U.S. patent application number 15/090912 was filed with the patent office on 2016-10-13 for decreasing fouling in hydrocarbon-based fluids.
This patent application is currently assigned to BAKER HUGHES INCORPORATED. The applicant listed for this patent is BAKER HUGHES INCORPORATED. Invention is credited to Thomas J. Falkler, Roger D. Metzler.
Application Number | 20160298039 15/090912 |
Document ID | / |
Family ID | 57072922 |
Filed Date | 2016-10-13 |
United States Patent
Application |
20160298039 |
Kind Code |
A1 |
Falkler; Thomas J. ; et
al. |
October 13, 2016 |
DECREASING FOULING IN HYDROCARBON-BASED FLUIDS
Abstract
An effective amount of at least one first component and an
effective amount of at least one second component may contact a
hydrocarbon-based fluid or be introduced into a hydrocarbon-based
fluid having at least one foulant for decreasing the fouling by the
foulant(s) as compared to an otherwise identical hydrocarbon-based
fluid absent the first component(s) and second component(s). The
first component(s) may be considered a dispersant, and the second
component(s) may be considered free radical inhibitors in a
non-limiting embodiment.
Inventors: |
Falkler; Thomas J.;
(Missouri City, TX) ; Metzler; Roger D.; (Sugar
Land, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BAKER HUGHES INCORPORATED |
Houston |
TX |
US |
|
|
Assignee: |
BAKER HUGHES INCORPORATED
Houston
TX
|
Family ID: |
57072922 |
Appl. No.: |
15/090912 |
Filed: |
April 5, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62144649 |
Apr 8, 2015 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 47/00 20130101;
C10G 75/04 20130101; C10G 2300/80 20130101 |
International
Class: |
C10G 75/04 20060101
C10G075/04 |
Claims
1. A method for decreasing fouling during the refining of a
hydrocarbon-based fluid comprising at least one foulant; wherein
the method comprises: contacting the hydrocarbon-based fluid with
an effective amount of at least one first component to decrease
fouling by the at least one foulant; wherein the at least one first
component is selected from the group consisting of an acrylate
vinyl pyrolidinone copolymer, a succinimide, an alpha olefin and
maleic anhydride reaction product, a reaction product from nonyl
phenol reaction with ethylene diamine, a C.sub.24-C.sub.28 olefin
and maleic anhydride copolymer, a Mannich reaction product, a
dodecyl/tert-octyl phenol resin, a sulfonic acid, an inorganic
overbase, and combinations thereof; contacting the
hydrocarbon-based fluid with an effective amount of at least one
second component to decrease fouling by the at least one foulant;
wherein the at least one second component is selected from the
group consisting of 2,6-di-tert-butyl-4-methylphenol;
4-sec-butyl-2,6-di-tert-butylphenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; quinones;
amino-para-cresols; and combinations thereof; wherein the
contacting the hydrocarbon-based fluid with the at least one first
component and the at least one second component occurs at the same
time or a different time; and decreasing the fouling by the at
least one foulant within the hydrocarbon-based fluid as compared to
an otherwise identical hydrocarbon-based fluid absent the
contacting the hydrocarbon-based fluid with the at least one first
component and the at least one second component.
2. The method of claim 1, wherein the contacting the
hydrocarbon-based fluid with the at least one first component
occurs at a location selected from the group consisting of upstream
from an ebullated bed hydrocracking unit, into an ebullated bed
hydrocracking unit, into an interstage separator, into a vacuum
distillation unit, into an atmospheric distillation unit, and
combinations thereof.
3. The method of claim 1, wherein the contacting the
hydrocarbon-based fluid with the at least one second component
occurs at a location selected from the group consisting of upstream
from an ebullated bed hydrocracking unit, into an ebullated bed
hydrocracking unit, into an interstage separator, into a vacuum
distillation unit, into an atmospheric distillation unit, and
combinations thereof.
4. The method of claim 1, wherein the hydrocarbon-based fluid is
selected from the group consisting of a crude oil, a bitumen, a
shale oil, a tight oil, a refinery fluid, and combinations
thereof.
5. The method of claim 4, wherein the hydrocarbon-based fluid is a
crude oil blend having at least two different crude oils.
6. The method of claim 1, wherein the effective amount of the at
least one first component ranges from about 0.1 ppm to about 10,000
ppm based on the total amount of the hydrocarbon-based fluid.
7. The method of claim 1, wherein the effective amount of the at
least one second component ranges from about 0.1 ppm to about
10,000 ppm based on the total amount of the hydrocarbon-based
fluid.
8. The method of claim 1, wherein the at least one foulant is
selected from the group consisting of asphaltenes, coke precursors,
coke, polyolefins, and combinations thereof.
9. A method for decreasing fouling during the refining of a
hydrocarbon-based fluid comprising at least one foulant; wherein
the method comprises: introducing an additive into the
hydrocarbon-based fluid in an amount ranging from about 0.1 ppm to
about 10,000 ppm based on the total amount of the hydrocarbon-based
fluid to decrease fouling by the at least one foulant; wherein the
additive comprises at least one first component and at least one
second component; wherein the at least one first component is
selected from the group consisting of an acrylate vinyl
pyrolidinone copolymer, a succinimide, an alpha olefin and maleic
anhydride reaction product, a reaction product from nonyl phenol
reaction with ethylene diamine, a C.sub.24-C.sub.28 olefin and
maleic anhydride copolymer, a Mannich reaction product, a
dodecyl/tert-octyl phenol resin, a sulfonic acid, an inorganic
overbase, and combinations thereof; wherein the at least one second
component is selected from the group consisting of
2,6-di-ter-butyl-4-methylphenol,
4-sec-butyl-2,6-di-tert-butylphenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; quinones;
amino-para-cresols; and combinations thereof; and decreasing the
fouling by the at least one foulant within the hydrocarbon-based
fluid as compared to an otherwise identical hydrocarbon-based fluid
absent the introducing the additive into the hydrocarbon-based
fluid; wherein the hydrocarbon-based fluid is selected from the
group consisting of a crude oil, a bitumen, a shale oil, a tight
oil, a refinery fluid, and combinations thereof.
10. The method of claim 9, wherein the introducing the additive
into the hydrocarbon-based fluid occurs at a location selected from
the group consisting of upstream from an ebullated bed
hydrocracking unit, into an ebullated bed hydrocracking unit, into
an interstage separator, into a vacuum distillation unit, into an
atmospheric distillation unit, and combinations thereof.
11. The method of claim 9, wherein the hydrocarbon-based fluid is a
crude oil blend having at least two different crude oils.
12. The method of claim 9, wherein the at least one foulant is
selected from the group consisting of asphaltenes, coke precursors,
coke, polyolefins, and combinations thereof.
13. A treated hydrocracked hydrocarbon-based fluid composition
comprising: a hydrocarbon-based fluid selected from the group
consisting of a crude oil, a bitumen, a shale oil, a tight oil, a
refinery fluid, and combinations thereof; at least one first
component in an amount ranging from about 0.1 ppm to about 10,000
ppm based on the total amount of the hydrocarbon-based fluid;
wherein the at least first component is selected from the group
consisting of an acrylate vinyl pyrolidinone copolymer, a
succinimide, an alpha olefin and maleic anhydride reaction product,
a reaction product from nonyl phenol reaction with ethylene
diamine, a C.sub.24-C.sub.28 olefin and maleic anhydride copolymer,
a Mannich reaction product, a dodecyl/tert-octyl phenol resin, a
sulfonic acid, an inorganic overbase, and combinations thereof; at
least one second component in an amount ranging from about 0.1 ppm
to about 10,000 ppm based on the total amount of the
hydrocarbon-based fluid; wherein the at least one second component
is selected from the group consisting of
2,6-di-ter-butyl-4-methylphenol;
4-sec-butyl-2,6-di-tert-butylphenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; quinones;
amino-para-cresols; and combinations thereof; at least one foulant;
and wherein the treated hydrocracked hydrocarbon-based fluid
composition comprises a decreased amount of the at least one
foulant as compared to an otherwise identical hydrocracked
hydrocarbon-based fluid composition absent the at least one first
component and the at least one second component.
14. The composition of claim 13, wherein the treated hydrocracked
hydrocarbon-based fluid is present at a location selected from the
group consisting of upstream from an ebullated bed hydrocracking
unit, into an ebullated bed hydrocracking unit, into an interstage
separator, into a vacuum distillation unit, into an atmospheric
distillation unit, and combinations thereof.
15. The composition of claim 13, wherein the hydrocarbon-based
fluid is a crude oil is a crude oil blend having at least two
different crude oils.
16. The composition of claim 13, wherein the at least one foulant
is selected from the group consisting of asphaltenes, coke
precursors, coke, polyolefins, and combinations thereof.
17. A treated hydrocracked hydrocarbon-based fluid composition
comprising: a crude oil; at least one first component selected from
the group consisting of an acrylate vinyl pyrolidinone copolymer, a
succinimide, an alpha olefin and maleic anhydride reaction product,
a reaction product from nonyl phenol reaction with ethylene
diamine, a C.sub.24-C.sub.28 olefin and maleic anhydride copolymer,
a Mannich reaction product, a dodecyl/tert-octyl phenol resin, a
sulfonic acid, an inorganic overbase, and combinations thereof; at
least one second component selected from the group consisting of
2,6-di-ter-butyl-4-methylphenol;
4-sec-butyl-2,6-di-tert-butylphenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; quinones;
amino-para-cresols; and combinations thereof; at least one foulant;
wherein the volume ratio of the at least one first component to the
at least one second component ranges from about 1:1 to about 1:20;
and wherein the treated hydrocracked hydrocarbon-based fluid
composition comprises a decreased amount of the at least one
foulant as compared to an otherwise identical hydrocracked
hydrocarbon-based fluid composition absent the at least one first
component and the at least one second component.
18. The composition of claim 17, wherein the crude oil is a crude
oil blend having at least two different crude oils.
19. The composition of claim 17, wherein the at least one foulant
is selected from the group consisting of asphaltenes, coke
precursors, coke, and combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional
Patent Application Ser. No. 62/144,649 filed Apr. 8, 2015,
incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] The present invention relates to methods and compositions
for decreasing or preventing fouling of a hydrocarbon-based fluid,
and more specifically relates to methods and compositions for
decreasing foulants within hydrocarbon-based fluids in a
refinery.
BACKGROUND
[0003] As the price or shortage of high quality crude oil
increases, there will be an ever-increasing demand to find ways to
better exploit lower quality feedstocks and extract fuel values
therefrom. Lower quality feedstocks may have relatively high
quantities of foulants, such as asphaltenes, coke, and coke
pre-cursors, acid gases, carbon dioxide (CO.sub.2), hydrogen
sulfide (H.sub.2S), mercaptans (R--SH), which are difficult to
process and commonly cause fouling of conventional catalysts and
hydroprocessing equipment. As more economical ways to process lower
quality feedstocks become available, such feedstocks may possibly
catch, or even surpass, higher quality crude oils, in the
not-too-distant future, as the primary source of refined fossil
fuels used to operate automobiles, trucks, farm equipment,
aircraft, and other vehicles that rely on internal combustion.
[0004] Hydrocracking is used in the petroleum industry to process
crude oil and/or other petroleum products for commercial use by
preventing or inhibiting the fouling by the foulants. Hydrocracking
is a catalytic cracking process using an elevated partial pressure
of hydrogen gas to purify the hydrocarbon stream. Ebullated-bed
hydrocracking is one type of hydrocracking that may be used for
resid conversion, and the ebullated-bed hydrocrackers may have a
continuous addition and/or removal of catalysts. However,
hydrocracking is subject to asphaltene precipitation as the
saturates and aromatics contained in the hydrocarbon-based fluid
that hold the asphaltenes in solution are removed or converted,
which is driven by asphaltene-solubility chemistry. Fouling may
occur downstream from the ebullated bed hydrocracker reactor, such
as in bottom stream areas, atmospheric column bottoms,
vacuum-column bottoms, vacuum-column furnaces, high- and
mid-pressure separators, and the like. Extensive fouling may result
in unplanned shutdowns, downtime and lost production and
consequently increased operating costs.
[0005] Conversion reaction rates (thermal cracking), leading to
fouling by asphaltenes decomposition, increase more rapidly with
rising temperatures compared to the hydrogen-saturation reactions
that inhibit sediment formation. Accordingly, temperatures and
conversions above pre-determined limits may lead to uncontrolled
sediments and coke generation. However, operating below the
pre-determined limits only results in lost conversion with no major
advantages in terms of sediment deposition control and run
lengths.
[0006] Asphaltenes are most commonly defined as that portion of
petroleum, which is soluble in xylene and toluene, but insoluble in
heptane or pentane. Asphaltenes exist in crude oil as both soluble
species and in the form of colloidal dispersions stabilized by
other components in the crude oil. Asphaltenes have higher
molecular weights and are the more polar fractions of crude oil,
and can precipitate upon pressure, temperature, and compositional
changes in crude oil resulting from blending or other mechanical or
physicochemical processing. Asphaltene precipitation and deposition
can cause problems in subterranean reservoirs, upstream production
facilities, mid-stream transportation facilities, refineries, and
fuel blending operations. In petroleum production facilities,
asphaltene precipitation and deposition can occur in near wellbore
reservoir regions, wells, flowlines, separators, and other
equipment. Once deposited, asphaltenes present numerous problems
for crude oil producers. For example, asphaltene deposits can plug
downhole tubulars, wellbores, choke off pipes and interfere with
the functioning of safety shut-off valves, and separator equipment.
Asphaltenes have caused problems in refinery processes such as
desalters, crude oil distillation preheat units, and cokers.
[0007] In addition to carbon and hydrogen in the composition,
asphaltenes may contain nitrogen, oxygen and sulfur species, and
may also contain metal species such as nickel, vanadium, and iron.
Typical asphaltenes are known to have different solubilities in the
formation fluid itself or in certain solvents like carbon disulfide
or aromatic solvents, such as benzene, toluene, xylene, and the
like. However, the asphaltenes are insoluble in solvents like
paraffinic compounds, including but not limited to pentane,
heptane, octane, etc. Asphaltene stability can even be disturbed by
mixing hydrocarbon-based fluids i.e. such as mixing two types of
crude oils together, two types of shale oils together, condensates,
and others, of different origins at certain ratios as the chemistry
of the hydrocarbon-based fluids from different sources may be
incompatible and induce destabilization of the asphaltenes therein.
In non-limiting examples, such as during refining or fuel blending,
two or more hydrocarbon-based fluids may be mixed together.
Sometimes, changes in physical conditions are sufficient to induce
destabilization, or even the mixture of different hydrocarbon-based
fluids that have incompatible chemistries. Said differently, even
if neither hydrocarbon-based fluid, alone, has destabilized
foulants or the hydrocarbon-based fluid would not act as a
destabilizing additive by itself, the mixing or the mixture of two
or more hydrocarbon-based fluids may destabilize the foulants
present in either hydrocarbon-based fluid.
[0008] Coke is an insoluble organic portion of crude oil,
distillation residua, or residua from thermal/catalytic conversion
processes, such as including, but not limited to, visbreaker tar or
LC finer/H oil residuum. Coke may have polyaromatic hydrocarbons
(PAHs) dispersed therein with a ring structure of about 4 to about
5 or more condensed aromatic rings.
[0009] Coke precursors are the fragments that make up the coke.
They are often formed by thermal cracking, dealkylation and/or
dehydrogenation processes commonly used for the breaking down of
complex organic molecules. They are barely soluble in the crude oil
and/or residual, but they tend to precipitate. Once they
precipitate, the coke precursors tend to polymerize or conglomerate
and form coke.
[0010] Accordingly, there are large incentives to mitigate fouling
during refining. There are large costs associated with shutting
down production units because of the foulants within, as well as
the cost to clean the units. The foulants may create an insulating
effect within the production unit, reduce the efficiency and/or
reactivity, and the like. In either case, reducing the amount of
fouling would reduce the cost to produce hydrocarbon-based fluids
and the products derived therefrom.
[0011] Conventional individual antifoulants have not been working
well to improve fouling control in refinery processes running
shale, tight oils and/or blends with tight oils. The fouling
mechanisms of shale oils are not as well defined or understood. It
is suspected that some of the foulant precursors or initiators may
be below detection limits, or that they are more intermittent in
nature, which makes the discovery and definition of the mechanism
more difficult.
[0012] There is an ongoing need to prevent or inhibit the fouling
by the foulants in a hydrocarbon-based fluid.
SUMMARY
[0013] There is provided, in one form, a method for decreasing
fouling during the refining of a hydrocarbon-based fluid comprising
at least one foulant. The method may include contacting the
hydrocarbon-based fluid with an effective amount of at least one
first component and an effective amount of at least one second
component to decrease fouling by the at least one foulant as
compared to an otherwise identical hydrocarbon-based fluid absent
the first component(s) and the second component(s). The contacting
of the hydrocarbon-based fluid with the first component(s) and the
second component(s) may occur at the same time or a different time.
The first component(s) may be or include an acrylate vinyl
pyrolidinone copolymer, a succinimide, an alpha olefin and maleic
anhydride reaction product, a reaction product from nonyl phenol
reaction with ethylene diamine, a C.sub.24-C.sub.28 olefin and
maleic anhydride copolymer, a Mannich reaction product, a
dodecyl/tert-octyl phenol resin, a sulfonic acid, an inorganic
overbase, and combinations thereof. The second component(s) may be
or include N,N'-di-sec-butyl-p-phenylenediamine;
2,6-di-ter-butyl-4-methylphenol;
4-sec-butyl-2,6-di-tert-butyl-phenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; blend of
substituted p-phenylenediamines; quinones; amino-para-cresols; and
combinations thereof.
[0014] In an alternative non-limiting embodiment, a treated
hydrocracked hydrocarbon-based fluid composition is provided that
may include a hydrocarbon-based fluid, at least one first component
in an amount ranging from about 0.1 ppm by volume to about 10,000
ppm based on the total treated fluid, at least one second component
in an amount ranging from about 0.1 ppm to about 10,000 ppm based
on the total treated fluid, and at least one foulant. The
hydrocarbon-based fluid may be or include a crude oil, a bitumen, a
shale oil, a tight oil, a refinery fluid, and combinations thereof.
The first component(s) may be or include an acrylate vinyl
pyrolidinone copolymer, a succinimide, an alpha olefin and maleic
anhydride reaction product, a reaction product from nonyl phenol
reaction with ethylene diamine, a C.sub.24-C.sub.28 olefin and
maleic anhydride copolymer, a Mannich reaction product, a
dodecyl/tert-octyl phenol resin, a sulfonic acid, an inorganic
overbase, and combinations thereof. The second component(s) may be
or include N,N'-di-sec-butyl-p-phenylenediamine;
2,6-di-ter-butyl-4-methylphenol;
4-sec-butyl-2,6-di-tert-butylphenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; blend of
substituted p-phenylenediamines; quinones; amino-para-cresols; and
combinations thereof.
[0015] The first component(s) and the second component(s) appear to
decrease the amount of fouling by the foulant(s) as compared to an
otherwise identical hydrocarbon-based fluid absent both the first
component(s) and the second component(s).
BRIEF DESCRIPTION OF THE DRAWING
[0016] FIG. 1 is a graph depicting the stability of four different
samples in the presence or absence of various components.
DETAILED DESCRIPTION
[0017] It has been discovered that an effective amount of at least
one first component and at least one second component may decrease
and/or inhibit at least one foulant within a hydrocarbon-based
fluid by contacting the hydrocarbon-based fluid with the first and
second component(s) or introducing the component(s) into the
hydrocarbon-based fluid. The foulant(s) may be or include, but are
not limited to, asphaltenes, coke precursors, coke, polyolefins,
and combinations thereof. Inorganic materials such as carbon
dioxide, hydrogen sulfide, mercaptans, carbonyl derivatives, and
combinations thereof, if present can contribute to the total
foulant content, but in non-limiting embodiment, can contribute to
the total foulant content, but are generally thought to be caught
in the organic matrix. The method thus reduces the potential of the
inorganic materials to deposit and cause fouling. The formation of
the organic matrix and the potential of the inorganic materials to
deposit is reduced.
[0018] The first component(s) and second component(s) may decrease,
prevent, and/or inhibit the fouling by the foulant(s) therein as
compared to an otherwise identical hydrocarbon-based fluid absent
both the first component(s) and second component(s). In one
non-limiting embodiment, the first component(s) can increase the
dispersion of the foulant(s) within the hydrocarbon-based fluid.
Use of the first component(s) can be dosed into the hydrocracking
fluid and decrease the aggregation and/or precipitation of the
foulant(s) in a non-limiting embodiment. The second component(s)
can inhibit the free radicals produced from the foulant(s).
[0019] "Inhibit" is defined herein to mean that the antifoulant(s)
may suppress or reduce the amount of total fouling by the
foulant(s) within the hydrocarbon-based fluid, assuming there are
foulant(s) present within the fluid. That is, it is not necessary
for fouling to be entirely prevented for the methods and
compositions discussed herein to be considered effective, although
complete prevention is a desirable goal. Moreover, the fouling by
the foulant(s) may be prevented or inhibited by decreasing the
ability of the foulant(s) from polymerizing or otherwise
agglomerating, reducing the ability of the foulant(s) to form
deposits or precipitates, and the like.
[0020] The methods described are considered successful if the first
component(s) and the second component(s) together decrease an
amount of fouling than would otherwise occur in the absence of the
first and second components. Alternatively, success is obtained if
a majority of the fouling is decreased or inhibited or inactivated,
i.e. at least 51 wt %, alternatively from about 70 wt %
independently to about 99.9 wt %, or from about 90 wt %
independently to about 96 wt % in another non-limiting
embodiment.
[0021] The foulants may or may not already exist in the
hydrocarbon-based fluid prior to refining (e.g. hydrocracking) of
the hydrocarbon-based fluid. In one non-limiting example,
asphaltenes may crack and/or polymerize during the reaction process
of hydrocracking. Thus, regardless of whether the foulant(s) are
present in the hydrocarbon-based fluid before or after
hydrocracking, the foulant(s) may precipitate, or the asphaltenes
may form into coke precursors and possibly coke, in a non-limiting
embodiment.
[0022] The first component(s) may be or include, but is not
necessarily limited to, an acrylate vinyl pyrolidinone copolymer, a
succinimide, an alpha olefin and maleic anhydride reaction product,
a reaction product from nonyl phenol reaction with ethylene diamine
(EDA), a C.sub.24-C.sub.28 olefin and maleic anhydride copolymer, a
Mannich reaction product, a dodecyl/tert-octyl phenol resin, a
sulfonic acid, an inorganic overbase, and combinations thereof.
Non-limiting examples of the Mannich reaction product may be or
include, but are not necessarily limited to tetraethylenepentamine
(TEPA), aromatic amine derivatives, poly alkyl amine, and
combinations thereof. Non-limiting examples of the sulfonic acid
may be or include dodecylbenzenesulfonic acid (DDBSA),
polyalkylsulfonic acid, polyaromaticsulfonic acid, and combinations
thereof.
[0023] Non-limiting examples of the inorganic overbase may be or
include, but are not necessarily limited to magnesium sulfonates,
magnesium oxides, magnesium carboxylates, calcium sulfonates,
calcium oxides, calcium carboxylates, and combinations thereof.
"Overbase" as used herein refers to where the amount of base is
more than the amount of metal within the first component. The
inorganic overbase refers to inorganic compounds with a great
capacity of neutralizing acids. For example, when a magnesium oxide
overbase is used as a first component, the amount of oxide is lower
than the amount of magnesium to form the inorganic overbase. The
inorganic overbase may be prepared in any manner known to those of
ordinary skill in the art.
[0024] The second component(s) may be or include, but is
non-limiting embodiment not limited to,
N,N'-di-sec-butyl-p-phenylenediamine,
2,6-di-ter-butyl-4-methylphenol,
4-sec-butyl-2,6-di-tert-butylphenol (a g. ISONOX.RTM. 132); mixed
tertiary butyl phenols (e.g. ISONOX.RTM. 133); mixed hindered
phenols; butylated hydroxytoluene (BHT); blend of substituted
p-phenylenediamines (e.g. NAUGARD.RTM. R); quinones;
amino-para-cresols; and combinations thereof. Non-limiting examples
of the mixed hindered phenols include polyalkyl substituted phenol,
hydroquinone derivatives, and combinations thereof. Non-limiting
examples of the quinones may be or include substituted alkyl
quinone, benzoquinone derivatives, substituted quinone methide, and
combinations thereof. A non-limiting example of the
amino-para-cresol may be or include nitroso phenol derivatives.
[0025] The first component(s) and the second component(s) may
contact or be introduced into the hydrocarbon-based fluid as an
additive mixture (i.e. at the same time), or at different times.
The terms "first component" and "second component" are not used
herein to denote an order that the components must be added;
"first" and "second" are simply used to distinguish the two groups
of chemicals from each other. Said differently, the "second
component" may be added before the "first component".
[0026] The effective amount of the first component(s) and the
second component(s) is difficult to predict in advance because it
would depend on the particular hydrocarbon-based fluid, the type of
targeted foulant, the operating conditions (e.g. temperature), and
the like. However, in one non-limiting embodiment, the effective
amount of the first component(s) may range from about 1 ppm
independently to about 10,000 ppm based on the total
hydrocarbon-based fluid. Alternatively, the amount of the first
component(s) may range from about 10 ppm independently to about
1,000 ppm, or from about 50 ppm independently to about 300 ppm, in
another non-limiting embodiment. As used herein with respect to a
range, "independently" means that any lower threshold may be used
together with any upper threshold to give a suitable alternative
range.
[0027] In one non-limiting embodiment, the effective amount of the
second component(s) may range from about 1 ppm independently to
about 10,000 ppm based on the total hydrocarbon-based fluid.
Alternatively, the amount of the second component(s) may range from
about 10 ppm independently to about 1,000 ppm, or from about 50 ppm
independently to about 300 ppm, in another nonlimiting
embodiment.
[0028] In a non-limiting embodiment, the volume ratio of the
formulated product of the first component to the second component
may range from about 1:1 independently to about 1:20, alternatively
from about 2:1 independently to about 20:1.
[0029] The first component(s) and second component(s) may be
introduced into the hydrocarbon stream at one or more of a variety
of locations, such as but not limited to, upstream from or into an
ebullated bed hydrocracking unit (e.g. an LC finer or H-oil
reactor), into an interstage separator, into a crude oil vacuum
distillation unit, into an atmospheric crude oil distillation
units, and combinations thereof. The first component(s) and second
component(s) may be added into the hydrocarbon-based fluid by
adding them into a distillate fluxant blended with a distillate
residua feed, adding them into the hydrocracking unit feed by a
connected feed line, and combinations thereof. The first
component(s) and second component(s) may be added into the
hydrocarbon-based fluid at a pre-determined rate, which may be a
continuous rate, an intervallic rate, an intermittent rate, and
combinations thereof. "Distillate fluxant" is used herein to refer
to an atmospheric or vacuum distillation cut or distillate from a
conversion process, such as but not limited to gasoline, kerosene,
gas oil, vacuum gas oil, visbreaker gas oil, FCC light cycle oil,
FCC slurry oil, and the like.
[0030] The term "hydrocracking" is defined herein to mean a process
where the primary purpose is to decrease the boiling range of a
heavy oil feedstock and where a substantial portion of the
feedstock is converted into products with boiling ranges lower than
that of the original feedstock. Hydrocracking generally involves
fragmentation of larger hydrocarbon molecules into smaller
molecular fragments having a fewer number of carbon atoms and a
higher hydrogen-to-carbon ratio. Hydrocracking may involve the
formation of hydrocarbon free radicals during fragmentation, which
may be followed by capping the free radical ends or moieties with
hydrogen. The hydrogen atoms or radicals that react with
hydrocarbon free radicals during hydrocracking may be generated at
or by active catalyst sites of an ebullated bed hydrocracking
unit.
[0031] The operating conditions of the hydrocarbon-based fluid may
require the temperature, pressure, and the like to be within a
particular range. In a non-limiting example, the temperature of the
hydrocarbon-based fluid may range from about 25.degree. C.
independently to about 500.degree. C., alternatively from about
50.degree. C. independently to about 250.degree. C. The pressure
surrounding the hydrocarbon-based fluid may range from about 0 bars
(0 kPa); independently to about 250 bars (approximately 25,000
kPa); alternatively from about 10 bars (1,000 kPa) independently to
about 200 bars (approximately 20,000 kPa).
[0032] The hydrocarbon-based fluid may be a still fluid, or it may
be part of a hydrocarbon feed or hydrocarbon-based fluid or flowing
stream; "hydrocarbon-based fluid" is defined herein to include
both. In a non-limiting embodiment, the hydrocarbon fluid may be a
liquid, a gas, or a combination thereof. Non-limiting examples of
the hydrocarbon-based fluid may be or include a crude oil, a
bitumen, a shale oil, a tight oil, a refinery fluid, and
combinations thereof. In a non-limiting embodiment, the crude oil
may a combination or mixture of at least two different crude oils.
"Crude oil" as used herein includes water-in-crude emulsions, a
fluid that is only crude oil, and mixtures thereof.
[0033] The invention will be further described with respect to the
following Example, which is not meant to limit the invention, but
rather to further illustrate the various embodiments.
EXAMPLE 1
[0034] Now turning to FIG. 1, which is a graph depicting the
stability of four different samples in the presence or absence of
various components. Sample 1 included a shale oil without the
addition of the first component nor the second component. Sample 2
included the same shale oil in the presence of 3000 ppm of the
first component, which was an alpha olefin copolymer. Sample 3
included the same shale oil in the presence of 3000 ppm of the
first component and the second component, which were the alpha
olefin copolymer and a blended phenolic antioxidant. Sample 4
included the same shale oil in the presence of 3000 ppm of the
second component, which was a blended phenolic antioxidant.
[0035] Each sample was analyzed to obtain the inflection point
value (IPV) thereof. To do this, a non-solvent was added to each
sample in an intervallic fashion; the amount of non-solvent is
noted on the x-axis. At each interval of non-solvent added, the
transmittance was measured with a near infrared spectrometer; the
transmittance is noted on the y-axis. An inflection point value was
determined for each interval of non-solvent added. The non-solvent
was n-heptane.
[0036] The IPV continued to rise for each sample until the point of
asphaltene flocculation, and then the IPV decreased. The near
infrared transmittance data obtained from the hydrocarbon-based
fluid was plotted on the graph vs. volume of non-solvent added. The
maximum inflection point value is the representative value of the
amount of non-solvent required to cause the foulants (e.g.
asphaltenes and/or polynuclear aromatics in this instance) in the
hydrocarbon-based fluid to become unstable and precipitate. The
more non-solvent added correlates to a more stable
hydrocarbon-based fluid.
[0037] As noted by FIG. 1, sample 3 (the shale oil, the first
component, and the second component) using the composition and
method described herein was the most stable.
[0038] Hydrocarbon fluids that contain little to no asphaltenes
and/or polynuclear aromatics may form asphaltenes and/or
polynuclear aromatics upon heating. The purpose of a thermal stress
test in the case of a hydrocarbon-based fluid (e.g. a shale oil in
a non-limiting example), such as by heating the fluid at sub
cracking to near cracking temperatures to form asphaltenes and/or
polynuclear aromatics. Heating stressing of the sample may be
required if the samples do not have sufficient asphaltenes to see a
flocculation point in the titration test on the crude sample as
received. Shale oils are very paraffinic in nature and they
inherently destabilize asphaltenes and cannot support them in
solution. Thus, most of the naturally occurring asphaltenes are
probably left down-hole or have dropped out during recovery and
transport. Therefore, refinery processes running high percentages
of shale oil in their crude blends (70-100 vol %) may contain very
low levels (<0.5 wt %) of "naturally occurring" asphaltenes and
this may be below the detection limit of common commercial optical
devices used to detect the flocculation point by titration, or
alternatively the amount of flocculated asphaltenes simply do not
create a great enough optical density to be detected. The shale
oils also contain relatively high levels of waxy material. The
heavy waxes (C28-C72 have been identified as commonly present) and
other asphaltenic resinous material can thermally react at refinery
process systems and form PNAs (poly-nuclear aromatics) which behave
similarly to asphaltenes with respect to process fouling and in the
titration test--essentially, "asphaltenes" forming in-situ at
process temperatures. The heating, or thermal stressing, in the
test is required to evaluate this potential effect and to evaluate
the additives on that effect for crude samples that do not generate
a detectable floc point as received.
[0039] In the foregoing specification, the invention has been
described with reference to specific embodiments thereof, and has
been described as effective in providing methods and compositions
for decreasing the fouling by foulant(s) within a hydrocarbon-based
fluid. However, it will be evident that various modifications and
changes can be made thereto without departing from the broader
spirit or scope of the invention as set forth in the appended
claims. Accordingly, the specification is to be regarded in an
illustrative rather than a restrictive sense. For example, specific
first components, specific second components, hydrocarbon-based
fluids, foulants, proportions, addition procedures, and locations
within a refinery where the components may contact the
hydrocarbon-based fluid falling within the claimed parameters, but
not specifically identified or tried in a particular composition or
method, are expected to be within the scope of this invention.
[0040] The present invention may suitably comprise, consist of or
consist essentially of the elements disclosed and may be practiced
in the absence of an element not disclosed. For instance, the
method for decreasing fouling during the refining of a
hydrocarbon-based fluid comprising at least one foulant may consist
of or consist essentially of contacting the hydrocarbon-based fluid
with an effective amount of at least one of a first component and
an effective amount of at least one of a second component to
decrease fouling by the foulant(s) as compared to an otherwise
identical hydrocarbon-based fluid absent the first component(s) and
the second component(s); the contacting of the hydrocarbon-based
fluid with the first component(s) and the second component(s) may
occur at the same time or a different time; the first component(s)
may be or include an acrylate vinyl pyrolidinone copolymer, a
succinimide, an alpha olefin and maleic anhydride reaction product,
a reaction product from nonyl phenol reaction with ethylene
diamine, a C.sub.24-C.sub.28 olefin and maleic anhydride copolymer,
a Mannich reaction product, a dodecyl/tert-octyl phenol resin, a
sulfonic acid, an inorganic overbase, and combinations thereof; and
the second component(s) may be or include
N,N'-di-sec-butyl-p-phenylenediamine;
2,6-di-ter-butyl-4-methylphenol;
4-sec-butyl-2,6-di-tert-butyl-phenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; blend of
substituted p-phenylenediamines; quinones; amino-para-cresols; and
combinations thereof.
[0041] The treated hydrocracked hydrocarbon-based fluid composition
may suitably comprise, consist of or consist essentially of a
hydrocarbon-based fluid, at least one first component in an amount
ranging from about 0.1 ppm to about 10,000 ppm based on the total
treated fluid, at least one second component in an amount ranging
from about 0.1 ppm to about 10,000 ppm based on the total treated
fluid, and at least one foulant; the hydrocarbon-based fluid may be
or include a crude oil, a bitumen, a shale oil, a tight oil, a
refinery fluid, and combinations thereof; the first component(s)
may be or include an acrylate vinyl pyrolidinone copolymer, a
succinimide, an alpha olefin and maleic anhydride reaction product,
a reaction product from nonyl phenol reaction with ethylene
diamine, a C.sub.24-C.sub.28 olefin and maleic anhydride copolymer,
a Mannich reaction product, a dodecyl/tert-octyl phenol resin, a
sulfonic acid, an inorganic overbase, and combinations thereof; the
second component(s) may be or include
N2,6-di-ter-butyl-4-methylphenol,
4-sec-butyl-2,6-di-tert-butylphenol; mixed tertiary butyl phenols;
mixed hindered phenols; butylated hydroxytoluenes; quinones;
amino-paracresols; and combinations thereof.
[0042] The words "comprising" and "comprises" as used throughout
the claims, are to be interpreted to mean "including but not
limited to" and "includes but not limited to", respectively. As
used herein, the terms "comprising," "including," "containing,"
"characterized by," and grammatical equivalents thereof are
inclusive or open-ended terms that do not exclude additional,
unrecited elements or method acts, but also include the more
restrictive terms "consisting of" and "consisting essentially of"
and grammatical equivalents thereof. As used herein, the term "may"
with respect to a material, structure, feature or method act
indicates that such is contemplated for use in implementation of an
embodiment of the disclosure and such term is used in preference to
the more restrictive term "is" so as to avoid any implication that
other, compatible materials, structures, features and methods
usable in combination therewith should or must be, excluded.
[0043] As used herein, the singular forms "a," "an," and "the" are
intended to include the plural forms as well, unless the context
clearly indicates otherwise.
[0044] As used herein, the term "and/or" includes any and all
combinations of one or more of the associated listed items.
[0045] As used herein, relational terms, such as "first," "second,"
"top," "bottom," "upper," "lower," "over," "under," etc., are used
for clarity and convenience in understanding the disclosure and
accompanying drawings and do not connote or depend on any specific
preference, orientation, or order, except where the context clearly
indicates otherwise.
[0046] As used herein, the term "substantially" in reference to a
given parameter, property, or condition means and includes to a
degree that one of ordinary skill in the art would understand that
the given parameter, property, or condition is met with a degree of
variance, such as within acceptable manufacturing tolerances. By
way of example, depending on the particular parameter, property, or
condition that is substantially met, the parameter, property, or
condition may be at least 90.0% met, at least 95.0% met, at least
99.0% met, or even at least 99.9% met, regardless of the type of
percentage.
[0047] As used herein, the term "about" in reference to a given
parameter is inclusive of the stated value and has the meaning
dictated by the context (e.g., it includes the degree of error
associated with measurement of the given parameter).
* * * * *