorganic salt catalyst may
exhibit increased conductivity relative to individual inorganic
salts during heating of the inorganic salt catalyst in a
temperature range from about 200-600.degree. C., about
300-500.degree. C., or about 350-450.degree. C. Increased
conductivity of the inorganic salt catalyst is generally attributed
to the particles in the inorganic salt catalyst becoming mobile.
The ionic conductivity of some inorganic salt catalysts changes at
a lower temperature than the temperature at which ionic
conductivity of a single component of the inorganic salt catalyst
changes.
[0260] Ionic conductivity of inorganic salts may be determined by
applying Ohm's law: V=IR, where V is voltage, I is current, and R
is resistance. To measure ionic conductivity, the inorganic salt
catalyst may be placed in a quartz vessel with two wires (for
example, copper wires or platinum wires) separated from each other,
but immersed in the inorganic salt catalyst.
[0261] FIG. 7 is a schematic of a system that may be used to
measure ionic conductivity. Quartz vessel 156 containing sample 158
may be placed in a heating apparatus and heated incrementally to a
desired temperature. Voltage from source 160 is applied to wire 162
during heating. The resulting current through wires 162 and 164 is
measured at meter 166. Meter 166 may be, but is not limited to, a
multimeter or a Wheatstone bridge. As sample 158 becomes less
homogeneous (more mobile) without decomposition occurring, the
resistivity of the sample should decrease and the observed current
at meter 166 should increase.
[0262] In some embodiments, at a desired temperature, the inorganic
salt catalyst may have a different ionic conductivity after
heating, cooling, and then heating. The difference in ionic
conductivities may indicate that the crystal structure of the
inorganic salt catalyst has been altered from an original shape
(first form) to a different shape (second form) during heating. The
ionic conductivities, after heating, are expected to be similar or
the same if the form of the inorganic salt catalyst does not change
during heating.
[0263] In certain embodiments, the inorganic salt catalyst has a
particle size in a range of about 10-1000 microns, about 20-500
microns, or about 50-100 microns, as determined by passing the
inorganic salt catalyst through a mesh or a sieve.
[0264] The inorganic salt catalyst may soften when heated to
temperatures above 50.degree. C. and below 500.degree. C. As the
inorganic salt catalyst softens, liquids and catalyst particles may
co-exist in the matrix of the inorganic salt catalyst. The catalyst
particles may, in some embodiments, self-deform under gravity, or
under a pressure of at least 0.007 MPa, or at most 0.101 MPa, when
heated to a temperature of at least 300.degree. C., or at most
800.degree. C., such that the inorganic salt catalyst transforms
from a first form to a second form. Upon cooling of the inorganic
salt catalyst to about 20.degree. C., the second form of the
inorganic salt catalyst is incapable of returning to the first form
of the inorganic salt catalyst. The temperature at which the
inorganic salt transforms from the first form to a second form is
referred to as the "deformation" temperature. The deformation
temperature may be a temperature range or a single temperature. In
certain embodiments, the particles of the inorganic salt catalyst
self-deform under gravity or pressure upon heating to a deformation
temperature below the deformation temperature of any of the
individual inorganic metal salts. In some embodiments, an inorganic
salt catalyst includes two or more inorganic salts that have
different deformation temperatures. The deformation temperature of
the inorganic salt catalyst differs, in some embodiments, from the
deformation temperatures of the individual inorganic metal
salts.
[0265] In certain embodiments, the inorganic salt catalyst is
liquid and/or semiliquid at, or above, the TAP and/or DSC
temperature. In some embodiments, the inorganic salt catalyst is a
liquid or a semiliquid at the minimum TAP and/or DSC temperature.
At or above the minimum TAP and/or DSC temperature, liquid or
semiliquid inorganic salt catalyst mixed with the crude feed may,
in some embodiments, form a separate phase from the crude feed. In
some embodiments, the liquid or semiliquid inorganic salt catalyst
has low solubility in the crude feed (for example, from about 0
grams to about 0.5 grams, about 0.0000001-0.2 grams, or about
0.0001-0.1 grams of inorganic salt catalyst per gram of crude feed)
or is insoluble in the crude feed (for example, from about 0 grams
to about 0.05 grams, about 0.000001-0.01 grams, or about
0.00001-0.001 grams of inorganic salt catalyst per gram of crude
feed) at the minimum TAP temperature.
[0266] In some embodiments, powder x-ray diffraction methods are
used to determine the spacing of the atoms in the inorganic salt
catalyst. A shape of the D.sub.001 peak in the x-ray spectrum may
be monitored and the relative order of the inorganic salt particles
may be estimated. Peaks in the x-ray diffraction represent
different compounds of the inorganic salt catalyst. In powder x-ray
diffraction, the D.sub.001 peak may be monitored and the spacing
between atoms may be estimated. In an inorganic salt catalyst that
contains highly ordered inorganic salt atoms, a shape of the
D.sub.001 peak is relatively narrow. In an inorganic salt catalyst
(for example, a K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/- Cs.sub.2CO.sub.3
catalyst) that contains randomly ordered inorganic salt atoms, the
shape of the D.sub.001 peak may be relatively broad or the
D.sub.001 peak may be absent. To determine if the disorder of
inorganic salt atoms changes during heating, an x-ray diffraction
spectrum of the inorganic salt catalyst may be taken before heating
and compared with an x-ray diffraction spectrum taken after
heating. The D.sub.001 peak (corresponding to the inorganic salt
atoms) in the x-ray diffraction spectrum taken at temperatures
above 50.degree. C. may be absent or broader than the D.sub.001
peaks in the x-ray diffraction spectrum taken at temperatures below
50.degree. C. Additionally, the x-ray diffraction pattern of the
individual inorganic salt may exhibit relatively narrow D.sub.001
peaks at the same temperatures.
[0267] Contacting conditions may be controlled such that the total
product composition (and thus, the crude product) may be varied for
a given crude feed in addition to limiting and/or inhibiting
formation of by-products. The total product composition includes,
but is not limited to, paraffins, olefins, aromatics, or mixtures
thereof. These compounds make up the compositions of the crude
product and the non-condensable hydrocarbon gases.
[0268] Controlling contacting conditions in combination with the
catalyst described herein may produce a total product with lower
than predicted coke content. Comparison of the MCR content of
various crudes may allow crudes to be ranked based on their
tendency to form coke. For example, a crude with a MCR content of
about 0.1 grams of MCR per gram of crude would be expected to form
more coke than a crude with a MCR content of about 0.001 grams of
MCR per gram of crude. Disadvantaged crudes typically have MCR
contents of at least 0.05 grams of MCR per gram of disadvantaged
crude.
[0269] In some embodiments, the residue content and/or coke content
deposited on the catalyst during a reaction period may be at most
0.1 grams, at most 0.05 grams, or at most 0.03 grams of residue
and/or coke per gram of catalyst. In certain embodiments, the
weight of residue and/or coke deposited on the catalyst is in a
range from about 0.0001-0.1 grams, 0.001-0.05 grams, or about
0.01-0.03 grams. In some embodiments, used catalyst is
substantially free of residue and/or coke. In certain embodiments,
contacting conditions are controlled such that at most 0.015 grams,
at most 0.01 grams, at most 0.005 grams, or at most 0.003 grams of
coke is formed per gram of crude product. Contacting a crude feed
with the catalyst under controlled contacting conditions produces a
reduced quantity of coke and/or residue relative to a quantity of
coke and/or residue produced by heating the crude feed in the
presence of a refining catalyst, or in the absence of a catalyst,
using the same contacting conditions.
[0270] The contacting conditions may be controlled, in some
embodiments, such that, per gram of crude feed, at least 0.5 grams,
at least 0.7 grams, at least 0.8 grams, or at least 0.9 grams of
the crude feed is converted to the crude product. Typically,
between about 0.5-0.99 grams, about 0.6-0.9 grams, or about 0.7-0.8
grams of the crude product per gram of crude feed is produced
during contacting. Conversion of the crude feed to a crude product
with a minimal yield of residue and/or coke, if any, in the crude
product allows the crude product to be converted to commercial
products with a minimal amount of pre-treatment at a refinery. In
certain embodiments, per gram of crude feed, at most 0.2 grams, at
most 0.1 grams, at most 0.05 grams, at most 0.03 grams, or at most
0.01 grams of the crude feed is converted to non-condensable
hydrocarbons. In some embodiments, from about 0 to about 0.2 grams,
about 0.0001-0.1 grams, about 0.001-0.05 grams, or about 0.01-0.03
grams of non-condensable hydrocarbons per gram of crude feed is
produced.
[0271] Controlling a contacting zone temperature, rate of crude
feed flow, rate of total product flow, rate and/or amount of
catalyst feed, or combinations thereof, may be performed to
maintain desired reaction temperatures. In some embodiments,
control of the temperature in the contacting zone may be performed
by changing a flow of a gaseous hydrogen source and/or inert gas
through the contacting zone to dilute the amount of hydrogen and/or
remove excess heat from the contacting zone.
[0272] In some embodiments, the temperature in the contacting zone
may be controlled such that a temperature in the contacting zone is
at, above, or below desired temperature "T.". In certain
embodiments, the contacting temperature is controlled such that the
contacting zone temperature is below the minimum TAP temperature
and/or the minimum DSC temperature. In certain embodiments, T.sub.1
may be about 30.degree. C. below, about 20.degree. C. below, or
about 10.degree. C. below the minimum TAP temperature and/or the
minimum DSC temperature. For example, in one embodiment, the
contacting temperature may be controlled to be about 370.degree.
C., about 380.degree. C., or about 390.degree. C. during the
reaction period when the minimum TAP temperature and/or minimum DSC
temperature is about 400.degree. C.
[0273] In other embodiments, the contacting temperature is
controlled such that the temperature is at, or above, the catalyst
TAP temperature and/or the catalyst DSC temperature. For example,
the contacting temperature may be controlled to be about
450.degree. C., about 500.degree. C., or about 550.degree. C.
during the reaction period when the minimum TAP temperature and/or
minimum DSC temperature is about 450.degree. C. Controlling the
contacting temperature based on catalyst TAP temperatures and/or
catalyst DSC temperatures may yield improved crude product
properties. Such control may, for example, decrease coke formation,
decrease non-condensable gas formation, or combinations
thereof.
[0274] In certain embodiments, the inorganic salt catalyst may be
conditioned prior to addition of the crude feed. In some
embodiments, the conditioning may take place in the presence of the
crude feed. Conditioning the inorganic salt catalyst may include
heating the inorganic salt catalyst to a first temperature of at
least 100.degree. C., at least 300.degree. C., at least 400.degree.
C., or at least 500.degree. C., and then cooling the inorganic salt
catalyst to a second temperature of at most 250.degree. C., at most
200.degree. C., or at most 100.degree. C. In certain embodiments,
the inorganic salt catalyst is heated to a temperature in a range
from about 150-700.degree. C., about 200-600.degree. C., or about
300-500.degree. C., and then cooled to a second temperature in a
range from about 25-240.degree. C., about 30-200.degree. C., or
about 50-90.degree. C. The conditioning temperatures may be
determined by determining ionic conductivity measurements at
different temperatures. In some embodiments, conditioning
temperatures may be determined from DSC temperatures obtained from
heat/cool transitions obtained by heating and cooling the inorganic
salt catalyst multiple times in a DSC. Conditioning of the
inorganic salt catalyst may allow contact of a crude feed to be
performed at lower reaction temperatures than temperatures used
with conventional hydrotreating catalysts.
[0275] In some embodiments, a content of naphtha, distillate, VGO,
or mixtures thereof, in the total product, may be varied by
changing a rate of total product removal from a contacting zone.
For example, decreasing a rate of total product removal tends to
increase contacting time of the crude feed with the catalyst.
Alternately, increasing pressure relative to an initial pressure
may increase contacting time, may increase a yield of a crude
product, may increase incorporation of hydrogen from the gases into
a crude product for a given mass flow rate of crude feed or
hydrogen source, or may alter combinations of these effects.
Increased contacting times of the crude feed with the catalyst may
produce an increased amount of diesel, kerosene, or naphtha and a
decreased amount of VGO relative to the amounts of diesel,
kerosene, naphtha, and VGO produced at shorter contacting times.
Increasing the contacting time of the total product in the
contacting zone may also change the average carbon number of the
crude product. Increased contacting time may result in a higher
weight percentage of lower carbon numbers (and thus, a higher API
gravity).
[0276] In some embodiments, the contacting conditions may be
changed over time. For example, the contacting pressure and/or the
contacting temperature may be increased to increase the amount of
hydrogen that the crude feed uptakes to produce the crude product.
The ability to change the amount of hydrogen uptake of the crude
feed, while improving other properties of the crude feed, increases
the types of crude products that may be produced from a single
crude feed. The ability to produce multiple crude products from a
single crude feed may allow different transportation and/or
treatment specifications to be satisfied.
[0277] Uptake of hydrogen may be assessed by comparing H/C of the
crude feed to H/C of the crude product. An increase in the H/C of
the crude product relative to H/C of the crude feed indicates
incorporation of hydrogen into the crude product from the hydrogen
source. Relatively low increase in H/C of the crude product (about
20%, as compared to the crude feed) indicates relatively low
consumption of hydrogen gas during the process. Significant
improvement of the crude product properties, relative to those of
the crude feed, obtained with minimal consumption of hydrogen is
desirable.
[0278] The ratio of hydrogen source to crude feed may also be
altered to alter the properties of the crude product. For example,
increasing the ratio of the hydrogen source to crude feed may
result in crude product that has an increased VGO content per gram
of crude product.
[0279] In certain embodiments, contact of the crude feed with the
inorganic salt catalyst in the presence of light hydrocarbons
and/or steam yields more liquid hydrocarbons and less coke in a
crude product than contact of a crude feed with an inorganic salt
catalyst in the presence of hydrogen and steam. In embodiments that
include contact of the crude feed with methane in the presence of
the inorganic salt catalyst, at least a portion of the components
of the crude product may include atomic carbon and hydrogen (from
the methane) which has been incorporated into the molecular
structures of the components.
[0280] In certain embodiments, the volume of crude product produced
from a crude feed contacted with the hydrogen source in the
presence of the inorganic salt catalyst is at least 5% greater, at
least 10% greater, or at least 15%, or at most 100% greater than a
volume of crude product produced from a thermal process at STP. The
total volume of crude product produced by contact of the crude feed
with the inorganic salt catalyst may be at least 110 vol % of the
volume of the crude feed at STP. The increase in volume is believed
to be due to a decrease in density. Lower density may generally be
at least partially caused by hydrogenation of the crude feed.
[0281] In certain embodiments, a crude feed having, per gram of
crude feed, at least 0.02 grams, at least 0.05 grams, or at least
0.1 grams of sulfur, and/or at least 0.001 grams of Ni/V/Fe is
contacted with a hydrogen source in the presence of an inorganic
salt catalyst without diminishing the activity of the catalyst.
[0282] In some embodiments, the inorganic salt catalyst can be
regenerated, at least partially, by removal of one or more
components that contaminate the catalyst. Contaminants include, but
are not limited to, metals, sulfides, nitrogen, coke, or mixtures
thereof. Sulfide contaminants may be removed from the used
inorganic salt catalyst by contacting steam and carbon dioxide with
the used catalyst to produce hydrogen sulfide. Nitrogen
contaminants may be removed by contacting the used inorganic salt
catalyst with steam to produce ammonia. Coke contaminants may be
removed from the used inorganic salt catalyst by contacting the
used inorganic salt catalyst with steam and/or methane to produce
hydrogen and carbon oxides. In some embodiments, one or more gases
are generated from a mixture of used inorganic salt catalyst and
residual crude feed.
[0283] In certain embodiments, a mixture of used inorganic salt
(for example, K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3;
KOH/Al.sub.2O.sub.3; Cs.sub.2CO.sub.3/CaCO.sub.3; or
NaOH/KOH/LiOH/ZrO.sub.2), unreacted crude feed and/or residue
and/or coke may be heated to a temperature in a range from about
700-1000.degree. C. or from about 800-900.degree. C. until the
production of gas and/or liquids is minimal in the presence of
steam, hydrogen, carbon dioxide, and/or light hydrocarbons to
produce a liquid phase and/or gas. The gas may include an increased
quantity of hydrogen and/or carbon dioxide relative to reactive
gas. For example, the gas may include from about 0.1-99 moles or
from about 0.2-8 moles of hydrogen and/or carbon dioxide per mole
of reactive gas. The gas may contain a relatively low amount of
light hydrocarbons and/or carbon monoxide. For example, less than
about 0.05 grams of light hydrocarbons per gram of gas and less
than about 0.01 grams of carbon monoxide per gram of gas. The
liquid phase may contain water, for example, greater than 0.5-0.99
grams, or greater than 0.9-0.9 grams of water per gram of
liquid.
[0284] In some embodiments, the used catalyst and/or solids in the
contacting zone may be treated to recover metals (for example,
vanadium and/or nickel) from the used catalyst and/or solids. The
used catalyst and/or solids may be treated using generally known
metal separation techniques, for example, heating, chemical
treating, and/or gasification.
EXAMPLES
[0285] Non-limiting examples of catalyst preparations, testing of
catalysts, and systems with controlled contacting conditions are
set forth below.
Example 1
[0286] Preparation of a K--Fe Sulfide Catalyst. A K--Fe sulfide
catalyst was prepared by combining 1000 grams of iron oxide
(Fe.sub.2O.sub.3) and 580 g of potassium carbonate with 412 grams
of de-ionized water to form a wet paste. The wet paste was dried at
200.degree. C. to form an iron oxide/potassium carbonate mixture.
The iron oxide/potassium carbonate mixture was calcined at
500.degree. C. to form an iron oxide/potassium carbonate mixture.
The iron oxide/potassium carbonate mixture was reacted with
hydrogen to form a reduced intermediate solid that included iron
metal. Hydrogen addition was performed over 48 hours at 450.degree.
C. and 11.5-12.2 MPa (about 1665-1765 psi). The intermediate solid
was passed through a 40-mesh sieve with minimal force.
[0287] The intermediate solid was added incrementally at a rate to
control the evolution of heat and produced gas to a
VGO/m-xylene/elemental sulfur mixture at 100.degree. C. After
addition of the intermediate solid, the resulting mixture was
incrementally heated to 300.degree. C. and maintained at
300.degree. C. for about 1 hour. The solvent/catalyst mixture was
cooled to below 100.degree. C. and the sulfurized catalyst was
separated from the mixture. The sulfurized catalyst was isolated by
filtration in a dry-box under an argon atmosphere, and washed with
m-xylene to produce 544.7 grams of the K--Fe sulfide catalyst. The
K--Fe sulfide catalyst was powdered by passing the catalyst through
a 40-mesh sieve.
[0288] The resulting K--Fe sulfide catalyst was analyzed using
x-ray diffraction techniques. From analysis of the x-ray
diffraction spectrum, it was determined that the catalyst included
troilite (FeS), K--Fe sulfide (KFeS.sub.2), pyrrhotite, and iron
oxides (for example, magnetite, Fe.sub.3O.sub.4). A peak associated
with iron disulfide (for example, pyrite, FeS.sub.2) was not
observed in the x-ray diffraction spectrum.
Example 2
[0289] Contact of a Crude Feed With a Hydrogen Source in the
Presence of a K--Fe Sulfide Catalyst. A 600 mL continuously stirred
tank reactor (composed of 316 stainless steel) was fitted with a
bottom inlet feed port, a single vapor effluent port, three
thermocouples located in the reactor interior, and a shaftdriven
1.25-inch diameter six-blade Rushton turbine.
[0290] The K--Fe sulfide catalyst (110.3 grams) prepared as
described in Example 1 was charged to the reactor. Hydrogen gas was
metered at about 8,000 Nm.sup.3/m.sup.3 (50,000 SCFB) into the
reactor and mixed with bitumen (Lloydminster region of Canada). The
bitumen entered the reactor through the bottom inlet feed port to
form a hydrogen/crude feed mixture. During the reaction run period
of about 185 hours, hydrogen gas and crude feed were continuously
fed into the reactor and product was continuously removed through
the effluent vapor port of the reactor. Crude feed was fed at a
rate of 67.0 g/hr to maintain the crude feed liquid level at about
60% of the reactor volume. A 50 milli-curie .sup.137Cs gamma ray
source and a sodium iodide scintillation detector were used to
measure the liquid level in the reactor.
[0291] The hydrogen gas/crude feed was contacted with the catalyst
at an average internal reactor temperature of 430.degree. C.
Contacting of the hydrogen/crude feed with the catalyst produced a
total product in the form of the reactor effluent vapor. The
reactor effluent vapor exited the vessel through the single upper
exit port. The reactor head was electrically heated to 430.degree.
C. to prevent internal condensation of the reactor effluent vapor
on the reactor head.
[0292] After exiting the reactor, the reactor effluent vapor was
cooled and separated in a high pressure gas/liquid separator and a
low-pressure gas/liquid separator to produce a liquid stream and a
gas stream. The gas stream was sent to a countercurrent flow
caustic scrubber to remove acidic gases, and thereafter quantified
using standard chromatographic techniques. The total product
included, per gram of total product, 0.918 grams of crude product
and 0.089 grams of non-condensable hydrocarbon gases. About 0.027
grams of solids per gram of crude feed remained in the reactor.
Properties and compositions of the crude product and the
non-condensable hydrocarbon gases produced by this method are
summarized in Table 1 in FIG. 8, Table 2 in FIG. 9, and Table 3 in
FIG. 10.
[0293] This example demonstrates a method of contacting a crude
feed with hydrogen in the presence of the transition metal sulfide
catalyst to produce a total product with minimal concomitant
generation of coke. The total product included a crude product that
was a liquid mixture at STP and has at most 0.1 grams of
non-condensable hydrocarbon gases per gram of total product.
[0294] By comparing the results of the MCR content for the crude
feed (13.7 wt %) in Table 1 to the solids formed during the process
(2.7 wt %), it is possible to see that the combination of the
controlled conditions and the catalyst produced a lower quantity of
coke than that indicated by the ASTM Method D4530.
[0295] The non-condensable hydrocarbons included C.sub.2, C.sub.3,
and C.sub.4 hydrocarbons. From the sum of the weight percentages of
the C.sub.2 hydrocarbons listed in Table 2 (20.5 grams), the
ethylene content per gram of total C.sub.2 hydrocarbons may be
calculated. The C.sub.2 hydrocarbons of the hydrocarbon gases
included 0.073 grams of ethylene per gram of total C.sub.2
hydrocarbons. From the sum of the weight percentages of the C.sub.3
hydrocarbons listed in Table 2 (23.9 grams), the propene content
per gram of total C.sub.3 hydrocarbons may be calculated. The
C.sub.3 hydrocarbons of the non-condensable hydrocarbon gases
included 0.21 grams of propene per gram of total C.sub.3
hydrocarbons. The C.sub.4 hydrocarbons of the non-condensable
hydrocarbon gases had an iso-butane to n-butane weight ratio of
0.2.
[0296] This example demonstrates a method to produce a crude
product that includes at least 0.001 grams of hydrocarbons with a
boiling range distribution of at most 204.degree. C. (400.degree.
F.) at 0.101 MPa, at least 0.001 grams of hydrocarbons with a
boiling range distribution between about 204.degree. C. and about
300.degree. C. at 0.101 MPa, at least 0.001 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 of
hydrocarbons with a boiling range distribution between about
400.degree. C. and about 538.degree. C. (1,000.degree. F.) at 0.101
MPa. The hydrocarbons that had a boiling range distribution below
204.degree. C. included iso-paraffins and n-paraffins, and the
ratio of such iso-paraffins to the n-paraffins was at most 1.4.
[0297] The crude product included boiling point distributions that
are associated with naphtha, kerosene, diesel, and VGO. The crude
product had at least 0.001 grams of naphtha and the naphtha portion
of the crude product had an octane number of at least 70. The
naphtha portion of the crude product had a benzene content of at
most 0.01 grams of benzene per gram of naphtha. The naphtha portion
of the crude product had at most 0.15 grams of olefins per gram of
naphtha. The naphtha portion of the crude product had at least 0.1
grams of monocyclic ring aromatics per gram of naphtha.
[0298] The crude product had at least 0.001 grams of kerosene. The
kerosene portion of the crude product had a freezing point below
-30.degree. C. The kerosene portion of the crude product included
aromatics, and the kerosene portion of the crude product had an
aromatics content of at least 0.3 grams of aromatics per gram of
kerosene. The kerosene portion of the crude product had at least
0.2 grams of monocyclic ring aromatics per gram of kerosene.
[0299] The crude product had at least 0.001 grams of diesel. The
diesel fraction of the crude product included aromatics, and the
diesel fraction of the crude product had an aromatics content of at
least 0.4 grams of aromatics per gram of diesel.
[0300] The crude product had at least 0.001 grams of VGO. The VGO
portion of the crude product included aromatics, and the VGO had an
aromatics content of at least 0.5 grams of aromatics per gram of
VGO.
Example 3
[0301] Preparation of a K--Fe Sulfide Catalyst in the Absence of
Hydrocarbon Diluent. A K--Fe sulfide catalyst was prepared by
combining 1000 g of iron oxide and 173 g of potassium carbonate
with 423 g of de-ionized water to form a wet paste. The wet paste
was processed as described in Example 1 to form the intermediate
solid. The intermediate solid was passed through a 40-mesh sieve
with minimal force.
[0302] In contrast to Example 2, the intermediate solid was mixed
with elemental sulfur in the absence of a hydrocarbon diluent. In a
dry-box using an argon atmosphere, the intermediate solid was mixed
with powdered elemental sulfur, placed in a sealed carbon steel
cylinder, heated to 400.degree. C., and maintained at 400.degree.
C. for about 1 hour. The sulfurized catalyst was recovered from the
carbon steel reactor as a solid. The potassium-iron sulfide
catalyst was crushed to a powder using a mortar and pestle such
that the resulting catalyst powder passed through a 40-mesh
sieve.
[0303] The resulting potassium iron sulfide catalyst was analyzed
using x-ray diffraction techniques. From analysis of the x-ray
diffraction spectrum, it was determined that the catalyst included
pyrite (FeS.sub.2), iron sulfide (FeS), and pyrrhotite
(Fe.sub.1,-xS). Mixed potassium-iron sulfide or iron oxide species
were not detected using x-ray diffraction techniques.
Example 4
[0304] Contact of a Crude Feed With a Hydrogen Source in the
Presence of a K--Fe Sulfide Catalyst at an Increased Ratio of
Gaseous Hydrogen to Crude Feed. The apparatus, crude feed, and
reaction procedure were the same as in Example 2, except that the
ratio of hydrogen gas to crude feed was about 16,000
Nm.sup.3/m.sup.3 (100,000 SCFB). The K--Fe sulfide catalyst (75.0
grams), prepared as described in Example 3, was charged to the
reactor.
[0305] Properties of the crude product produced from this method
are summarized in Table 1 in FIG. 8 and in Table 3 in FIG. 10. The
weight percentage of VGO produced in Example 4 is greater than the
weight percentage of VGO produced in Example 2. The weight
percentage of distillate produced in Example 4 is less than the
weight percentage of distillate produced in Example 2. The API
gravity of the crude product produced in Example 4 is lower than
the API gravity of the crude product produced in Example 2. A
higher API gravity indicates hydrocarbons with a higher carbon
number were produced.
[0306] After contact with the crude feed, the TMS catalyst in the
reactor was analyzed. From this analysis, the transition metal
sulfide catalyst, after being in the presence of the crude feed and
hydrogen, included K.sub.3Fe.sub.10S.sub.14.
Example 5
[0307] TAP Testing of a
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 Catalyst and the
Individual Inorganic Salts. In all TAP testing, a 300 mg sample was
heated in a reactor of a TAP system from room temperature (about
27.degree. C.) to 500.degree. C. at a rate of about 50.degree. C.
per minute. Emitted water vapor and carbon dioxide gas were
monitored using a mass spectrometer of the TAP system.
[0308] The K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst supported on alumina showed a current inflection of
greater than 0.2 volts for emitted carbon dioxide and a current
inflection of 0.01 volts for emitted water from the inorganic salt
catalyst at about 360.degree. C. The minimum TAP temperature was
about 360.degree. C., as determined by plotting the log 10 of the
ion current versus temperature. FIG. 11 is a graphical
representation of log 10 plots of ion current of emitted gases from
the K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst
("log (I)") versus temperature ("T"). Curves 168 and 170 are log 10
values for the ion currents for emitted water and CO.sub.2 from the
inorganic salt catalyst. Sharp inflections for emitted water and
CO.sub.2 from the inorganic salt catalyst occurs at about
360.degree. C.
[0309] In contrast to the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.- 3 catalyst,
potassium carbonate and cesium carbonate had non-detectable current
inflections at 360.degree. C. for both emitted water and carbon
dioxide.
[0310] The substantial increase in emitted gas for the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst
demonstrates that inorganic salt catalysts composed of two or more
different inorganic salts may be more disordered than the
individual pure carbonate salts.
Example 6
[0311] DSC Testing of an Inorganic Salt Catalyst and Individual
Inorganic Salts. In all DSC testing, a 10 mg sample was heated to
520.degree. C. at a rate of 10.degree. C. per min, cooled from
520.degree. C. to 0.0.degree. C. at rate of 10.degree. C. per
minute, and then heated from 0.degree. C. to 600.degree. C. at a
rate of 10.0.degree. C. per min using a differential scanning
calorimeter (DSC) Model DSC-7, manufactured by Perkin-Elmer
(Norwalk, Conn., U.S.A.).
[0312] DSC analysis of a
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst during
second heating of the sample shows that the mixture exhibited a
broad heat transition between 219.degree. C. and 260.degree. C. The
midpoint of the temperature range was about 250.degree. C. The area
under heat transition curve was calculated to be -1.75 Joules per
gram. The beginning of crystal disorder was determined to start at
the minimum DSC temperature of 219.degree. C.
[0313] In contrast to these results, no definite heat transitions
were observed for cesium carbonate.
[0314] DSC analysis of a mixture of Li.sub.2CO.sub.3,
Na.sub.2CO.sub.3, and K.sub.2CO.sub.3 during the second heating
cycle shows that the
Li.sub.2CO.sub.3/Na.sub.2CO.sub.3/K.sub.2CO.sub.3 mixture exhibited
a sharp heat transition between 390.degree. C. to 400.degree. C.
The midpoint of the temperature range was about 385.degree. C. The
area under heat transition curve was calculated to be -182 Joules
per gram. The beginning of mobility is determined to start at the
minimum DSC temperature of 390.degree. C. The sharp heat transition
indicates a substantially homogeneous mixture of salts.
Example 7
[0315] Ionic Conductivity Testing of an Inorganic Salt Catalysts or
an Individual Inorganic Salt Relative to K.sub.2CO.sub.3. All
testing was conducted by placing 3.81 cm (1.5 inches) of the
inorganic salt catalysts or the individual inorganic salts in a
quartz vessel with platinum or copper wires separated from each
other, but immersed in the sample in a muffle furnace. The wires
were connected to a 9.55 volt dry cell and a 220,000 ohm current
limiting resistor. The muffle furnace was heated to 600.degree. C.
and the current was measured using a microammeter.
[0316] FIG. 12 is a graphical representation of log plots of the
sample resistance relative to potassium carbonate resistance ("log
(rK.sub.2CO.sub.3)") versus temperature ("T"). Curves 172, 174,
176, 178, and 180 are log plots of K.sub.2CO.sub.3 resistance, CaO
resistance, K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst resistance,
Li.sub.2CO.sub.3/K.sub.2CO.sub.3/Cs.sub.2CO.sub.3 resistance, and
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst resistance, respectively.
[0317] CaO (curve 174) exhibits relatively large stable resistance
relative to K.sub.2CO.sub.3 (curve 172) at temperatures in a range
between 380-500.degree. C. A stable resistance indicates an ordered
structure and/or ions that tend not to move apart from one another
during heating. The
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst,
Li.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst, and
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2C-
O.sub.3 catalyst (see curves 176, 178, and 180) show a sharp
decrease in resistivity relative to K.sub.2CO.sub.3 at temperatures
in a range from 350-500.degree. C. A decrease in resistivity
generally indicates that current flow was detected during
application of voltage to the wires embedded in the inorganic salt
catalyst. The data from FIG. 12 demonstrate that the inorganic salt
catalysts are generally more mobile than the pure inorganic salts
at temperatures in a range from 350-600.degree. C.
[0318] FIG. 13 is a graphical representation of log plots of
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst resistance relative to K.sub.2CO.sub.3 resistance ("log
(rK.sub.2CO.sub.3)") versus temperature ("T"). Curve 182 is a plot
of a ratio of
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub-
.3 catalyst resistance relative to K.sub.2CO.sub.3 resistance
(curve 172) versus temperature during heating of the
Na.sub.2CO.sub.3/K.sub.2CO.sub.3-
/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst. After heating, the
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst was cooled to room temperature and then heated in the
conductivity apparatus. Curve 184 is a log plot of
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst resistance relative to K.sub.2CO.sub.3 resistance versus
temperature during heating of the inorganic salt catalyst after
being cooled from 600.degree. C. to 25.degree. C. The ionic
conductivity of the reheated
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub-
.3 catalyst increased relative to the ionic conductivity of the
original
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst.
[0319] From the difference in ionic conductivities of the inorganic
salt catalyst during the first heating and second heating, it may
be inferred that the inorganic salt catalyst forms a different form
(a second form) upon cooling that is not the same as the form (a
first form) before any heating.
Example 8
[0320] Flow Property Testing of an Inorganic Salt Catalyst. A 1-2
cm thick layer of powdered
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst was
placed in a quartz dish. The dish was placed in a furnace and
heated to 500.degree. C. for about 1 hour. To determine flow
properties of the catalyst, the dish was manually tilted in the
oven after heating. The
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst did not
flow. When pressed with a spatula, the catalyst had a consistency
of taffy.
[0321] In contrast, the individual carbonate salts were free
flowing powders under the same conditions.
[0322] A
Na.sub.2CO.sub.3/K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.-
3 catalyst became liquid and readily flowed (similar, for example
water) in the dish under the same conditions.
Examples 9-10
[0323] Contact of a Crude Feed With a Hydrogen Source in the
Presence of a K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
Catalyst and Steam. The following equipment and general procedure
was used in Examples 9-27 except where variations are
described.
[0324] Reactor: A 250 mL Hastelloy C Parr Autoclave (Parr Model
#4576) rated at 35 MPa working pressure (5000 psi) at 500.degree.
C., was fitted with a mechanical stirrer and an 800 watt Gaumer
band heater on a Eurotherm controller capable of maintaining the
autoclave at .+-.5.degree. C. from ambient to 625.degree. C., a gas
inlet port, a steam inlet port, one outlet port, and a thermocouple
to register internal temperature. Prior to heating, the top of the
autoclave was insulated with glass cloth.
[0325] Addition Vessel: An addition vessel (a 250 mL, 316 stainless
steel hoke vessel) was equipped with a controlled heating system,
suitable gas control valving, a pressure relief device,
thermocouples, a pressure gauge, and a high temperature control
valve (Swagelok Valve # SS-4UW) capable of regulating flow of a
hot, viscous, and/or pressurized crude feed at a flow rate from
0-500 g/min. An outlet side of the high temperature control valve
was attached to the first inlet port of the reactor after crude
feed was charged to the addition vessel. Prior to use, the addition
vessel line was insulated.
[0326] Product Collection: Vapor from the reactor exited the outlet
port of the reactor and was introduced into a series of cold traps
of decreasing temperatures (dip tubes connected to a series of 150
mL, 316 stainless steel hoke vessels). Liquid from the vapor was
condensed in the cold traps to form a gas stream and a liquid
condensate stream. Flow rate of the vapor from the reactor and
through the cold traps was regulated, as needed, using a back
pressure regulator. A rate of flow and a total gas volume for the
gas stream exiting the cold traps were measured using a wet test
meter (Ritter Model # TG 05 Wet Test Meter). After exiting the wet
test meter, the gas stream was collected in a gas bag (a Tedlar gas
collection bag) for analysis. The gas was analyzed using GC/MS
(Hewlett-Packard Model 5890, now Agilent Model 5890; manufactured
by Agilent Technologies, Zion Ill., U.S.A.). The liquid condensate
stream was removed from the cold traps and weighed. Crude product
and water were separated from the liquid condensate stream. The
crude product was weighed and analyzed.
[0327] Procedure: Cerro Negro (137.5 grams) was charged to the
addition vessel. The crude feed had an API gravity of 6.7. The
crude feed had, per gram of crude feed, a sulfur content of 0.042
grams, a nitrogen content of 0.011 grams, and a total Ni/V content
of 0.009 grams. The crude feed was heated to 150.degree. C. The
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.- 2CO.sub.3 catalyst (31.39
grams) was charged to the reactor.
[0328] The K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/CS.sub.2CO.sub.3
catalyst was prepared by combining of 16.44 grams of
K.sub.2CO.sub.3, 19.44 g Rb.sub.2CO.sub.3, and 24.49 grams of
Cs.sub.2CO.sub.3. The
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst had a
minimum TAP temperature of 360.degree. C. The
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs- .sub.2CO.sub.3 catalyst had a
DSC temperature of 250.degree. C. The individual salts
(K.sub.2CO.sub.3, Rb.sub.2CO.sub.3, and Cs.sub.2CO.sub.3) did not
exhibit DSC temperatures in a range from 50-500.degree. C. This TAP
temperature is above the DSC temperature of the inorganic salt
catalyst and below the DSC temperature of the individual metal
carbonates.
[0329] The catalyst was heated rapidly to 450.degree. C. under an
atmospheric pressure flow of methane of 250 cm.sup.3/min. After
reaching the desired reaction temperature, steam at a rate of 0.4
mL/min, and methane at rate of 250 cm.sup.3/min, was metered to the
reactor. The steam and methane were continuously metered during the
addition of the crude feed to the reactor over about 2.6 hours. The
crude feed was pressurized into the reactor using 1.5 MPa (229 psi)
of CH.sub.4 over 16 minutes. Residual crude feed (0.56 grams)
remained in the addition vessel after the addition of the crude
feed was complete. A decrease in temperature to 370.degree. C. was
observed during the addition of the crude feed.
[0330] The catalyst/crude feed mixture was heated to a reaction
temperature of 450.degree. C. and maintained at that temperature
for about 2 hours. After two hours, the reactor was cooled and the
resulting residue/catalyst mixture was weighed to determine a
percentage of coke produced and/or not consumed in the
reaction.
[0331] From a difference in initial catalyst weight and
coke/catalyst mixture weight, 0.046 grams of coke remained in the
reactor per gram of crude feed. The total product included 0.87
grams of a crude product with an average API gravity of 13 and gas.
The gas included unreacted CH.sub.4, hydrogen, C.sub.2 and
C.sub.4-C.sub.6 hydrocarbons, and CO.sub.2 (0.08 grams of CO.sub.2
per gram of gas).
[0332] The crude product had, per gram of crude product, 0.01 grams
of sulfur and 0.000005 grams of a total Ni and V. The crude product
was not further analyzed.
[0333] In Example 10, the reaction procedures, conditions, crude
feed, and catalyst were the same as in Example 9. The crude product
of Example 10 was analyzed to determine boiling range distributions
for the crude product. The crude product had, per gram of crude
product, 0.14 grams of naphtha, 0.19 grams of distillate, 0.45
grams of VGO, and residue content of 0.001 grams, and
non-detectable amounts of coke.
[0334] Examples 9 and 10 demonstrate that contact of the crude feed
with a hydrogen source in the presence of at most 3 grams of
catalyst per 100 grams of crude feed produces a total product that
includes a crude product that is a liquid mixture at STP. The crude
product had a residue content of at most 30% of the residue content
of the crude feed. The crude product had a sulfur content and total
Ni/V content of at most 90% of the sulfur content and Ni/V content
of the crude feed.
[0335] The crude product included at least 0.001 grams of
hydrocarbons with a boiling range distribution of at most
200.degree. C. at 0.101 MPa, at least 0.001 grams of hydrocarbons
with a boiling range distribution between 200-300.degree. C. at
0.101 MPa, at least 0.001 grams of hydrocarbons with a boiling
range distribution between 400-538.degree. C. (1000.degree. F.) at
0.101 MPa.
Examples 11-12
[0336] Contact of a Crude Feed with a Hydrogen Source in the
Presence of the K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
Catalyst and Steam. The reaction procedures, conditions, and the
K.sub.2CO.sub.3/Rb.sub.2CO.s- ub.3/Cs.sub.2CO.sub.3 catalyst in
Examples 11 and 12 were the same as in Example 9, except that 130
grams of crude feed (Cerro Negro) and 60 grams of the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst were
used. In Example 11, methane was used as the hydrogen source. In
Example 12, hydrogen gas was used as the hydrogen source. A
graphical representation of the amounts of non-condensable gas,
crude product, and coke is depicted in FIG. 14. Bars 186 and 188
represent wt % coke produced, bars 190 and 192 represent wt %
liquid hydrocarbons produced, and bars 194 and 196 represent wt %
gas produced, based on the weight of the crude feed.
[0337] In Example 11, 93 wt % of crude product (bar 192), 3 wt % of
gas (bar 196), and 4 wt % of coke (bar 188), based on the weight of
the Cerro Negro, was produced.
[0338] In Example 12, 84 wt % of crude product (bar 190), 7 wt % of
gas (bar 194), and 9 wt % of coke were produced (bar 186), based on
the weight of the Cerro Negro.
[0339] Examples 11 and 12 provide a comparison of the use of
methane as a hydrogen source to the use of hydrogen gas as a
hydrogen source. Methane is generally less expensive to produce
and/or transport than hydrogen, thus a process that utilizes
methane is desirable. As demonstrated, methane is at least as
effective as hydrogen gas as a hydrogen source when contacting a
crude feed in the presence of an inorganic salt catalyst to produce
a total product.
Examples 13-14
[0340] Producing a Crude Product with a Selected API Gravity. The
apparatus, reaction procedure and the inorganic salt catalyst were
the same as in Example 9, except that the reactor pressure was
varied.
[0341] Example 13, the reactor pressure was 0.1 MPa (14.7 psi)
during the contacting period. A crude product with API gravity of
25 at 15.5.degree. C. was produced. The total product had
hydrocarbons with a distribution of carbon numbers in a range from
5 to 32 (see curve 198 in FIG. 15).
[0342] In Example 14, the reactor pressure was 3.4 MPa (514.7 psi)
during the contacting period. A crude product with API gravity of
51.6 at 15.5.degree. C. was produced. The total product had
hydrocarbons with a distribution of carbon numbers in a range from
5 to 15 (see curve 200 in FIG. 15).
[0343] These examples demonstrate methods for contacting the crude
feed with hydrogen in the presence of an inorganic salt catalyst at
various pressures to produce a crude product with a selected API
gravity. By varying the pressure, a crude product with a higher or
lower API gravity was produced.
Examples 15-16
[0344] Contact of a Crude Feed in the Presence of a
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 Catalyst or
Silicon in the Absence of an External Hydrogen Source. In Examples
15 and 16, the apparatus, crude feed, and reaction procedure were
the same as in Example 9, except that the crude feed and catalyst
(or silicon carbide) were directly charged into the reactor at the
same time. Carbon dioxide (CO.sub.2) was used as a carrier gas. In
Example 15, 138 grams of Cerro Negro was combined with 60.4 grams
of the K.sub.2CO.sub.3/Rb.sub.2CO.sub.- 3/Cs.sub.2CO.sub.3 catalyst
(same catalyst as in Example 9). In Example 16, 132 g of Cerro
Negro was combined with 83.13 grams of silicon carbide (40 mesh,
Stanford Materials; Aliso Viejo, Calif.). Such silicon carbide is
believed to have low, if any, catalytic properties under the
process conditions described herein.
[0345] In each example, the mixture was heated to a reaction
temperature of 500.degree. C. over a period of about 2 hours. The
CO.sub.2 was metered into the reactor at a rate of 100
cm.sup.3/min. Vapor generated from the reactor was collected in the
cold traps and a gas bag using a back pressure of about 3.2 MPa
(479.7 psi). Crude product from the cold traps was consolidated and
analyzed.
[0346] In Example 15, 36.82 grams (26.68 wt %, based on the weight
of the crude feed) of a colorless hydrocarbon liquid with API
gravity of at least 50 was produced from contact of the crude feed
with the inorganic salt catalyst in the carbon dioxide
atmosphere.
[0347] In Example 16, 15.78 grams (11.95 wt %, based on the weight
of the crude feed) of a yellow hydrocarbon liquid with an API
gravity of 12 was produced from contact of the crude feed with
silicon carbide in the carbon dioxide atmosphere.
[0348] Although the yield in Example 15 is low, the in-situ
generation of a hydrogen source in the presence of the inorganic
salt catalyst is greater than the in-situ generation of hydrogen
under non-catalytic conditions. The yield of crude product in
Example 16 is one-half of the yield of crude product in Example 15.
Example 15 also demonstrates that hydrogen is generated during
contact of the crude feed in the presence of the inorganic salt and
in the absence of a gaseous hydrogen source.
Examples 17-20
[0349] Contact of a Crude Feed with a Hydrogen Source in the
Presence of K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
Catalyst, Calcium Oxide, and Silicon Carbide at Atmospheric
Conditions. The apparatus, reaction procedure, crude feed and the
inorganic salt catalyst were the same as in Example 9, except that
the Cerro Negro was added directly to the reactor instead of
addition through the addition vessel and hydrogen gas was used as
the hydrogen source. The reactor pressure was 0.101 MPa (14.7 psi)
during the contacting period. The hydrogen gas flow rate was 250
cm.sup.3/min. Reaction temperatures, steam flow rates, and
percentages of crude product, gas, and coke produced are tabulated
in Table 4 in FIG. 16.
[0350] In Examples 17 and 18, the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.- 2CO.sub.3 catalyst was
used. In Example 17, the contacting temperature was 375.degree. C.
In Example 18, the contacting temperature was in a temperature
range from 500-600.degree. C.
[0351] As shown in Table 4 (FIG. 16), for Examples 17 and 18, when
the temperature was increased from 375.degree. C. to 500.degree.
C., production of gas increased from 0.02 grams to 0.05 grams of
gas per gram of total product. Coke production, however, decreased
from 0.17 grams to 0.09 grams of coke per gram of crude feed at the
higher temperature. The sulfur content of the crude product also
decreased from 0.01 grams to 0.008 grams of sulfur per gram of
crude product at the higher temperature. Both crude products had
H/C of 1.8.
[0352] In Example 19, a crude feed was contacted with CaCO.sub.3
under conditions similar to the conditions described for Example
18. Percentages of crude product, gas, and coke production are
tabulated in Table 4 in FIG. 16. Gas production increased in
Example 19 relative to the gas production in Example 18.
Desulfurization of the crude feed was not as effective as in
Example 18. The crude product produced in Example 19 had, per gram
of crude product, 0.01 grams of sulfur as compared to the sulfur
content of 0.008 grams per gram of crude product for the crude
product produced in Example 18.
[0353] Example 20 is a comparative example for Example 18. In
Example 20, 83.13 grams of silicon carbide instead of the inorganic
salt catalyst was charged to the reactor. Gas production and coke
production significantly increased in Example 20 relative to the
gas production and coke production in Example 18. Under these
non-catalytic conditions, 0.22 grams of coke per gram of crude
product, 0.25 grams of non-condensable gas, and 0.5 grams of crude
product were produced. The crude product produced in Example 20 had
0.036 grams of sulfur per gram of crude product, compared to of
0.01 grams of sulfur per gram of crude product produced in Example
18.
[0354] These examples demonstrated that the catalysts used in
Examples 17 and 18 provide improved results over non-catalytic
conditions and conventional metal salts. At 500.degree. C., and a
hydrogen flow rate of 250 cm.sup.3/min, the amounts of coke and
non-condensable gas were significantly lower than the amounts of
coke and of non-condensable gas produced under non-catalytic
conditions.
[0355] In examples using inorganic salt catalysts (See Examples
17-18 in Table 4, FIG. 16), a decrease was observed in the weight
percent of produced gas relative to the produced gas formed during
the control experiment (for example, Example 20 in Table 4, FIG.
16). From the quantity of hydrocarbons in the produced gas, the
thermal cracking of the crude feed is estimated to be at most 20 wt
%, at most 15 wt %, at most 10 wt %, at most 5 wt %, or none, based
on the total amount of crude feed contacted with a hydrogen
source.
Examples 21 and 22
[0356] Contact of a Crude Feed with a Gaseous Hydrogen Source In
the Presence of Water and a
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.- sub.3 Catalyst
or Silicon Carbide. Apparatus in Examples 21 and 22 were the same
as in Example 9 except that hydrogen gas was used as the hydrogen
source. In Example 21, 130.4 grams of Cerro Negro was combined with
30.88 grams of the
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.- sub.3 catalyst
to form a crude feed mixture. In Example 22, 139.6 grams of Cerro
Negro was combined with 80.14 grams of silicon carbide to form the
crude feed mixture.
[0357] The crude feed mixture was charged directly into the
reactor. The hydrogen gas was metered at 250 cm.sup.3/min into the
reactor during the heating and holding periods. The crude feed
mixture was heated to 300.degree. C. over about 1.5 hours and
maintained at 300.degree. C. for about 1 hour. The reaction
temperature was increased to 400.degree. C. over about 1 hour and
maintained at 400.degree. C. for about 1 hour. After the reaction
temperature reached 400.degree. C., water was introduced into the
reactor at a rate of 0.4 g/min in combination with the hydrogen
gas. Water and hydrogen were metered into the reactor for the
remaining heating and holding periods. After maintaining the
reaction mixture at 400.degree. C., the reaction temperature was
increased to 500.degree. C. and maintained at 500.degree. C. for
about 2 hours. Generated vapor from the reactor was collected in
the cold traps and a gas bag. Liquid product from the cold traps
was consolidated and analyzed.
[0358] In Example 21, 86.17 grams (66.1 wt %, based on the weight
of the crude feed) of a dark reddish brown hydrocarbon liquid
(crude product) and water (97.5 g) were produced as a vapor from
contact of the crude feed with the
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst in
the hydrogen atmosphere.
[0359] In Example 22, water vapor and a small amount of gas was
produced from the reactor. The reactor was inspected, and a dark
brown viscous hydrocarbon liquid was removed from the reactor. Less
than 50 wt % of the dark brown viscous liquid was produced from
contact of the crude feed with silicon carbide in the hydrogen
atmosphere. A 25% increase in yield of crude product was observed
in Example 21 relative to a yield of crude product produced in
Example 22.
[0360] Example 21 demonstrates an improvement of the properties of
the crude product produced using methods described herein relative
to a crude product produced using hot water. Specifically, the
crude product in Example 21 was lower boiling than the crude
product from Example 22, as demonstrated by the crude product
produced in Example 22 not being able to be produced as a vapor.
The crude product produced in Example 21 had enhanced flow
properties relative to the crude product produced in Example 22, as
determined by visual inspection.
Examples 23-24
[0361] Contact of a Crude Feed with a Hydrogen Source in the
Presence of a
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 Catalyst to
Produce a Crude Product with Increased Volume Relative to a Crude
Product Volume Produced under Non-Catalytic Conditions. The
apparatus, crude feed, inorganic catalyst, and reaction procedure
was the same as described in Example 9, except the crude feed was
directly charged to the reactor and hydrogen gas was used as the
hydrogen source. The crude feed (Cerro Negro) had an API gravity
6.7 and a density of 1.02 g/mL at 15.5.degree. C.
[0362] In Example 23, 102 grams of the crude feed (about 100 mL of
crude feed) and 31 grams of
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.su- b.3 catalyst
were charged to the reactor. A crude product (87.6 grams) with an
API gravity of 50 and a density of 0.7796 g/mL at 15.5.degree. C.
(112 mL) was produced.
[0363] In Example 24, 102 grams of crude feed (about 100 mL of
crude feed) and 80 grams of silicon carbide were charged to the
reactor. A crude product (70 grams) of with an API gravity of 12
and a density of 0.9861 g/mL at 15.5.degree. C. (about 70 mL) was
produced.
[0364] Under these conditions, the volume of the crude product
produced from Example 23 was approximately 10% greater than the
volume of the crude feed. The volume of the crude product produced
in Example 24 was significantly less (40% less) than the volume of
crude product produced in Example 23. A significant increase in
volume of product enhances a producer's ability to generate more
volume of crude product per volume of input crude.
Example 25
[0365] Contact of a Crude Feed with a Hydrogen Source in the
Presence of a
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 Catalyst,
Sulfur, and Coke. The apparatus and reaction procedure were the
same as in Example 9, except that the steam was metered into the
reactor at 300 cm.sup.3/min. The
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst was
prepared by combining 27.2 grams of K.sub.2CO.sub.3, 32.2 grams of
Rb.sub.2CO.sub.3 and 40.6 grams of Cs.sub.2CO.sub.3.
[0366] The crude feed (130.35 grams) and
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.s- ub.3/Cs.sub.2CO.sub.3 catalyst
(31.6 grams) was charged to the reactor. The Cerro Negro crude
included, per gram of crude feed, 0.04 grams total aromatics
content in a boiling range distribution between 149-260.degree. C.
(300-500.degree. F.), 0.000640 grams of nickel and vanadium
combined, 0.042 grams of sulfur, and 0.56 grams of residue. API
gravity of the crude feed was 6.7.
[0367] Contact of the crude feed with methane in the presence of
the K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst
produced, per gram of crude feed, 0.95 grams of total product, and
0.041 grams of coke.
[0368] The total product included, per gram of total product, 0.91
grams of crude product and 0.028 grams of hydrocarbon gas. The
total gas collected included, per mole of gas, 0.16 moles of
hydrogen, 0.045 moles of carbon dioxide, and 0.025 moles of C.sub.2
and C.sub.4-C.sub.6 hydrocarbons, as determined by GC/MS. The
balance of the gas was methane, air, carbon monoxide, and a,trace
(0.004 moles) of evaporated crude product.
[0369] The crude product was analyzed using a combination of gas
chromatography and mass spectrometry. The crude product included a
mixture of hydrocarbons with a boiling range between
100-538.degree. C. The total liquid product mixture included 0.006
grams ethyl benzene (a monocyclic ring compound with a boiling
point of 136.2.degree. C. at 0.101 MPa) per gram of mixture. This
product was not detected in the crude feed.
[0370] The used catalyst ("first used catalyst") was removed from
the reactor, weighed, and then analyzed. The first used catalyst
had an increase in weight from 31.6 grams to a total weight of
37.38 grams (an increase of 18 wt %, based on the weight of the
original K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst). The first used catalyst included 0.15 grams of
additional coke, 0.0035 grams of sulfur, 0.0014 grams of Ni/V, and
0.845 grams of
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 per gram of
used catalyst.
[0371] Additional crude feed (152.71 grams) was contacted with the
first used catalyst (36.63 grams) to produce 150 grams of recovered
total product after losses. The total product included, per gram of
total product, 0.92 grams of liquid crude product, 0.058 grams of
additional coke, and 0.017 grams of gas. The gas included, per mole
of gas, 0.18 moles of hydrogen, 0.07 grams of carbon dioxide, and
0.035 moles of C.sub.2-C.sub.6 hydrocarbons. The balance of the gas
was methane, nitrogen, some air, and traces of evaporated oil
product (<1% mole).
[0372] The crude product included a mixture of hydrocarbons with a
boiling range between 100-538.degree. C. The portion of the mixture
with a boiling range distribution below 149.degree. C. included,
per mole of total liquid hydrocarbons, 0.018 mole % of ethyl
benzene, 0.04 mole % of toluene, 0.03 mole % of meta-xylene, and
0.060 mole % of para-xylene (monocyclic ring compounds with a
boiling points below 149.degree. C. at 0.101 MPa). These products
were not detectable in the crude feed.
[0373] The used catalyst ("second used catalyst") was removed from
the reactor, weighed, and then analyzed. The second used catalyst
had an increase in weight from 36.63 grams to a total weight of
45.44 grams (an increase of 43 wt %, based on the weight of the
original K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst). The second used catalyst included 0.32 grams of coke,
and 0.01 grams of sulfur, and 0.67 grams per gram of second used
catalyst.
[0374] Additional crude feed (104 grams) was contacted with the
second used catalyst (44.84 grams) to produce, per gram of crude
feed, 104 grams of total product and 0.114 grams of coke was
collected. A portion of the coke was attributed to coke formation
in the addition vessel due to overheating the addition vessel since
104.1 grams of the 133 grams of crude feed transferred was crude
feed.
[0375] The total product included, per gram of total product, 0.86
grams of crude product and 0.025 grams of hydrocarbon gas. The
total gas included, per mole of gas, 0.18 moles of hydrogen, 0.052
moles of carbon dioxide, and 0.03 moles of C.sub.2-C.sub.6
hydrocarbons. The balance of the gas was methane, air, carbon
monoxide, hydrogen sulfide, and a small trace of evaporated
oil.
[0376] The crude product included a mixture of hydrocarbons with a
boiling range between 100-538.degree. C. The portion of the mixture
with a boiling range distribution below 149.degree. C. included,
per gram of hydrocarbon mixture, 0.021 grams ethyl benzene, 0.027
grams of toluene, 0.042 grams of meta-xylene, and 0.020 grams of
para-xylene, determined as before by GC/MS.
[0377] The used catalyst ("third used catalyst") was removed from
the reactor, weighed, and then analyzed. The third used catalyst
had an increase in weight from 44.84 grams to a total weight of
56.59 grams (an increase of 79 wt %, based on the weight of the
original K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst). Detailed elemental analysis of the third used catalyst
was performed. The third used catalyst included, per gram of
additional matter, 0.90 grams of carbon, 0.028 grams of hydrogen,
0.0025 grams of oxygen, 0.046 grams of sulfur, 0.017 grams of
nitrogen, 0.0018 grams of vanadium, 0.0007 grams of nickel, 0.0015
grams of iron, and 0.00025 grams of chloride with the balance being
other transition metals such as chromium, titanium and
zirconium.
[0378] As demonstrated in this example, coke, sulfur, and/or metals
deposited on and/or in the inorganic salt catalyst do not affect
the overall yield of crude product (at least 80% for each run)
produced by contact of a crude feed with a hydrogen source in the
presence of the inorganic salt catalyst. The crude product had a
monocyclic aromatics content at least 100 times the monocyclic ring
aromatics content of the crude feed in a boiling range distribution
below 149.degree. C.
[0379] For the three runs, the average crude product yield (based
on the weight of the crude feed) was 89.7 wt %, with a standard
deviation of 2.6%; the average coke yield was 7.5 wt % (based on
the weight of the crude feed), with a standard deviation of 2.7%,
and the average weight yield of gaseous cracked hydrocarbons was
2.3 wt % (based on the weight of the crude feed) with a standard
deviation of 0.46%. The comparatively large standard deviation of
both liquid and coke was due to the third trial, in which the
temperature controller of the feed vessel failed, overheating the
crude feed in the addition vessel. Even so, there is no apparent
significant deleterious effect of even the large amounts of coke
tested here on the activity of the catalyst system.
[0380] The ratio of C.sub.2 olefins to total C.sub.2 was 0.19. The
ratio of C.sub.3 olefin to total C.sub.3 was 0.4. The alpha olefins
to internal olefins ratio of the C.sub.4 hydrocarbons was 0.61. The
C.sub.4 cis/trans olefins ratio was 6.34. This ratio was
substantially higher than the predicted thermodynamic C.sub.4
cis/trans olefins ratio of 0.68. The alpha olefins to internal
olefins ratio of the C.sub.5 hydrocarbons was 0.92. This ratio was
greater than the predicted thermodynamic C.sub.5 alpha olefins to
C.sub.5 internal olefins ratio of 0.194. The C.sub.5 cis/trans
olefins ratio was 1.25. This ratio was greater than the predicted
thermodynamic C.sub.5 cis/trans olefins ratio of 0.9.
Example 26
[0381] Contact of a Relatively High Sulfur Containing Crude Feed
with a Hydrogen Source in the Presence of the
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.su- b.3/Cs.sub.2CO.sub.3 Catalyst.
The apparatus and reaction procedure were the same as described in
Example 9, except that the crude feed, methane, and steam were
continuously fed to the reactor. The level of feed in the reactor
was monitored using a change in weight of the reactor. Methane gas
was continuously metered at 500 cm.sup.3/min to the reactor. Steam
was continuously metered at 6 g/min to the reactor.
[0382] The inorganic salt catalyst was prepared by combining 27.2
grams of K.sub.2CO.sub.3, 32.2 grams of Rb.sub.2CO.sub.3 and 40.6
grams of Cs.sub.2CO.sub.3. The
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.su- b.3 catalyst
(59.88 grams) was charged to the reactor.
[0383] A crude feed (bitumen, Lloydminster, Canada) having an API
gravity of 9.4, a sulfur content of 0.02 grams of sulfur, and a
residue content of 0.40 grams, per gram of crude feed, was heated
in the addition vessel to 150.degree. C. The hot bitumen was
continuously metered from the addition vessel at 10.5 g/min to the
reactor in an attempt to maintain the crude feed liquid level of
50% of the reactor volume, however, the rate was insufficient to
maintain that level.
[0384] The methane/steam/crude feed was contacted with the catalyst
at an average internal reactor temperature of 456.degree. C.
Contacting of the methane/steam/crude feed with the catalyst
produced a total product (in this example in the form of the
reactor effluent vapor).
[0385] A total of 1640 grams of crude feed was processed over 6
hours. From a difference in initial catalyst weight and
residue/catalyst mixture weight, 0.085 grams of coke per gram of
crude feed remained in the reactor. From contact of the crude feed
with the methane in the presence of the
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst,
0.93 grams of total product per gram of crude feed was produced.
The total product included, per gram of total product, 0.03 grams
of gas and 0.97 grams of crude product, excluding the amount of
methane and water used in the reaction.
[0386] The gas included, per gram of gas, 0.014 grams of hydrogen,
0.018 grams of carbon monoxide, 0.08 grams of carbon dioxide, 0.13
grams of hydrogen sulfide, and 0.68 grams of non-condensable
hydrocarbons. From the amount of hydrogen sulfide generated, it may
be estimated that the sulfur content of the crude feed was reduced
by 18 wt %. As shown in this example, hydrogen, carbon monoxide,
and carbon dioxide were produced. The molar ratio of carbon
monoxide to carbon dioxide was 0.4.
[0387] The C.sub.2-C.sub.5 hydrocarbons included, per gram of
hydrocarbons, 0.30 grams of C.sub.2 compounds, 0.32 grams of
C.sub.3 compounds, 0.26 grams of C.sub.4 compounds, and 0.10 grams
of C.sub.5 compounds. The weight ratio of iso-pentane to n-pentane
in the non-condensable hydrocarbons was 0.3. The weight ratio of
isobutane to n-butane in the non-condensable hydrocarbons was
0.189. The C.sub.4 compounds had, per gram of C.sub.4 compounds, a
butadiene content of 0.003 grams. A weight ratio of alpha C.sub.4
olefins to internal C.sub.4 olefins was 0.75. A weight ratio of
alpha C.sub.5 olefins to internal C.sub.5 olefins was 1.08.
[0388] The data in Example 25 demonstrates that continuous
processing of a relatively high sulfur crude feed with the same
catalyst in the presence of coke did not diminish the activity of
the inorganic salt catalyst, and produced a crude product suitable
for transportation.
Example 27
[0389] Contact of a Crude Feed with a Hydrogen Source in the
Presence of a
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 Catalyst and
Coke. The apparatus and reaction procedure was performed using
conditions as described in Example 26. The
K.sub.2.sub.CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub- .2CO.sub.3 catalyst
(56.5 grams) was charged to the reactor. A total of 2550 grams of
crude feed was processed over 6 hours. From a difference in initial
catalyst weight and residue/catalyst mixture weight, 0.114 grams of
coke per gram of crude feed remained in the reactor, based on the
weight of the crude feed. A total of 0.89 grams of total product
per gram of crude feed was produced. The total product included,
per gram of total product, 0.04 grams of gas and 0.96 grams of
crude product, excluding the amount of methane and water used in
the reaction.
[0390] The gas included, per gram of gas, 0.021 grams of hydrogen,
0.018 grams of carbon monoxide, 0.052 grams of carbon dioxide, 0.18
grams of hydrogen sulfide, and 0.65 grams of non-condensable
hydrocarbons. From the amount of hydrogen sulfide produced, it may
be estimated that the sulfur content of the crude feed was reduced
by 14 wt %, based on the weight of the crude feed. As shown in this
example, hydrogen, carbon monoxide, and carbon dioxide were
produced. The molar ratio of carbon monoxide to carbon dioxide was
0.6.
[0391] The C.sub.2-C.sub.6 hydrocarbons included, per gram of
C.sub.2-C.sub.6 hydrocarbons, 0.44 grams of C.sub.2 compounds, 0.31
grams of C.sub.3 compounds, 0.19 grams of C.sub.4 compound and
0.068 grams of C.sub.5 compounds. The weight ratio of iso-pentane
to n-pentane in the non-condensable hydrocarbons was 0.25. The
weight ratio of iso-butane to n-butane in the non-condensable
hydrocarbons was 0.15. The C.sub.4 compounds had, per gram of
C.sub.4 compounds, a butadiene content of 0.003 grams.
[0392] This example demonstrates that repeated processing of the a
relatively high sulfur crude feed (2550 grams of crude feed) with
the same catalyst (56.5 grams) in the presence of coke did not
diminish the activity of the inorganic salt catalyst, and produced
a crude product suitable for transportation.
[0393] 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.
[0394] 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.
* * * * *