U.S. patent application number 12/055901 was filed with the patent office on 2009-10-01 for oxidative desulfurization of fuel oil.
This patent application is currently assigned to GENERAL ELECTRIC COMPANY. Invention is credited to John Mathew Bablin, Deborah Ann Haitko, Grigorii Lev Soloveichik.
Application Number | 20090242460 12/055901 |
Document ID | / |
Family ID | 41060750 |
Filed Date | 2009-10-01 |
United States Patent
Application |
20090242460 |
Kind Code |
A1 |
Soloveichik; Grigorii Lev ;
et al. |
October 1, 2009 |
OXIDATIVE DESULFURIZATION OF FUEL OIL
Abstract
A method for purifying a sulfur-containing fuel oil comprising
(a) contacting the fuel oil with a supported exogenous binary
catalyst and oxygen at a temperature in a range of from about
25.degree. C. to about 150.degree. C., and at a pressure in a range
of from about 1 atmosphere to about 150 atmospheres to provide a
first oxidized mixture; and (b) separating at least one oxidized
sulfur compound from the first oxidized mixture to a provide a
purified fuel oil. In one embodiment, the sulfur-containing fuel
oil is deasphalted prior to contacting with the supported exogenous
binary catalyst and oxygen.
Inventors: |
Soloveichik; Grigorii Lev;
(Latham, NY) ; Bablin; John Mathew; (Malta,
NY) ; Haitko; Deborah Ann; (Schenectady, NY) |
Correspondence
Address: |
GENERAL ELECTRIC COMPANY;GLOBAL RESEARCH
PATENT DOCKET RM. BLDG. K1-4A59
NISKAYUNA
NY
12309
US
|
Assignee: |
GENERAL ELECTRIC COMPANY
SCHENECTADY
NY
|
Family ID: |
41060750 |
Appl. No.: |
12/055901 |
Filed: |
March 26, 2008 |
Current U.S.
Class: |
208/213 |
Current CPC
Class: |
C10G 27/04 20130101;
C10G 2300/202 20130101; C10G 2300/206 20130101; C10G 2300/802
20130101 |
Class at
Publication: |
208/213 |
International
Class: |
C10G 45/04 20060101
C10G045/04 |
Claims
1. A method for purifying a sulfur-containing fuel oil, the method
comprising: (a) contacting the fuel oil with a supported exogenous
binary catalyst and oxygen at a temperature in a range of from
about 25.degree. C. to about 150.degree. C., and at a pressure in a
range of from about 1 atmosphere to about 150 atmospheres to
provide a first oxidized mixture; and (b) separating at least one
oxidized sulfur compound from the first oxidized mixture to a
provide a purified fuel oil.
2. The method according to claim 1, wherein the sulfur-containing
fuel oil comprises less than 5 weight percent sulfur.
3. The method according to claim 1, wherein the sulfur-containing
fuel oil comprises less than 3 weight percent sulfur.
4. The method according to claim 1, wherein the supported exogenous
binary catalyst comprises a metal oxide solid support selected from
the group consisting of alumina, silica, magnesia, titania, ceria,
and combinations of at least two of the foregoing.
5. The method according to claim 4, wherein the metal oxide solid
support is alumina.
6. The method according to claim 1, wherein the exogenous binary
catalyst comprises a first component selected from the group
consisting of oxides and salts vanadium, manganese and copper, and
combinations thereof, and a second component selected from the
group consisting of oxides and salts of cerium, iron, titanium,
manganese, cobalt, nickel, copper and combinations thereof.
7. The method according to claim 6, wherein the first component
comprises an oxide or a salt of vanadium.
8. The method according to claim 6, wherein the first component
comprises an oxide or a salt of manganese.
9. The method according to claim 6, wherein the second component
comprises an oxide or a salt of cobalt.
10. The method according to claim 6, wherein the second component
comprises an oxide or a salt of copper.
11. The method according to claim 1, wherein the oxygen is provided
as a mixture with an inert gas.
12. The method according to claim 1, wherein the oxygen is provided
as air.
13. The method according to claim 1, wherein the sulfur-containing
fuel oil is deasphalted prior to contacting the sulfur-containing
fuel oil with the binary catalyst, hydrogen peroxide and the
water-soluble acid by contacting the sulfur-containing fuel with an
inert diluent.
14. The method according to claim 13, wherein the inert diluent is
selected from the group consisting of liquid saturated
hydrocarbons, liquid cyclic hydrocarbons, and mixtures of at least
two of the foregoing inert diluents.
15. The method according to claim 13, wherein the inert diluent is
selected from the group consisting of propane, butane, petroleum
ether, cyclohexane, decalin and mixtures thereof.
16. The method according to claim 1, wherein the separating is
carried out using solid-liquid extraction.
17. The method according to claim 1, wherein the separating is
carried out using liquid-liquid extraction.
18. The method according to claim 1, wherein the sulfur-containing
fuel oil comprises benzothiophene, dibenzothiophene, alkyl
substituted benzothiophenes, and alkyl substituted
dibenzothiophenes.
19. The method according to claim 1, further comprising a step of
recovering the binary catalyst.
20. A method for purifying a sulfur-containing fuel oil, the method
comprising: (a) contacting the sulfur-containing fuel oil with a
hydrocarbon diluent, an alumina supported exogenous binary
catalyst, and oxygen at a temperature in a range of from about
50.degree. C. to about 120.degree. C., and at a pressure in a range
of from about 1 atmosphere to about 150 atmospheres to provide a
first oxidized mixture; (b) separating at least one oxidized sulfur
compound from the first oxidized mixture; and (c) recovering the
diluent to provide a purified fuel oil.
21. The method according to claim 20, wherein the exogenous binary
catalyst comprises a first component selected from the group
consisting of oxides and salts vanadium, manganese and copper, and
combinations thereof, and a second component selected from the
group consisting of oxides and salts of cerium, iron, titanium,
manganese, cobalt, nickel, copper and combinations thereof.
22. The method according to claim 20, further comprising a step of
recovering the binary catalyst.
23. A method for purifying a sulfur-containing fuel oil, the method
comprising: (a) contacting a sulfur-containing fuel oil comprising
benzothiophene, dibenzothiophene, alkyl substituted
benzothiophenes, and alkyl substituted dibenzothiophenes with
petroleum-ether, a supported exogenous binary catalyst, and oxygen
at a temperature in a range of from about 50.degree. C. to about
120.degree. C., and at a pressure in a range of from about 1
atmosphere to about 150 atmospheres to provide a first oxidized
mixture comprising sulfoxides and sulfones of benzothiophene,
dibenzothiophene, alkyl substituted benzothiophenes, and alkyl
substituted dibenzothiophenes; (b) separating at least one oxidized
sulfur compound from the first oxidized mixture; and (c) recovering
petroleum-ether to provide a purified fuel oil.
24. The method according to claim 23, wherein the exogenous binary
catalyst comprises a first component selected from the group
consisting of oxides and salts vanadium, manganese and copper, and
combinations thereof, and a second component selected from the
group consisting of oxides and salts of cerium, iron, titanium,
manganese, cobalt, nickel, copper and combinations thereof.
25. The method according to claim 23, further comprising a step of
recovering the binary catalyst.
Description
BACKGROUND
[0001] The invention includes embodiments that generally relate to
a method for purifying sulfur-containing fuel oil using air and a
catalyst.
[0002] Raw/fossil fuels, such as fuel oil including a crude oil and
oil distillates and refinery products like gasoline, kerosene,
diesel fuel, naphtha, heavy fuel oil, natural gas, liquefied
natural gas and liquefied petroleum gas, and like hydrocarbons, are
useful for a number of different processes, particularly as a fuel
source, and most particularly for use in a power plant. Virtually
all of these fuels contain relatively high levels of naturally
occurring, organic sulfur compounds, such as, but not limited to,
sulfides, mercaptans and thiophenes. Hydrogen generated in the
presence of such sulfur compounds has a poisoning effect on
catalysts used in many chemical processes, particularly catalysts
used in fuel cell processes, resulting in shortening the life
expectancy of the catalysts. When present in a feed stream in a
fuel cell process, sulfur compounds may also poison the fuel cell
stack itself. Because of the relatively high levels of sulfur
compounds that may be present in many crude fuel feed streams, it
is necessary that these feed streams be desulfurized.
[0003] Furthermore, desulfurization of fuels has become an
important problem due to the upcoming regulatory requirements that
require a reduction in current sulfur emissions. Two major tasks in
the sulfur removal from fuel include (i) the deep desulfurization
of diesel fuel (reducing S content from .about.500 parts per
million to below 15 parts per million) and, (ii) sulfur removal
from crude and heavy fuel oils used for energy production (reducing
S content from 3-4 percent to less than 0.5 percent). Conventional
hydrodesulfurization (HDS) method using hydrogen have not only been
insufficient to effect the deep desulfurization of diesel fuels but
are also relatively expensive for the direct sulfur removal from a
crude and heavy fuel oils due to high cost of hydrogen and the use
of high temperature and pressure. Alternatively oxidative
desulfurization (ODS) methods using oxidants like hydrogen
peroxide, molecular oxygen or ozone, require somewhat less
demanding operating conditions when compared to the operating
conditions employed in HDS methods. Further, where oxygen may be
used as the stoichiometric oxidant, ODS methods may be cost
competitive with HDS methods.
[0004] Thus, there exists a need for efficient and cost effective
ODS methods for sulfur removal from fuel, to provide desulfurized
fuels that meet modern engineering and regulatory standards.
BRIEF DESCRIPTION
[0005] In one embodiment, the present invention provides a method
for purifying a sulfur-containing fuel oil comprising (a)
contacting the fuel oil with a supported exogenous binary catalyst
and oxygen at a temperature in a range of from about 25.degree. C.
to about 150.degree. C., and at a pressure in a range of from about
1 atmosphere to about 150 atmospheres to provide a first oxidized
mixture; and (b) separating at least one oxidized sulfur compound
from the first oxidized mixture to a provide a purified fuel
oil.
[0006] In another embodiment, the present invention provides a
method for purifying a sulfur-containing fuel oil comprising (a)
contacting the sulfur-containing fuel oil with a hydrocarbon
diluent, an alumina supported exogenous binary catalyst, and oxygen
at a temperature in a range of from about 50.degree. C. to about
120.degree. C., and at a pressure in a range of from about 1
atmosphere to about 50 atmospheres to provide a first oxidized
mixture; (b) separating at least one oxidized sulfur compound from
the first oxidized mixture; and (c) recovering the diluent to
provide a purified fuel oil.
[0007] In yet another embodiment, the present invention provides a
method for purifying a sulfur-containing fuel oil comprising (a)
contacting a sulfur-containing fuel oil comprising benzothiophene,
dibenzothiophene, alkyl substituted benzothiophenes, and alkyl
substituted dibenzothiophenes with petroleum-ether, a supported
exogenous binary catalyst, and oxygen at a temperature in a range
of from about 50.degree. C. to about 120.degree. C., and at a
pressure in a range of from about 1 atmosphere to about 50
atmospheres to provide a first oxidized mixture comprising
sulfoxides and sulfones of benzothiophene, dibenzothiophene, alkyl
substituted benzothiophenes, and alkyl substituted
dibenzothiophenes; (b) separating at least one oxidized sulfur
compound from the first oxidized mixture; and (c) recovering
petroleum-ether to provide a purified fuel oil.
[0008] These and other features, aspects, and advantages of the
present invention may be understood more readily by reference to
the following detailed description.
DETAILED DESCRIPTION
[0009] In the following specification and the claims, which follow,
reference will be made to a number of terms, which shall be defined
to have the following meanings.
[0010] The singular forms "a", "an", and "the" include plural
referents unless the context clearly dictates otherwise.
[0011] "Optional" or "optionally" means that the subsequently
described event or circumstance may or may not occur, and that the
description includes instances where the event occurs and instances
where it does not.
[0012] Approximating language, as used herein throughout the
specification and claims, may be applied to modify any quantitative
representation that could permissibly vary without resulting in a
change in the basic function to which it is related. Accordingly, a
value modified by a term or terms, such as "about" and
"substantially", are not to be limited to the precise value
specified. In at least some instances, the approximating language
may correspond to the precision of an instrument for measuring the
value. Here and throughout the specification and claims, range
limitations may be combined or interchanged, such ranges are
identified and include all the sub-ranges contained therein unless
context or language indicates otherwise.
[0013] In one embodiment, the present invention provides a method
for purifying a sulfur-containing fuel oil comprising (a)
contacting the fuel oil with a supported exogenous binary catalyst
and oxygen at a temperature in a range of from about 25.degree. C.
to about 150.degree. C., and at a pressure in a range of from about
1 atmosphere to about 150 atmospheres to provide a first oxidized
mixture; and (b) separating at least one oxidized sulfur compound
from the first oxidized mixture to a provide a purified fuel
oil.
[0014] In one embodiment, the sulfur-containing fuel oil is a crude
oil, for example Saudi sweet crude oil, West Texas Intermediate
crude oil, Dubai crude oil, and Brent crude oil. In an alternate
embodiment, the sulfur-containing fuel oil is a crude oil, which
has been subjected to asphaltene removal. In one embodiment, the
sulfur-containing fuel oil is a distillate or other refinery
products of a crude oil like gasoline, kerosene, diesel fuel,
naphtha, heavy fuel oil, natural gas, liquefied natural gas and
liquefied petroleum gas. In one embodiment, the sulfur-containing
fuel oil comprises dibenzothiophene, benzothiophene, alkyl
substituted dibenzothiophenes, and alkyl substituted
benzothiophenes.
[0015] In one embodiment, the sulfur-containing fuel oil comprises
less than 5 weight percent sulfur based on the weight of
sulfur-containing fuel oil. In another embodiment, the
sulfur-containing fuel oil comprises less than 3 weight percent
sulfur based on the weight of sulfur-containing fuel oil. In
another embodiment, the sulfur-containing fuel oil comprises less
than 2 weight percent sulfur based on the weight of
sulfur-containing fuel oil.
[0016] In one embodiment, the supported exogenous binary catalyst
comprises a solid support comprising a metal oxide. As used herein
the phrase "supported exogenous binary catalyst" means a "supported
external binary catalyst" that is combined in a first reaction
mixture with a sulfur-containing fuel oil. In one embodiment, the
metal oxide solid support may be selected from the group consisting
of alumina, silica, magnesia, titania, ceria, and combinations of
at least two of the foregoing. In one embodiment, the solid support
is alumina.
[0017] In one embodiment, the binary catalyst comprises a first
component, a catalyst and a second component, a promoter. In one
embodiment the binary catalyst comprises a first component selected
from the group consisting of oxides and salts of vanadium,
manganese and copper, and combinations thereof, and a second
component selected from the group consisting of oxides and salts of
cerium, iron, titanium, manganese, cobalt, nickel, copper and
combinations thereof. In another embodiment, the first component
comprises an oxide or a salt of vanadium. In yet another
embodiment, the first component comprises an oxide or a salt of
manganese. In another embodiment, the second component comprises an
oxide or a salt of cobalt. In yet another embodiment, the second
component comprises an oxide or a salt of copper.
[0018] In one embodiment, the binary catalyst comprises an active
metal component which is present in an amount corresponding to from
about 1 weight percent to about 10 weight percent based on the
weight of the support. In another embodiment, the binary catalyst
comprises an active metal component which is present in an amount
corresponding to from about 2 weight percent to about 8 weight
percent based on the weight of the support. In yet another
embodiment, the binary catalyst comprises an active metal component
which is present in an amount corresponding to from about 4 weight
percent to about 6 weight percent based on the weight of the
support.
[0019] In one embodiment, when the amount of active metal component
is in a range of from about 1 weight percent to about 10 weight
percent based on the support, the amount of binary catalyst on the
metal oxide support employed in the oxidation reaction is in a
range of from about 0.25 weight percent to about 10 weight percent
based on the amount of the sulfur-containing fuel oil. In another
embodiment, the amount of binary catalyst on the metal oxide
support employed in the oxidation reaction is in a range of from
about 0.5 weight percent to about 8 weight percent based on the
amount of the sulfur-containing fuel oil. In yet another
embodiment, the amount of binary catalyst on the metal oxide
support employed in the oxidation reaction is in a range of from
about 1 weight percent to about 5 weight percent based on the
amount of the sulfur-containing fuel oil. One skilled in the art
can easily determine the amount of metal catalyst on a metal oxide
support required for the oxidation reaction based on the amount
active metal content present in the metal oxide support and the
amount of sulfur-containing fuel oil being purified.
[0020] In one embodiment, the amount of second component is in a
range of from about 4 weight percent to about 50 weight percent
based on the amount of the first component employed. In another
embodiment, the amount of second component is in a range of from
about 5 weight percent to about 12 weight percent based on the
amount of the first component employed. In yet another embodiment,
the amount of second component is in a range of from about 6 weight
percent to about 10 weight percent based on the amount of the first
component employed.
[0021] In one embodiment, the at least one oxidized sulfur compound
may be separated from the first oxidized mixture using a
solid-liquid extraction process, for example an adsorption process,
to provide the purified fuel oil. In one embodiment, the at least
one oxidized sulfur compound may be separated from the first
oxidized mixture using a liquid-liquid extraction process, to
provide the purified fuel oil. One skilled in the art can easily
determine the process and the conditions required to achieve
satisfactory separation.
[0022] In one embodiment, the method for purifying the
sulfur-containing fuel oil further comprises a step of recovering
the supported binary catalyst. In one embodiment, the supported
binary catalyst is recovered from the first oxidized mixture by
filtration or centrifuging/decantation, using methods known to one
skilled in the art.
[0023] In one embodiment, the first oxidized mixture is contacted
with a porous silica adsorbent material, wherein the adsorbent
material is characterized by a Brunauer-Emmett-Teller (BET) surface
area value (total) of at least about 15 m.sup.2/g; and a
Barrett-Joyner-Halenda (BJH) pore volume (total) of at least about
0.5 cc/g. Such porous adsorbent materials and their use are
described in copending U.S. patent application Ser. No. 11/934298
filed Nov. 2, 2007 which is incorporated herein by reference in its
entirety. In instances wherein the sulfur-containing fuel oil
comprises other metallic impurities such as vanadium compounds,
such contact results in removal of these other metallic impurities
or their oxidation products from the first oxidized mixture.
[0024] In one embodiment, the pressure at which the oxidation (also
referred to as contacting the fuel oil with a supported exogenous
binary catalyst and oxygen at a temperature in a range of from
about 25.degree. C. to about 150.degree. C., and at a pressure in a
range of from about 1 atmosphere to about 150 atmospheres to
provide a first oxidized mixture) is carried out is in range of
from about 1 atmosphere to about 150 atmospheres. In another
embodiment, the pressure at which the oxidation is carried out is
in range of from about 5 atmospheres to about 45 atmospheres. In
yet another embodiment, the pressure at which the oxidation is
carried out is in range of from about 10 atmospheres to about 40
atmospheres.
[0025] In one embodiment, the temperature at which the oxidation is
carried out is in a range from about 25.degree. C. to about
150.degree. C. In another embodiment, the temperature at which the
oxidation is carried out is in a range from about 50.degree. C. to
about 120.degree. C. In yet another embodiment, the temperature at
which the oxidation is carried out is in a range from about
60.degree. C. to about 90.degree. C.
[0026] In one embodiment, the oxygen required for contacting the
sulfur-containing fuel oil is provided as a mixture with an inert
gas. Non-limiting suitable examples of gases suitably inert to the
conditions employed include nitrogen and argon. In one embodiment,
the oxygen is provided as air.
[0027] In another embodiment, the sulfur-containing fuel oil is
deasphalted prior to contacting the sulfur-containing fuel oil with
the binary catalyst and oxygen. Deasphaltation of the
sulfur-containing fuel oil may be carried out by methods known to
one skilled in the art. Typically, deasphaltation is carried out by
contacting the sulfur-containing fuel oil with an inert diluent and
filtering or centrifuging the resultant mixture to separate the
fuel oil from the insoluble asphaltenes to provide a deasphalted
fuel oil. In one embodiment, the inert diluent is selected from the
group consisting of liquid saturated hydrocarbons, liquid cyclic
hydrocarbons, and mixtures of at least two of the foregoing inert
diluents. Suitable non-limiting examples of liquid cyclic
hydrocarbons include cyclohexane, cycloheptane, and decalin.
Suitable non-limiting examples of liquid saturated hydrocarbons
include propane, butane, and petroleum ether. In one embodiment,
the method for purifying the sulfur-containing fuel oil further
comprises a step of recovering the inert diluent. In one
embodiment, the inert diluent is recovered from the first oxidized
mixture by distillation, using methods known to one skilled in the
art.
[0028] In another embodiment, the present invention provides a
method for purifying a sulfur-containing fuel oil comprising (a)
contacting the sulfur-containing fuel oil with a hydrocarbon
diluent, an alumina supported exogenous binary catalyst, and oxygen
at a temperature in a range of from about 50.degree. C. to about
120.degree. C., and at a pressure in a range of from about 1
atmosphere to about 150 atmospheres to provide a first oxidized
mixture; (b) separating at least one oxidized sulfur compound from
the first oxidized mixture; and (c) recovering the diluent to
provide a purified fuel oil.
[0029] In yet another embodiment, the present invention provides a
method for purifying a sulfur-containing fuel oil comprising (a)
contacting a sulfur-containing fuel oil comprising benzothiophene,
dibenzothiophene, alkyl substituted benzothiophenes, and alkyl
substituted dibenzothiophenes with petroleum-ether, a supported
exogenous binary catalyst, and oxygen at a temperature in a range
of from about 50.degree. C. to about 120.degree. C., and at a
pressure in a range of from about 1 atmosphere to about 50
atmospheres to provide a first oxidized mixture comprising
sulfoxides and sulfones of benzothiophene, dibenzothiophene, alkyl
substituted benzothiophenes, and alkyl substituted
dibenzothiophenes; (b) separating at least one oxidized sulfur
compound from the first oxidized mixture; and (c) recovering
petroleum-ether to provide a purified fuel oil.
[0030] The following examples are intended only to illustrate
methods and embodiments in accordance with the invention, and as
such should not be construed as imposing limitations upon the
claims.
EXAMPLES
[0031] Reagents and certain of the catalysts employed herein were
obtained from Aldrich Chemical Company.
[0032] Catalysts were prepared using an INCIPIENT WETNESS protocol
known in the art incorporating a gamma-alumina support and aqueous
solutions of nitrate or acetate salts of a transition metal (In one
instance vanadyl acetylacetonate was used for the preparation of
vanadium pentoxide). After impregnation of the catalyst in the
alumina support, the samples were dried at 120.degree. C. and
calcined in air at about 550.degree. C. for about 5 hours. The
temperature was increased from 120.degree. C. to about 550.degree.
C. at a rate of 5.degree. C./min. The amount of active metal
component used was about 5 weight percent based on the weight of
the alumina support.
Examples 1 to 9 and Comparative Examples CE-1 to CE-2
Effect Of Oxidative Desulfurization on a Sulfur-Containing Fuel Oil
Model Mixture
[0033] A sulfur-containing model mixture was prepared from tetralin
and dioctylsulfide (DOS), benzothiophene (BT), and dibenzothiophene
(DBT) wherein the sulfur-containing compounds were present in a
2:2:3 weight ratio. The model mixture was shown to comprise about 3
weight percent sulfur, when tested using a Varian Saturn 2000 GCMS.
7 milliliters (ml) of the mixture and 50 milligram (mg) supported
exogenous binary catalyst were placed in each of 6 four-dram vials
equipped with magnetic cross-like stirbars. The vials were placed
in an aluminum heating block. The block with the vials was placed
in a one-gallon autoclave equipped with a magnetic stirrer. The
autoclave was maintained under an air pressure of 2000 pounds per
square inch at a temperature of about 150.degree. C. for a period
of about 6 hours. The autoclave was then depressurized and the
oxidized samples analyzed using the Varian Saturn 2000 GCMS. The
results are presented in Table 1 below.
TABLE-US-00001 TABLE 1 Conversion of sulfur compounds in a fuel oil
model mixture under air oxidation in the presence of exogenous
binary catalysts supported on alumina. Catalyst Conversion
Percentage Example 1.sup.st component 2.sup.nd component BT DBT DOS
1 MnO.sub.2 Co.sub.3O.sub.4 23.0 42.6 100 2 MnO.sub.2 CuO 31.0 41.4
100 3 MnO.sub.2 Co.sub.3O.sub.4 25.3 44.4 100 4 MnO.sub.2
Fe.sub.2O.sub.3 31.0 38.0 96.2 5 CuO Co.sub.3O.sub.4 24.1 43.5 100
6 NaVO.sub.3 MnO.sub.2 46.2 19.7 99.3 7 V.sub.2O.sub.5 MnO.sub.2
39.6 33.6 98.6 8 V.sub.2O.sub.5 CuO 37.6 17.0 98.1 9 MoO.sub.3
Co.sub.3O.sub.4 23.0 23.9 99.1 CE-1 CuO -- 20.0 33.0 99.1 CE-2
NaVO.sub.3 -- 32.9 35.1 96.9
[0034] Examples 1 to 9 demonstrate that, in general, the binary
catalyst system outperforms systems containing a single catalyst
(Comparative Examples 1 and 2). Systems comprising a binary
catalyst which failed to outperform the corresponding single
catalyst system are regarded as not fully optimized in terms of the
relative amounts of the components of the binary catalyst (See for
example, Example 9 in which the conversion efficiencies for DBT and
BT are relatively low in comparison to other Examples representing
embodiments of the invention.
[0035] In each of Examples 1 to 9 the oxidized sulfur compounds may
be separated from the reaction mixture (first oxidized mixture)
using any of the techniques disclosed herein as being effective for
that purpose. In one embodiment, the reaction mixture of Example 1
is filtered through a pad of silica gel to remove both the oxidized
sulfur compounds and the supported exogenous binary catalyst which
may be recovered therefrom.
Example 10
[0036] Saudi Crude 100 ml is first mixed with petroleum ether (PE)
in a volume ratio of PE:Oil=2:1. The mixture is centrifuged at 2100
rpm for 10 min and then decanted to separate the solid asphaltenes
and passed through an adsorption column filled with silica to
remove heavy metals to provide a deasphalted oil fraction having a
sulfur content of about 3.3 weight percent as determined using a
Spectro Phoenix II XRF analyzer. 6.4 g of the deasphalted oil
fraction and a supported exogenous binary catalyst 106 mg (same as
that used in Example 3) are placed in a four-dram vial equipped
with magnetic cross-like stirbars. The vials are placed in an
aluminum heating block. The block with the vials is placed in a
one-gallon autoclave equipped with a magnetic stirrer. The
autoclave is maintained under an air pressure of 2000 pounds per
square inch at a temperature of about 150.degree. C. for a period
of about 6 hours. The autoclave is then depressurized and the
oxidized sample is washed with 2 ml 75 percent acetic acid and then
with 2 ml of water. The oil fraction (6.1 g) contained 2.05 weight
percent sulfur as analyzed by a Spectro Phoenix II XRF analyzer.
This demonstrates that 37 percent of the sulfur containing
components of the crude are converted into the corresponding
oxidized derivatives (sulfones, sulfoxides) at about 95 percent
yield of oil.
[0037] In one embodiment, the reaction mixture comprising the crude
oil and the petroleum ether is filtered through a pad of silica gel
to remove both the oxidized sulfur compounds and the supported
exogenous binary catalyst which may be recovered therefrom. In
general, the oxidized sulfur compounds may be separated from the
crude oil containing reaction mixture (first oxidized mixture)
using any of the techniques disclosed herein as being effective for
that purpose.
[0038] The foregoing examples are merely illustrative, serving to
illustrate only some of the features of the invention. The appended
claims are intended to claim the invention as broadly as it has
been conceived and the examples herein presented are illustrative
of selected embodiments from a manifold of all possible
embodiments. Accordingly, it is Applicants' intention that the
appended claims are not to be limited by the choice of examples
utilized to illustrate features of the present invention. As used
in the claims, the word "comprises" and its grammatical variants
logically also subtend and include phrases of varying and differing
extent such as for example, but not limited thereto, "consisting
essentially of" and "consisting of." Where necessary, ranges have
been supplied, those ranges are inclusive of all sub-ranges there
between. It is to be expected that variations in these ranges will
suggest themselves to a practitioner having ordinary skill in the
art and where not already dedicated to the public, those variations
should where possible be construed to be covered by the appended
claims. It is also anticipated that advances in science and
technology will make equivalents and substitutions possible that
are not now contemplated by reason of the imprecision of language
and these variations should also be construed where possible to be
covered by the appended claims.
* * * * *