Note: Descriptions are shown in the official language in which they were submitted.
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METHODS FOR UPGRADING OF CONTAMINATED
HYDROCARBON STREAMS
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation in part of Serial No. 13/560,584,
filed July 27,
2012, entitled Methods for Upgrading of Contaminated Hydrocarbon Streams,
which is a
continuation in part of Serial No. 12/904,446, filed October 14, 2010,
entitled Methods for
Upgrading of Contaminated Hydrocarbon Streams, which is a continuation in part
of Serial No.
12/933,898, filed September 22, 2010, entitled Sulfoxidation Catalysts and
Method of Using the
Same), which claims priority under 35 USC 371 based upon PCT/U508/82095,
entitled
Sulfoxidation Catalysts and Method of Using the Same), which claims priority
to provisional
patent application 61/039,619, entitled Sulfoxidation Catalysts and Method of
Using the
Same); and this application is a continuation in part of Serial No.
12/888,049, filed September
22, 2010, entitled Reaction System and Products Therefrom, the disclosure of
each is hereby
incorporated by reference to the extent not inconsistent with the present
disclosure.
BACKGROUND
[0002] As is well known in the industry, crude oil contains heteroatom
contaminants
including, but not limited to, sulfur, nitrogen, phosphorus, nickel, vanadium,
and iron and acidic
oxygenates in quantities that negatively impact the refinery processing of the
crude oil fractions.
Light crude oils or condensates contain heteroatoms in concentrations as low
as 0.001 wt %. In
contrast, heavy crude oils contain heteroatoms as high as 5-7 wt %. The
heteroatom content of
crude oil increases with increasing boiling point and the heteroatom content
increases with
decreasing API gravity. These contaminants must be removed during refining
operations to
meet the environmental regulations for the final product specifications (e.g.,
gasoline, diesel, fuel
oil) or to prevent the contaminants from decreasing catalyst activity,
selectivity, and lifetime in
downstream refining operations. Contaminants such as sulfur, nitrogen,
phosphorus, nickel,
vanadium, iron, and total acid number (TAN) in the crude oil fractions
negatively impact these
downstream processes, and others, including hydrotreating, hydrocracking and
FCC to name just
a few. These contaminants are present in the crude oil fractions in various
organic hydrocarbon
molecules and in various concentrations.
[0003] Many heteroatom contaminants appear in hydrocarbon streams in both
oxidized
and unoxidized form. For example, sulfur can appear in oxidized form as, for
example, a
sulfoxide, sulfone, or sulfonate, or in unoxidized form as, for example, a
thiophene. Naturally
occurring hydrocarbon streams include both oxidized and unoxidized
heteroatoms, including
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both oxidized and unoxidized forms of sulfur. The oxidized heteroatom content
of a hydrocarbon
stream may also be increased through artificial processes. Figure 1 describes
a table of available
oxidation states for organic heteroatom compounds.
[0004] Sulfur is widely recognized as the most egregious heteroatom
contaminant as a
result of the environmental hazard caused by its release into the environment
after combustion.
It is believed, sulfur oxides from combustion (known collectively as SO,
emissions) contribute
to the formation of acid rain and also to the reduction of the efficiency of
catalytic converters in
automobiles. Furthermore, sulfur compounds are thought to ultimately increase
the particulate
content of combustion products. Nitrogen, phosphorus, and other heteroatom
contaminants
present similar environmental risks.
[0005] A variety of methods have been implemented for removing sulfur
compounds
either from fuels before combustion or from emission gases afterward. Most
refineries employ
hydrodesulfurization (HDS) as the predominant process for removing sulfur from
hydrocarbon
streams. HDS remains a cost-effective option for light streams with sulfur
levels up to about 2%
(w/w) elemental sulfur, but the environmental and economic benefits of HDS are
offset in very
heavy and sour (>2% elemental sulfur) streams because the energy input to the
reaction, the high
pressures and the amount of hydrogen necessary to remove the sulfur
paradoxically create a
substantial CO2 emission problem.
[0006] Because of these issues, reduction of contaminants and, in particular,
of the
sulfur content in hydrocarbon streams has become a major objective of
environmental legislation
worldwide. Sulfur is regulated in the United States for on-road diesel at a
maximum
concentration of 15 ppm. By October 2012, sulfur specifications will be 15 ppm
for non-road,
locomotive, and marine diesel fuel. In the European Union that specification
is expected to
tighten to 10 ppm in January 2011 for diesels intended for inland waterways
and for on-road and
off-road diesel operated equipment. In China, the on-road diesel specification
will be 10 ppm by
2012. Currently the tightest specifications in the world are in Japan, where
the on-road diesel
specification is 10 ppm.
[0007] Refiners typically use catalytic hydrodesulfurizing ("HDS", commonly
referred
to as "hydrotreating") methods to lower the sulfur content of hydrocarbon
fuels, decrease the
total acid number, and increase the API gravity. In HDS, a hydrocarbon stream
that is derived
from petroleum distillation is treated in a reactor that operates at
temperatures ranging between
575 and 750 F. (about 300 to about 400 C.), a hydrogen pressure that ranges
between 430 to
14,500 psi (3000 to 10,000 kPa or 30 to 100 atmospheres) and hourly space
velocities ranging
between 0.5 and 4 h-1. Dibenzothiophenes in the feed react with hydrogen when
in contact with a
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catalyst arranged in a fixed bed that comprises metal sulfides from groups VI
and VIII (e.g.,
cobalt and molybdenum sulfides or nickel and molybdenum sulfides) supported on
alumina.
Because of the operating conditions and the use of hydrogen, these methods can
be costly both in
capital investment and operating costs.
[0008] As is currently known, HDS or hydrotreating may provide a treated
product in
compliance with the current strict sulfur level targets. However, due to the
presence of sterically
hindered refractory sulfur compounds such as substituted dibenzothiophenes,
the process is not
without issues. For example, it is particularly difficult to eliminate traces
of sulfur using such
catalytic processes when the sulfur is contained in molecules such as
dibenzothiophene with
alkyl substituents in position 4-, or 4- and 6-positions of the parent ring.
Attempts to completely
convert these species, which are more prevalent in heavier stocks such as
diesel fuel and fuel oil,
have resulted in increased equipment costs, more frequent catalyst
replacements, degradation of
product quality due to side reactions, and continued inability to comply with
the strictest sulfur
requirements for some feeds.
[0009] This has prompted many to pursue non-hydrogen alternatives to
desulfurization,
such as oxydesulfurization. One attempt at solving the problem discussed above
includes
selectively desulfurizing dibenzothiophenes contained in the hydrocarbon
stream by oxidizing
the dibenzothiophenes into a sulfone in the presence of an oxidizing agent,
followed by
optionally separating the sulfone compounds from the rest of the hydrocarbon
stream and further
reacting the sulfones with a caustic to remove the sulfur moiety from the
hydrocarbon fragment.
[0010] Oxidation has been found to be beneficial because oxidized sulfur
compounds
can be removed using a variety of separation processes that rely on the
altered chemical
properties such as the solubility, volatility, and reactivity of the sulfone
compounds. An
important consideration in employing oxidation is chemical selectivity.
Selective oxidation of
sulfur heteroatom moieties without oxidizing the plethora of olefins and
benzylic hydrocarbons
found in crude oils, refinery intermediates, and refinery products remains a
significant challenge.
One selective sulfoxidation method and system is disclosed in International
Publication Number
WO 2009/120238 Al, to Litz et al. The inventors of the present disclosure have
further
discovered that the catalyst of the above-mentioned international publication
number is further
capable of oxidizing additional heteroatoms, including, but not limited to
nitrogen and
phosphorus found as naturally abundant contaminants in crude oils, refinery
intermediates, and
refinery products as organic heteroatom-containing compounds. Figure 1
describes a table of
available oxidation states for organic heteroatom compounds.
[0011] Another concern with heteroatom oxidation lies in the fate of the
oxidized
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organic heteroatom compounds produced. If the oxidized organic heteroatom
compounds are
hydrotreated, they may be converted back to the original heteroatom compounds
thereby
regenerating the original problem. The feed heteroatom content may be likely
to be in the range
of 0% to 10% by weight heteroatom. Heteroatoms, on average, comprise about 15
wt % of
substituted and unsubstituted organic heteroatom molecules. Therefore, up to
67 wt % of the oil
may be removed as oxidized organic heteroatom extract if not removed from the
organic
molecules. For a typical refinery processing 40,000 barrels per day of crude
oil, up to 27,000
barrels per day of oxidized organic heteroatom oil will be generated, which is
believed to be too
much to dispose conventionally as a waste product. Further, the disposal of
oxidized organic
heteroatom oil also wastes valuable hydrocarbons, which could theoretically be
recycled if an
efficient process were available.
[0012] A considerable challenge presented to heteroatom removal remains the
removal
of the oxidized heteroatom fragment from the oxidized organic heteroatom
compounds found in
naturally occurring hydrocarbons or created by oxidation of the initial
organic heteroatom
species, without producing substantial oxygenated by-product. Therefore, a
need exists for
methods and systems for upgrading heteroatom-contaminated hydrocarbon feed
streams by
removing heteroatom contaminants from hydrocarbon streams with the added
benefit of
decreasing the total acid number and increasing the API gravity of the
resulting product relative
to the contaminated hydrocarbon feed stream.
SUMMARY OF THE DISCLOSURE
[0013] The present disclosure is directed to systems and methods for upgrading
hydrocarbon streams by decreasing the content of undesired heteroatom
contaminants, including,
but not limited to, sulfur, nitrogen, phosphorus, nickel, vanadium, iron.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The features of the disclosure are set forth in the appended claims.
The
disclosure itself, however, will be best understood by reference to the
following detailed
description of illustrative embodiments when read in conjunction with the
accompanying
drawings, wherein:
[0015] Figure 1 is a graphic representation of the various oxidation states of
certain
heteroatoms, in accordance with embodiments of the present disclosure.
[0016] Figure 2 is a generic process flow diagram of an embodiment of an
oxidized
heteroatom cleavage process, in accordance with embodiments of the present
disclosure.
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[0017] Figure 3 is a more detailed process flow diagram of an embodiment of an
oxidized heteroatom cleavage process followed by recovery of caustic and
selectivity promoter
byproduct, in accordance with embodiments of the present disclosure.
[0018] Figure 4 is an alternative detailed process flow diagram of an
embodiment of a
combination oxidized-heteroatom-containing hydrocarbon extraction followed by
oxidized
heteroatom cleavage, in accordance with embodiments of the present invention.
[0019] Figure 5 is a generic process flow diagram of an embodiment of a
combination
heteroatom oxidation process followed by oxidized heteroatom cleavage, in
accordance with
embodiments of the present disclosure.
[0020] Figure 6A is a more detailed process flow diagram of an embodiment of a
combination heteroatom oxidation process followed by oxidized heteroatom
cleavage, in
accordance with embodiments of the present disclosure.
[0021] Figure 6B is an alternative more detailed process flow diagram of an
embodiment of a combination heteroatom oxidation process followed by oxidized
heteroatom
cleavage, in accordance with embodiments of the present disclosure.
[0022] Figure 7 is an even more detailed process flow diagram of an embodiment
of a
combination heteroatom oxidation process followed by oxidized heteroatom
cleavage, in
accordance with embodiments of the present disclosure.
[0023] Figure 8 is an alternative even more detailed process flow diagram of
an
embodiment of a combination heteroatom oxidation process followed by oxidized
heteroatom
cleavage, in accordance with embodiments of the present disclosure.
[0024] Figure 9 illustrates various decomposition modes for dibenzothiophene
sulfone.
DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EMBODIMENTS
[0025] While this disclosure contains many specific details, it should be
understood
that various changes and modifications may be made without departing from the
scope of the
technology herein described. The scope of the technology shall in no way be
construed as being
limited to the number of constituting components, the concentration of
constituting components,
the materials thereof, the shapes thereof, the relative arrangement thereof,
the temperature
employed, the order of combination of constituents thereof, etc., and are
disclosed simply as
examples. The depictions and schemes shown herein are intended for
illustrative purposes and
shall in no way be construed as being limiting in the number of constituting
components,
connectivity, reaction steps, the materials thereof, the shapes thereof, the
relative arrangement
thereof, the order of reaction steps thereof, etc., and are disclosed simply
as an aid for
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understanding. The examples described herein relate to the removal of oxidized
heteroatoms
from hydrocarbon streams including crude oil, refinery intermediate streams,
and refinery
products.
[0026] Unless otherwise indicated, all numbers expressing quantities of
ingredients,
properties such as molecular weight, reaction conditions, and so forth used in
this specification
and claims are to be understood as being modified in all instances by the term
"about."
Accordingly, unless indicated to the contrary, the numerical parameters set
forth in the following
specification and attached claims are approximations that may vary depending
upon the desired
properties sought to be obtained by the present disclosure. At the very least,
and not as an
attempt to limit the application of the doctrine of equivalents to the scope
of the claims, each
numerical parameter should at least be construed in light of the number of
reported significant
digits and by applying ordinary rounding techniques.
[0027] Notwithstanding that the numerical ranges and parameters setting forth
the
broad scope of the disclosure are approximations, the numerical values set
forth in the specific
examples are reported as precisely as possible. Any numerical value, however,
inherently
contain certain errors necessarily resulting from the standard deviation found
in their respective
testing measurements.
[0028] As used in this application, the term "promoted-caustic visbreaker"
means a
heated reactor that contains a caustic and a selectivity promoter that react
with oxidized
heteroatoms to remove sulfur, nickel, vanadium, iron and other heteroatoms,
increase API
gravity and decrease total acid number.
[0029] As used in this application, the term "contaminated hydrocarbon stream"
is a
mixture of hydrocarbons containing heteroatom constituents. "Heteroatoms" is
intended to
include all elements other than carbon and hydrogen.
[0030] As used in this application, the term "sulfoxidation" is a reaction or
conversion,
whether or not catalytic, that produces sulfoxide or organo-sulfoxide, sulfone
or organo-sulfone,
sulfonate or organo-sulfonate, or sulfonic acid or organo-sulfonic acid
compounds (and/or
mixtures thereof) from organosulfur compounds. A sulfone is a chemical
compound containing
a sulfonyl functional group attached to two carbon atoms. The central
hexavalent sulfur atom is
double bonded to each of two oxygen atoms and has a single bond to each of two
carbon atoms,
usually in two separate hydrocarbon substituents. The general structural
formula is R-S(=0)2-R'
where R and R' are the organic groups which may be hydrogen or an organic
compound (which
may be further substituted) including, but not limited to, straight, branched
and cyclic alkyl
groups; straight, branched and cyclic alkenyl groups; and aromatic or
polycyclic aromatic
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groups. Further substituents where R is an organic may include hydroxide
groups, carbonyl
groups, aldehyde groups, ether groups, carboxylic acid and carboxylate groups,
phenol or
phenolate groups, alkoxide groups, amine groups, imine groups, cyano groups,
thiol or thiolate
groups, thioether groups, disulfide groups, sulfate groups, and phosphate
groups.
00
V/
, 0,
R R'
[0031] A sulfoxide is a chemical compound containing a sulfinyl (SO)
functional group
attached to two carbon atoms. It is a polar functional group. Sulfoxides are
the oxidized
derivatives sulfides. Sulfoxides are generally represented with the structural
formula R¨S(=0)¨
R', where R and R' are organic groups which may be hydrogen or an organic
compound (which
may be further substituted) including, but not limited to, straight, branched
and cyclic alkyl
groups; straight, branched and cyclic alkenyl groups; and aromatic or
polycyclic aromatic
groups. Further substituents where R is an organic may include hydroxide
groups, carbonyl
groups, aldehyde groups, ether groups, carboxylic acid and carboxylate groups,
phenol or
phenolate groups, alkoxide groups, amine groups, imine groups, cyano groups,
thiol or thiolate
groups, thioether groups, disulfide groups, sulfate groups, and phosphate
groups. The bond
between the sulfur and oxygen atoms is intermediate of a dative bond and a
polarized double
bond.
O ::,=-= '
-
S-
[0032] A sulfonate is a salt or ester of a sulfonic acid. It contains the
functional group
R-S020-. The R groups may be any of the R groups described in reference to the
sulfoxides
above.
0
R-S _____________________________________ 0
1
0
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[0033] A sulfonic acid (or sulphonic acid) refers to a member of the class of
organosulfur compounds with the general formula RS(=0)2-0H, where R may be any
of the R
groups described in reference to the sulfoxides above and the S(=0)2-0H group
a sulfonyl
hydroxide.
00
õOH
[0034] As used in this application, a reaction or conversion of nitrogen may
also occur,
whether or not catalytic, that produces an amine oxide, a nitroso compound, a
nitrate, or a nitro
compound. Amine oxide is also known as amine-N-oxide and N-oxide, is a
chemical compound
that contains the functional group R3N+-0-, an N-0 bond with three additional
hydrogen and/or
hydrocarbon side chains attached to N. The R groups may be organic groups
which may be
hydrogen or an organic compound (which may be further substituted) including,
but not limited
to, straight, branched and cyclic alkyl groups; straight, branched and cyclic
alkenyl groups; and
aromatic or polycyclic aromatic groups. Further substituents where R is an
organic may include
hydroxide groups, carbonyl groups, aldehyde groups, ether groups, carboxylic
acid and
carboxylate groups, phenol or phenolate groups, alkoxide groups, amine groups,
imine groups,
cyano groups, thiol or thiolate groups, thioether groups, disulfide groups,
sulfate groups, and
phosphate groups. The R groups may also be attached to each other by means of
a chemical
bond.
IDI e R2
/
80 R3
[0035] A nitroso compound is a chemical compound that contains the functional
group
R-N=0, an N=0 bond with one additional hydrogen and/or hydrocarbon side chains
attached to
N. The R group may be any of the R groups described above in reference to
amine oxide.
[0036] Nitrate is a polyatomic ion with the molecular formula NO3. The R group
may
be any of the R groups described above in reference to amine oxide.
[0037] Nitro compounds are organic compounds that contain one or more nitro
functional groups (¨NO2). The R group may be any of the R groups described
above in
reference to amine oxide.
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p
R¨N e
,
0
[0038] In one embodiment, the invention provides a method of upgrading an
oxidized-
heteroatom-containing hydrocarbon feed by removing oxidized heteroatom
contaminants, the
method comprising: contacting at least one of sulfone, sulfoxide, sulfonate,
sulfonic acid and
combinations thereof in the oxidized-heteroatom-containing hydrocarbon feed
with at least one
caustic and at least one selectivity promoter to form a first intermediate
stream; and removing the
oxidized-heteroatom contaminants from the first intermediate stream. The
oxidized-heteroatom-
containing hydrocarbon feed may include one or both of naturally occurring
oxidized
heteroatoms and artificially created oxidized heteroatoms.
[0039] In an alternative embodiment, the invention provides a method of
upgrading an
oxidized-heteroatom-containing hydrocarbon feed by removing oxidized-
heteroatom
contaminants, the method comprising: contacting at least one of sulfone,
sulfoxide, sulfonate,
sulfonic acid and combinations thereof in the oxidized-heteroatom-containing
hydrocarbon feed
with at least one caustic and at least one selectivity promoter to form a
first intermediate stream;
removing the oxidized-heteroatom contaminants from the first intermediate
stream; and
recovering the at least one caustic and at least one selectivity promoter for
reuse. The oxidized-
heteroatom-containing hydrocarbon feed may include one or both of naturally
occurring oxidized
heteroatoms and artificially created oxidized heteroatoms.
[0040] In another embodiment, the invention provides a method of upgrading an
oxidized-heteroatom-containing hydrocarbon feed by removing oxidized
heteroatom
contaminants, the method comprising: extracting at least one of sulfone,
sulfoxide, sulfonate,
sulfonic acid and combinations thereof from the oxidized-heteroatom-containing
hydrocarbon
feed to form a first intermediate stream; contacting the first intermediate
stream with at least one
caustic and at least one selectivity promoter to form a second intermediate
stream; and removing
the oxidized-heteroatom contaminants from the second intermediate stream. The
oxidized-
heteroatom-containing hydrocarbon feed may include one or both of naturally
occurring oxidized
heteroatoms and artificially created oxidized heteroatoms.In another
embodiment, the invention
provides a method of upgrading a heteroatom-containing hydrocarbon feed by
removing
heteroatom contaminants, the method comprising: contacting the heteroatom-
containing feed
with an oxidant to oxidize at least a portion of the heteroatom contaminants
to form a first
intermediate stream; contacting the first intermediate stream with at least
one caustic and at least
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one selectivity promoter to form a second intermediate stream; separating a
substantially
heteroatom-free hydrocarbon product from the second intermediate stream. The
oxidant may be
used in the presence of a catalyst.
[0041] In another embodiment, the invention provides a method of upgrading a
heteroatom-containing hydrocarbon feed by removing heteroatom contaminants,
the method
comprising:
contacting the heteroatom-containing hydrocarbon feed with an oxidant to
oxidize at least
a portion of the heteroatom contaminants to form a first intermediate stream;
contacting the first
intermediate stream with at least one caustic and at least one selectivity
promoter to form a
second intermediate stream; separating a substantially heteroatom- free
hydrocarbon product
from the second intermediate stream; recovering the at least one caustic and
at least one
selectivity promoter from the second intermediate stream; and recycling the
recovered at least
one caustic and at least one selectivity promoter.
[0042] In a further embodiment, the invention provides a method of upgrading a
heteroatom-containing hydrocarbon feed by removing heteroatom contaminants,
the method
comprising oxidizing dibenzothiophenes to sulfones, reacting the sulfones with
caustic and a
selectivity promoter, and separating a substantially heteroatom-free
hydrocarbon product for
fuel.
[0043] Other features, aspects, and advantages of the present invention will
become
better understood with reference to the following description.
[0044] The oxidation reaction may be carried out at a temperature of about 20
C to
about 120 C, at a pressure of about 0.5 atmospheres to about 10 atmospheres,
with a contact time
of about 2 minutes to about 180 minutes. The oxidant employed may be any
oxidant which,
optionally in the presence of a catalyst, oxidizes heteroatoms in the
heteroatom-containing
hydrocarbon feed, for example, but not limited to, hydrogen peroxide,
peracetic acid, benzyl
hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, sodium
hypochlorite,
oxygen, air, etc, and more presently preferably an oxidant which does not
oxidize the
heteroatom-free hydrocarbons in the contaminated hydrocarbon feed. Even more
preferably, the
catalyst employed therein may be any catalyst capable of utilizing an oxidant
to oxidize
heteroatoms in the heteroatom-containing hydrocarbon feed
[0045] Suitable catalysts include, but are not limited to, catalyst
compositions
represented by the formula MO(OR), where M is a metal complex, such as, for
example,
titanium or any metal, including, but not limited to, rhenium, tungsten or
other transition metals
alone or in combination that causes the chemical conversion of the sulfur
species, as described
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herein. R is carbon group having at least 3 carbon atoms, where at each
occurrence R may
individually be a substituted alkyl group containing at least one OH group, a
substituted
cycloalkyl group containing at least one OH group, a substituted
cycloalkylalkyl group
containing at least one OH group, a substituted heterocyclyl group containing
at least one OH
group, or a heterocyclylalkyl containing at least one OH group. The subscripts
m and n may
each independently be integers between about 1 and about 8. R may be
substituted with
halogens such as F, Cl, Br, and I. In some embodiments, the metal alkoxide
comprises
bis(glycerol)oxotitanium(IV)), where M is Ti, m is 1, n is 2, and R is a
glycerol group. Other
examples of metal alkoxides include bis(ethyleneglycol)oxotitanium (IV),
bis(erythritol)oxotitanium (IV), and bis(sorbitol)oxotitanium (IV), as
disclosed in International
Publication Number WO 2009/120238 Al, to Litz et al.
[0046] Other suitable catalysts include, but are not limited to, catalyst
compositions
prepared by the reaction of Q-R-Q' with a bis(polyol)oxotitanium(IV) catalyst,
wherein Q and
Q' each independently comprise an isocyanate, anhydride, sulfonyl halide,
benzyl halide,
carboxylic acid halide, phosphoryl acid halide, silyl chloride, or any
chemical functionality
capable of reacting with the -OH pendant group of the catalyst, and wherein R
comprises a
linking group. The R linking group is selected from the group consisting of
alkyl groups
(including linear, branched, saturated, unsaturated, cyclic, and substituted
alkyl groups, and
wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus,
and the like can be
present in the alkyl group), typically with from 1 to about 22 carbon atoms,
preferably with from
1 to about 12 carbon atoms, and more preferably with from 1 to about 7 carbon
atoms, although
the number of carbon atoms can be outside of these ranges, aryl groups
(including substituted
aryl groups), typically with from about 6 to about 30 carbon atoms, preferably
with from about 6
to about 15 carbon atoms, and more preferably with from about 6 to about 12
carbon atoms,
although the number of carbon atoms can be outside of these ranges, arylalkyl
groups (including
substituted arylalkyl groups), typically with from about 7 to about 30 carbon
atoms, preferably
with from about 7 to about 15 carbon atoms, and more preferably with from
about 7 to about 12
carbon atoms, although the number of carbon atoms can be outside of these
ranges, such as
benzyl or the like, alkylaryl groups (including substituted alkylaryl groups),
typically with from
about 7 to about 30 carbon atoms, preferably with from about 7 to about 15
carbon atoms, and
more preferably with from about 7 to about 12 carbon atoms, although the
number of carbon
atoms can be outside of these ranges, silicon or phosphorus, typically with
from 1 to about 22
carbon atoms, preferably with from 1 to about 12 carbon atoms, and more
preferably with from 1
to about 7 carbon atoms, although the number of carbon atoms can be outside of
these ranges,
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polyalkyleneoxy groups (including substituted polyalkyleneoxy groups), such as
polyethyleneoxy groups, polypropyleneoxy groups, polybutyleneoxy groups, and
the like,
typically with from about 3 to about 60 repeat alkyleneoxy units, preferably
with from about 3 to
about 30 repeat alkyleneoxy units, and more preferably with from about 3 to
about 20 repeat
alkyleneoxy units, although the number of repeat alkyleneoxy units can be
outside of these
ranges, as disclosed in International Publication Number WO 2009/120238 Al, to
Litz et al.
[0047] The solvent used in extracting the oxidized heteroatoms from the
oxidized
heteroatom-containing hydrocarbon stream (e.g. in a liquid-liquid extractor)
may be any solvent
with relatively low solubility in oil but relatively high solubility of
oxidized heteroatom-
containing hydrocarbons, including, but not limited to, acetone, methanol,
ethanol, ethyl lactate,
N-methylpyrollidone, dimethylacetamide, dimethylformamide, gamma-
butyrolactone, dimethyl
sulfoxide, propylene carbonate, acetonitrile, acetic acid, sulfuric acid,
liquid sulfur dioxide, etc,
which is capable of extracting the oxidized heteroatoms from the heteroatom
containing
hydrocarbon stream and producing a substantially oxidized-heteroatom-free
hydrocarbon
product
[0048] The caustic of the present invention may be any compound which exhibits
basic
properties including, but not limited to, metal hydroxides and sulfides, such
as alkali metal
hydroxides and sulfides, including, but not limited to, Li0H, NaOH, KOH and
Na2S; alkali earth
metal hydroxides, such as Ca(OH)2, Mg(OH)2 and Ba(OH); carbonate salts, such
as alkali metal
carbonates, including, but not limited to, Na2CO3 and K2CO3, alkali earth
metal carbonates, such
as CaCO3, MgCO3 and BaCO3; phosphate salts, including, but not limited to,
alkali metal
phosphates, such as sodium pyrophosphate, potassium pyrophosphate, sodium
tripolyphosphate
and potassium tripolyphosphate; and alkali earth metal phosphates, such as
calcium
pyrophosphate, magnesium pyrophosphate, barium pyrophosphate, calcium
tripolyphosphate,
magnesium tripolyphosphate and barium tripolyphosphate; silicate salts, such
as, alkali metal
silicates, such as sodium silicate and potassium silicate, and alkali earth
metal silicates, such as
calcium silicate, magnesium silicate and barium silicate, organic alkali
compounds expressed by
the general formula: R-E MmT-1, where R is hydrogen or an organic compound
(which may
be further substituted) including, but not limited to, straight, branched and
cyclic alkyl groups;
straight, branched and cyclic alkenyl groups; and aromatic or polycyclic
aromatic groups.
Further substituents where R is an organic may include hydroxide groups,
carbonyl groups,
aldehyde groups, ether groups, carboxylic acid and carboxylate groups, phenol
or phenolate
groups, alkoxide groups, amine groups, imine groups, cyano groups, thiol or
thiolate groups,
thioether groups, disulfide groups, sulfate groups, and phosphate groups. En-
represents an atom
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with a negative charge (where n = -1, -2, -3, -4 etc.) such as oxygen, sulfur,
selenium, tellurium,
nitrogen, phosphorus, and carbon; and MI' is any cation (m = +1, +2, +3, +4
etc.), such as a
metal ion, including, but not limited to, alkali metals, such as Li, Na, and
K, alkali earth metals,
such as Mg and Ca, and transition metals, such as Zn, and Cu. When m > +1, Q
may be the same
as En-R or an atom with a negative charge such as Br-, Cl-, I, or an anionic
group that supports
the charge balance of the cation Mm' including but not limited to, hydroxide,
cyanide, cyanate,
and carboxylates.
[0049] Examples of the straight or branched alkyl groups may include methyl,
ethyl, n-
, i-, sec- and t-butyl, octyl, 2-ethylhexyl and octadecyl. Examples of the
straight or branched
alkenyl groups may include vinyl, propenyl, ally' and butenyl. Examples of the
cyclic alkyl and
cyclic alkenyl groups may include cyclohexyl, cyclopentyl, and cyclohexene.
Examples of the
aromatic or polycyclic aromatic groups may include aryl groups, such as
phenyl, naphthyl,
andanthracenyl; aralkyl groups, such as benzyl and phenethyl; alkylaryl
groups, such as
methylphenyl, ethylphenyl, nonylphenyl, methylnaphthyl and ethylnaphthyl.
[0050] Preferred caustic compounds, based on reaction conversion and
selectivity, are
alkali metal hydroxides and sulfides, such as NaOH, KOH, Na2S, and/or mixtures
thereof
[0051] In one embodiment of the present invention, the caustic may be in the
molten
phase. Presently preferred molten phase caustics include, but are not limited
to, eutectic
mixtures of the inorganic hydroxides with melting points less than 350 C, such
as, for example,
a 51 mole % NaOH / 49 mole % KOH eutectic mixture which melts at about 170 C.
[0052] In another embodiment of the present invention, the caustic may be
supported
on an inorganic support, including, but not limited to, oxides, inert or
active, such as, for
example, a porous support, such as talc or inorganic oxides.
[0053] Suitable inorganic oxides include, but are not limited to, oxides of
elements of
groups TB, II-A and II-B, III-A and II-B, IV-A and IV-B, V-A and V-B, VI-B, of
the Periodic
Table of the Elements. Examples of oxides preferred as supports include copper
oxides, silicon
dioxide, aluminum oxide, and/or mixed oxides of copper, silicon and aluminum.
Other suitable
inorganic oxides which may be used alone or in combination with the
abovementioned preferred
oxide supports may be, for example, MgO, Zr02, Ti02, CaO and/or mixtures
thereof
[0054] The support materials used may have a specific surface area in the
range from
to 1000 m 2/g, a pore volume in the range from 0.1 to 5 ml/g and a mean
particle size of from
0.1 to 10 cm. Preference may be given to supports having a specific surface
area in the range
from 0.5 to 500 m 2/g a pore volume in the range from 0.5 to 3.5 ml/g and a
mean particle size
in the range from 0.5 to 3 cm. Particular preference may be given to supports
having a specific
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surface area in the range from 200 to 400 m 2/g and a pore volume in the range
from 0.8 to 3.0
ml/g.
[0055] The selectivity promoter of the present invention may be any organic
compound
having at least one acidic proton. Generally, the selectivity promoter has a
pKa value (as
measured in DMSO) in the range of from about 9 to about 32, preferably in the
range of from
about 18 to about 32. Examples of the selectivity promoter include, but are
not limited to,
hydroxyl-functional organic compounds; straight, branched, or cyclic amines
having at least one
H substituent; and/or mixtures thereof The selectivity promoter may further
include crown
ethers.
[0056] Suitable hydroxyl-functional organic compounds include, but are not
limited to:
(i) straight-, branched-, or cyclic-alkyl alcohols (which may be further
substituted) such as
methanol, ethanol, isopropanol, ethylhexanol, cyclohexanol, ethanolamine, di-,
and tri-
ethanolamine, mono- and di-methylaminoethanol; including -diols such as
ethylene glycol,
propylene glycol, 1,3-propanediol, and 1,2-cyclohexanediol; and ¨polyols, such
as glycerol,
erythritol, xylitol, sorbitol, etc; -monosaccharides, such as glucose,
fructose, galactose, etc; -
disaccharides, such as sucrose, lactose, and maltose; -polysaccharides, such
as starch, cellulose,
glycogen, chitan, wood chips and shavings; (ii) straight-, branched-, or
cyclic-alkenyl alcohols
(which may be further substituted), such as vinyl alcohol, and ally' alcohol;
(iii)aryl- and aralkyl-
alcohols (which may be further substituted), such as phenol, and benzyl
alcohol; (iv) polycyclic
aryl- and aralkyl- alcohols (which may be further substituted), such as
naphthol, and a-tetralol;
and (v) ammonium salts, such as choline hydroxide, and benzyltrimethylammonium
hydroxide.
[0057] Examples of straight or branched alkyls may include: methyl, ethyl, n-,
i-, sec-
and t-butyl, octyl, 2-ethylhexyl and octadecyl. Examples of the straight or
branched alkenyls
may include: vinyl, propenyl, ally' and butenyl. Examples of the cyclic-alkyls
may include:
cyclohexyl, and cyclopentyl. Examples of aryls, aralkyls and polycyclics
include: aryls, such as
phenyl, naphthyl, anthracenyl; aralkyls, such as benzyl and phenethyl;
alkylaryl, such as
methylphenyl, ethylphenyl, nonylphenyl, methylnaphthyl and ethylnaphthyl.
[0058] Suitable amines, include, but are not limited to, straight-, branched-,
and cyclic-
amines having at least one H substituent, which may be further substituted,
including, but not
limited to, mono-, or di-substituted amines, such as methylamine, ethylamine,
2-
ethylhexylamine, piperazine, 1,2-diaminoethane and/or mixtures thereof
[0059] Suitable crown ethers, which may be further substituted, include, but
are not
limited to, 18-crown-6, 15-crown-5, etc; and/or mixtures thereof
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[0060] Preferred selectivity promoters, based on reaction conversion and
selectivity,
are ethylene glycol, propylene glycol, triethanolamine, and/or mixtures
thereof
[0061] The selectivity promoter is believed to decrease the likelihood of
oxygenated
byproduct formation as a result of the oxidized hetero atom removal.
[0062] In one embodiment of the present invention the at least one caustic and
the at
least one selectivity promoter may be different components. In another
embodiment of the
present invention the at least one caustic and the at least one selectivity
promoter may be the
same component. When the at least one caustic and the at least one selectivity
promoter are the
same component they may be referred to as a caustic selectivity promoter.
Moreover, a suitable
caustic selectivity promoter may possess the properties of both the at least
one caustic and the at
least one selectivity promoter. That is, combinations of caustics with
selectivity promoters may
react (in situ or a priori) to form a caustic selectivity promoter which has
the properties of both a
caustic and a selectivity promoter.
[0063] The caustic selectivity promoter may react with the oxidized heteroatom-
containing compounds, such as dibenzothiophene sulfoxides, dibenzothiophene
sulfones, and/or
mixtures thereof, to produce substantially non-oxygenated hydrocarbon
products, such as
biphenyls. Non-limiting examples of caustic selectivity promoters include, but
are not limited
to, sodium ascorbate, sodium erythorbate, sodium gluconate, 4-hydroxyphenyl
glycol, sodium
salts of starch or cellulose, potassium salts of starch or cellulose, sodium
salts of chitan or
chitosan, potassium salts of chitan or chitosan, sodium glycolate,
glyceraldehyde sodium salt, 1-
thio-beta-D-glucose sodium salt, and/or mixtures thereof
[0064] For example, the caustic, such as sodium hydroxide and/or potassium
hydroxide
and the selectivity promoter, such as ethylene glycol, may react in situ or
prior to contacting with
the oxidized heteroatom-containing hydrocarbon feed, to form water and a
caustic selectivity
promoter, such as the sodium or potassium salt of ethylene glycol. Generally,
an excess molar
ratio of selectivity promoter hydroxyl groups to caustic cations is preferred
for conversion and
selectivity. The step of contacting may be any process that leads to
transformation of the
reactants or reagents from one set of chemical substance to another at various
temperatures,
reaction rates and chemical concentrations.
[0065] The promoted-caustic visbreaker reaction may take place at a
temperature in the
range of from about 150 C to about 350 C, at a pressure in the range of from
about 0 psig to
about 2000 psig, with a contact time in the range of from about 2 minutes to
about 180
minutes. Without being limited to any particular theory, the reaction
mechanism is believed to
include a solvolysis reaction; particularly alcoholysis when the selectivity
promoter is an alcohol,
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and aminolysis when the selectivity promoter is an amine; without the
selectivity promoter of the
present invention, the reaction mechanism may involve hydrolysis which leads
to the undesirable
formation of substantially oxygenated product.
[0066] Generally, the mole ratio of caustic to selectivity promoter is in the
range of
from about 10:1 to about 1:10, preferably the mole ratio of caustic to
selectivity promoter is in
the range of from about 3:1 to about 1:3, and more preferably the mole ratio
of caustic to
selectivity promoter is in the range of from about 2:1 to about 1:2.
[0067] Generally, the mole ratio of caustic and selectivity promoter to
oxidized
heteroatom in the heteroatom-containing hydrocarbon feed oil is in the range
of from about
100:1 to about 1:1, preferably the mole ratio of caustic and selectivity
promoter to oxidized
heteroatom in the heteroatom-containing hydrocarbon feed oil is in the range
of from about 10:1
to about 1:1, and more preferably the mole ratio of caustic and selectivity
promoter to oxidized
heteroatom in the heteroatom-containing hydrocarbon feed oil is in the range
of from about 3:1
to about 1:1. Separation of the heavy caustic phase from the light oil phase
may be by gravity.
Other suitable methods include, but are not limited to, solvent extraction of
the caustic or oil
phases, such as by washing with water, centrifugation, distillation, vortex
separation, and
membrane separation and combinations thereof Trace quantities of caustic and
selectivity
promoter may be removed according to known methods by those skilled in the
art.
[0068] As a result of removing the oxidized heteroatom contaminants from the
oxidized heteroatom-containing hydrocarbon feed and producing few oxygenated
by-products,
the light oil phase product has a lower density and viscosity than the
untreated, contaminated
feed. The heavy caustic phase density is generally in the range of from about
1.0 to about 3.0
g/mL and the light product oil phase density is generally in the range of from
about 0.7 to about
1.1 g/mL.
[0069] Without the selectivity promoter the treated stream contains
substantial
oxygenated by-products. Generally, the method of the present invention
produces less than
about 70% oxygenated by-products, preferably less than about 40% oxygenated by-
products, and
more preferably less than about 20% oxygenated by-products in the treated
stream. This
beneficial effect is more clearly demonstrated in the non-limiting examples
below.
[0070] In the above embodiments, a number of oxidized heteroatom byproducts
have
been observed as a result of the oxidized heteroatom cleavage process. For
example, the
cleavage of oxidized sulfur from oxidized-heteroatom-containing hydrocarbons
has been
observed to result in the formation of a number of oxidized heteroatom
byproducts including, for
example, sulfite and sulfate.
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[0071] As illustrated in Figure 2, an oxidized-heteroatom-containing
hydrocarbon feed
250 is reacted with a caustic (e.g., sodium hydroxide, potassium hydroxide,
eutectic mixtures
thereof etc.) and a selectivity promoter 256 in reactor 251 to produce a
biphasic first intermediate
stream 252. First intermediate stream 252 is transferred to product separator
253 where oxidized
heteroatom byproducts 255 are removed. A hydrocarbon product with reduced
oxidized
heteroatom content 254 is obtained.
[0072] As illustrated in Figure 3, an oxidized-heteroatom-containing
hydrocarbon feed
270 is reacted with a caustic and a selectivity promoter 278 in reactor 271 to
produce a biphasic
first intermediate stream 272. First intermediate stream 272 is then sent to a
product separator
273 where caustic, selectivity promoter and oxidized heteroatom byproduct 275
are removed
from the hydrocarbon stream. Optionally, oxidized heteroatom byproduct 276 may
be
subsequently removed from the caustic and selectivity promoter 278 in recovery
vessel 277,
allowing for reuse of the caustic and selectivity promoter. A hydrocarbon
product with reduced
oxidized heteroatom content 274 is obtained.
[0073] As illustrated in Figure 4, an oxidized-heteroatom-containing
hydrocarbon feed
210 is contacted with a solvent 212 in product separator 211 to produce first
intermediate stream
214 and substantially oxidized heteroatom-free hydrocarbon product stream 213.
First
intermediate stream 214 comprises an oxidized-heteroatom-contaminated
hydrocarbon stream
with an increased oxidized-heteroatom concentration. First intermediate stream
214 is then sent
to solvent extraction vessel 215 where solvent extract 225 is removed to
produce second
intermediate stream 216.
[0074] Second intermediate stream 216 may be reacted with caustic and
selectivity
promoter 224 in reactor vessel 217 to produce a biphasic third intermediate
stream 218. Third
intermediate stream 218 is transferred to second product separator 219 from
which a
hydrocarbon product with reduced oxidized heteroatom content 220 is obtained.
The denser
phase 221 containing the selectivity promoter and caustic and oxidized
heteroatom byproducts
may be transferred to a recovery vessel 223 in which the selectivity promoter
and caustic 224
may be recovered to reactor 217 and the oxidized heteroatom-containing
byproduct 222 may be
sent to a recovery area for further processing, as would be understood by
those skilled in the art.
[0075] As illustrated in Figure 5, a heteroatom-containing hydrocarbon feed 10
may be
combined with an oxidant 11 and subjected to an oxidizing process in an
oxidizer vessel 12 in
order to meet current and future environmental standards. The oxidizer vessel
12 may optionally
contain a catalyst or promoter (not shown).
[0076] After subjecting a hydrocarbon stream to oxidation conditions in
oxidizer vessel
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12, thereby oxidizing at least a portion of the heteroatom compounds (e.g.,
oxidizing
dibenzothiophenes to sulfones), a first intermediate stream 13 may be
generated. The first
intermediate stream 13 may be reacted with caustic (e.g., sodium hydroxide,
potassium
hydroxide, eutectic mixtures thereof etc.) and a selectivity promoter 24 to
produce a biphasic
second intermediate stream 16.
[0077] Second intermediate stream 16 may be transferred to a product separator
18
from which a substantially heteroatom-free hydrocarbon product 20 may be
recovered from the
light phase. The denser phase 21 containing the selectivity promoter and
caustic and oxidized
heteroatom by-products may be transferred to a recovery vessel 22 in which the
selectivity
promoter and caustic 24 may be recovered and recycled to reactor 14 and the
oxidized
heteroatom-containing byproduct 26 may be sent to a recovery area for further
processing, as
would be understood by those skilled in the art.
[0078] In a more specific embodiment, as illustrated in Figure 6A, a
heteroatom-
containing hydrocarbon feed 30 may be combined with a hydroperoxide 32 in a
catalytic
oxidizer 34 thereby oxidizing the heteroatoms yielding a first intermediate
stream 36. First
intermediate stream 36 may be fed to a by-product separator 38 from which the
hydroperoxide
by-product may be recovered and recycled for reuse in catalytic oxidizer 34
(as would be
understood by those skilled in the art) yielding a second intermediate stream
39. The second
intermediate stream 39 may be reacted with a selectivity promoter and caustic
feed 42 in
promoted-caustic visbreaker 40 producing a third intermediate biphasic stream
44 that may be
separated in product separator 46 to produce a substantially heteroatom-free
hydrocarbon
product 48 from the light phase. The dense phase 49 from product separator 46
may be
transferred to heteroatom by-product separator 50 from which a oxidized
heteroatom-containing
byproduct stream 52 and selectivity promoter and caustic feed 42 may be
independently
recovered, as would be known by those skilled in the art.
[0079] In still another embodiment, as illustrated in Figure 6B, the
heteroatom-
containing hydrocarbon feed 30 may be combined with hydroperoxide 32 and
contacted with a
catalyst in catalytic oxidizer 34 yielding first intermediate stream 60 which
may be transferred to
a promoted- caustic visbreaker 40 where it reacts with selectivity promoter
and caustic feed 42
producing a biphasic second intermediate stream 62. Second intermediate stream
62 may be
transferred to a product separator 38 from which a substantially heteroatom-
free hydrocarbon
product stream 48 may be removed as the light phase and transported to storage
or commercial
use. The byproduct separator 54 may separate the dense phase 64 into two
streams: an oxidizied
heteroatom-containing by-product stream 52 (which may be transported to
storage or
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commercial use) and a by-product mixture stream 66 containing the selectivity
promoter, caustic,
and hydroperoxide by-products for recovery and recycle, as would be known by
those skilled in
the art.
[0080] In yet another embodiment, as illustrated in Figure 7, the heteroatom-
containing
hydrocarbon feed 30 may be mixed with a hydroperoxide feed 32 and may be
reacted with a
catalyst or promoter (not shown) in the catalytic oxidizer 34 producing a
first intermediate
stream 36. Stream 36 may be transferred to a by-product separator 38 from
which the
hydroperoxide by-product 37 may be separated producing a second intermediate
stream 70.
Stream 70 may be extracted by solvent 78 in product separator 46 (e.g. a
liquid-liquid extraction
column) from which a substantially heteroatom-free hydrocarbon product 72 may
be withdrawn
resulting in a third intermediate stream 74. Stream 74 may be fed to solvent
recovery 76 from
which solvent 78 may be recovered and recycled to product separator 46,
producing a fourth
intermediate stream 80. Stream 80 may be treated in the promoted-caustic
visbreaker 40
containing selectivity promoter and caustic feed 42 producing a biphasic fifth
intermediate
stream 82. The two phases of stream 82 may be separated in product separator
84 as a light
phase 48 and a dense phase 86. The light phase 48 may comprise a substantially
heteroatom-free
hydrocarbon product that may be shipped to storage or commercial use. The
dense phase 86
may be transferred to a heteroatom by-product separator 88 from which an
oxidized heteroatom-
containing byproduct stream 52 may be separated from resulting in a stream 42
containing a
selectivity promoter and caustic that may be recovered and recycled for reuse
in the promoted-
caustic visbreaker 40, as would be understood by those skilled in the art.
[0081] In still another embodiment, as illustrated in Figure 8, the heteroatom-
containing hydrocarbon feed 30 may be fed to a catalytic oxidizer 34 where it
may be reacted
with catalyst stream 90 in the catalytic oxidizer 34 producing a first
intermediate stream 92.
Stream 92 may be transferred to catalyst separator 94 from which a second
intermediate stream
70 and a depleted catalyst stream 96 may be separated. Stream 96 may be fed to
catalyst
regenerator 98 for regeneration by oxidant feed 100 producing catalyst stream
90 and an oxidant
by-product stream 102. Oxidant by-product stream 102 may be optionally
recovered, recycled,
and reused as would be understood by those skilled in the art. Stream 70 may
be extracted by
solvent 78 in product separator 46 (e.g. a liquid-liquid extraction column)
from which a
substantially heteroatom-free hydrocarbon product 72 may be withdrawn
resulting in a third
intermediate stream 74. Stream 74 may be fed to solvent recovery 76 from which
solvent 78
may be recovered and recycled to product separator 46, producing a fourth
intermediate stream
80. Stream 80 may be treated in the promoted-caustic visbreaker 40 containing
selectivity
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promoter and caustic feed 42 producing a biphasic fifth intermediate stream
82. The two phases
of stream 82 may be separated in product separator 84 as a light phase 48 and
a dense phase 86.
The light phase 48 may comprise a substantially heteroatom-free hydrocarbon
product that may
be shipped to storage or commercial use. The dense phase 86 may be transferred
to a heteroatom
by-product separator 88 from which an oxidized heteroatom-containing byproduct
stream 52
may be separated from resulting in a stream 42 containing a selectivity
promoter and caustic that
may be recovered and recycled for reuse in the promoted-caustic visbreaker 40,
as would be
understood by those skilled in the art.
[0082] Figure 9 illustrates how the selectively of the reaction of the present
disclosure
is improved to form more valuable products. Dibenzothiophene sulfone was
chosen as a model
sulfur compound because most of the sulfur in an average diesel fuel is in the
form of substituted
or unsubstituted dibenzothiophene. Equation (1) illustrates how hydroxide
attacks the sulfur
atom of dibenzothiophene sulfone (A), forming biphenyl-2-sulfonate (B).
Equation (2)
illustrates how hydroxide may attack B at the carbon atom adjacent to the
sulfur atom, forming
biphenyl-2-ol (C) and sulfite salts (D). Compound C may ionize in basic media,
and may
dissolve in the aqueous or molten salt layer. Equation (3) illustrates how
hydroxide may attack
the sulfur atom of B to form biphenyl (E) and sulfate salts (F). Equation (4)
illustrates how, in
the presence of a primary alcohol, including, but not limited to, methanol,
methoxide ions
generated in-situ may attack the carbon atom, forming ether compounds, such as
2-
methoxybiphenyl (G). Equation (5) illustrates the reaction of dibenzothiophene
sulfone with
alkoxides alone, not in the presence of hydroxide, as taught by Aida et al, to
form bipheny1-2-
methoxy-2'-sulfinate salt (H), which may be substantially soluble in the
caustic. Using aqueous
or molten hydroxide without the presently disclosed selectivity promoter will
cause reaction (1)
to occur, followed predominantly by reaction (2). When the vicinal diol
selectivity promoter
disclosed herein is used, reaction (1) occurs, followed predominantly by
reaction (3). When the
primary selectivity promoter (alcohol) disclosed herein is used, reaction (1)
occurs, followed
predominantly by reaction (4). It can be seen that the hydrogen atoms that
become attached to
biphenyl come from hydroxide. When water is used in the regeneration of the
caustic, the
ultimate source of the hydrogen atoms added to the biphenyl may be water.
[0083] The following non-limiting examples illustrate certain aspects of the
present
invention.
[0084] Examples
[0085] Example 1
[0086] Preparation of Pelletized Polymeric Titanyl Catalyst
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[0087] A dimethyl sulfoxide (DMSO) solution of co-monomer (e.g. 4,4'-bisphenol
A
dianhydride (BPADA)) is prepared and is combined with a DMSO solution of the
titanyl (e.g.
bis(glycerol)oxotitanium(IV)) with stirring at 70 C for about 4 hrs to produce
a copolymer
solution. Then, the solution is cooled to room temperature, and the polymer
product is
precipitated with excess acetone. The polymeric precipitate is collected by
vacuum filtration and
is dried. The yield of precipitated polymeric titanyl catalyst is greater than
90%.
[0088] A blend of bonding agent (Kynar0), optional inert filler (silica or
alumina), and
the polymeric titanyl catalyst is prepared in a solid mixer or blender. The
blended mixture is
then extruded or pelletized by compression producing uniform catalyst pellets
with hardness test
strength preferably greater than 2 kp.
[0089] Example 2
[0090] Continuous Catalytic Removal of Heteroatoms from a Heteroatom-
contaminated Light Atmospheric Gas Oil
[0091] Straight- run light atmospheric gas oil (LAGO) (3.45 % sulfur) and
cumene
hydroperoxide (30% in cumene, fed at a rate of 2.1 mole equivalents to sulfur
in LAGO feed) are
fed to a fixed bed reactor containing pelletized titanyl polymeric catalyst,
prepared in accordance
with Example 1, at about 85 C with a combined LHSV of about 1.0 hr-1 producing
a first
intermediate stream. The first intermediate stream is vacuum distilled at -25
in Hg to remove
and recover a low boiling distillate comprising cumene, cumyl alcohol, alpha-
methylstyrene, and
acetophenone from a heavy second intermediate stream. The heavy second
intermediate stream
essentially comprises light atmospheric gas oil with oxidized heteroatom
compounds. The
second intermediate stream is then fed into a heated reactor wherein it
combines with a feed
stream containing caustic and ethylene glycol (the combined liquid residence
time is 1.0 hr-1) to
produce a biphasic mixture that exits the reactor. The biphasic mixture is
then separated by
gravity to produce a light phase product comprising essentially heteroatom-
free LAGO and a
heavy phase by-product stream comprising essentially caustic, ethylene glycol,
and heteroatom-
containing salts. Sulfur removal from the light phase product is greater than
50%, nitrogen
removal is greater than 50%, vanadium removal is greater than 50%, nickel
removal is greater
than 50%, and iron removal is greater than 50% when the samples are measured
for elemental
composition and compared against the LAGO feed composition. The heavy phase by-
product is
further treated according to known methods to recover and recycle the caustic
and ethylene
glycol from the heteroatom by-products.
[0092] Examples 3-12
[0093] Desulfonylation Using Hydroxide and Various Alcohols
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[0094] A mixture of dibenzothiophene sulfone in 1,2,3,4-tetrahydronaphthalene
is
reacted with six molar equivalents of various alcohols, three molar
equivalents sodium
hydroxide, and three molar equivalents potassium hydroxide. Reactions are
performed at 275 C
for one hour. The products of the reaction are acidified with aqueous
hydrochloric acid, and then
extracted with dichloromethane. The dichloromethane extract is analyzed by
high pressure liquid
chromatography ( HPLC) to determine percent conversion of dibenzothiophene
sulfone, and
mole percent yield of biphenyl and ortho-phenylphenol. The results are given
below in Table 1.
Example Alcohol
Biphenyl o-Phenylphenol Conversion
3 None 7% 64% 93%
4 Ethylene Glycol 65% 9% 89%
Propylene Glycol 37% 17% 99%
6 Glycerol 41% 51% 99%
7 1,3-Propanediol 16% 45% 95%
8 Pinacol 13% 56% 100%
9 Ethanolamine 20% 21% 100%
Diethanolamine 47% 27% 97%
11 Triethanolamine 41% 32% 100%
12 4-(2- 8% 31% 100%
hydroxyethyl)morpholine
[0095] Examples 13-26
[0096] Desulfonylation Using Phenoxide and Various Alcohols
[0097] A mixture of dibenzothiophene sulfone in 1,2,3,4-tetrahydronaphthalene
is
reacted with six molar equivalents of various alcohols, and six molar
equivalents of sodium
phenoxide monohydrate. Reactions are performed at 300 C for fifteen minutes.
The products of
the reaction are acidified with aqueous hydrochloric acid, and then extracted
with
dichloromethane. The dichloromethane extract is analyzed by HPLC to determine
percent
conversion of dibenzothiophene sulfone, and mole percent yield of biphenyl and
ortho-
phenylphenol. The results are given below in Table 2.
Example Alcohol
Biphenyl o-Phenylphenol Conversion
13 None 1% 5% 77%
14 Ethylene Glycol 23% 59% 97%
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15 Propylene Glycol 32% 20% __
97%
16 Glycerol 19% 18% 59%
17 1,3-Propanediol 25% 7% 79%
18 Pinacol 4% 4% 35%
19 Ethanolamine 23% 18% 91%
20 Diethanolamine 20% 50% 85%
21 Triethanolamine 19% 26%
100%
22 4-(2- 5% 33% 71%
hydroxyethyl)morpholine
23 Methanol 15% 9% 42%
24 t-Butanol 10% 9% 42%
25 Catechol 0% 0% 0%
26 Hydroquinone 40% 5% 95%
[0098] Examples 27-38
[0099] Desulfonylation Using Acetate and Various Alcohols
[00100] A mixture of dibenzothiophene sulfone in 1,2,3,4-tetrahydronaphthalene
is
reacted with six molar equivalents of various alcohols, and six molar
equivalents of a salt
mixture comprising 57 mole % cesium acetate and 43 mole % potassium acetate.
Reactions are
performed at 300 C for fifteen minutes. The products of the reaction are
acidified with aqueous
hydrochloric acid, and then extracted with dichloromethane. The
dichloromethane extract is
analyzed by HPLC to determine percent conversion of dibenzothiophene sulfone,
and mole
percent yield of biphenyl and ortho-phenylphenol. The results are given below
in Table 3.
Example Alcohol
Biphenyl o-Phenylphenol Conversion
27 None 0% 0% 0%
28 Ethylene Glycol 19% 6% 35%
29 Propylene Glycol 26% 3% 88%
30 Glycerol 3% 2% 70%
31 1,3-Propanediol 12% 7% 84%
32 Pinacol 0% 0% 54%
33 Ethanolamine 24% 5% 50%
34 Diethanolamine 35% 9% 69%
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35 Triethanolamine 41% 13% 79% _____
36 Cellulose Powder 14% 0% 25%
37 Methanol 8% 5% 37%
38 t-Butanol 0% 0% 11%
[00101] Examples 39-45
[00102] Desulfonylation Using Ethylene Glycol and Various Nucleophiles.
[00103] A mixture of dibenzothiophene sulfone in 1,2,3,4-tetrahydronaphthalene
is
reacted with six molar equivalents of ethylene glycol, and six molar
equivalents of various
nucleophiles. Example 41 used the following molar equivalents to
dibenzothiophene sulfone: 1.8
molar equivalents sodium hydroxide, 1.8 molar equivalents potassium hydroxide,
0.7 molar
equivalents sodium sulfide nonahydrate and 3.5 molar equivalents ethylene
glycol. Reactions are
performed at 300 C for fifteen minutes. The products of the reaction are
acidified with aqueous
hydrochloric acid, and then extracted with dichloromethane. The
dichloromethane extract is
analyzed by HPLC to determine percent conversion of dibenzothiophene sulfone,
and mole
percent yield of biphenyl and ortho-phenylphenol. The results are given below
in Table 4.
Example Nucleophile
Biphenyl o-Phenylphenol Conversion
39 None 0 0 0
40 Sodium sulfide 55 3 87
nonahydrate
41 Sodium sulfide 76 13 98
nonahydrate, sodium
hydroxide, potassium
hydroxide
42 Potassium t-butoxide 40 23 100
43 Sodium methoxide 3 0 69
44 Sodium hydrosulfide 3 0 89
45 Sodium thiophenolate 4 3 98
monohydrate
[00104] Examples 46-48
[00105] Desulfonylation Using Hydroxide, Sulfide, and Ethylene Glycol
[00106] A mixture of an aromatic sulfone in 1,2,3,4-tetrahydronaphthalene is
reacted
with 3.5 molar equivalents of ethylene glycol, 1.8 molar equivalents of a
sodium hydroxide, 1.8
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molar equivalents of potassium hydroxide, and 0.7 molar equivalents of sodium
sulfide
nonahydrate. Reactions are performed at 275 C for sixty minutes. The products
of the reaction
are acidified with aqueous hydrochloric acid, and then extracted with
dichloromethane. The
dichloromethane extract is analyzed by HPLC to determine percent conversion of
sulfone, and
mole percent yield of organic products as compared to the initial moles of
starting sulfone. The
results are given below in Table 5.
Example Sulfone Conversion Products (mole percent)
46 Diphenyl sulfone 16% Benzene (6%)
Phenol (0.7%)
47 Thianthrene disulfone 100% Benzene
(99%)
Phenol (30%)
Biphenyl (0.3%)
Dibenzothiophene sulfone (3%)
48 Benzothiophene sulfone 100% Styrene
(1.3%)
[00107] Examples 49-51
[00108] Desulfonylation Using Phenoxide, and Propylene Glycol
[00109] A mixture of an aromatic sulfone in 1,2,3,4-tetrahydronaphthalene is
reacted
with six molar equivalents of propylene glycol, and six molar equivalents of
sodium phenoxide
monohydrate. Reactions are performed at 275 C for sixty minutes. The products
of the reaction
are acidified with aqueous hydrochloric acid, and then extracted with
dichloromethane. The
dichloromethane extract is analyzed by HPLC to determine percent conversion of
sulfone, and
mole percent yield of organic products as compared to the initial moles of
starting sulfone. The
results are given below in Table 6.
Example Sulfone Conversion Products (mole percent)
49 Diphenyl sulfone 32% Benzene
(61%)
Biphenyl (1%)
50 Thianthrene disulfone 100% Benzene
(78%)
Diphenyl sulfone (3%)
Dibenzothiophene sulfone (0.5%)
51 Benzothiophene sulfone 100% Styrene (17%)
[00110] Examples 52-54
[00111] Desulfonylation Using Acetate and Triethanolamine
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[00112] An aromatic sulfone is reacted with twelve molar equivalents of
triethanolamine, and twelve molar equivalents of a salt mixture comprised of
57 mole % cesium
acetate and 43 mole % potassium acetate. Reactions are performed at 275 C for
sixty minutes.
The products of the reaction are acidified with aqueous hydrochloric acid, and
then extracted
with dichloromethane. The dichloromethane extract is analyzed by HPLC to
determine percent
conversion of sulfone, and mole percent yield of organic products as compared
to the initial
moles of starting sulfone. The results are given below in Table 7.
Example Sulfone Conversion Products (mole percent)
52 Diphenyl sulfone 69% Benzene (118%)
Biphenyl (1%)
Phenol (2%)
Dibenzothiophene sulfone (2%)
53 Thianthrene disulfone 100% Benzene (30%)
Phenol (3%)
Diphenyl sulfone (29%)
Dibenzothiophene sulfone (5%)
Biphenyl (1%)
Benzene sulfonate (29%)
Dibenzothiophene (3)
54 Benzothiophene sulfone 100% Styrene (13%)
[00113] Example 55
[00114] Oxidation of Nitrogen Compounds
[00115] The oxidation of model nitrogen compounds (e.g., pyridine, quinolone,
isoquinoline) was carried out by first dissolving the compounds to a dilution
of 3mg/g in 35%
tert-butyl hydroperoxide in toluene. The samples were then heated in a water
bath to 95 C. Once
this temperature was reached, silica supported titanyl catalyst was added at a
ratio of lml catalyst
to lg oxidant. Lastly, the solutions were lightly agitated at 95 C for a
maximum of 4 hours, in
which full conversion of nitrogen compound to N-oxide was observed.
[00116] The foregoing description of the embodiments of this invention has
been
presented for purposes of illustration and description. It is not intended to
be exhaustive or to
limit the invention to the precise form disclosed, and obviously, many
modifications and
variations are possible. Such modifications and variations that may be
apparent to a person
skilled in the art are intended to be included within the scope of the above
described invention.
