U.S. patent application number 15/931176 was filed with the patent office on 2021-11-18 for polybenzoxazine asphaltene inhibitors.
This patent application is currently assigned to Baker Hughes Oilfield Operations LLC. The applicant listed for this patent is David W. Jennings, Joey Dacula Mangadlao, Gordon Rivers, Jerry Weers. Invention is credited to David W. Jennings, Joey Dacula Mangadlao, Gordon Rivers, Jerry Weers.
Application Number | 20210355387 15/931176 |
Document ID | / |
Family ID | 1000005940980 |
Filed Date | 2021-11-18 |
United States Patent
Application |
20210355387 |
Kind Code |
A1 |
Mangadlao; Joey Dacula ; et
al. |
November 18, 2021 |
POLYBENZOXAZINE ASPHALTENE INHIBITORS
Abstract
A method of stabilizing asphaltenes in a petroleum hydrocarbon
fluid is disclosed. The method includes contacting the petroleum
hydrocarbon fluid with a polybenzoxazine comprising repeating
structural units of Formula (I): ##STR00001## wherein R.sub.1 is
hydrogen, a C.sub.1-30 alkyl, a C.sub.3-30 cycloalkyl, a C.sub.6-30
aryl, a C.sub.7-30 alkylarylene, a C.sub.7-30 arylalkyl, a
C.sub.5-30 heteroaryl, or a C.sub.3-30 heterocycloalkyl; and
R.sub.2 is a C.sub.1-30 alkyl, a C.sub.3-30 cycloalkyl, a
C.sub.6-30 aryl, a C.sub.7-30 alkylarylene, a C.sub.7-30 arylalkyl,
a C.sub.5-30 heteroaryl, or a C.sub.3-30 heterocycloalkyl.
Inventors: |
Mangadlao; Joey Dacula;
(Sugar Land, TX) ; Rivers; Gordon; (Houston,
TX) ; Jennings; David W.; (Houston, TX) ;
Weers; Jerry; (Richmond, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mangadlao; Joey Dacula
Rivers; Gordon
Jennings; David W.
Weers; Jerry |
Sugar Land
Houston
Houston
Richmond |
TX
TX
TX
TX |
US
US
US
US |
|
|
Assignee: |
Baker Hughes Oilfield Operations
LLC
Houston
TX
|
Family ID: |
1000005940980 |
Appl. No.: |
15/931176 |
Filed: |
May 13, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 73/06 20130101;
C10G 29/20 20130101 |
International
Class: |
C10G 29/20 20060101
C10G029/20; C08G 73/06 20060101 C08G073/06 |
Claims
1. A method of stabilizing asphaltenes in a petroleum hydrocarbon
fluid, the method comprising: contacting the petroleum hydrocarbon
fluid with a polybenzoxazine comprising repeating structural units
of Formula (I): ##STR00008## wherein R.sub.1 is hydrogen, a
C.sub.1-30 alkyl, a C.sub.3-30 cycloalkyl, a C.sub.6-30 aryl, a
C.sub.7-30 alkylarylene, a C.sub.7-30 arylalkyl, a C.sub.5-30
heteroaryl, or a C.sub.3-30 heterocycloalkyl; and R.sub.2 is a
C.sub.1-30 alkyl, a C.sub.3-30 cycloalkyl, a C.sub.6-30 aryl, a
C.sub.7-30 alkylarylene, a C.sub.7-30 arylalkyl, a C.sub.5-30
heteroaryl, or a C.sub.3-30 heterocycloalkyl.
2. The method of claim 1, wherein R.sub.1 and R.sub.2 are each
independently a C.sub.1-20 alkyl group.
3. The method of claim 1, wherein R.sub.1 and R.sub.2 are each
independently a dodecyl group or a nonyl group.
4. The method of claim 1, wherein an amount of the polybenzoxazine
is about 50 ppm to about 5,000 ppm based on a total volume of the
petroleum hydrocarbon fluid.
5. The method of claim 1, wherein an additive is used together with
the polybenzoxazine to treat the petroleum hydrocarbon fluid, and
the additive comprises an amine, a polyamine, a phenol aldehyde
resin, or a combination comprising at least one of the
foregoing.
6. The method of claim 1, wherein the petroleum hydrocarbon fluid
further contains water, brine, a gas, or a combination comprising
at least one of the foregoing.
7. The method of claim 1, wherein the contacting is conducted
during production, storage, transportation, and refining of the
petroleum hydrocarbon fluid.
8. The method of claim 1, wherein the contacting is conducted at a
temperature of about -50.degree. C. to about 250.degree. C. and a
pressure of about 14.7 psig to about 40,000 psig.
9. A petroleum hydrocarbon fluid comprising: an asphaltene
inhibitor or dispersion composition that contains a polybenzoxazine
having the formula: ##STR00009## wherein R.sub.1 is hydrogen, a
C.sub.1-30 alkyl, a C.sub.3-30 cycloalkyl, a C.sub.6-30 aryl, a
C.sub.7-30 alkylarylene, a C.sub.7-30 arylalkyl, a C.sub.5-30
heteroaryl, or a C.sub.3-30 heterocycloalkyl; and R.sub.2 is a
C.sub.1-30 alkyl, a C.sub.3-30 cycloalkyl, a C.sub.6-30 aryl, a
C.sub.7-30 alkylarylene, a C.sub.7-30 arylalkyl, a C.sub.5-30
heteroaryl, or a C.sub.3-30 heterocycloalkyl.
10. The petroleum hydrocarbon fluid of claim 9, wherein R.sub.1 and
R.sub.2 are each independently a C.sub.1-20 alkyl group.
11. The petroleum hydrocarbon fluid of claim 9, wherein R.sub.1 and
R.sub.2 are each independently a C.sub.4-18 alkyl group.
12. The petroleum hydrocarbon fluid of claim 9, wherein the
polybenzoxazine is present in an amount of about 50 ppm to about
5000 ppm based on a total volume of the petroleum hydrocarbon
fluid.
13. The petroleum hydrocarbon fluid of claim 9, further comprising
water, brine, a gas, or a combination comprising at least one of
the foregoing.
14. The petroleum hydrocarbon fluid of claim 9, further comprising
an additive, and the additive comprises an amine, a polyamine, a
phenol aldehyde resin, or a combination comprising at least one of
the foregoing.
15. The petroleum hydrocarbon fluid of claim 9, further comprising
a phenol aldehyde resin derived from an aldehyde and an
alkyl-substituted monophenol or unsubstituted monophenol.
16. The petroleum hydrocarbon fluid of claim 9, further comprising
dispersants, corrosion inhibitors, scale inhibitors, paraffin
inhibitors, hydrate inhibitors, demulsifiers, sulfide scavengers,
or a combination comprising at least one of the foregoing.
Description
BACKGROUND
[0001] Asphaltenes are heterocyclic macromolecules present in
petroleum that cause adverse effects in both the production and
refining of petroleum. In petroleum production operations,
asphaltenes have deposited or accumulated in various locations
ranging from the formation to well tubulars to flowlines to
processing equipment causing a reduction or complete stoppage of
production. Asphaltenes have also caused failure of critical safety
valves. In petroleum refining, asphaltenes have been responsible
for catalyst poisoning, coke formation, and fouling in heat
exchangers. One method to reduce asphaltene deposition and
asphaltene related fluid processing problems is to apply asphaltene
inhibitor chemistries to the petroleum fluids. Various asphaltene
inhibitors are known in the art. However, due to the high demand
for asphaltene inhibitors, alternative materials and methods for
preventing or reducing asphaltene deposition and/or accumulation
would be well received in the art.
BRIEF DESCRIPTION
[0002] A method of stabilizing asphaltenes in a petroleum
hydrocarbon fluid comprises contacting the petroleum hydrocarbon
fluid with a polybenzoxazine comprising repeating structural units
of Formula (I):
##STR00002##
wherein R.sub.1 is hydrogen, a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylarylene, a
C.sub.7-30 arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl; and R.sub.2 is a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylarylene, a
C.sub.7-30 arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl.
[0003] A petroleum hydrocarbon fluid comprises an asphaltene
inhibitor or dispersion composition that contains a polybenzoxazine
having the Formula (I).
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] The following descriptions should not be considered limiting
in any way. With reference to the accompanying drawings, like
elements are numbered alike:
[0005] FIG. 1 compares the asphaltene control performance of phenol
aldehydes with polybenzoxazines on Crude Oil #1 at 60.degree.
C.;
[0006] FIG. 2 compares the asphaltene control performance of a
phenol aldehyde with a polybenzoxazine on Crude Oil #2 at
60.degree. C.; and
[0007] FIG. 3 compares the asphaltene control performance of a
commercial asphaltene inhibitor with a polybenzoxazine on Crude Oil
#1 at 60.degree. C.
DETAILED DESCRIPTION
[0008] The inventors hereof have found that polybenzoxazines can be
used as asphaltene stabilizers and deposition inhibitors.
"Polybenzoxazines" as used herein mean homopolymers or copolymers
having repeating structural units of Formula (I):
##STR00003##
wherein R.sub.1 is hydrogen, a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylaryl, a C.sub.7-30
arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl; and R.sub.2 is a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylaryl, a C.sub.7-30
arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl.
[0009] In an aspect, R.sub.1 is hydrogen, a C.sub.1-20 alkyl, a
C.sub.5-20 cycloalkyl, a C.sub.6-18 aryl, a C.sub.7-25
alkylarylene, a C.sub.7-25 arylalkyl, a C.sub.5-20 heteroaryl, or a
C.sub.5-30 heterocycloalkyl; and R.sub.2 is a C.sub.1-20 alkyl, a
C.sub.5-20 cycloalkyl, a C.sub.6-18 aryl, a C.sub.7-25
alkylarylene, a C.sub.7-25 arylalkyl, a C.sub.5-20 heteroaryl, or a
C.sub.5-30 heterocycloalkyl.
[0010] Preferably each of R.sub.1 and R.sub.2 is independently a
C.sub.4-18 alkyl or a C.sub.4-12 alkyl such as dodecyl, nonyl,
hexyl, t-butyl, and the like. R.sub.1 and R.sub.2 can be
substituted or unsubstituted regardless whether substituted or
unsubstituted is specifically mentioned or not.
[0011] As used herein, the term "alkyl" refers to a straight or
branched chain, saturated monovalent hydrocarbon group regardless
whether straight or branched chain is specifically mentioned or
not. "Cycloalkyl" refers to a non-aromatic monovalent monocyclic or
multicylic hydrocarbon group having at least three carbon atoms
with cyclohexyl and cyclopentyl being exemplary cycloalkyl group.
"Aryl" refers to an aromatic monovalent group containing only
carbon in the aromatic ring or rings with phenyl being an exemplary
aryl group. "Alkylaryl" refers to an aryl group that has been
substituted with an alkyl group as defined above, with
4-methylphenyl being an exemplary alkylaryl group. "Arylalkyl"
refers to an alkyl group that has been substituted with an aryl
group or an alkylaryl group as defined above, with benzyl and xylyl
being exemplary arylalkyl groups. "Heteroaryl" refers to an
aromatic monovalent group containing carbon and at least a
heteroatom in the aromatic ring or rings, wherein the heteroatom
includes N, O, or S with pyridinyl being an exemplary heteroaryl
group. "Heterocycloalkyl" refers to a non-aromatic monovalent
monocyclic or multicylic group having at least three carbon atoms
and at least one heteroatom such as N, O, or S.
[0012] Unless otherwise indicated, each of the foregoing groups for
R.sub.1 and R.sub.2 can be unsubstituted or substituted, provided
that the substitution does not significantly adversely affect
synthesis, stability, or use of the compound. The term
"substituted" as used herein means that at least one hydrogen on
the designated atom or group is replaced with another group,
provided that the designated atom's normal valence is not exceeded.
Exemplary groups that can be present on a "substituted" position
include, but are not limited to, a halogen, a group having an N, S,
O, or F atom, alkyl, cycloalkyl, alkenyl, or alkynyl.
[0013] Polybenzoxazines can be derived from monophenols, aldehydes,
and amines. The monophenols can be substituted or unsubstituted.
The substituents can be attached to the para, ortho, or both
positions of the monophenol. Preferably the substituents are
attached to the para position of the monophenol. More than one
monophenols or more than one amines can be used.
[0014] The monophenol has a structure represented by Formula
(II)
##STR00004##
wherein R.sub.1 is the same as defined herein in the context of
Formula (I). Substituted phenol can be an alkyl substituted
monophenol. The alkyl substituents include C.sub.1-20, C.sub.4-18,
or C.sub.4-12 branched or linear alkyl groups. Exemplary phenols
having branched alkyl groups include branched dodecyl phenol,
branched nonyl phenol, tert-butylphenol, t-amyl phenol, and
branched hexyl phenols such as 4-(1-methylpentyl) phenol,
4-(1,2-dimethylbutyl)phenol, and 4-(1-ethylbutyl) phenol, and
4-(1-ethyl-2-methylpropyl) phenol.
[0015] Examples of aldehydes include formaldehyde,
paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
glyoxal, glutaraldehyde, 1,9-nonanedial, or a combination
comprising at least one of the foregoing. Paraformaldehyde and
formaldehyde are preferred.
[0016] The amines are preferably primary amines with the Formula
(III) NH.sub.2--R.sub.2, wherein R.sub.2 is the same as define
herein in the context of Formula (1). An example of the primary
amine is dodecyl amine.
[0017] The polybenzoxazines as described herein are excellent
asphaltene stabilizers. The amount of the polybenzoxazines used to
treat petroleum hydrocarbon fluids that contain asphaltenes can
vary depending on the specific polybenzoxazines used, the specific
chemistry of the petroleum hydrocarbon fluids as well as the
conditions such as the pressure and temperature that the petroleum
hydrocarbon fluids are exposed to during production, refining, and
storage. In an embodiment, about 50 ppm to about 5000 ppm, or about
100 ppm to about 2500 ppm, or about 625 ppm to about 1250 ppm of
the polybenzoxazines are used to treat petroleum hydrocarbon
fluids. The amounts disclosed herein are based on the volume of the
polybenzoxazines, not based on the volume of the polybenzoxazines
solutions or dispersions that contain a solvent for the
polybenzoxazines.
[0018] The polybenzoxazines can be used alone or in combination
with co-additives such as amines, polyamines, phenolic resins for
control of asphaltene precipitation. Examples of amines and
polyamines include fatty acid based imidazoline,
diethylenetriamine, tetraethylenetetramine, tetraethylenepentamine,
or a combination comprising at least one of the foregoing. The
phenol aldehyde resins include structural repeating units having
the Formula (IV)
##STR00005##
wherein R is C.sub.1-20, C.sub.4-18, or C.sub.4-12 branched or
linear alkyl groups. The phenolic resin can be derived from
formaldehyde and one or more substituted or unsubstituted
monophenol.
[0019] The relative amounts of the co-additives and the
polybenzoxazines can be determined depending on the specific
chemistry of the petroleum hydrocarbon fluids to be treated as well
as the conditions such as the pressure and temperature the
petroleum hydrocarbon fluids are exposed to during production,
refining, and storage. In an embodiment, the co-additives are used
at dosages of about 1 to about 50% of the amount of the
polybenzoxazines by weight. In another embodiment, the weight ratio
of the polybenzoxazines relative to the synergistic additive is
about 99:1 to about 1:99, or about 99:1 to about 1:10, or about
95:1 to about 5:1.
[0020] It is appreciated that both the polybenzoxazines and the
co-additives can be added to the petroleum hydrocarbon fluids in
the form of solutions or dispersions. The amounts disclosed herein
are based on the weight of the co-additive and polybenzoxazines,
not based on the weight of the co-additive/polybenzoxazines
solutions or dispersions in another solvent.
[0021] The polybenzoxazines and the co-additives, if used, can be
separately added to the petroleum hydrocarbon fluids to be treated.
Alternatively or in addition, the polybenzoxazines and the
co-additives can be combined first to provide an asphaltene
inhibitor composition, and the petroleum hydrocarbon fluids are
contacted with the asphaltene inhibitor composition containing both
the polybenzoxazines and the co-additive.
[0022] In addition to the polybenzoxazines and the optional
co-additives, the asphaltene inhibitor compositions can further
include other components in the formulations. These components may
be included to provide formulations with desirable physical
properties or stability characteristics for process injection or
storage considerations. Exemplary formulation components include
solvents such as aromatic hydrocarbons, aliphatic hydrocarbons,
alcohols, ethers, ketones, and aldehydes. The asphaltene inhibitor
compositions can be formulated in various forms including, but are
not limited to, solutions, dispersions, emulsions, and the like.
Depending on the form of the asphaltene inhibitor compositions,
additives such as water, surfactants, dispersants, emulsifiers, or
a combination comprising at least one of the foregoing may be
present.
[0023] Known additives can be added to enhance the performance of
the asphaltene inhibitor compositions, such as in reducing
asphaltene deposition and accumulation or for providing additional
benefits to the products. Exemplary additives to provide additional
benefits include dispersants, corrosion inhibitors, scale
inhibitors, paraffin inhibitors, hydrate inhibitors, demulsifiers,
sulfide scavengers, or a combination comprising at least one of the
foregoing. Any known dispersants, corrosion inhibitors, scale
inhibitors, paraffin inhibitors, hydrate inhibitors, demulsifiers,
and sulfide scavengers can be used as long as the additives do not
adversely affect the asphaltene inhibiting efficiency of the mixed
phenolic aldehydes and the optional co-additives.
[0024] The polybenzoxazines and the co-additives can be used to
reduce or prevent asphaltene deposition and/or accumulation from
petroleum hydrocarbon fluids. As used herein, petroleum hydrocarbon
fluids include crude oil, natural gas condensate, shale oil, shale
gas condensate, bitumen, diluted bitumen (dil-bit), refinery
fractions, finished fuel, finished petroleum products, and
combinations thereof. Petroleum hydrocarbon fluids can further
contain water, brines, gases such as hydrocarbon gases, or a
combination comprising at least one of the foregoing. A method of
treating a petroleum hydrocarbon fluid comprises contacting the
petroleum hydrocarbon fluid with the polybenzoxazines and the
optional co-additives if used.
[0025] The contacting can be conducted at a temperature of about
-50.degree. C. to about 250.degree. C., for example about
-5.degree. C. to about 200.degree. C. or about 20.degree. C. to
about 150.degree. C. and a pressure of about 14.7 pounds per square
inch absolute (psia) to about 40,000 psia or about 14.7 psia to
about 20,000 psia.
[0026] The contacting can be conducted during the production,
storage, transportation, and/or refining of the petroleum
hydrocarbon fluids. In an embodiment for the production of
petroleum, the contacting is conducted in a reservoir. Any known
methods of introducing the polybenzoxazines into the reservoir can
be used. For example, a squeeze process can be used to deliver the
polybenzoxazines to a reservoir. In another embodiment for the
production of petroleum, the polybenzoxazines can be applied in a
continuous or batch injection process through a capillary line,
down the backside of well annuluses, through an umbilical line, or
through an umbilical/capillary line combination. When the
contacting is conducted during storage, transportation and
refinery, the polybenzoxazines can be added to the petroleum
hydrocarbon fluids in storage tanks, pipes, processing units,
refinery streams and the like.
[0027] The petroleum hydrocarbon fluids with the polybenzoxazines
as disclosed herein can have reduced asphaltene deposition and/or
accumulation, in terms of the amount, tendency, and/or the rate of
deposition and/or accumulation. In an embodiment, provided are
petroleum hydrocarbon fluids containing the polybenzoxazines and
the optional co-additives or derivatives thereof in amounts as
disclosed herein.
[0028] The asphaltene inhibitors are further illustrated by the
following non-limiting examples.
Examples
[0029] A Baker Hughes' internally developed asphaltene deposition
method was used to evaluate the performance of the samples. In the
examples shown below, deposition percentage is plotted for various
crude oil treated with Samples 1 to 5.
[0030] Sample 1 is a phenol aldehyde resin derived from nonylphenol
and formaldehyde.
[0031] Sample 2 is a phenol aldehyde resin derived from dodecyl
phenol and formaldehyde.
[0032] Sample 3 is a polybenzoxazine derived from nonylphenol,
dodecylamine, and paraformaldehyde.
[0033] Sample 4 is a polybenzoxazine derived from dodecylphenol,
dodecylamine, and paraformaldehyde.
[0034] Sample 5 is a commercial asphaltene inhibitor composed of a
mixture of a phenol aldehyde resin derived from dodecyl phenol and
formaldehyde and an amine additive.
Synthesis of Sample 3
[0035] To a 250 mL round bottomed flask equipped with a Dean-Stark
distilling apparatus was charged with 47.7 g of nonylphenol, 15.90
g of xylene, and 22.12 g of dodecylamine. The chemicals were mixed
at room temperature, then 14.29 g of paraformaldehyde was added.
The reaction mixture was refluxed at 160.degree. C. for 2 hours.
Then three drops of boron trifluoride etherate (approx. 0.1 g) was
added. The reaction mixture was further heated at reflux for 3
hours to form polybenzoxazine Sample 3.
Synthesis of Sample 4
[0036] To a 250 mL round bottomed flask equipped with a Dean-Stark
distilling apparatus was charged with 43.65 g of dodecylphenol,
14.55 g of xylene, and 30.83 g of dodecylamine. The chemicals were
mixed at room temperature then 10.98 g of paraformaldehyde was
added. The reaction mixture was refluxed at 160.degree. C. for 2
hours. Then three drops of boron trifluoride etherate (approx. 0.1
g) was added, and the reaction mixture was further heated at reflux
for 3 hours to form polybenzoxazine Sample 4.
[0037] Samples 1-5 were evaluated for efficiency as asphaltene
inhibitors on Crude Oil #1 or Crude Oil #2 at 60.degree. C. The
results are illustrated graphically in FIGS. 1-3.
[0038] As seen from FIG. 1, without using any corrosion inhibitor,
the blank (Crude Oil #1) had 100% asphaltene deposition. When
phenol aldehyde resin sample 1 or phenol aldehyde resin sample 2
was used in an amount of 1250 ppm, the percent of asphaltene
deposition did not change compared to the blank. On the other hand,
when polybenzoxazine sample 3 or polybenzoxazine sample 4 according
to the disclosure was used at the same loading level, the percent
of asphaltene deposition was reduced to 65% and 70% respectively
compared to the blank. The results indicate that the
polybenzoxazines as disclosed herein can be more effective
asphaltene inhibitors than certain phenol aldehyde corrosion
inhibitors.
[0039] FIG. 2 compares the efficiency of phenol aldehyde sample 2
and polybenzoxazine sample 4 as asphaltene inhibitors on Crude Oil
#2 at 60.degree. C. As seen from FIG. 2, the phenol formaldehyde
sample 2 at 625 ppm loading level did not shown any improvement
over the blank. On the other hand, when polybenzoxazine sample 4
was used at the same loading level and tested at the same
temperature, 65% less deposition was achieved over the blank, which
is much better than the phenol formaldehyde sample 2.
[0040] As shown in FIG. 3, without using any corrosion inhibitor,
the blank (Crude Oil #1) had 100% asphaltene deposition. When
sample 5 (a commercial corrosion inhibitor) was used, the amount of
asphaltene deposition was reduced to 80%. Surprisingly when
polybenzoxazine sample 3 according to the disclosure was used, the
% of asphaltene deposition was reduced to about 56% compared to the
blank. The results indicate that the polybenzoxazines as disclosed
herein can be more effective asphaltene inhibitor than certain
commercial corrosion inhibitors containing dodecyl phenol resin and
an amine.
[0041] Set forth are various embodiments of the disclosure.
Embodiment 1
[0042] A method of stabilizing asphaltenes in a petroleum
hydrocarbon fluid, the method comprising: contacting the petroleum
hydrocarbon fluid with a polybenzoxazine comprising repeating
structural units of Formula (I):
##STR00006##
wherein R.sub.1 is hydrogen, a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylarylene, a
C.sub.7-30 arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl; and R.sub.2 is a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylarylene, a
C.sub.7-30 arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl.
Embodiment 2
[0043] The method as in any prior embodiment, wherein R.sub.1 and
R.sub.2 are each independently a C.sub.1-20 alkyl group.
Embodiment 3
[0044] The method as in any prior embodiment, wherein R.sub.1 and
R.sub.2 are each independently a dodecyl group or a nonyl
group.
Embodiment 4
[0045] The method as in any prior embodiment, wherein an amount of
the polybenzoxazine is about 50 ppm to about 5,000 ppm based on a
total volume of the petroleum hydrocarbon fluid.
Embodiment 5
[0046] The method as in any prior embodiment, wherein an additive
is used together with the polybenzoxazine to treat the petroleum
hydrocarbon fluid, and the additive comprises an amine, a
polyamine, a phenol aldehyde resin, or a combination comprising at
least one of the foregoing.
Embodiment 6
[0047] The method as in any prior embodiment, wherein the petroleum
hydrocarbon fluid further contains water, brine, a gas, or a
combination comprising at least one of the foregoing.
Embodiment 7
[0048] The method as in any prior embodiment, wherein the
contacting is conducted during production, storage, transportation,
and refining of the petroleum hydrocarbon fluid.
Embodiment 8
[0049] The method as in any prior embodiment, wherein the
contacting is conducted at a temperature of about -50.degree. C. to
about 250.degree. C. and a pressure of about 14.7 psig to about
40,000 psig.
Embodiment 9
[0050] A petroleum hydrocarbon fluid comprising: an asphaltene
inhibitor or dispersion composition that contains a polybenzoxazine
having the formula:
##STR00007##
wherein R.sub.1 is hydrogen, a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylarylene, a
C.sub.7-30 arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl; and R.sub.2 is a C.sub.1-30 alkyl, a C.sub.3-30
cycloalkyl, a C.sub.6-30 aryl, a C.sub.7-30 alkylarylene, a
C.sub.7-30 arylalkyl, a C.sub.5-30 heteroaryl, or a C.sub.3-30
heterocycloalkyl.
Embodiment 10
[0051] The petroleum hydrocarbon fluid as in any prior embodiment,
wherein R.sub.1 and R.sub.2 are each independently a C.sub.1-20
alkyl group.
Embodiment 11
[0052] The petroleum hydrocarbon fluid as in any prior embodiment,
wherein R.sub.1 and R.sub.2 are each independently a C.sub.4-18
alkyl group.
Embodiment 12
[0053] The petroleum hydrocarbon fluid as in any prior embodiment,
wherein the polybenzoxazine is present in an amount of about 50 ppm
to about 5000 ppm based on a total volume of the petroleum
hydrocarbon fluid.
Embodiment 13
[0054] The petroleum hydrocarbon fluid as in any prior embodiment,
further comprising water, brine, a gas, or a combination comprising
at least one of the foregoing.
Embodiment 14
[0055] The petroleum hydrocarbon fluid as in any prior embodiment,
further comprising an additive, and the additive comprises an
amine, a polyamine, a phenol aldehyde resin, or a combination
comprising at least one of the foregoing.
Embodiment 15
[0056] The petroleum hydrocarbon fluid as in any prior embodiment,
further comprising a phenol aldehyde resin derived from an aldehyde
and an alkyl-substituted monophenol or unsubstituted
monophenol.
Embodiment 16
[0057] The petroleum hydrocarbon fluid as in any prior embodiment,
further comprising dispersants, corrosion inhibitors, scale
inhibitors, paraffin inhibitors, hydrate inhibitors, demulsifiers,
sulfide scavengers, or a combination comprising at least one of the
foregoing.
Embodiment 17
[0058] The petroleum hydrocarbon fluid as in any prior embodiment
further comprising asphaltene.
[0059] All ranges disclosed herein are inclusive of the endpoints,
and the endpoints are independently combinable with each other. As
used herein, "combination" is inclusive of blends, mixtures,
alloys, reaction products, and the like. All references are
incorporated herein by reference.
[0060] The use of the terms "a" and "an" and "the" and similar
referents in the context of describing the invention (especially in
the context of the following claims) are to be construed to cover
both the singular and the plural, unless otherwise indicated herein
or clearly contradicted by context. "Or" means "and/or." The
modifier "about" used in connection with a quantity 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
particular quantity).
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