U.S. patent application number 11/425989 was filed with the patent office on 2006-12-28 for methods for producing a total product in the presence of sulfur.
Invention is credited to Thomas Fairchild BROWNSCOMBE, William Douglas GILLESPIE, Weijian MO, Eswarachandra Kumar PARUCHURI, Susan Secor PFREHM, Chen Elizabeth RAMACHANDRAN, David William WALLACE, Scott Lee WELLINGTON.
Application Number | 20060289340 11/425989 |
Document ID | / |
Family ID | 46064611 |
Filed Date | 2006-12-28 |
United States Patent
Application |
20060289340 |
Kind Code |
A1 |
BROWNSCOMBE; Thomas Fairchild ;
et al. |
December 28, 2006 |
METHODS FOR PRODUCING A TOTAL PRODUCT IN THE PRESENCE OF SULFUR
Abstract
Methods of producing a total product are described. A method
includes continuously contacting a feed with a hydrogen source in
the presence of one or more inorganic salt catalysts and steam to
produce a total product, wherein the feed has at least 0.02 grams
of sulfur, per gram of feed; and producing a total product that
includes coke and the crude product. The crude product has a sulfur
content of at most 90% of the sulfur content of the feed.
Inventors: |
BROWNSCOMBE; Thomas Fairchild;
(Houston, TX) ; WELLINGTON; Scott Lee; (Bellaire,
TX) ; PARUCHURI; Eswarachandra Kumar; (Richmond,
TX) ; MO; Weijian; (Sugar Land, TX) ;
GILLESPIE; William Douglas; (Katy, TX) ;
RAMACHANDRAN; Chen Elizabeth; (Houston, TX) ; PFREHM;
Susan Secor; (Houston, TX) ; WALLACE; David
William; (Sugar Land, TX) |
Correspondence
Address: |
SHELL OIL COMPANY
P O BOX 2463
HOUSTON
TX
772522463
US
|
Family ID: |
46064611 |
Appl. No.: |
11/425989 |
Filed: |
June 22, 2006 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11014299 |
Dec 16, 2004 |
|
|
|
11425989 |
Jun 22, 2006 |
|
|
|
60531506 |
Dec 19, 2003 |
|
|
|
60618814 |
Oct 14, 2004 |
|
|
|
Current U.S.
Class: |
208/209 |
Current CPC
Class: |
C10G 45/00 20130101;
C10L 1/04 20130101; C10G 65/04 20130101 |
Class at
Publication: |
208/209 |
International
Class: |
C10G 45/00 20060101
C10G045/00 |
Claims
1. A method of producing a total product, comprising: continuously
contacting a feed with a hydrogen source in the presence of one or
more inorganic salt catalysts and steam to produce a total product,
wherein the feed has at least 0.02 grams of sulfur, per gram of
feed; and producing a total product that includes coke and the
crude product, wherein the crude product has a sulfur content of at
most 90% of the sulfur content of the feed and the content of coke
is at most 0.2 grams, per gram of feed.
2. The method of claim 1, wherein at least one of the inorganic
salt catalysts comprises one or more alkaline-earth metals and/or
one or more compounds of one or more alkaline-earth metals.
3. The method of claim 1, wherein at least one of the inorganic
salt catalysts comprises one or more alkali metals and/or one or
more compounds of one or more alkali metals.
4. The method of claim 1, wherein the inorganic salt catalyst
comprises one or more alkali metals, one or more compounds of one
or more alkali metals, one or more alkaline-earth metals, one or
more compounds of one or more alkaline-earth metals or combinations
thereof.
5. The method of claim 1, wherein at least one of the inorganic
salt catalysts is limestone and/or dolomite.
6. The method of claim 1, wherein at least one of the inorganic
salt catalysts is supported, and the support comprises limestone,
carbon, coke, nonvolatile charcoal, activated carbon, fly ash,
dolomite, clay, TiO.sub.2, ZrO.sub.2, aluminosilicate, spent
hydroprocessing catalyst, metals and/or compounds of metals
recovered from the a total product/feed mixture, one or more metals
from Columns 5-10 of the Periodic Table, one or more compounds of
one or more metals from Columns 5-10 of the Periodic Table, or
combinations thereof.
7. The method of claim 1, wherein at least one of the inorganic
salt catalysts comprises one or more metal sulfides.
8. The method of claim 1, wherein at least one of the inorganic
salt catalysts comprises nickel sulfide and/or vanadium
sulfide.
9. The method of claim 1, wherein contacting conditions comprise
controlling temperature in a range from about 300.degree. C. to
about 1000.degree. C.
10. The method of claim 1, wherein contacting conditions comprise
controlling temperature in a range from about 400.degree. C. to
about 900.degree. C.
11. The method of claim 1, wherein contacting conditions comprise
controlling temperature in a range from about 500.degree. C. to
about 800.degree. C.
12. The method of claim 1, wherein the hydrogen source comprises
methane, hydrogen gas, hydrocarbons having a carbon number of at
most 6, or combinations thereof.
13. The method of claim 1, wherein the contacting zone is a
circulating fluidized bed and/or a circulating fluidized riser.
14. The method of claim 1, wherein the feed has a total asphaltenes
content of at least 0.01 grams of asphaltenes per gram of feed.
15. The method of claim 1, wherein the feed has a total residue
content of at least 0.01 grams per gram of feed.
16. The method of claim 1, wherein the feed has at least 0.5 grams
of hydrocarbons having a boiling point below 538.degree. C., per
gram of feed.
17. The method of claim 1, wherein the contacting is performed in
the presence of hydrogen sulfide.
18. The method of claim 1, further comprising providing the total
product to a separation zone, wherein the total product is
separated into crude product and/or gas.
19. The method of claim 1, wherein the total product comprises
syngas.
20. The method of claim 1, wherein the total product comprises
carbon oxide gases and hydrogen.
21. The method of claim 1, wherein the total product includes a
crude product and the crude product has greater than 0 grams, but
less than 0.01 grams of the inorganic salt catalysts.
22. The method of claim 1, wherein the total product comprises a
crude product, and the method further comprises fractionating the
crude product into one or more distillate fractions, and producing
transportation fuel from at least one of the distillate fractions.
Description
PRIORITY
[0001] This application is a continuation-in-part application
claiming priority to U.S. patent application Ser. No. 11/014,299
filed Dec. 16, 2004, which claims priority to U.S. Provisional
Patent Application No. 60/531,506 filed Dec. 19, 2003 and U.S.
Provisional Patent Application No. 60/618,814 filed Oct. 14,
2004.
FIELD OF THE INVENTION
[0002] The present invention generally relates to systems and
methods for treating feed, and to compositions that are produced,
for example, using such systems and methods.
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 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
also be needed to inhibit unsaturated fragments from forming coke.
Processes such as reforming that are used to produce hydrogen are
generally endothermic and, typically, require additional heat.
Hydrogen and/or heat 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 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. 3,847,797 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.
4,437,980 to Heredy et al.; and U.S. Pat. No. 4,665,261 to Mazurek;
all of which are incorporated herein by reference, describe various
processes and systems used to treat crudes. U.S. Published
Application Nos. 20050133405; 20050133406; 20050135997;
20050139512; 20050145536; 20050145537; 20050145538; 20050155906;
20050167321; 20050167322; 20050167323; 20050170952; and 20050173298
to Wellington et al. all of which are incorporated herein by
reference, describe contact of a feed in the presence of a catalyst
to produce a crude product. 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 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 system for
producing a total product, comprising: a contacting zone, the
contacting zone being configured to fluidize a supported inorganic
salt catalyst in the presence of a feed, steam and a hydrogen
source to produce the total product; a regeneration zone configured
to receive at least a portion of the supported inorganic salt
catalyst from the contacting zone and remove at least a portion of
contaminants from the supported inorganic salt catalyst; and a
recovery zone, the recovery zone being configured to receive
combustion gas from the regeneration zone, wherein the recovery
zone is configured to separate at least a portion of inorganic
salts from the combustion gas.
[0015] In certain embodiments, the invention provides a method of
producing total product, comprising: providing a feed to a
contacting zone; providing an inorganic salt catalyst to the
contacting zone; contacting the inorganic salt catalyst with the
feed in the presence of a hydrogen source and steam in the
contacting zone; producing a total product and a used inorganic
salt catalyst; heating the used inorganic salt catalyst to remove
at least a portion of contaminants from the inorganic salt
catalyst, wherein a combustion gas is produced during the heating
of the used inorganic salt catalyst; and recovering inorganic salts
from the combustion gas.
[0016] In certain embodiments, the invention provides a method of
producing total product, comprising: providing a feed to a
contacting zone; providing an inorganic salt catalyst to the
contacting zone; contacting the inorganic salt catalyst with the
feed in the presence of a hydrogen source and steam such that the
inorganic salt catalyst becomes fluidized in the contacting zone;
and producing a total product.
[0017] In certain embodiments, the invention provides a method of
producing a total product, comprising: providing a feed to a
contacting zone; providing a supported inorganic salt catalyst to
the contacting zone; contacting the supported inorganic salt
catalyst with the feed in the presence of a hydrogen source and
steam in the contacting zone; and producing the total product.
[0018] In certain embodiments, the invention provides a method of
producing a crude product, comprising: providing a feed to a
contacting zone, wherein the feed has at total content, per gram of
feed, of at least 0.9 grams of hydrocarbons having a boiling range
distribution between 343.degree. C. and 538.degree. C.; providing a
supported inorganic salt catalyst to the contacting zone;
contacting the supported inorganic salt catalyst with the feed in
the presence of a hydrogen source and steam such that the supported
inorganic salt catalyst becomes fluidized; and producing a total
product that includes a crude product, and the crude product having
a total content of at least 0.2 grams per gram of crude product of
hydrocarbon have a boiling range distribution between 204.degree.
C. and 343.degree. C.
[0019] In certain embodiments, the invention provides a method of
producing a total product, comprising: contacting a feed with a
hydrogen source in the presence of one or more inorganic salt
catalysts and steam to produce a total product; and controlling
contacting conditions such that the conversion of feed to
hydrocarbon gas and hydrocarbon liquid is between 5% and 50%, based
on the molar amount of carbon in the feed.
[0020] In certain embodiments, the invention provides a method of
producing a total product, comprising: contacting a feed with light
hydrocarbons in the presence of one or more inorganic salt
catalysts and steam to produce a total product; and controlling
contacting conditions such that at least 50% of the light
hydrocarbons are recovered; and producing a total product, wherein
a ratio of atomic hydrogen to carbon (H/C) in the total product is
between 80% and 120% of the atomic H/C of the feed.
[0021] In certain embodiments, the invention provides a method of
producing a total product, comprising: providing a feed to a
contacting zone; providing a supported inorganic salt catalyst to
the contacting zone; contacting the supported inorganic salt
catalyst with the feed in the presence of a hydrogen source and
steam in the contacting zone at a temperature of at most
1000.degree. C. and a total operating pressure of at most 4 MPa;
and producing the total product.
[0022] In certain embodiments, the invention provides a method of
producing a total product, comprising: continuously contacting a
feed with a hydrogen source in the presence of one or more
inorganic salt catalysts and steam to produce a total product,
wherein the feed has at least 0.02 grams of sulfur, per gram of
feed; and producing a total product that includes that includes
coke and the crude product, wherein the crude product has a sulfur
content of at most 90% of the sulfur content of the feed and the
content of coke is at most 0.2 grams, per gram of feed.
[0023] 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.
[0024] In further embodiments, total products are obtainable by any
of the methods and systems described herein.
[0025] In further embodiments, additional features may be added to
the specific embodiments described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] 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:
[0027] FIG. 1 is a schematic of an embodiment of a contacting
system for contacting the feed with a hydrogen source in the
presence of one or more catalysts to produce the total product.
[0028] FIG. 2 is a schematic of another embodiment of a contacting
system for contacting the feed with a hydrogen source in the
presence of one or more catalysts to produce the total product.
[0029] FIG. 3 is a schematic of an embodiment of a contacting
system for fluidly contacting the feed with a hydrogen source in
the presence of one or more catalyst to produce the total
product.
[0030] FIG. 4 is a schematic of another embodiment of a contacting
system for fluidly contacting the feed with a hydrogen source in
the presence of one or more catalyst to produce the total
product.
[0031] FIG. 5 is a schematic of an embodiment of a separation zone
in combination with a contacting system.
[0032] FIG. 6 is a schematic of an embodiment of a blending zone in
combination with a contacting system.
[0033] FIG. 7 is a schematic of an embodiment of a separation zone,
a contacting system, and a blending zone.
[0034] FIG. 8 is a schematic of an embodiment of multiple
contacting systems.
[0035] FIG. 9 is a schematic of an embodiment of an ionic
conductivity measurement system.
[0036] FIG. 10 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.
[0037] FIG. 11 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.
[0038] FIG. 12 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.
[0039] FIG. 13 is a graphical representation of weight percent of
coke, liquid hydrocarbons, and gas versus various hydrogen sources
produced from embodiments of contacting the feed with the inorganic
salt catalyst.
[0040] FIG. 14 is a graphical representation of weight percentage
versus carbon number of crude products produced from embodiments of
contacting the feed with the inorganic salt catalyst.
[0041] FIG. 15 is a tabulation of components produced from
embodiments of contacting the feed with inorganic salt catalysts, a
metal salt, or silicon carbide.
[0042] FIG. 16 is a graphical representation of product selectivity
versus calcium oxide, magnesium oxide, zirconium oxide, and silicon
carbide.
[0043] FIG. 17 is a tabulation of components produced from
embodiments of contacting the feed with a supported inorganic salt
catalyst and an E-Cat.
[0044] FIG. 18 is a graphical representation of components produced
from embodiments of contacting the feed with a supported inorganic
salt catalyst and an E-Cat.
[0045] 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
[0046] The above problems may be addressed using systems, methods,
and catalysts described herein. For example, a feed and an
inorganic salt catalyst may be provided to a contacting zone.
Contact of the inorganic salt catalyst with the feed may be
performed such that the inorganic salt catalyst becomes fluidized
in the contacting zone and a total product is produced.
[0047] Certain embodiments of the inventions are described herein
in more detail. Terms used herein are defined as follows.
[0048] "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.
[0049] "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.
[0050] "AMU" refers to atomic mass unit.
[0051] "ASTM" refers to American Standard Testing and
Materials.
[0052] "Asphaltenes" refers to organic materials that are found in
crudes that are not soluble in straight-chain hydrocarbons such as
n-pentane or n-heptane. Asphaltene, in some embodiments, include
aromatic and naphthenic ring compounds containing heteroatoms.
[0053] Atomic hydrogen percentage and atomic carbon percentage of
feed, crude product, naphtha, kerosene, diesel, and VGO are as
determined by ASTM Method D5291.
[0054] "API gravity" refers to API gravity at 15.5.degree. C. API
gravity is as determined by ASTM Method D6822.
[0055] "Bitumen" refers to one type of crude produced and/or
retorted from a hydrocarbon formation.
[0056] Boiling range distributions for the 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.
[0057] "Bronsted-Lowry acid" refers to a molecular entity with the
ability to donate a proton to another molecular entity.
[0058] "Bronsted-Lowry base" refers to a molecular entity that is
capable of accepting protons from another molecular entity.
Examples of Bronsted-Lowry bases include hydroxide (OH.sup.-),
water (H.sub.2O), carboxylate (RCO.sub.2.sup.-), halide (Br.sup.-,
Cl.sup.-, F.sup.-, I.sup.-), bisulfate (HSO.sub.4.sup.-), and
sulfate (SO.sub.4.sup.2-).
[0059] "Catalyst" refers to one or more supported catalysts, one or
more unsupported catalysts, or mixtures thereof.
[0060] "Carbon number" refers to the total number of carbon atoms
in a molecule.
[0061] "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.
[0062] "Content" refers to the weight of a component in a substrate
(for example, a crude, 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.
[0063] "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.
[0064] "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.
[0065] "DSC" refers to differential scanning calorimetry.
[0066] "Feed" refers to a crude, disadvantaged crude, a mixture of
hydrocarbons, or combinations thereof that are to be treated as
described herein.
[0067] "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.
[0068] "GC/MS" refers to gas chromatography in combination with
mass spectrometry.
[0069] "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.
[0070] "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.
[0071] "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.
[0072] "Hydrogen source" refers to hydrogen, and/or a compound
and/or compounds when in the presence of a feed and the catalyst
react to provide hydrogen to one or more compounds in the 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 feed.
[0073] "Inorganic salt" refers to a compound that is composed of a
metal cation and an anion.
[0074] "IP" refers to the Institute of Petroleum, now the Energy
Institute of London, United Kingdom.
[0075] "Iso-paraffins" refer to branched-chain saturated
hydrocarbons.
[0076] "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.
[0077] "Lewis acid" refers to a compound or a material with the
ability to accept one or more electrons from another compound.
[0078] "Lewis base" refers to a compound and/or material with the
ability to donate one or more electrons to another compound.
[0079] "Light Hydrocarbons" refer to hydrocarbons having carbon
numbers in a range from 1 to 6.
[0080] "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.
[0081] "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.
[0082] "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.
[0083] "Ni/V/Fe" refers to nickel, vanadium, iron, or combinations
thereof.
[0084] "Ni/V/Fe content" refers to Ni/V/Fe content in a substrate.
Ni/V/Fe content is as determined by ASTM Method D5863.
[0085] "Nm.sup.3/m.sup.3" refers to normal cubic meters of gas per
cubic meter of feed.
[0086] "Nonacidic" refers to Lewis base and/or Bronsted-Lowry base
properties.
[0087] "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").
[0088] "n-Paraffins" refer to normal (straight chain) saturated
hydrocarbons.
[0089] "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.
[0090] "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.
[0091] "Periodic Table" refers to the Periodic Table as specified
by the International Union of Pure and Applied Chemistry (IUPAC),
November 2003.
[0092] "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.
[0093] "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.
[0094] "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.
[0095] "SCFB" refers to standard cubic feet of gas per barrel of
feed.
[0096] "Spent hydroprocessing catalyst" refers to any catalyst that
is no longer considered acceptable for use in a hydrotreating
and/or a hydrocracking catalytic process. Spent hydroprocessing
catalysts include, but are not limited to, nickel sulfide, vanadium
sulfide, and/or molybdenum sulfide.
[0097] "Superbase" refers to a material that can deprotonate
hydrocarbons such as paraffins and olefins under reaction
conditions.
[0098] "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.
[0099] "TAP" refers to temporal-analysis-of-products.
[0100] "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.
[0101] "WHSV" refers to a weight of feed/unit time divided by a
volume of catalyst expressed as hours.sup.-1.
[0102] 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.
[0103] 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.
[0104] 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.
[0105] 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.
[0106] 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 Pas; 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, at least 0.02
grams, at least 0.03 grams, or at least 0.04 grams. In some
embodiments, disadvantaged crudes may have a nitrogen content of at
least 0.001 grams, at least 0.005 grams, at least 0.01 grams, or at
least 0.02 grams per gram of disadvantaged crude.
[0107] 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 0.01 grams of hydrocarbons with a boiling range
distribution between about 300.degree. C. and about 400.degree. C.
at 0.101 MPa; and at least 0.001 grams, at least 0.005 grams, or at
least 0.01 grams of hydrocarbons with a boiling range distribution
between about 400.degree. C. and about 700.degree. C. at 0.101 MPa,
or combinations thereof.
[0108] 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 0.1 grams.
[0109] 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.
In some embodiments, disadvantaged crudes include at least 0.1
grams, at least 0.5 grams, at least 0.8 grams, or at least 0.99
grams of asphaltenes per gram of disadvantaged crude. Disadvantaged
crudes may include from about 0.01 grams to about 0.99 grams, from
about 0.1 grams to about 0.9 grams, or from about 0.5 grams to
about 0.8 grams of asphaltenes per gram of disadvantage crude.
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.
[0110] Treatment of disadvantaged crudes may enhance the properties
of the disadvantaged crudes such that the crudes are acceptable for
transportation and/or treatment. The feed may be topped as
described herein. The crude product resulting from treatment of the
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
feed, or closer to the corresponding properties of Brent crude than
the feed, and thereby have enhanced economic value relative to the
economic value of the 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.
[0111] Methods of contacting a 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.
[0112] In some embodiments, feeds that have boiling point
distributions from about 10.degree. C. to 1200.degree. C. (for
example, asphaltenes, VGO, kerosene, diesel, naphtha, or mixtures
thereof) may be contacted in accordance with the systems, methods
and catalysts described herein. The feed may include, per gram of
feed, at least 0.01 grams, at least 0.1 grams, at least 0.5 grams
or at least 0.9 grams of a mixture of hydrocarbons having boiling
point distributions with an initial boiling point above 538.degree.
C. In some embodiments, the feed may include, per gram of feed,
from about 0.01 grams to about 0.9 grams, from about 0.1 grams to
about 0.8 grams, from about 0.5 grams to about 0.7 grams of a
mixture of hydrocarbons having boiling point distributions with an
initial boiling point above 538.degree. C.
[0113] Hydrocarbon mixtures that have at least 0.01 grams, at least
0.1 grams, at least 0.5 grams, at least 0.8 grams, or at least 0.99
grams of VGO per gram of hydrocarbon mixture, may be treated in
accordance with the system and methods described herein to produce
various amounts of naphtha, kerosene, diesel, or distillate. A
hydrocarbon mixture having, per gram of hydrocarbon mixture, from
about 0.01 grams to about 0.99 grams, from about 0.05 grams to
about 0.9 grams, from about 0.1 grams to about 0.8 grams, from
about 0.2 grams to about 0.7 grams, or from about 0.3 grams to
about 0.6 grams of VGO may be treated to produce various products
having a boiling point distribution lower than the boiling point
distribution of VGO.
[0114] The 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.
[0115] 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 feed with the inorganic salt
catalyst at temperatures in a range from about 200-1200.degree. C.,
about 300-1000.degree. C., about 400-900.degree. C., or about
500-800.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.
[0116] 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.
[0117] 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 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.
[0118] Contacting conditions typically include temperature,
pressure, 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.
[0119] 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 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 feed is in a range from about 0.01-10
kilograms, about 0.03-5 kilograms, or about 0.1-1 kilogram of
steam, per kilogram of feed. A flow rate of feed may be sufficient
to maintain the volume of 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 feed in the contacting
zone is about 40%, about 60%, or about 80% of the total volume of
the contacting zone. In some embodiments, WHSV in a contacting zone
ranges from about 0.1 to about 30 h.sup.-1, about 0.5 to about 20
h.sup.-1, or about 1 to about 10 h.sup.-1. 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.
[0120] FIG. 1 is a schematic of an embodiment of contacting system
100 used to produce the total product as a vapor. The feed exits
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 gram to 1000 grams, about 2 grams to 500 grams, about 3
grams to 200 grams, about 4 grams to 100 grams, about 5 grams to 50
grams, about 6 grams to 80 grams, about 7 grams to 70 grams, or
about 8 grams to 60 grams, per 100 grams of feed in the contacting
zone. In some embodiments, contacting zone 102 includes one or more
fluidized bed reactors, one or more fixed bed reactors, or
combinations thereof.
[0121] In certain embodiments, a diluent may be added to the feed
to lower the viscosity of the feed. In some embodiments, the feed
enters a bottom portion of contacting zone 102 via conduit 104. In
certain embodiments, the 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 feed to contacting zone 102. Typically,
the feed may be heated to a temperature in a range from about
100-500.degree. C. or about 200-400.degree. C.
[0122] In some embodiments, the catalyst is combined with the feed
and transferred to contacting zone 102. The 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 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 feed/catalyst mixture is a slurry. In certain
embodiments, TAN of the feed may be reduced prior to introduction
of the feed into the contacting zone. For example, when the
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 feed may be formed. The formation of
these alkali salts may remove some acidic components from the feed
to reduce the TAN of the feed.
[0123] In some embodiments, the feed is added continuously to
contacting zone 102. Mixing in contacting zone 102 may be
sufficient to inhibit separation of the catalyst from the
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.
[0124] In some embodiments, the feed and/or a mixture of 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 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.21 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.).
[0125] 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 feed as the
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.
[0126] 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 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 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 feed.
[0127] 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 feed and/or coke.
[0128] 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).
[0129] FIG. 2 depicts contacting system 122 for treating 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 feed may enter
contacting zone 102 as described herein via conduit 104. In some
embodiments, the feed is received from the 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 feed may be contacted with the catalyst in
contacting zone 102 to produce a total product.
[0130] 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 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.
[0131] 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 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.
[0132] In some embodiments, contact of a catalyst with gas and a
feed may be performed under fluidization conditions. Fluidization
of the catalyst may allow operation of the reaction to be preformed
at less stringent conditions. For example, fluidization of the
catalyst may lower the total amount of heat required to produce the
total product, thus the contacting zone may be operated at reduced
temperatures and pressures relative to a slurry or fixed bed
process. For example, catalytic cracking and steam reformation
processes may be performed at temperatures of at most 1000.degree.
C., at most 900.degree. C., at most 800.degree. C., at most
700.degree. C., or at most 600.degree. C. and at pressures of at
most 4 MPa, at most 3.5 MPa, at most, 3 MPa, or at most 2 MPa when
using a supported inorganic salt catalyst in a fluidized catalyst
contacting zone. Fluidization of the catalyst may also allow an
increased surface area of contact for the feed with the catalyst.
An increased surface area of contact may lead to increased
conversion of feed to total products. Additionally, coke production
may be minimized at elevated temperatures when the process is
conducted under fluidization conditions (for example, at
temperatures of at least 500.degree. C., at least 700.degree. C.,
at least 800.degree. C.). In some embodiments, an inorganic salt
catalyst is a supported catalyst. Supported inorganic salt
catalysts may be more readily fluidized than unsupported inorganic
salt catalysts.
[0133] FIG. 3 depicts contacting system 130 for treating a feed
with one or more catalysts to produce a total product that may be
gas and/or liquid. Contacting zone 102 may be a fluidized reactor.
The feed may enter contacting zone 102 via conduit 104. The feed
may be heated as previously described, emulsified, and/or mixed
with catalyst as previously described. Conduit 104 may include gas
inlet port 112 and steam inlet port 114. Steam inlet ports 114',
114'' may directly enter contacting zone 102. In some embodiments,
gas inlet port 112 may directly enter contacting zone 102. In
certain embodiments, steam inlet ports 114' and 114'' are not
necessary. The catalyst may enter contacting zone via conduit 132.
A quantity of the catalyst used in the contacting zone may range
from about 1 gram to 1000 grams, about 2 grams to 500 grams, about
3 grams to 200 grams, about 4 grams to 100 grams, about 5 grams to
50 grams, about 6 grams to 80 grams, about 7 grams to 70 grams, or
about 8 grams to 60 grams, per 100 grams of feed in the contacting
zone. In some embodiments, the catalyst may enter contacting zone
at various elevations of the contacting zone (for example, bottom
elevation, middle elevation, and/or upper elevation). Conduit 106
allows at least a portion of the total product/feed mixture to be
recycled.
[0134] The catalyst may be fluidized through the upward lift of gas
and feed and/or recycled total product/feed mixture, which are
distributed across the contacting zone through distributor 134 and
a grid plate 136. Spent catalyst and/or a portion of the total
product/feed mixture may exit contacting zone 102 via conduit 138.
Pump 140 controls the flow of fluidized liquid obtained from
internal vapor/liquid separator 142. The height of the fluidized
bed is adjusted by varying the speed of pump 140 using methods
known in the art.
[0135] In some embodiments, during contacting impurities (for
example, coke, nitrogen containing compounds, sulfur containing
compounds, and/or metals such as nickel and/or vanadium) form on
the catalyst. Removal of the impurities in situ may enhance
contacting run times as compared to ending the run and removing all
the catalyst from the contacting zone. In situ removal of the
impurities may be performed through combustion of the catalyst. In
some embodiments, an oxygen source (for example, air and/or oxygen)
may be introduced into contacting zone 102 to allow combustion of
impurities on the catalyst to occur. An oxygen source may be added
at a rate sufficient to from a combustion front, but the formed
combustion front is inhibited from entering the headspace of
contacting zone 102 (for example, oxygen may be added at a rate
sufficient to maintain the total mole percent of oxygen in the
head-space below 7 percent). Heat from the combustion process may
lessen the requirement for heat from an external source to be added
to contacting zone 102 during use.
[0136] Feed may be fluidly contacted with hydrogen in the presence
of one or more catalysts in contacting zone 102 to produce a total
product. Total product may exit contacting zone 102 via conduit 108
and enter separation zone 144. Separation zone may be similar, or
the same as, previously described separation zones or separation
zones know in the art. Total product may include crude product,
gas, water, solids, catalyst, or combinations thereof. Temperatures
in contacting zone 102 may range from about 300.degree. C. to about
1000.degree. C., about 400.degree. C. to about 900.degree. C., from
about 500.degree. C. to about 800.degree. C., about 600.degree. C.
to about 700.degree. C. or about 750.degree. C.
[0137] In separation zone 144, the total product is separated to
form crude product and/or gas. Crude product may exit separation
zone 144 via conduit 146. Gas may exit separation zone 144 via
conduit 148. The crude product and/or gas may be used as is or
further processed. In some embodiments, separated catalyst may be
regenerated and/or combined with fresh catalyst entering contacting
zone 102.
[0138] Fluidly contacting the feed with a hydrogen source in the
presence of one or more inorganic metal salt catalysts may be an
endothermic process. In some embodiments, fluidly contacting a feed
with the inorganic metal salt catalyst may be up to 4 times as
endothermic as a conventional fluidized catalytic cracking process.
To provide sufficient heat transfer, an external heat source may be
used to supply heat to the contacting zone. The external heat
supply may be a combustor, a catalyst regeneration zone, a power
plant, or any source of heat known in the art.
[0139] FIG. 4 depicts contacting system 150. Contacting system 150
may be a fluidized catalytic cracking system and/or a modified
fluidized catalytic cracking system. Contacting system 150 includes
contacting zone 102, regeneration zone 152, and recovery zone 154.
In some embodiments, contacting zone 102 and regeneration zone 152
are combined as one zone. Contacting zone 102 includes fluidizer
156 and internal separators 158, 158'. Feed enters contacting zone
102 via conduit 104. Catalyst enters contacting zone 102 via inlet
port 160. A quantity of the catalyst used in the contacting zone
may range from about 1-1000 grams, about 2-500 grams, about 3-200
grams, about 4-100 grams, about 5-50 grams, about 6-80 grams, about
7-70 grams, or about 8-60 grams, per 100 grams of feed in the
contacting zone. Conduit 104 may include catalyst inlet port 160,
gas inlet port 112, and steam inlet port 114. In some embodiments,
steam, gas, and/or a hydrogen source may be mixed with the feed and
catalyst prior to entering contacting zone 102.
[0140] In some embodiments, contacting zone 102 may include steam
inlet port 114'. Steam inlet port 114' may allow additional steam
or superheated steam to be added to the contacting zone. Heat from
the steam may allow more controlled heating of the fluidizer 156.
Fluidization of the feed and catalyst in fluidizer 156 may be
performed using atomization nozzles, spray nozzles, pumps, and/or
other fluidizing methods known in the art. In some embodiments, an
oxygen source may be added to contacting zone 102 as described for
contacting system 130.
[0141] Internal separators 158, 158' may separate a portion of the
catalyst from the total product/feed mixture and recycle the total
product/feed mixture to fluidizer 156. Separated catalyst may exit
contacting zone 102 via conduit 162. Separated catalyst refers to
used catalyst and/or a mixture of used catalyst and new catalyst.
Used catalyst refers to catalyst that has been contacted with feed
in the contacting zone.
[0142] Separated catalyst may enter regeneration zone 152 via
conduit 166. Valve 164 may regulate flow of separated catalyst as
it enters regeneration zone 152. An oxygen source may enter
regeneration zone 152 via gas inlet port 168. At least a portion of
the catalyst may be regenerated by removal of impurities from the
catalyst through combustion. During combustion, combustion gas
(flue gas) and regenerated catalyst are formed. Heat generated from
the combustion process may be transferred to contacting zone 102.
Transferred heat may range from about 500.degree. C. to about
1000.degree. C., from about 600.degree. C. to about 900.degree. C.,
or from about 700.degree. C. to about 800.degree. C.
[0143] At least a portion of regenerated catalyst may exit
regeneration zone 152 via conduit 170. Valve 172 may be used to
regulate flow of catalyst into conduit 104. In some embodiments,
new catalyst and/or spent hydroprocessing catalyst is added to
conduit 170 via conduit 174. New catalyst and/or spent
hydroprocessing catalyst may be combined with regenerated catalyst
in conduit 170. In some embodiments, the catalyst is added to
conduit 170 and/or contacting zone 102 using a sprayer.
[0144] Combustion gas may exit regeneration zone 152 and enter
recovery zone 154 via conduit 178. Combustion gas may include
entrained inorganic salts of the catalyst. In some embodiments, the
combustion gas may include catalyst particles, which may be removed
using physical separation methods. In recovery zone 154, the
combustion gas is separated from catalyst and/or the inorganic
salts. In some embodiments, the combustion gas includes a fluidized
bed with particles that may combine with the inorganic salts of the
catalyst. The combined particle/inorganic salts may be separated
from the combustion gas. The separated particle/inorganic salts may
be used as and/or combined with the catalyst entering contacting
zone 102.
[0145] In some embodiments, the combustion gas may be treated with
water to partially dissolve inorganic salts entrained in the
combustion gas to form an aqueous inorganic salt solution. The
aqueous inorganic salt solution may be separated from the
combustion gas using gas/liquid separation methods known in the
art. The aqueous inorganic salt solution may be heated to remove
the water to form an inorganic salt catalyst and/or recover the
inorganic salts (for example, recover cesium, magnesium, calcium,
and/or potassium salts). The recovered inorganic salts and/or
formed catalyst may be used as and/or combined with the catalyst
entering contacting zone 102. In some embodiments, the recovered
inorganic salts may be sprayed into contacting zone 102 and/or
conduit 174. In some embodiments, the recovered inorganic salts may
be deposited on a catalyst support and the result supported
inorganic salts may enter and/or be sprayed into contacting zone
102 and/or conduit 174.
[0146] Contact of the feed with a hydrogen source in the presence
of one or more catalysts and steam in contacting system 150
produces a total product. The total product may exit from an upper
elevation of contacting zone via conduit 108. The total product
enters separation zone 144 and is separated into crude product
and/or gas. Crude product may exit separation zone 144 via conduit
146. Gas may exit separation zone 144 via conduit 148. The crude
product and/or gas may be used as is or further processed.
[0147] 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.
[0148] In some embodiments, separation of at least a portion of a
feed is performed before the feed enters the contacting zone. FIG.
5 is a schematic of an embodiment of a separation zone in
combination with a contacting system. Contacting system 190 may be
contacting system 100, contacting system 122, contacting system
130, contacting system 150, or combinations thereof (shown in FIGS.
1 through 4). The feed enters separation zone 192 via conduit 104.
In separation zone 192, at least a portion of the feed is separated
using standard separation techniques to produce a separated feed
and hydrocarbons. The separated 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 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. In some
embodiments, the separated feed is VGO. The hydrocarbons separated
from the feed exit separation zone 192 via conduit 194 to be
transported to other processing units, treatment facilities,
storage facilities, or combinations thereof.
[0149] At least a portion of the separated feed exits separation
zone 192 and enters contacting system 190 via conduit 196 to be
further processed to form the crude product, which exits contacting
system 130 via conduit 198.
[0150] In some embodiments, the crude product produced from a feed
by any method described herein is blended with a crude that is the
same as or different from the 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.
[0151] FIG. 6 is a schematic of an embodiment of a combination of
blending zone 200 and contacting system 190. In certain
embodiments, at least a portion of the crude product exits
contacting system 190 via conduit 198 and enters blending zone 200.
In blending zone 200, 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 feeds,
or naphtha), a crude, a feed, or mixtures thereof, to produce a
blended product. The process streams, feed, crude, or mixtures
thereof, are introduced directly into blending zone 200 or upstream
of the blending zone via conduit 202. A mixing system may be
located in or near blending zone 200. 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 200 via conduit 204 to be transported
and/or processed.
[0152] 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 feed to form a
feed/methanol mixture. Combining methanol with the feed tends to
lower the viscosity of the feed. Heating the feed/methanol mixture
to at most 500.degree. C. may reduce TAN of the feed to less than
1.
[0153] FIG. 7 is a schematic of an embodiment of a separation zone
in combination with a contacting system in combination with a
blending zone. The feed enters separation zone 192 through conduit
104. The feed is separated as previously described to form a
separated feed. The separated feed enters contacting system 190
through conduit 196. The crude product exits contacting system 190
and enters blending zone 200 through conduit 198. In blending zone
200, other process stream and/or crudes introduced via conduit 202
are combined with the crude product to form a blended product. The
blended product exits blending zone 200 via conduit 204.
[0154] FIG. 8 is a schematic of multiple contacting system 206.
Contacting system 208 (for example, contacting systems shown in
FIGS. 1 through 4) may be positioned before contacting system 210.
In an alternate embodiment, the positions of the contacting systems
can be reversed. Contacting system 208 includes an inorganic salt
catalyst. Contacting system 210 may include one or more catalysts.
The catalyst in contacting system 210 may be an additional
inorganic salt catalyst and/or commercial catalysts. The feed
enters contacting system 208 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 208 via conduit 108. The hydrogen generated from
contact of the inorganic salt catalyst with the feed may be used as
a hydrogen source for contacting system 210. At least a portion of
the generated hydrogen is transferred to contacting system 210 from
contacting system 208 via conduit 212.
[0155] In an alternate embodiment, such generated hydrogen may be
separated and/or treated, and then transferred to contacting system
210 via conduit 212. In certain embodiments, contacting system 210
may be a part of contacting system 208 such that the generated
hydrogen flows directly from contacting system 208 to contacting
system 210. In some embodiments, a vapor stream produced from
contacting system 208 is directly mixed with the feed entering
contacting system 210.
[0156] A second feed enters contacting system 210 via conduit 214.
In contacting system 210, contact of the 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 210 via conduit 216.
[0157] In certain embodiments, a system that includes contacting
systems, contacting zones, separation zones, and/or blending zones,
as shown in FIGS. 1-8, may be located at or proximate to a
production site that produces disadvantaged feed. After processing
through the catalytic system, the feed and/or crude product may be
considered suitable for transportation and/or for use in a refinery
process.
[0158] 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.
[0159] The total product includes, in some embodiments, at most 0.2
grams of coke, at most 0.1 grams of coke, 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.
[0160] 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 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.
[0161] 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.
[0162] In certain embodiments, hydrogen gas, carbon dioxide, carbon
monoxide, or combinations thereof can be formed in situ by contact
of steam, light hydrocarbons, and feed with the inorganic salt
catalyst. Certain embodiments of this kind of process are generally
referred to as steam reforming. Reaction of feed, steam, hydrogen,
and an inorganic salt catalyst may occur under circulating
fluidization conditions. The inorganic salt catalysts used may
include supported and non-supported inorganic salt catalysts.
[0163] In some embodiments, an inorganic salt catalyst may be
selected to produce mostly gas or mostly crude product. For
example, an inorganic salt catalyst that is an alkaline-earth metal
oxide may be selected to produce gas and a minimal amount of crude
product from a feed. The produced gas may include an enhanced
amount of carbon oxides. An inorganic salt catalyst that is a
mixture of carbonates may be selected to produce mostly crude
product and a minimal amount of gas (e.g., in a catalytic cracking
process). In some embodiments, a supported inorganic salt catalyst
may be used in a fluidized catalytic cracking process.
[0164] The total amount of carbon monoxide and carbon dioxide
produced may be at least 0.1 grams, at least 0.3 grams, at least
0.5 grams, at least 0.8 grams, at least 0.9 grams per gram of gas.
The total amount of carbon monoxide and carbon dioxide produce may
range from about 0.1 grams to 0.99 grams, about 0.2 grams to about
0.9 grams, about 0.3 grams to about 0.8 grams or about 0.4 grams to
about 0.7 grams per gram of gas. 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, at least 0.7, at least
1, at least 1.5, at least 2, or at least 3. In some embodiments, a
molar ratio of the generated carbon monoxide to the generated
carbon dioxide is in a range from about 1:4, about 2:3, about 3:2,
or about 4:1. 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.
[0165] In some embodiments, the total product as produced herein
may include crude product, hydrocarbon gases, and carbon oxide
gases (carbon monoxide and carbon dioxide). A conversion of feed,
based on molar amount of carbon in the feed, to total hydrocarbons
(combined crude product and hydrocarbon gases) produced may be at
most 50%, at most 40%, at most 30, at most 20%, at most 10%, at
most 1%. A conversion of feed, based on molar amount of carbon in
the feed, to hydrocarbons produced may range from 0 to about 50%,
about 0.1% to about 40%, about 1% to about 30%, about 5% to about
20% or about 3% to about 10%.
[0166] A conversion of feed, based on molar amount of carbon in the
feed, to total carbon oxide gases (combined carbon monoxide and
carbon dioxide) produced may be at least 1%, at least 10%, at least
20%, at least 50%, at least 60%, at least 70%, at least 80%, at
least 90%, or at least 95%. A conversion of feed, based on molar
amount of carbon in the feed, to hydrocarbons produce may range
from 0 to about 99%, about 1% to about 90%, about 5% to about 80%,
about 10% to about 70%, about 20% to about 60%, about 30% to about
50%.
[0167] In some embodiments, a content of hydrogen in the total
product is less than a content of hydrogen in feed, based on molar
amount of hydrogen in the feed. A decreased amount of hydrogen in
the total product may result in products that differ from products
produced using conventional cracking, hydrotreating, and/or
hydroprocessing methods.
[0168] 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.
[0169] 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 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 feed by a factor of at most 1,000,
at most 500, at most 300, or at most 250.
[0170] 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.
[0171] 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.
[0172] 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.
[0173] In some embodiments, contact of a 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.
[0174] 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.
[0175] 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 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.
[0176] 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 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.
[0177] 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 feed. In certain embodiments, API
gravity of the crude product is between about 13-50, about 15-30,
or about 16-20.
[0178] 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 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 feed.
[0179] 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 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.
[0180] 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 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.
[0181] 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 atomic 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 atomic H/C of the crude product is about 80-120%,
or about 90-110% of the atomic H/C of the feed. In other
embodiments, the atomic H/C of the crude product is about 100-120%
of the atomic H/C of the feed. A crude product atomic H/C within
20% of the feed atomic H/C indicates that uptake and/or consumption
of hydrogen in the process is minimal.
[0182] 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.
In some embodiments, the crude product includes, per gram of crude
product, from about 0.001 grams to about 0.9 grams, from about
0.005 grams to about 0.8 grams, from about 0.01 grams to about 0.7
grams, or from about 0.1 gram to about 0.6 grams of hydrocarbons
with a boiling range distribution between about 204.degree. C. and
343.degree. C.
[0183] 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.
[0184] 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.
[0185] 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.
[0186] 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.
[0187] 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 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 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
feed.
[0188] 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.
[0189] 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.
[0190] 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.
[0191] 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.
[0192] 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.
[0193] 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.
[0194] 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 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.
[0195] 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.
[0196] The catalyst used for treatment of a 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 feed
containing sulfur is contacted with the catalyst precursor.
[0197] The catalysts used in contacting the feed with a hydrogen
source to produce the total product may assist in the reduction of
the molecular weight of the feed. Not to be bound by theory, the
catalyst in combination with the hydrogen source may reduce a
molecular weight of components in the feed through the action of
basic (Lewis basic or Bronsted-Lowry basic) and/or superbasic
components in the catalyst. Examples of catalysts that may have
Lewis base and/or Bronsted-Lowry base properties include catalysts
described herein.
[0198] 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.
[0199] 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/KHCO.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/CaCO.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.2/K.sub.2CO.sub.3/Rb.sub.2O;
K.sub.2CO.sub.3/CaCO.sub.3/Rb.sub.2CO.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/Cs.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. In some
embodiments, the inorganic salt catalyst is limestone (CaCO.sub.3)
or dolomite (CaMg(CO.sub.3).sub.2).
[0200] In some embodiments, the inorganic salt catalyst is a
alkaline-earth metal oxide or a combination of alkaline-metal
oxides In some embodiments, the inorganic salt catalyst also
includes alkaline-earth metal oxides and/or oxides of metals from
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), magnesium oxide (MgO), or aluminum
oxide (Al.sub.2O.sub.3).
[0201] 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.
[0202] 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.
[0203] 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.
[0204] 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), Bronsted-Lowry acids (for example,
H.sub.3O.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) Bronsted-Lowry acids; or e)
mixtures thereof.
[0205] 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.
[0206] In some embodiments, inorganic salts of the inorganic salt
catalyst may be incorporated into a support to form a supported
inorganic salt catalyst. The support, in some embodiments, exhibits
chemical resistance to the basicity of the inorganic salt at high
temperatures. The support may have the ability to absorb heat (for
example, have a high heat capacity). The ability of the support of
the inorganic salt catalyst to absorb heat may allow temperatures
in the contacting zone to be reduced as compared to the temperature
of the contacting zone when an unsupported inorganic salt catalyst
is used. Examples of supports include, but are not limited to,
zirconium oxide, calcium oxide, magnesium oxide, titanium oxide,
hydrotalcite, germania, iron oxide, nickel oxide, zinc oxide,
cadmium oxide, antimony oxide, calcium magnesium carbonate,
aluminosilicate, limestone, dolomite, activated carbon, nonvolatile
charcoal, 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. In certain embodiments,
the compound of a Columns 6-10 metal is a metal sulfide (for
example, nickel sulfide, vanadium sulfide, molybdenum sulfide,
tungsten sulfide, iron sulfide). 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. In some embodiments, a spent hydroprocessing catalyst is
combined with the inorganic salt catalyst support and/or used with
an inorganic salt catalyst. In some embodiments, metals and/or
compounds of metals recovered from a total product/feed mixture is
combined the inorganic salt catalyst support and/or used with an
inorganic salt catalyst.
[0207] In some embodiments, an inorganic salt catalyst is mixed
with a Column 4 metal oxide. Column 4 metal oxides include, but are
not limited to, ZrO.sub.2 and/or TiO.sub.2. A molar ratio of
inorganic salt catalyst to Column 4 metal oxide may range from
about 0.01 to about 5, from about 0.5 to about 4, or from about 1
to about 3.
[0208] In some embodiments, the supported inorganic salt catalyst
is characterized using particle size. The particle size of a
supported inorganic salt catalyst may range from about 20
micrometers to about 500 micrometers, from about 30 micrometers to
about 400 micrometers, from about 50 micrometers to about 300
micrometers, or from about 100 to 200 micrometers.
[0209] In some embodiments, 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 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 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
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 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.
[0210] 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.
[0211] 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".
[0212] The emitted gas inflection exhibited by inorganic salt
catalysts suitable for contact with a 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.
[0213] 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.
[0214] 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.
[0215] "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
DSC temperature". The inorganic salt catalyst may exhibit a heat
transition in a range between about 200-500.degree. C., about
250-450.degree. C., or about 300-400.degree. C.
[0216] 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.
[0217] 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 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 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.
[0218] 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.
[0219] 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.
[0220] 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, feed) to liquid products.
[0221] 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.
[0222] 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.
[0223] FIG. 9 is a schematic of a system that may be used to
measure ionic conductivity. Quartz vessel 220 containing sample 222
may be placed in a heating apparatus and heated incrementally to a
desired temperature. Voltage from source 224 is applied to wire 226
during heating. The resulting current through wires 226 and 228 is
measured at meter 230. Meter 230 may be, but is not limited to, a
multimeter or a Wheatstone bridge. As sample 222 becomes less
homogeneous (more mobile) without decomposition occurring, the
resistivity of the sample should decrease and the observed current
at meter 230 should increase.
[0224] 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.
[0225] In certain embodiments, the inorganic salt catalyst has a
particle size in a range of about 10-1000 micrometers, about 20-500
micrometers, or about 50-100 micrometers, as determined by passing
the inorganic salt catalyst through a mesh or a sieve.
[0226] 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.
[0227] 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 feed may, in some
embodiments, form a separate phase from the feed. In some
embodiments, the liquid or semiliquid inorganic salt catalyst has
low solubility in the 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 feed) or is insoluble
in the 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 feed) at the minimum TAP
temperature.
[0228] 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.
[0229] Contacting conditions may be controlled such that the total
product composition (and thus, the crude product) may be varied for
a given 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.
[0230] 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.
[0231] In some embodiments, the residue content and/or coke content
deposited on the catalyst during a reaction period may be at most
0.2 grams, 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
0.2 grams, at most 0.1 grams, at most 0.05 grams, 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
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 feed in the
presence of a refining catalyst, or in the absence of a catalyst,
using the same contacting conditions.
[0232] The contacting conditions may be controlled, in some
embodiments, such that, per gram of feed, at least 0.5 grams, at
least 0.7 grams, at least 0.8 grams, or at least 0.9 grams of the
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 feed is produced during contacting.
Conversion of the 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 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 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 feed is produced.
[0233] Controlling a contacting zone temperature, rate of feed
flow, rate of total product flow, rate and/or amount of catalyst
feed, rate of steam flow, 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.
[0234] 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.sub.1". 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.
[0235] 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.
[0236] In certain embodiments, the inorganic salt catalyst may be
conditioned prior to addition of the feed. In some embodiments, the
conditioning may take place in the presence of the 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 feed to be performed
at lower reaction temperatures than temperatures used with
conventional hydroprocessing catalysts.
[0237] In certain embodiments, varying a ratio of catalyst to feed
may affect the amount of gas, crude product, and/or coke formed
during contacting. A ratio supported inorganic catalyst to feed may
range from 2-10 or be greater than 10. The conversion of feed to
total product may be at least 50%, at least 60%, at least 80%, at
least 90%, at least 99%. The content of gas in the total product
may range be, per gram of feed, at least 0.1 grams, at least 0.5
grams, at least 0.7 grams, at least 0.9 grams or at least 0.95
grams. The content of produced product may range, per gram of feed,
from about 0.1 grams to 0.99 grams, 0.3 grams to 0.9 grams, or from
about 0.5 gram to about 0.7 grams. The content crude product in the
total product may range be, per gram of feed, at least 0.1 grams,
at least 0.5 grams, at least 0.7 grams, at least 0.9 grams or at
least 0.95 grams. The content of produced crude product may range,
per gram of feed, from about 0.1 grams to 0.99 grams, 0.3 grams to
0.9 grams, or from about 0.5 gram to about 0.7 grams. At most, per
gram of feed, 0.2 grams, at most 0.1 grams, at most 0.05 grams of
coke may be formed.
[0238] 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 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 feed or hydrogen
source, or may alter combinations of these effects. Increased
contacting times of the 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).
[0239] 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 feed uptakes to produce the crude product. The
ability to change the amount of hydrogen uptake of the feed, while
improving other properties of the feed, increases the types of
crude products that may be produced from a single feed. The ability
to produce multiple crude products from a single feed may allow
different transportation and/or treatment specifications to be
satisfied.
[0240] Contacting a feed with an inorganic salt catalyst in the
presence of light hydrocarbons and steam generates hydrogen and
carbon monoxide in situ. The carbon monoxide reacts with more steam
to produce carbon dioxide and more hydrogen. The hydrogen may be
incorporated into the feed under basic conditions to form new
products. Controlling the amount of steam, the temperature of the
contacting zone, and selection of catalyst may produce hydrocarbons
from the feed that differ from hydrocarbons obtained from
conventional catalytic cracking methods.
[0241] Uptake of hydrogen may be assessed by comparing the atomic
H/C of the feed to H/C of the crude product. An increase in the
atomic H/C of the crude product relative to the atomic H/C of the
feed indicates incorporation of hydrogen into the crude product
from the hydrogen source. Relatively low increase in the atomic H/C
of the crude product (about 20%, as compared to the feed) indicates
relatively low consumption of hydrogen gas during the process.
Significant improvement of the crude product properties, relative
to those of the feed, obtained with minimal consumption of hydrogen
is desirable.
[0242] Depending on the desired composition of the total product,
the amount of steam may be varied. To produce a total product that
has increased amounts of gas relative to liquid, more steam may be
added to the contacting zone. A weight ratio of steam to feed may
range from 0.001 to 100 from 0.01 to 10, from 0.05 to 5, or from 1
to 3 depending on the properties of the feed. For liquid or
semiliquid feed a steam to feed ratio may be at least 0.001, at
least 0.01, at least 0.02, or at least 1. For solid and/or
semisolid feed a steam to feed ratio may be at least 1, at least 2,
at least 3, at least 5 or at least 10. Varying the amount of steam
also changes the ratio of carbon monoxide to carbon dioxide. The
ratio of carbon monoxide to carbon dioxide in the produced gas may
be varied from 0.01 to 10, or from 0.02 to 6, or from 0.03 to 5, or
from 1 to 4 by altering the weight ratio of steam to feed in the
contacting zone. For example, by increasing the ratio of steam to
feed in the contacting zone the ratio of carbon monoxide to carbon
dioxide is decreased.
[0243] The ratio of hydrogen source to feed may also be altered to
alter the properties of the crude product. For example, increasing
the ratio of the hydrogen source to feed may result in crude
product that has an increased VGO content per gram of crude
product.
[0244] In some embodiments, the feed may include significant
amounts of sulfur as described herein which may be converted to
hydrogen sulfide during contacting of the feed using systems,
method and/or catalysts described herein. The feed may also include
entrained hydrogen sulfide gas prior to contacting. Sulfur, present
as organosulfur or hydrogen sulfide is known to poison and/or
reduce the activity of catalysts used in processing of feeds to
make commercial products. In some refinery operations, feeds are
treated to remove sulfur prior to treatment to obtain commercial
products such as transportation fuel, thus a sulfur resistant
catalyst are desirable. A content of sulfur, measured as hydrogen
sulfide, per gram of feed, ranging from about 0.00001 grams to
about 0.01 grams or from about 0.0001 grams to about 0.001 grams
hydrogen sulfide may poison and/or reduce the activity of
conventional catalysts used for hydrotreating and/or catalytic
cracking processes.
[0245] In some embodiments, contact of the feed with a hydrogen
source in the presence of the inorganic salt catalyst and a
sulfur-containing compound may produce a total product that
includes a crude product and/or gas. The feed, in some embodiments,
is contacted in the presence of hydrogen sulfide for at least 500
hours, at least 1000 hours, or at least 2000 hours without
replacement of the inorganic salt catalyst. The presence of sulfur,
in some embodiments, may enhance the production of carbon oxide
gases (for example, carbon monoxide and carbon dioxide) when a feed
is contacted with a hydrogen source and steam in the presence of
sulfur containing compounds relative to contacting under the same
conditions in the absence of sulfur. In some embodiments, contact
of the feed with a hydrogen source in the presence of the inorganic
salt catalyst and hydrogen sulfide produces a total product that
has a carbon oxide gases content, per gram of feed, of at least 0.2
grams, at least 0.5 grams, at least 0.8 grams, or at least 0.9
grams of carbon oxide gases.
[0246] In certain embodiments, contact of the 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 feed with an inorganic salt
catalyst in the presence of hydrogen and steam. In embodiments that
include contact of the 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.
[0247] In certain embodiments, the volume of crude product produced
from a 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 feed with the
inorganic salt catalyst may be at least 110 vol % of the volume of
the 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 feed.
[0248] In certain embodiments, a feed having, per gram of 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.
[0249] 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 feed.
[0250] In certain embodiments, a mixture of used inorganic salt
catalyst (for example, a supported inorganic salt catalyst, a
mixture of ZrO.sub.2 and CaO, a mixture of ZrO.sub.2 and MgO,
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 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.
[0251] 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
[0252] Non-limiting examples of catalyst preparations, testing of
catalysts, and systems with controlled contacting conditions are
set forth below.
Example 1
TAP Testing of a K.sub.2CO.sub.31Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
Catalyst and the Individual Inorganic Salts
[0253] 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.
[0254] 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. 10 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 232 and 234 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.
[0255] 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.
[0256] 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 2
DSC Testing of an Inorganic Salt Catalyst and Individual Inorganic
Salts
[0257] 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.).
[0258] 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 salt 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.
[0259] In contrast to these results, no definite heat transitions
were observed for cesium carbonate.
[0260] 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 3
Ionic Conductivity Testing of an Inorganic Salt Catalysts or an
Individual Inorganic Salt Relative to K.sub.2CO.sub.3
[0261] 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.
[0262] FIG. 11 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 240, 242,
244, 246, and 248 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/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst 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.
[0263] CaO (curve 242) exhibits relatively large stable resistance
relative to K.sub.2CO.sub.3 (curve 240) 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.2CO.sub.3
catalyst (see curves 244, 246, and 248) 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. 11 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.
[0264] FIG. 12 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 250 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 240) 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 252 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.
[0265] 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 4
Flow Property Testing of an Inorganic Salt Catalyst
[0266] 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.
[0267] In contrast, the individual carbonate salts were free
flowing powders under the same conditions.
[0268] 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,
to water) in the dish under the same conditions.
Examples 5 and 6
Contact of a 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
[0269] The following equipment and general procedure was used in
Examples 5-23 except where variations are described.
[0270] 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.
[0271] 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 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 feed was
charged to the addition vessel. Prior to use, the addition vessel
line was insulated.
[0272] 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.
[0273] Procedure: Cerro Negro (137.5 grams) was charged to the
addition vessel. The feed had an API gravity of 6.7. The feed had,
per gram of 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 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.
[0274] 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 grams of 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.
[0275] 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 feed to the reactor over about 2.6 hours. The feed
was pressurized into the reactor using 1.5 MPa (229 psi) of
CH.sub.4 over 16 minutes. Residual feed (0.56 grams) remained in
the addition vessel after the addition of the feed was complete. A
decrease in temperature to 370.degree. C. was observed during the
addition of the feed.
[0276] The catalyst/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.
[0277] From a difference in initial catalyst weight and
coke/catalyst mixture weight, 0.046 grams of coke remained in the
reactor per gram of 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).
[0278] 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.
[0279] In Example 6, the reaction procedures, conditions, feed, and
catalyst were the same as in Example 5. The crude product of
Example 6 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.
[0280] Examples 5 and 6 demonstrate that contact of the feed with a
hydrogen source in the presence of at most 3 grams of catalyst per
100 grams of 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 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 feed.
[0281] 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 7-8
Contact of a 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
[0282] The reaction procedures, conditions, and the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst in
Examples 7 and 8 were the same as in Example 5, except that 130
grams of 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 7, methane was used as the hydrogen source. In
Example 8, 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. 13. Bars 254 and 256
represent wt % coke produced, bars 258 and 260 represent wt %
liquid hydrocarbons produced, and bars 262 and 264 represent wt %
gas produced, based on the weight of the feed.
[0283] In Example 7, 93 wt % of crude product (bar 260), 3 wt % of
gas (bar 264), and 4 wt % of coke (bar 256), based on the weight of
the Cerro Negro, was produced.
[0284] In Example 8, 84 wt % of crude product (bar 258), 7 wt % of
gas (bar 262), and 9 wt % of coke were produced (bar 254), based on
the weight of the Cerro Negro.
[0285] Examples 7 and 8 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 feed in the
presence of an inorganic salt catalyst to produce a total
product.
Examples 9-10
Producing a Crude Product with Selected API Gravity
[0286] The apparatus, reaction procedure and the inorganic salt
catalyst were the same as in Example 5, except that the reactor
pressure was varied.
[0287] Example 9, 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 266 in FIG. 14).
[0288] In Example 10, 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 268 in FIG. 12).
[0289] These examples demonstrate methods for contacting the 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 11-12
Contact of a Feed in the Presence of a
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 Catalyst or
Silicon Carbide in the Absence of an External Hydrogen Source
[0290] In Examples 11 and 12, the apparatus, feed, and reaction
procedure were the same as in Example 5, except that the 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 11, 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 5). In Example 12, 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.
[0291] 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.
[0292] In Example 11, 36.82 grams (26.68 wt %, based on the weight
of the feed) of a colorless hydrocarbon liquid with API gravity of
at least 50 was produced from contact of the feed with the
inorganic salt catalyst in the carbon dioxide atmosphere.
[0293] In Example 12, 15.78 grams (11.95 wt %, based on the weight
of the feed) of a yellow hydrocarbon liquid with an API gravity of
12 was produced from contact of the feed with silicon carbide in
the carbon dioxide atmosphere.
[0294] Although the yield in Example 11 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 12 is one-half of the yield of crude product in Example 11.
Example 11 also demonstrates that hydrogen is generated during
contact of the feed in the presence of the inorganic salt and in
the absence of a gaseous hydrogen source.
Examples 13-16
Contact of a 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
Carbonate, and Silicon Carbide at Atmospheric Conditions
[0295] The apparatus, reaction procedure, feed and the inorganic
salt catalyst were the same as in Example 5, 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 1 in FIG.
15.
[0296] In Examples 13 and 14, the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst was
used. In Example 13, the contacting temperature was 375.degree. C.
In Example 14, the contacting temperature was in a temperature
range from 500-600.degree. C.
[0297] As shown in Table 1 (FIG. 15), for Examples 13 and 14, 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 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
atomic H/C of 1.8.
[0298] In Example 15, a feed was contacted with CaCO.sub.3 under
conditions similar to the conditions described for Example 14.
Percentages of crude product, gas, and coke production are
tabulated in Table 1 in FIG. 13. Gas production increased in
Example 15 relative to the gas production in Example 14.
Desulfurization of the feed was not as effective as in Example 14.
The crude product produced in Example 15 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 14.
[0299] Example 16 is a comparative example for Example 14. In
Example 16, 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 16 relative to the
gas production and coke production in Example 14. 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 16 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
14.
[0300] These examples demonstrated that the catalysts used in
Examples 13 and 14 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.
[0301] In examples using inorganic salt catalysts (See Examples
13-14 in Table 1, FIG. 15), a decrease was observed in the weight
percent of produced gas relative to the produced gas formed during
the control experiment (for example, Example 16 in Table 1, FIG.
15). From the quantity of hydrocarbons in the produced gas, the
thermal cracking of the 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 feed contacted with a hydrogen source.
Examples 17 and 18
Contact of a Feed with a Gaseous Hydrogen Source In the Presence of
Water and a K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
Catalyst or Silicon Carbide
[0302] Apparatus in Examples 17 and 18 were the same as in Example
5 except that hydrogen gas was used as the hydrogen source. In
Example 17, 130.4 grams of Cerro Negro was combined with 30.88
grams of the K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst to form a feed mixture. In Example 18, 139.6 grams of
Cerro Negro was combined with 80.14 grams of silicon carbide to
form the feed mixture.
[0303] The 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 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.
[0304] In Example 17, 86.17 grams (66.1 wt %, based on the weight
of the feed) of a dark reddish brown hydrocarbon liquid (crude
product) and water (97.5 g) were produced as a vapor from contact
of the feed with the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst in the
hydrogen atmosphere.
[0305] In Example 18, 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 feed with silicon carbide in the hydrogen
atmosphere. A 25% increase in yield of crude product was observed
in Example 17 relative to a yield of crude product produced in
Example 18.
[0306] Example 17 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 17 was lower boiling than the crude
product from Example 18, as demonstrated by the crude product
produced in Example 18 not being able to be produced as a vapor.
The crude product produced in Example 17 had enhanced flow
properties relative to the crude product produced in Example 18, as
determined by visual inspection.
Examples 19-20
Contact of a 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 to
Produce a Crude Product with Increased Volume Relative to a Crude
Product Volume Produced under Non-Catalytic Conditions
[0307] The apparatus, feed, inorganic catalyst, and reaction
procedure was the same as described in Example 5, except the feed
was directly charged to the reactor and hydrogen gas was used as
the hydrogen source. The feed (Cerro Negro) had an API gravity 6.7
and a density of 1.02 g/mL at 15.5.degree. C.
[0308] In Example 19, 102 grams of the feed (about 100 mL of feed)
and 31 grams of K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.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.
[0309] In Example 20, 102 grams of feed (about 100 mL of 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.
[0310] Under these conditions, the volume of the crude product
produced from Example 19 was approximately 10% greater than the
volume of the feed. The volume of the crude product produced in
Example 20 was significantly less (40% less) than the volume of
crude product produced in Example 19. 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 21
Contact of a 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, Sulfur,
and Coke
[0311] The apparatus and reaction procedure were the same as in
Example 5, except that the steam was metered into the reactor at
300 cm.sup.3/min. The
K.sub.2CO.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.
[0312] The feed (130.35 grams) and
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst (31.6
grams) was charged to the reactor. The Cerro Negro crude included,
per gram of 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 feed was
6.7.
[0313] Contact of the feed with methane in the presence of the
K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst
produced, per gram of feed, 0.95 grams of total product, and 0.041
grams of coke.
[0314] 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.
[0315] 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 feed.
[0316] 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.2CO.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.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
per gram of used catalyst.
[0317] Additional 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).
[0318] 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 feed.
[0319] 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.2CO.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.
[0320] Additional feed (104 grams) was contacted with the second
used catalyst (44.84 grams) to produce, per gram of 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 feed transferred was feed.
[0321] 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.
[0322] 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.
[0323] 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.2CO.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.
[0324] 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 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 feed in a boiling range distribution below
149.degree. C.
[0325] For the three runs, the average crude product yield (based
on the weight of the 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 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 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 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.
[0326] 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 22
Contact of a Relatively High Sulfur Containing 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
[0327] The apparatus and reaction procedure were the same as
described in Example 5, except that the 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.
[0328] 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.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3 catalyst (59.88
grams) was charged to the reactor.
[0329] A 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 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 feed liquid level of 50% of the reactor volume,
however, the rate was insufficient to maintain that level.
[0330] The methane/steam/feed was contacted with the catalyst at an
average internal reactor temperature of 456.degree. C. Contacting
of the methane/steam/feed with the catalyst produced a total
product (in this example in the form of the reactor effluent
vapor).
[0331] A total of 1640 grams of 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 feed remained in
the reactor. From contact of the feed with the methane in the
presence of the K.sub.2CO.sub.3/Rb.sub.2CO.sub.3/Cs.sub.2CO.sub.3
catalyst, 0.93 grams of total product per gram of 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.
[0332] 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 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.
[0333] 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.
[0334] The data in Example 25 demonstrates that continuous
processing of a relatively high sulfur 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 23
Contact of a 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
Coke
[0335] The apparatus and reaction procedure was performed using
conditions as described in Example 22. The
K.sub.2CO.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 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 feed remained in the reactor, based on the weight of the
feed. A total of 0.89 grams of total product per gram of 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.
[0336] 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 feed was reduced by 14
wt %, based on the weight of the 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.
[0337] 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.
[0338] This example demonstrates that repeated processing of the a
relatively high sulfur feed (2550 grams of 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.
Example 24
Contact of a Feed with a Hydrogen Source in the Presence of
CaO/ZrO.sub.2 Catalyst to Produce a Total Product
[0339] The following reactor and conditions were used for Examples
24-27.
[0340] 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. The reactor includes a
screen with openings having a diameter of less than 16 mesh.
[0341] 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 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 feed was
charged to the addition vessel. Prior to use, the addition vessel
line was insulated.
[0342] 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.
[0343] Procedure: ZrO.sub.2 (8.5 grams) was positioned on the
screen in the reactor. The reactor was weighed to obtain an initial
weight. Feed (asphaltenes, 5.01 grams) was charged to the addition
vessel. The feed was obtained from deasphalting heavy oil. The feed
had a density of 1.04 g/cc and a softening point of 200.degree. C.
The feed had, per gram of feed, 0.0374 grams of sulfur and 0.0124
grams of nitrogen.
[0344] The feed was heated to 150.degree. C. A mixture of CaO
(15.03 grams, 0.26 moles) and ZrO.sub.2 (20.05 grams, 0.16 moles)
were added to the feed to produce an inorganic salt
catalyst/catalyst support/feed mixture. The resulting mixture
catalyst was metered to the reactor vessel over 20 minutes (a
calculated WHSV of 0.8 h.sup.-1) to maintain the feed liquid level
of 50% of the reactor volume under a nitrogen atmosphere. Once an
internal temperature of the reactor reached 731.degree. C., methane
and water (26.06 grams charged as steam) were charged to the
reaction vessel over 1 hour. The reaction was run until little or
no gas and/or liquid product was produced. The reactor was weighed
at the end of the run to obtain a final reactor weight.
[0345] The total product included 1.06 grams of a crude product,
and 8.152 grams of gas. The gas included 0.445 grams of
non-condensable hydrocarbons, 4.39 grams (0.10 moles) of CO.sub.2,
3.758 grams (0.13 moles) of CO, 0.627 grams of H.sub.2 gas, 0.03
grams of H.sub.2S and 0.296 grams of coke.
[0346] The selectivity for products containing carbon was
calculated based on the weight of carbon containing products
divided by weight of asphalt charged to the reactor. For five
experiments run as described in Example 24 the mean selectivity for
products containing carbon was determined to be: 67 wt % for
combined carbon monoxide and carbon dioxide, 7.47 wt % for
non-condensable hydrocarbons and 19.88 wt % for crude product and
4.94 wt % for coke.
[0347] This example demonstrates a method for contacting the feed
with an inorganic salt catalyst/support mixture in the presence of
a hydrogen source hydrogen source and steam to produce a crude
product and gas and less than 0.1 grams of coke per gram of feed.
In the presence of CaO, more the production of gas was increased
relative to the production of than crude product. The molar ratio
of CO to CO.sub.2 was calculated to be 1.3.
Example 25
Contact of a Feed with a Hydrogen Source in the Presence of
MgO/ZrO.sub.2 Catalyst to Produce a Crude Product
[0348] The feed and apparatus was the same as described in Example
24. ZrO.sub.2 (8.59 grams) was placed on the screen in the
reactor.
[0349] The feed was heated to 150.degree. C. MgO catalyst (19.82
grams, 0.49 moles) and ZrO.sub.2 (29.76 grams, 0.24 moles) were
charged to the feed (9.92 grams) to produce an inorganic salt
catalyst/catalyst support/feed mixture. The resulting mixture
catalyst was metered to the reactor vessel over 0.5 hour (a
calculated WHSV of 0.75 h.sup.-1) to maintain the feed liquid level
of 50% of the reactor volume under a nitrogen atmosphere. Once an
internal temperature of the reactor reached 731.degree. C., methane
and water (48.1 grams charged as steam) were charged to the
reaction vessel over 0.5 hour. The reaction was run until little or
no gas and/or liquid product was produced. The reactor was weighed
at the end of the run to obtain a final reactor weight.
[0350] The total product included 1.92 grams of a crude product,
and 18.45 grams of gas. The gas included 1.183 grams of
non-condensable hydrocarbons, 8.66 grams (0.19 moles) of CO.sub.2,
7.406 grams (0.26 moles) of CO, 1.473 grams of H.sub.2 gas, 0.125
grams of H.sub.2S, and 0.0636 grams of coke. The molar ratio of CO
to CO.sub.2 was calculated to be 1.4.
[0351] The selectivity for products containing carbon was
calculated based on the weight of carbon containing products
divided by weight of asphalt charged to the reactor. For three
experiments run as described in Example 25 the mean selectivity for
products containing carbon was determined to be: 65.88 wt % for
combined carbon monoxide and carbon dioxide, 11.74 wt % for
non-condensable hydrocarbons and 12.35 wt % for crude product and
8.78 wt % for coke.
[0352] This example demonstrates a method for contacting the feed
with an inorganic salt catalyst/support mixture in the presence of
a hydrogen source and steam to produce a crude product and gas and
less than 0.1 grams of coke per gram of feed. More gas than crude
product was produced in the presence of MgO as compared to Example
24.
Example 26
Contact of a Feed with a Hydrogen Source in the Presence of
ZrO.sub.2 to Produce a Crude Product
[0353] The feed and apparatus was the same as described in Example
24. ZrO.sub.2 (8.56 grams) was placed on the screen in the
reactor.
[0354] The feed was heated to 150.degree. C. ZrO.sub.2 (24.26
grams) was charged to the feed (5.85 grams) to produce a
ZrO.sub.2/feed mixture. The resulting mixture catalyst was metered
to the reactor vessel over 20 minutes (a calculated WHSV of 0.6
h.sup.-1) to maintain the feed liquid level of 50% of the reactor
volume under a nitrogen atmosphere. Once an internal temperature of
the reactor reached 734.degree. C., methane and water (24.1 grams
charged as steam) were charged to the reaction vessel over 20
minutes. The reaction was run until little or no gas and/or liquid
product was produced. The reactor was weighed at the end of the run
to obtain a final reactor weight.
[0355] The total product included 0.4 grams of a crude product, and
5.25 grams of gas. The gas included 0.881 grams of non-condensable
hydrocarbons, 2.989 grams of CO.sub.2, 1.832 grams of CO, 0.469
grams of H.sub.2 gas, and 0.34 grams of H.sub.2S. From the
difference in the initial and final weight of the reactor 1.67
grams of coke was formed. The molar ratio of CO to CO.sub.2 was
calculated to be 1.
[0356] The selectivity for products containing carbon was
calculated based on the weight of carbon containing products
divided by weight of asphalt charged to the reactor. For two
experiments run as described in Example 26 the mean selectivity for
products containing carbon was determined to be: 31.73 wt % for
combined carbon monoxide and carbon dioxide, 18.93 wt % for
non-condensable hydrocarbons and 10.34 wt % for crude product and
39 wt % for coke.
[0357] This example demonstrates that contacting a feed with a
catalyst support in the presence of a hydrogen source and steam
produces a minimal amount of crude product, gases, and coke.
Comparative Example 27
Contact of a Feed with a Hydrogen Source under Non-Catalytic
Conditions to Produce a Crude Product
[0358] The feed and apparatus was the same as described in Example
24. Silicon carbide, an inert material, (silicon carbide, 13.1
grams) was placed on the screen in the reactor.
[0359] The feed was heated to 150.degree. C. Silicon carbide (24.26
grams) was charged to the feed (4.96 grams) to produce a silicon
carbide/feed mixture. The resulting mixture catalyst was metered to
the reactor vessel over 0.5 hour (a calculated WHSV of 0.4
h.sup.-1) to maintain the feed liquid level of 50% of the reactor
volume under a nitrogen atmosphere. Once an internal temperature of
the reactor reached 725.degree. C., methane and water (24.1 grams
charged as steam) were charged to the reaction vessel over 0.5
hour. The reaction was run until little or no gas and/or liquid
product was produced. The reactor was weighed at the end of the run
to obtain a final reactor weight.
[0360] The total product included 0.222 grams of a crude product,
and 1.467 grams of gas. The gas included 0.248 grams of
non-condensable hydrocarbons, 0.61 grams (0.014 moles) of CO.sub.2,
0.513 grams (0.018 moles) of CO, and 0.091 grams of H.sub.2 gas.
From the difference in the initial and final weight of the reactor
3.49 grams of coke was formed.
[0361] This example demonstrates that contacting a feed with a
hydrogen source and steam produces a greater amount of coke than
when the feed is contacted with an inorganic salt catalyst and a
catalyst support in the presence of a hydrogen source and
steam.
[0362] The selectivity for products containing carbon was
calculated based on the weight of carbon containing products
divided by weight of asphalt charged to the reactor. For two
experiments run as described in Example 27 the mean selectivity for
products containing carbon was determined to be: 11.75 wt % for
combined carbon monoxide and carbon dioxide, 7.99 wt % for
non-condensable hydrocarbons and 9.32 wt % for crude product and
65.96 wt % for coke.
[0363] The mean selectivity for the products that contain carbon
for Examples 24-27 is depicted in FIG. 16. Data points 270
represents the total amount of carbon monoxide and carbon dioxide
gases produced. Data points 272 represents amount of
non-condensable hydrocarbons produced. Data points 274 represents
amount of crude product. Data points 276 represents amount of coke
produced and/or unreacted asphaltenes. As shown in FIG. 16, the
total amount of carbon monoxide and carbon dioxide gases is
enhanced when a feed is contacted with an inorganic salt catalyst
as compared to contact with a catalyst support or under thermal
conditions. When calcium oxide is used as the inorganic salt
catalyst more crude product is produced compared to magnesium
oxide, zirconium oxide, or the thermal experiment. Thus, selection
of catalyst and controlling the contacting conditions at a
temperature of at most 1000.degree. C. allows the composition of
the total product to be adjusted. In addition, controlling the
contacting conditions limited the conversion of feed to total
hydrocarbons is at most 50%, based on the molar amount of carbon in
the feed.
Example 28
Contact of a Feed with a Hydrogen Source in the Presence of a
Supported Inorganic Catalyst
[0364] An inorganic salt catalyst was supported on zeolite. The
supported inorganic salt catalyst contained, per gram of supported
inorganic salt catalyst, 0.049 grams of potassium, 0.069 grams of
rubidium, and 0.109 grams of cesium. The inorganic catalyst had a
surface area 5.3 m.sup.2/g at p/p0=0.03, an external surface area
of 3.7 m.sup.2/g, and a pore volume of 0.22 ml/g. A feed (Kuwait
long residue, WHSV of 1 h.sup.-1) was fluidly contacted with a
supported inorganic salt catalyst (modified Equilibrium c) in a
micro-activity test ("MAT") at 450.degree. C., 1 bar absolute (0.1
MPA) in the presence of steam (water flow rate of 0.36 gram/min to
produce the steam) using methane as the fluidization gas at a rate
of 45 NmL/min to produce a total product. Five runs were performed
with each run having a different catalyst to feed ratio of 3, 4, 5,
6, 7, and 8. The amount of gas, crude product, and coke formed for
each run is tabulated in Table 2, FIG. 17 and graphically depicted
in FIG. 18. Plot 280 represents the amount of gas produced. Plot
282 represents the amount of crude product produced, and Plot 284
represents the amount of coke produced for each run.
[0365] As shown in this example contacting a feed with a supported
inorganic salt catalyst produced in the presence of a hydrogen
source and steam produced a total product and at most 0.2 grams of
coke. At a catalyst to feed ratio 4, a total product that included
0.08 grams of gas, 0.73 grams of crude product and 0.16 grams of
coke, per gram of feed, was produced. At a catalyst to feed ratio
of 8, a total product that included 0.09 grams of gas, 0.7 grams of
crude product and 0.14 grams of coke, per gram of feed, was
produced. As shown, adjusting the catalyst to feed ratio from 4 to
8 lowered the amount of coke formed during contacting.
Comparative Example 29
Contact of a Feed with a Hydrogen Source in the Presence of an
E-Cat at Various Catalyst/Feed Ratios
[0366] The equipment, contacting conditions, feed, and catalyst to
feed ratios were the same as for Example 28. The catalyst was a
commercial Equilibrium fluidized catalytic cracking catalyst
("E-Cat", Akzo Nobel Cobra 553) that included 1541 ppmw of nickel,
807 ppmw of vanadium, 029 wt % sodium and 0.4 wt % iron. The E-Cat
had a surface area of 163 m.sup.2/g at p/p0=3, an external surface
areas of 26.3 m.sup.2/g, and a pore volume of 0.37 ml/g. The amount
of gas, crude product, and coke formed for each run is tabulated in
Table 3, FIG. 17 and graphically depicted in FIG. 18. Plot 286
represents the amount of gas produced. Plot 288 represents the
amount of crude product produced, and Plot 290 represents the
amount of coke produced for each run.
[0367] As shown in this comparative example, the amount of gas and
crude product formed from the feed using the new E-Cat remained
constant for at various catalyst to feed ratios. At an E-Cat to
feed ratio of 4, 0.23 grams of gas, 0.60 grams of crude product,
and 0.16 grams of coke of product, per gram of feed, was produced.
At an E-Cat to feed ratio of 8, 0.26 grams of feed, 0.43 grams of
crude product, and 0.21 grams of coke, per gram of feed, was
produced.
[0368] 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.
[0369] 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.
* * * * *