U.S. patent application number 14/328878 was filed with the patent office on 2015-01-08 for foam resin sealant for zonal isolation and methods for making and using same.
This patent application is currently assigned to CLEARWATER INTERNATIONAL, LLC. The applicant listed for this patent is CLEARWATER INTERNATIONAL, LLC. Invention is credited to Tina Garza, Sarkis R, Kakadjian, Frank Zamora.
Application Number | 20150011440 14/328878 |
Document ID | / |
Family ID | 44260726 |
Filed Date | 2015-01-08 |
United States Patent
Application |
20150011440 |
Kind Code |
A1 |
Zamora; Frank ; et
al. |
January 8, 2015 |
FOAM RESIN SEALANT FOR ZONAL ISOLATION AND METHODS FOR MAKING AND
USING SAME
Abstract
Foamable epoxy-based zonal isolation sealing compositions
include epoxy resin and a blowing agent and methods for isolating
zones in borehole of oil and gas wells using the compositions,
where the foam nature of the cured seals provide sufficient
compressibility and resiliency to be used with expandable tubing
without substantial loss in sealant integrity and in squeeze
operations.
Inventors: |
Zamora; Frank; (Ft. Worth,
TX) ; Kakadjian; Sarkis R,; (Houston, TX) ;
Garza; Tina; (San Antonio, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CLEARWATER INTERNATIONAL, LLC |
Houston |
TX |
US |
|
|
Assignee: |
CLEARWATER INTERNATIONAL,
LLC
Houston
TX
|
Family ID: |
44260726 |
Appl. No.: |
14/328878 |
Filed: |
July 11, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13053975 |
Mar 22, 2011 |
8851174 |
|
|
14328878 |
|
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Current U.S.
Class: |
507/202 |
Current CPC
Class: |
E21B 33/13 20130101;
C09K 8/44 20130101; C09K 8/42 20130101 |
Class at
Publication: |
507/202 |
International
Class: |
C09K 8/42 20060101
C09K008/42 |
Claims
1. A foamable epoxy-based composition comprising: an adjustable
resin amount of an epoxy resin system including one epoxy resin or
a plurality of epoxy resins, an adjustable curing amount of a cure
system including one curing agent or a plurality of curing agents,
where the curing agents comprise a first type of curing agents
including polyamine curing agents, alkoxylated polyamine curing
agents, or mixtures and combinations thereof, and a second type of
curing agents including heterocyclic amine curing agents, and one
blowing agent or a plurality of blowing agents, where the
adjustable resin amount, the adjustable curing amount, and a type
of curing agents are adjusted to form: 1) a low temperature
foamable epoxy-based composition curing at a low temperature range
between about 50.degree. F. of to about 90.degree. F.; 2) a mid
temperature foamable epoxy-based composition curing at a mid
temperature range between about 90.degree. F. to about 150.degree.
F.; or 3) a high temperature foamable epoxy-based composition
curing at a high curing temperature range between about 150.degree.
F. to about 300.degree. F., and where the compositions cure to form
a compressible cured foam zonal isolation structure that continues
to expand after setting allowing the structure to intrude into
surface cavities and crevices of a borehole penetrating a formation
or a formation zone, while adhering to an outer surface of a tubing
string disposed in the borehole resulting in improved sealing and
improved sealing integrity of the structure and when a section of
the tubing string is expanded to form a compressed structure, where
the compressed structure has substantially no loss in seal
integrity or zonal isolation.
2. The method of claim 1, wherein the zonal isolation structure
cures to form a cured foam epoxy composition having sufficient
compressibility and resilience properties to permit compression of
the composition without substantial loss in seal integrity or zonal
isolation.
3. The composition of claim 1, further comprising: a solvent system
including aromatic solvents, heterocyclic aromatic solvents, or
mixtures and combinations thereof.
4. The composition of claim 1, wherein the epoxy resins comprise:
(a) glycidyl ethers epoxy resin prepared by the reaction of
epichlorohydrin with a compound containing a hydroxyl group carried
out under alkaline reaction conditions; (b) epoxy resins prepared
by the reaction of epichlorohydrin with mononuclear di- and
tri-hydroxy phenolic compounds; (c) epoxidized derivatives of
natural oils with mixed long-chain saturated and unsaturated acids
having between about 14 and 20 carbon atoms; (d) polyepoxides
derived from esters of polycarboxylic acids with unsaturated
alcohols; (e) polyepoxides derived from esters prepared from
unsaturated alcohols and unsaturated carboxylic acids; (f)
epoxidized butadiene based polymers; (g) epoxidized derivatives of
dimers of dienes, and (h) mixtures or combinations thereof.
5. The composition of claim 4, wherein the epoxy resins have a
molecular weight between about 50 and about 10,000.
6. The composition of claim 1, wherein: the high temperature
foamable epoxy-based composition includes the first type of curing
agents, the mid temperature foamable epoxy-based composition
includes the second type of curing agents, and the low temperature
foamable epoxy-based composition includes the second type of curing
agents.
7. The composition of claim 1, wherein the alkoxylated polyamine
curing agents comprise alkoxylated aliphatic polyamines,
alkoxylated cycloaliphatic polyamines, alkoxylated aromatic
polyamines, alkoxylated heterocyclic polyamines or mixtures and
combinations thereof.
8. The method of claim 1, wherein the first type of curing agents
comprise alkoxylated N-alkyl- and N-alkylenyl-substituted
1,3-diaminopropanes or mixtures and combinations thereof.
9. The composition of claim 1, wherein the second type of curing
agents comprise pyrrolidine, alkyl pyrrolidines, oxazoline, alkyl
oxazolines, triazoles, alkyl triazoles, pyrazolidine, alkyl
pyrazolidine, piperidine, alkyl piperidines, piperazine, alkyl
piperazines, imidazoline, imidazolidine, alkyl imidazolidines,
azepane, alkyl azepane, azepine, alkyl azepines, morpholine, alkyl
morpho lines, diazapines, alkyl diazapines, or mixtures and
combinations thereof.
10. The composition of claim 1, wherein the solvent system comprise
alkyl pyridines and the first type of curing agents comprise an
ethoxylated N-tallow-1,3-diaminopropane, where the degree of
ethoxylation is approximately 10 moles ethoxylate per mole of
tallow diamine.
11. The composition of claim 1, wherein: the high temperature
foamable epoxy-based composition comprises: from about 60 wt. % to
about 85 wt. % of the epoxy resin system, from about 1 wt. % to
about 15 wt. % of the first type of curing agents, from 0 wt. % to
about 39 wt. % of the solvent system, and from about 5 wt. % to
about 15 wt. % the blowing agents based on the weight of the other
components; the mid temperature foamable epoxy-based composition
comprises: from about 70 wt. % to about 50 wt. % the epoxy resin
system, from about 30 wt. % to about 50 wt. % of the second type of
curing agents, from about 5 wt. % to about 15 wt. % the blowing
agent or the mixture of blowing agents based on the weight of the
other components, and from 0 wt. % to about 20 wt. % of a or
solvent system, and the low-temperature foamable epoxy-based
composition comprises: from about 75 wt. % to about 99 wt. % of the
epoxy resin system, from about 25 wt. % to about 1 wt. % of the
second type of curing agents, from about 5 wt. % to about 20 wt. %
the blowing agents or the mixture of blowing agents based on the
weight of the other components, and from 0 wt. % to about 20 wt. %
of a solvent system, where the solvent system reduces the viscosity
of the compositions for ease of pumping.
12. The composition of claim 11, wherein: the epoxy resin system
comprises glycidyl ethers epoxy resins, for the high temperature
foamable epoxy-based composition, the first type of curing agents
comprise alkoxylated polyamines, for the mid temperature and low
temperature foamable epoxy-based compositions, the second type of
curing agents comprise heterocyclic amines, the solvent system
comprises an aromatic heterocyclic solvent or a mixture of aromatic
heterocyclic solvents, and the blowing agents comprise aryl
hydrazides.
13. The composition of claim 12, wherein: the epoxy resin system
comprises a glycidyl ethers epoxy resin prepared by the reaction of
epichlorohydrin with a compound containing a hydroxyl group carried
out under alkaline reaction conditions, the first type of curing
agents comprise an ethoxylated N-tallow-1,3-diaminopropane, where
the degree of ethoxylation is approximately 10 moles ethoxylate per
mole of tallow diamine, the second type of curing agents comprise
heterocyclic amines, the solvent system comprises a mixture of
alkyl pyridines, and the blowing agent comprises
p-toluenesulfohydrazide, 4-methylbenzene p-toluenesulfohydrazide or
mixtures thereof.
14. A foamable epoxy-based composition comprising: from about 60
wt. % to about 85 wt. % of an epoxy resin system, from about 1 wt.
% to about 15 wt. % of a cure system, from about 0 wt. % to about
39 wt. % of a solvent system including aromatic solvents,
heterocyclic aromatic solvents, or mixtures and combinations
thereof, and from about 5 wt. % to about 15 wt. % a blowing agent
or a mixture of blowing agents based on the weight of the other
components, where the composition cures at a temperature between
about 150.degree. F. to about 300.degree. F. and where the
compositions cure to form a compressible zonal isolation structure
that continues to expand after setting allowing the structure to
intrude into surface cavities and crevices of a borehole
penetrating a formation or a formation zone, while adhering to an
outer surface of a tubing string disposed in the borehole resulting
in improved sealing and improved sealing integrity of the
structure.
15. The composition of claim 14, wherein: the epoxy resin system
comprises: (a) glycidyl ethers epoxy resin prepared by the reaction
of epichlorohydrin with a compound containing a hydroxyl group
carried out under alkaline reaction conditions; (b) epoxy resins
prepared by the reaction of epichlorohydrin with mononuclear di-
and tri-hydroxy phenolic compounds; (c) epoxidized derivatives of
natural oils with mixed long-chain saturated and unsaturated acids
having between about 14 and 20 carbon atoms; (d) polyepoxides
derived from esters of polycarboxylic acids with unsaturated
alcohols; (e) polyepoxides derived from esters prepared from
unsaturated alcohols and unsaturated carboxylic acids; (f)
epoxidized butadiene based polymers; (g) epoxidized derivatives of
dimers of dienes, and (h) mixtures or combinations thereof, and the
cure system comprises polyamine curing agents, alkoxylated
polyamine curing agents, or mixtures and combinations thereof,
where the alkoxylated polyamine curing agents comprise alkoxylated
aliphatic polyamines, alkoxylated cycloaliphatic polyamines,
alkoxylated aromatic polyamines, alkoxylated heterocyclic
polyamines or mixtures and combinations thereof.
16. The composition of claim 15, wherein the epoxy resins have a
molecular weight between about 50 and about 10,000.
17. The composition of claim 15, wherein: the epoxy resin system
comprises glycidyl ethers epoxy resins, the curing system comprises
alkoxylated polyamines, the solvent system comprises an aromatic
heterocyclic solvent or a mixture of aromatic heterocyclic
solvents, and the blowing agent or the mixture blowing agents
comprise aryl hydrazides.
18. The composition of claim 15, wherein: the epoxy resin system
comprises a glycidyl ethers epoxy resin prepared by the reaction of
epichlorohydrin with a compound containing a hydroxyl group carried
out under alkaline reaction conditions, the curing system comprises
an ethoxylated N-tallow-1,3-diaminopropane, where the degree of
ethoxylation is approximately 10 moles ethoxylate per mole of
tallow diamine, the solvent system comprises a mixture of alkyl
pyridines, and the blowing agent or the mixture blowing agents
comprise p-toluenesulfohydrazide, 4-methylbenzene
p-toluenesulfohydrazide or mixtures thereof.
19. A foamable epoxy-based composition comprising: from about 70
wt. % to about 50 wt. % the epoxy resin system, from about 30 wt. %
to about 50 wt. % of the cure system, from 0 wt. % to about 20 wt.
% of a solvent system including aromatic solvents, heterocyclic
aromatic solvents, or mixtures and combinations thereof, and from
about 5 wt. % to about 15 wt. % a blowing agent or a mixture of
blowing agents based on the weight of the other components, and
where the composition cures at a temperature between about
90.degree. F. to about 150.degree. F. and where the compositions
cure to form a compressible zonal isolation structure that
continues to expand after setting allowing the structure to intrude
into surface cavities and crevices of a borehole penetrating a
formation or a formation zone, while adhering to an outer surface
of a tubing string disposed in the borehole resulting in improved
sealing and improved sealing integrity of the structure.
20. The composition of claim 19, wherein: the epoxy resin system
comprises: (a) glycidyl ethers epoxy resin prepared by the reaction
of epichlorohydrin with a compound containing a hydroxyl group
carried out under alkaline reaction conditions; (b) epoxy resins
prepared by the reaction of epichlorohydrin with mononuclear di-
and tri-hydroxy phenolic compounds; (c) epoxidized derivatives of
natural oils with mixed long-chain saturated and unsaturated acids
having between about 14 and 20 carbon atoms; (d) polyepoxides
derived from esters of polycarboxylic acids with unsaturated
alcohols; (e) polyepoxides derived from esters prepared from
unsaturated alcohols and unsaturated carboxylic acids; (f)
epoxidized butadiene based polymers; (g) epoxidized derivatives of
dimers of dienes, and (h) mixtures or combinations thereof, and the
cure system comprises pyrrolidine, alkyl pyrrolidines, oxazoline,
alkyl oxazolines, triazoles, alkyl triazoles, pyrazolidine, alkyl
pyrazolidine, piperidine, alkyl piperidines, piperazine, alkyl
piperazines, imidazoline, imidazolidine, alkyl imidazolidines,
azepane, alkyl azepane, azepine, alkyl azepines, morpholine, alkyl
morpho lines, diazapines, alkyl diazapines, or mixtures and
combinations thereof.
21. The composition of claim 19, wherein: the epoxy resin system
comprises glycidyl ethers epoxy resins, the curing system comprises
heterocyclic amines, the solvent system comprises an aromatic
heterocyclic solvent or a mixture of aromatic heterocyclic
solvents, and the blowing agents comprise aryl hydrazides.
22. The composition of claim 19, wherein: the epoxy resin system
comprises a glycidyl ethers epoxy resin prepared by the reaction of
epichlorohydrin with a compound containing a hydroxyl group carried
out under alkaline reaction conditions, the curing system comprises
heterocyclic amines, the solvent system comprises a mixture of
alkyl pyridines, and the blowing agent comprises
p-toluenesulfohydrazide, 4-methylbenzene p-toluenesulfohydrazide or
mixtures thereof.
23. A foamable epoxy-based composition comprising: from about 75
wt. % to about 99 wt. % of an epoxy resin system, from about 1 wt.
% to about 25 wt. % of a cure system, from 0 wt. % to about 20 wt.
% of a solvent system including aromatic solvents, heterocyclic
aromatic solvents, or mixtures and combinations thereof, and from
about 5 wt. % to about 20 wt. % the blowing agents based on the
weight of the other components, where the composition cures at a
temperature between about 50.degree. F. of to about 90.degree. F.
band where the compositions cure to form a compressible zonal
isolation structure that continues to expand after setting allowing
the structure to intrude into surface cavities and crevices of a
borehole penetrating a formation or a formation zone, while
adhering to an outer surface of a tubing string disposed in the
borehole resulting in improved sealing and improved sealing
integrity of the structure.
24. The composition of claim 23, wherein: the epoxy resin system
comprises: (a) glycidyl ethers epoxy resin prepared by the reaction
of epichlorohydrin with a compound containing a hydroxyl group
carried out under alkaline reaction conditions; (b) epoxy resins
prepared by the reaction of epichlorohydrin with mononuclear di-
and tri-hydroxy phenolic compounds; (c) epoxidized derivatives of
natural oils with mixed long-chain saturated and unsaturated acids
having between about 14 and 20 carbon atoms; (d) polyepoxides
derived from esters of polycarboxylic acids with unsaturated
alcohols; (e) polyepoxides derived from esters prepared from
unsaturated alcohols and unsaturated carboxylic acids; (f)
epoxidized butadiene based polymers; (g) epoxidized derivatives of
dimers of dienes, and (h) mixtures or combinations thereof, and the
cure system comprises pyrrolidine, alkyl pyrrolidines, oxazoline,
alkyl oxazolines, triazoles, alkyl triazoles, pyrazolidine, alkyl
pyrazolidine, piperidine, alkyl piperidines, piperazine, alkyl
piperazines, imidazoline, imidazolidine, alkyl imidazolidines,
azepane, alkyl azepane, azepine, alkyl azepines, morpholine, alkyl
morpho lines, diazapines, alkyl diazapines, or mixtures and
combinations thereof.
25. The composition of claim 23, wherein: the epoxy resin system
comprises glycidyl ethers epoxy resins, the cure system comprises
heterocyclic amines, the solvent system comprises an aromatic
heterocyclic solvent or a mixture of aromatic heterocyclic
solvents, and the blowing agent or the mixture of blowing agents
comprise aryl hydrazides.
26. The composition of claim 23, wherein: the epoxy resin system
comprises a glycidyl ethers epoxy resin prepared by the reaction of
epichlorohydrin with a compound containing a hydroxyl group carried
out under alkaline reaction conditions, the cure system comprises
heterocyclic amines, the solvent system comprises a mixture of
alkyl pyridines, and the blowing agent or the mixture of blowing
agents comprises p-toluenesulfohydrazide, 4-methylbenzene
p-toluenesulfohydrazide or mixtures thereof.
Description
RELATED APPLICATIONS
[0001] This application is a divisional application and claims the
benefit of and priority to U.S. patent application Ser. No.
13/053,975, filed Mar. 22, 2011 now U.S. Pat. No. 8,851,174 issued
Oct. 7, 2014, which is a continuation-in-part of U.S. patent
application Ser. No. 12/784,479 filed May 20, 2010.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments of the present invention relate to methods and
systems for zonal isolation, where a zone isolation composition is
pumped into an annulus between a borehole and a tubular member
allowed to set to form a foamed isolation seal, where the seal has
a compressibility sufficient for expandable tubing to be expanded
without loss in seal integrity. The cured compositions are ideally
suited for use with expansion tubing, where the zonal isolation
composition must be compressible, while continuing to isolate the
zones.
[0004] More particularly, embodiments of the present invention
relate to methods and systems for zonal isolation, where the zone
isolation composition is pumped into an annulus between a borehole
and a tubular member allowed to test to form a foamed isolation
seal, where the seal has a compressibility sufficient for
expandable tubing to be expanded without loss in seal integrity.
The composition includes epoxy resins, hardening agents and blowing
agents in the presence or absence of solvent or solubilizing
agents. The invention contemplates different combinations of the
resins, the hardening agents, the blowing agents and optional the
solubilizing agents for different temperature applications. A low
temperature zonal isolation composition sets at a low temperature
range. A moderate temperature isolation composition sets at a
moderate temperature range. A temperature isolation composition
sets at a high temperature range. All of the compositions cure to
form a compressible zonal isolation, epoxy foam seal capable of use
in any application where compressibility is need such as with
expansion tubing.
[0005] 2. Description of the Related Art
[0006] Conventional sealants for zonal isolation are cements, foam
fluids or resins. In expandable tubing applications, the zonal
isolation sealant must be able to compress and to continue to seal
after the sealant is pumped behind the pipe and set. Conventional
zone isolation systems do not offer the compressible and/or
resilient properties necessary to permit expandable pipe to expand
without fracturing the system due to their hardness obviating zonal
isolation. Using such compositions requires that the expandable
pipe must expanded prior to the sealant setting. This requires
retarding the setting of the sealant for a time sufficient to
permit the expandable pipe to be expanded prior to sealant setting.
Once the tubing is expanded, the sealant sets. Problems arise when
expansion of expandable tubing cannot occur within the retarding
window for once the sealant sets, the expandable tubing cannot be
expanded due the incompressibility of the cured sealant.
[0007] Thus, there is a need in the art for a sealant that is
compressible and/or resilient permitting expandable tubing to be
expanded before, during and/or after sealant curing. The solution
to these problems is a sealant that is compressible and/or
resilient enough to allow expansion of the expandable pipe before,
during or after the material has harden, while maintaining a
effective zonal isolation seal.
SUMMARY OF THE INVENTION
[0008] Embodiments of the present invention provide methods and
systems for zonal isolation, where the zonal isolation compositions
are pumped into an annulus between a borehole and a tubular member
allowed to set and form a foam isolation seal, where the seal has
resiliency and/or compressibility properties sufficient to sustain
the casing and to permit expansion of the tubing without
substantial loss in seal integrity. Embodiments of the present
invention also provide methods and systems for squeeze jobs, where
a composition of this invention is squeezed or pumped into a zone
to form an in situ tight foam seal having desired resiliency and/or
compressibility properties, where the foam composition expands into
cavities and crevices and continuous to expand after curing.
Embodiments of the compositions of this invention include a epoxy
resin, a hardening agent, a blowing agent and optionally a solvent
or solubilizing agent, where the foam composition expands into
cavities and crevices and continuous to expand after curing. The
blowing agents generate gases at a desired decomposition
temperature to in situ create open celled and/or closed celled
foams, where the cured composition has a Poisson ratio of less than
about 0.5.
[0009] Embodiments of the present invention provide foamable epoxy
zonal isolation sealing compositions including one epoxy resin or a
plurality of epoxy resins, one hardening agent or a plurality of
hardening agents, one blowing agent or a plurality of blowing
agents and optionally a diluent, solvent, solubilizing system,
where the compositions cure to form epoxy foam zonal isolation
structures or seals having sufficient compressibility and/or
resiliency properties to permit compression of the structures or
seals without substantial loss in seal integrity or zonal
isolation. In certain embodiments, the compressibility is
sufficient to allow expansion of expansion tubing pipe during or
especially after setting or curing and blowing to form the foamed
seals. The sealing compositions are designed to have sufficient
strength and bonding characteristics so that the liner, expandable
tubing or other tubing inserted into the borehole is held in place
in the borehole. After setting, the borehole is sealed so that
there is substantially no migration of fluids from one zone to
another zone.
[0010] Embodiments of the present invention provide epoxy foamable
resin systems having desired mechanical properties, while having
improved compressibility and/or resiliency properties.
[0011] Embodiments of the present invention provide foamable
sealant compositions for use as squeeze materials to shut off
annular gas and/or liquid migration and/or to isolate zones during
primary casing or liner top isolation. The sealant compositions are
unique because the mechanical properties are set to allow the
compositions to be ductile and offer long term isolation. The
sealant compositions are also foams, which have greater
compressibility and/or resiliency properties and better flow
properties during curing and foaming so that the compositions form
superior seals by intruding into surface cavities and crevices of
the borehole, while adhering to the outer surface of the lining
tube or casing. Due to the foam nature of the sealing compositions,
the compositions have a Poisson ratio of less than or equal to
about 0.5. Moreover, the epoxy foam sealants of this invention
continue to expand after setting allowing the compositions to
intrude more deeply into formations and provide improved sealing
and long terms sealing integrity. This continued expansion operates
to ensure effective zonal isolation even after expansion of
expandable tubing or after settling of the tubular members into
their final configuration without adversely affecting sealant
properties.
[0012] Embodiments of the present invention provide methods for
zonal isolation including inserting a tubing into a borehole. After
tubing placement, pumping a composition of this invention into an
annulus between the wall of the borehole and an outer wall of the
tubing. Allowing sufficient time for the composition to cure and
foam to form a foamed seal sealing the annulus. The compositions
may be pumped in parts, the resins, the blowing agents and the
hardening agents all may be pumped separately downhole and mixed in
a static mixing chamber downhole prior to or as the components are
being pumped into the annulus. In the case of expansion tubing, the
methods may also include expanding the tubing, where the expansion
of the tubing results in a compression of the foam seals. Where the
seals maintain isolation after expansion. The expansion may be
performed after curing and/or during curing. In certain
embodiments, the expansion is performed during curing and foam
formation.
[0013] Embodiments of the present invention provide methods for
squeeze operations including pumping the composition into annulus
or a region thereof, where fluid (gas, liquid, or mixtures thereof)
migration is occurring, to form a seal to reduce or eliminate such
migration. The methods may also include isolating the region or
regions so that the composition locally reduces or prevents fluid
(gas, liquid, or mixture thereof) migration. The methods may also
include maintaining isolation until the composition is fully cured
and foamed.
[0014] Embodiments of the present invention provide methods for
zone isolation including pumping foamable epoxy-based compositions
into an annulus between a borehole and a tubing string. The
compositions are then allowed to cure to form foam zonal isolation
structures or seals comprising the cured foamed compositions of
this invention. The cured/foamed seals cure at a temperature range
between about 50.degree. and about 300.degree. F. and the blowing
agents are selected to decompose at the curing temperature. The
methods may also include prior to pumping, isolating a section of
an annulus between the borehole and the tubing string so that the
zonal isolation structure is localized along a length of the tubing
string. The methods may also include during or after curing,
expanding a section of the tubing string, where the compressibility
of the cured and foamed seals are sufficient to allow expansion of
expandable tubing without a substantial loss in seal integrity or
zonal isolation. The zonal isolation structure may also be located
at a distal end of the borehole. The foamable compositions comprise
one epoxy resin or a plurality of epoxy resins, one blowing agent
or a plurality of blowing agents, one hardening agent or a
plurality of hardening agents and optionally a diluent,
solubilizing or solvent system, where the compositions cure and
blowing agents decompose to form a cured foamed epoxy sealing
composition having sufficient compressibility and/or resiliency
properties to permit compression of the composition without
substantial loss in seal integrity or zonal isolation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The invention can be better understood with reference to the
following detailed description together with the appended
illustrative drawings in which like elements are numbered the
same:
[0016] FIG. 1A depicts an annulus between a borehole and a tubing
inserted into the borehole.
[0017] FIG. 1B depicts the annulus of FIG. 1A having an sealant
supply conduit inserted into the borehole with a packer to prevent
the sealant from filling the casing showing the annulus being
filled with an epoxy zonal isolation or sealant composition of this
invention.
[0018] FIG. 1C depicts the annulus of FIG. 1A after a zone of the
borehole has been filled with the epoxy zonal isolation
composition.
[0019] FIG. 1D depicts the zone of the annulus of FIG. 1A filled
with a compressible, cured epoxy zonal isolation composition after
curing.
[0020] FIG. 2A depicts an annulus between a borehole and a tubing
inserted into the borehole.
[0021] FIG. 2B depicts the annulus of FIG. 2A having an sealant
supply conduit inserted into the borehole with packers and an
isolation member to isolate a section of the annulus showing the
section being filled with an epoxy zonal isolation or sealant
composition of this invention.
[0022] FIG. 2C depicts the annulus of FIG. 2A after the section has
been filled with the epoxy zonal isolation composition.
[0023] FIG. 2D depicts the zone of the annulus of FIG. 2A filled
with a compressible, cured epoxy zonal isolation composition after
curing.
[0024] FIG. 3A depicts an annulus between a borehole and an
expandable tubing.
[0025] FIG. 3B depicts the annulus of FIG. 3A isolating and filling
a portion of the annulus with an epoxy zonal isolation composition
of this invention.
[0026] FIG. 3C depicts the annulus of FIG. 3A after the portion has
been filled with the epoxy zonal isolation composition and the
composition has cured and expanded.
[0027] FIG. 3D depicts the zone of the annulus of FIG. 3A after the
expansion tubing has been expanded and the composition
compressed.
[0028] FIG. 4A depicts a borehole including a casing having a
region through which production or other fluids may flow into the
structure from a formation or into the formation from the region
via an annulus.
[0029] FIG. 4B depicts the borehole of FIG. 4A after isolating the
region and filling the annulus around the region with an epoxy
composition of this invention.
[0030] FIG. 4C depicts the borehole of FIG. 4A after the annulus
around the structure has been filled with the epoxy zonal isolation
composition.
[0031] FIG. 4D depicts the borehole of FIG. 4A after the epoxy
zonal isolation composition has cured and expanded.
[0032] FIG. 5 depicts a photograph of a cured/foamed sealing
composition of this invention.
DEFINITIONS OF THE INVENTION
[0033] The term substantially no migration of fluids means that
there is less than or equal to 5% fluid migration from one zone to
another zone. In other embodiments, the term means that there is
less than or equal to 2.5% fluid migration from one zone to another
zone. In other embodiments, the term means that there is less than
or equal to 1% fluid migration from one zone to another zone. In
other embodiments, the term means that there is no fluid migration
from one zone to another zone.
[0034] The term without substantial loss of seal integrity means
that the seal integrity after compression is at least 75% of the
seal integrity before compression. In other embodiments, the term
means that the seal integrity after compression with is at least
80% of the seal integrity before compression. In other embodiments,
the term means that the seal integrity after compression with is at
least 85% of the seal integrity before compression. In other
embodiments, the term means that the seal integrity after
compression with is at least 90% of the seal integrity before
compression. In other embodiments, the term means that the seal
integrity after compression with is at least 95% of the seal
integrity before compression. In other embodiments, the term means
that the seal integrity after compression with is at least 99% of
the seal integrity before compression. In other embodiments, the
term means that the seal integrity after compression with is equal
to the seal integrity before compression.
[0035] The term "gpt" means gallons per thousand gallons.
[0036] The term "gptg" means gallons per thousand gallons.
[0037] The term "pptg" means pounds per thousand gallons.
[0038] The term "wt. %" means weight percent.
[0039] The term "w/w" means weight per weight.
DETAILED DESCRIPTION OF THE INVENTION
[0040] The inventors have found that thermal setting epoxy based
resin systems can be used as a zone isolation sealant in downhole
zone isolation operations. The epoxy based resin systems cure and
foam at an elevated temperature to form foam zonal isolation
structures or seals having a compressibility sufficient for use in
expansion tubing, squeeze or other operations requiring a
compressible and resilient seal. During tubing expansion, the cured
and foamed sealing compositions compress without substantial loss
in seal integrity. The inventors have also found that the
compositions may be pumped into an annulus between the wellbore and
the expansion tubing, and the tubing expanded while the
compositions are curing. The compositions of this invention are
designed to cure and foam after the compositions have been pumped
into a zone, where isolation is required or desired. In certain
embodiments, the hardening or curing agents and blowing agents have
delayed cure on-set. In other embodiments, the curing agents and
the blowing agents are added to the resins downhole, just prior to
the compositions being pumped into the zone. In these latter
embodiments, the resins and hardening or curing agents may pass
through a static mixer, mechanical mixer, electromechanical mixer
or other type of mixers to insure adequate dispersal of the
hardening or curing agents in the resin. In certain embodiments,
the curing agents and blowing agents are temperature sensitive so
that curing and blowing occur only when the composition achieves a
given elevated temperature.
[0041] Embodiments of the present invention broadly relate to
foamable epoxy-based zonal isolation compositions including one
epoxy resin or a plurality of epoxy resins, one curing agent or a
plurality of curing agents, and one blowing agent or a plurality of
blowing agents, and optionally a solvent system in the present or
absence of a diluent or solvent system. The compositions cure and
foam to form a cured and foamed epoxy-based zonal isolation seals
or structures having sufficient compressibility and/or resilience
properties to permit compression of the composition without
substantial loss in seal integrity or zonal isolation. In certain
embodiments, the compressibility is sufficient to allow expansion
of expansion tubing pipe during or especially after hardening or
curing of the composition. The sealant compositions are designed to
have sufficient strength and bonding characteristics so that the
liner, expandable tubing or other tubing inserted into the borehole
is held in place in the borehole and the borehole is sealed so that
there is no migration of fluids from one zone to another zone. In
certain embodiments, the compositions of this invention are low
temperature, foamable zonal isolation compositions, which set and
foam at a low temperature range between about 50.degree. F. and
about 90.degree. F. In other embodiments, the compositions of this
invention are moderate temperature, foamable zonal isolation
compositions, which set at a moderate temperature range between
about 90.degree. F. and about 150.degree. F. In certain
embodiments, the compositions of this invention are high
temperature, foamable zonal isolation compositions, which set at a
high temperature range between about 150.degree. F. to about
300.degree. F. All of the compositions cure and foam to form
compressible zonal isolation, epoxy foam seals capable of use in
any application, where compressibility and/or resiliency properties
are needed or desired such as with expansion tubing operations and
squeeze operations.
High Temperature Compositions
[0042] Embodiments of the present invention specifically relate to
high-temperature, foamable epoxy-based zonal isolation compositions
including one epoxy resin or a plurality of epoxy resins, one
curing agent or a plurality of curing agents, and one blowing agent
or a plurality of blowing agents in the present or absence of a
diluent or solvent system. The composition is designed to thermally
set at temperature between about 150.degree. F. to about
300.degree. F.
[0043] In certain embodiments, the high-temperature foamable zonal
isolation compositions include from about 60 wt. % to about 85 wt.
% of an epoxy resin or mixture of epoxy resins, from about 1 wt. %
to about 15 wt. % of a curing agent or mixture of curing agents,
from about 5 wt. % to about 15 wt. % of a blowing agent or mixture
of blowing agents and optionally from about 0 wt. % to about 39 wt.
% of a diluent or solvent system, based on the weight of the other
components. The diluent or solvent system is used to reduce the
viscosity of the composition.
[0044] In other embodiments, the high-temperature foamable zonal
isolation compositions include from about 65 wt. % to about 85 wt.
% of an epoxy resin or mixture of epoxy resins, from about 5 wt. %
to about 10 wt. % of a curing agent or mixture of curing agents,
from about 5 wt. % to about 15 wt. % of a blowing agent or mixture
of blowing agents and from about 5 wt. % to about 30 wt. % of a
diluent or solvent system, based on the weight of the other
components.
[0045] In other embodiments, the high-temperature zonal isolation
composition includes from about 75 wt. % to about 85 wt. % of an
epoxy resin or mixture of epoxy resins, from about 5 wt. % to about
10 wt. % of curing agent or mixture of curing agents, from about 5
wt. % to about 15 wt. % of a blowing agent or mixture of blowing
agents and from about 5 wt. % to about 20 wt. % of a diluent or
solvent system, based on the weight of the other components.
[0046] In other embodiments, the high-temperature zonal isolation
composition includes from about 80 wt. % to about 85 wt. % of an
epoxy resin or mixture of epoxy resins, from about 5 wt. % to about
10 wt. % of a curing agents, from about 5 wt. % to about 15 wt. % a
blowing agent or mixture of blowing agents, and from about 5 wt. %
to about 15 wt. % of a diluent or solvent system based on the
weight of the other components.
[0047] In certain embodiments, the epoxy resin is a glycidyl ethers
epoxy resin or mixture of glycidyl ethers epoxy resins, the curing
agent is an alkoxylated polyamine or mixture of alkoxylated
polyamines and the diluent is an aromatic heterocyclic solvent or
mixture of aromatic heterocyclic solvents.
[0048] In other embodiments, the epoxy resin is DURA COAT.TM. 1A
available from JACAM Chemicals, LLC, of Sterling, Kans., the curing
agent is DURA COAT.TM. 2B available from JACAM Chemicals, LLC, of
Sterling, Kans. and the diluent is AKOLIDINE.TM. 11 available from
Lonza Group Ltd, Joseph Colleluori, Muenchensteinerstrasse 38,
CH-4002 Basel, Switzerland.
Mid Temperature Compositions
[0049] Embodiments of the present invention specifically relate to
mid-temperature, foamable epoxy-based zonal isolation compositions
including one epoxy resin or a plurality of epoxy resins, one
curing agent or a plurality of curing agents, and one blowing agent
or a plurality of blowing agents in the present or absence of a
diluent or solvent system. The compositions are designed to
thermally set at temperature between about 90.degree. F. and about
150.degree. F.
[0050] In certain embodiments, the mid-temperature, foamable zonal
isolation compositions include from about 70 wt. % to about 50 wt.
% of an epoxy resin or mixture of epoxy resins, from about 30 wt. %
to about 50 wt. % of a hardening or curing agent or a mixture of
curing agents and from about 5 wt. % to about 15 wt. % a blowing
agent or mixture of blowing agents based on the weight of the other
components.
[0051] In other embodiments, the mid-temperature zonal isolation
composition includes from about 60 wt. % to about 50 wt. % of an
epoxy resin or mixture of epoxy resins, from about 40 wt. % to
about 50 wt. % of a hardening or curing agent or a mixture of
curing agents and from about 5 wt. % to about 15 wt. % a blowing
agent or mixture of blowing agents based on the weight of the other
components.
[0052] In other embodiments, the mid-temperature zonal isolation
composition includes from about 55 wt. % to about 50 wt. % of an
epoxy resin or mixture of epoxy resins and from about 45 wt. % to
about 50 wt. % of a hardening or curing agent or a mixture of
curing agents and from about 5 wt. % to about 15 wt. % a blowing
agent or mixture of blowing agents based on the weight of the other
components. The mid-temperature zonal isolation compositions may be
diluted with up to about 20 wt. % of a diluent or solvent, where
the diluent or solvent is used to reduce the viscosity of the
composition.
[0053] In other embodiments, the epoxy resin is glycidyl ethers
epoxy resin or mixture of glycidyl ethers epoxy resins and the
curing agent is a heterocyclic amine.
[0054] In certain embodiments, the epoxy resin is DURA COAT.TM. 1A
available from JACAM Chemicals, LLC, of Sterling, Kans., and the
curing agent is a imidazoline or mixture or imidazolines.
Low Temperature Compositions
[0055] Embodiments of the present invention specifically relate to
low-temperature epoxy-based zonal isolation compositions including
one epoxy resin or a plurality of epoxy resins, one curing agent or
a plurality of curing agents, and one blowing agent or a plurality
of blowing agents in the present or absence of a diluent or solvent
system. The composition is designed to thermally set at temperature
between about 50.degree. F. and about 90.degree. F.
[0056] In certain embodiments, the low-temperature zonal isolation
composition includes from about 75 wt. % to about 99 wt. % of an
epoxy resin or a mixture of epoxy resins, from about 25 wt. % to
about 1 wt. % of a hardening or curing agent or a mixture of curing
agents and from about 5 wt. % to about 20 wt. % the blowing agents
based on the weight of the other components.
[0057] In other embodiments, the low-temperature zonal isolation
composition includes from about 85 wt. % to about 97.5 wt. % of an
epoxy resin or a mixture of epoxy resins, from about 15 wt. % to
about 2.5 wt. % of a curing agent or a mixture of curing agents and
from about 5 wt. % to about 20 wt. % the blowing agents based on
the weight of the other components.
[0058] In other embodiments, the low-temperature zonal isolation
composition includes from about 90 wt. % to about 95 wt. % of an
epoxy resin or mixture of epoxy resins, from about 10 wt. % to
about 5 wt. % of a curing agent or a mixture of curing agents, and
from about 5 wt. % to about 20 wt. % a blowing agent or mixture of
blowing agents based on the weight of the other components. The
low-temperature zonal isolation compositions may be diluted with up
to about 20 wt. % of a diluent or solvent, where the diluent or
solvent is used to reduce the viscosity of the composition.
[0059] In other embodiments, the epoxy resin is glycidyl ethers
epoxy resin or mixture of glycidyl ethers epoxy resins and the
curing agent is a heterocyclic amine.
[0060] In certain embodiments, the epoxy resin is DURA COAT.TM. 1A
available from JACAM Chemicals, LLC, of Sterling, Kans., and the
curing agent is a imidazoline, pyrrolidine, pyrrole, pyridine,
piperidine or mixtures thereof.
Methods
[0061] Embodiments of the present invention also broadly relates to
methods for zonal isolation including inserting a tubing into a
borehole. After tubing placement, pumping a foamable composition of
this invention into an annulus between the wall of the borehole and
an outer wall of the tubing. The methods also include allowing
sufficient time for the compositions to cure and foam sealing the
annulus. The compositions may be pumped in parts. In certain
embodiments, the resins and the blowing agents and the hardening or
curing agents may be pumped separately downhole and mixed in a
static mixing chamber downhole prior to being pumped into the
annulus. In other embodiments, the resins and the hardening or
curing agents and the blowing agent pumped separately downhole and
mixed in a static mixing chamber downhole prior to being pumped
into the annulus.
[0062] Embodiments of the present invention also provide methods
for squeeze operations including pumping a composition of this
invention into annular spaces, regions or locations in a complete
well, where fluid migration is occurring to form a seal to reduce
or eliminate such migration.
[0063] In certain embodiments, the diluent system comprises
aromatic solvents and heterocyclic aromatic solvents or mixtures
and combinations thereof.
[0064] The epoxy resins may comprise: (a) glycidyl ethers epoxy
resin prepared by the reaction of epichlorohydrin with a compound
containing a hydroxyl group carried out under alkaline reaction
conditions; (b) epoxy resins prepared by the reaction of
epichlorohydrin with mononuclear di- and tri-hydroxy phenolic
compounds; (c) epoxidized derivatives of natural oils with mixed
long-chain saturated and unsaturated acids having between about 14
and 20 carbon atoms; (d) polyepoxides derived from esters of
polycarboxylic acids with unsaturated alcohols; (e) polyepoxides
derived from esters prepared from unsaturated alcohols and
unsaturated carboxylic acids; (f) epoxidized butadiene based
polymers; (g) epoxidized derivatives of dimers of dienes, and (h)
mixtures or combinations thereof. The epoxy resins may have a
molecular weight between about 50 and about 10,000.
[0065] The curing agents may comprise polyamine curing agents,
alkoxylated polyamine curing agents, heterocylic amine curing
agents, or similar compounds including a plurality of amino groups,
or mixtures and combinations thereof. The curing agents may
comprise alkoxylated aliphatic polyamines, alkoxylated
cycloaliphatic polyamines, alkoxylated aromatic polyamines,
alkoxylated heterocyclic polyamines or mixtures and combinations
thereof.
[0066] In certain embodiments, the temperature range is between
about 150.degree. F. to about 300.degree. F. and the composition
comprises from about 60 wt. % to about 85 wt. % of an epoxy resin
or a mixture of epoxy resins, from about 1 wt. % to about 15 wt. %
of a curing agent or a mixture of curing agents, and from about 5
wt. % to about 15 wt. % the blowing agent a mixture or blowing
agents and from about 39 wt. % to about 0 wt. % of a diluent or
solvent, based on the weight of the other components, where the
diluent or solvent is used to reduce the viscosity of the
composition. The epoxy resins are glycidyl ethers epoxy resins or
mixture of glycidyl ethers epoxy resins, the curing agent is an
alkoxylated polyamine or mixture of alkoxylated polyamines and the
diluent is an aromatic heterocyclic solvent or mixture of aromatic
heterocyclic solvents. The epoxy resin is DURA COAT.TM. 1A
available from JACAM Chemicals, LLC, of Sterling, Kans., the curing
agent is DURA COAT.TM. 2B available from JACAM Chemicals, LLC, of
Sterling, Kans., and the diluent is AKOLIDINE.TM. 11 available from
Lonza Group Ltd, Joseph Colleluori, Muenchensteinerstrasse 38,
CH-4002 Basel, Switzerland.
[0067] In certain embodiments the temperature range is between
about 90.degree. F. and about 150.degree. F. and the composition
comprises from about 70 wt. % to about 50 wt. % of an epoxy resin
or a mixture of epoxy resins, from about 30 wt. % to about 50 wt. %
of a hardening or curing agents or a mixture of curing agents and
from about 5 wt. % to about 20 wt. % a blowing agent or a mixture
of blowing agents based on the weight of the other components. The
epoxy resins may be glycidyl ethers epoxy resin or mixture of
glycidyl ethers epoxy resins and the curing agent may be a
heterocyclic amine. The epoxy resin may be DURA COAT.TM. 1A
available from JACAM Chemicals, LLC, of Sterling, Kans. and the
curing agent may be a imidazoline or mixture or imidazolines.
[0068] In certain embodiments the temperature range is between
about 50.degree. F. and about 90.degree. F. and the composition
comprises from about 75 wt. % to about 99 wt. % of an epoxy resin
or a mixture of epoxy resins, from about 25 wt. % to about 1 wt. %
of a hardening or curing agent or a mixture of curing agents, and
from about 5 wt. % to about 15 wt. % a blowing agent or a mixture
of blowing agents based on the weight of the other components. The
epoxy resins may be glycidyl ethers epoxy resin or mixture of
glycidyl ethers epoxy resins and the curing agent is a imidazoline,
pyrrolidine, pyrrole, pyridine, piperidine or mixtures thereof. The
epoxy resin may be DURA COAT.TM. 1A available from JACAM Chemicals,
LLC, of Sterling, Kans. and the curing agent may be a imidazoline,
pyrrolidine, pyrrole, pyridine, piperidine or mixtures thereof.
[0069] In certain embodiments the composition comprises from about
60 wt. % to about 85 wt. % of a epoxy resin or a mixture of epoxy
resins, from about 1 wt. % to about 15 wt. % of a hardening or
curing agent or a mixture of curing agents, from about 5 wt. % to
about 15 wt. % a blowing agent or a mixture of blowing agents and
from about 39 wt. % to about 0 wt. % of a solvent system, based on
the weight of the other components.
Suitable Materials for Use in the Invention
[0070] Suitable epoxy resin include, without limitation, (a)
glycidyl ethers epoxy resin prepared by the reaction of
epichlorohydrin with a compound containing a hydroxyl group (e.g.,
bisphenol A) carried out under alkaline reaction conditions; (b)
epoxy resins prepared by the reaction of epichlorohydrin with
mononuclear di- and tri-hydroxy phenolic compounds such as
resorcinol and phloroglucinol, selected polynuclear polyhydroxy
phenolic compounds such as bis(p-hydroxyphenyl)methane and
4,4'-dihydroxy biphenyl, or aliphatic polyols such as
1,4-butanediol and glycerol; (c) epoxidized derivatives of natural
oils such as the triesters of glycerol with mixed long-chain
saturated and unsaturated acids having between about 14 and 20
carbon atoms (e.g., 16, 18 and 20 carbon atoms) (soybean oil is a
typical triglyceride which can be converted to a polyepoxide); (d)
polyepoxides derived from esters of polycarboxylic acids such as
maleic acid, terephthalic acid, oxalic acid, succinic acid, azelaic
acid, malonic acid, tartaric acid, adipic acid or similar acids,
with unsaturated alcohols; (e) polyepoxides derived from esters
prepared from unsaturated alcohols and unsaturated carboxylic
acids; (f) epoxidized butadiene based polymers such as
butadiene-styrene copolymers, polyesters available as derivatives
of polyols such as ethylene glycol with unsaturated acid anhydrides
such as maleic anhydride and esters of unsaturated polycarboxylic
acids; (g) epoxidized derivatives of dimers of dienes such as
4-vinyl cyclohexene-1 from butadiene and dicyclopentadiene from
cyclopentadiene, and (h) mixtures or combinations thereof. Epoxy
resins suitable for use in the invention have molecular weights
generally within the range between about 50 and about 10,000. In
other embodiments, the range is between about 2000 and about 1500.
In other embodiments, the epoxy resin is commercially available
EPON.RTM. Resin 828 epoxy resin, a registered trademark of
Polysciences, Inc. of Warrington, Pa., a reaction product of
epichlorohydrin and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A)
and having a molecular weight of about 400, an epoxide equivalent
(ASTM D-1652) of about 185-192. Exemplary examples of some epoxy
resins include, without limitation: epoxidized esters of
2,3-epoxypentyl-3,4-epoxybutyrate;
2,3-epoxybutyl-3,4-epoxyhexanoate;
3,4-epoxyoctyl-2,3-epoxycyclohexane carboxylate;
2,3-epoxydodecyl-4,5-epoxyoctanoate;
2,3-epoxyisobutyl-4,5-epoxydodecanoate;
2,3-epoxycyclododedcyl-3,4-epoxypentanoate;
3,4-epoxyoctyl-2,3-epoxycyclododecane carboxylate or similar
compounds; and polyepoxides derived from the latter include the
following: dimethyl 3,4,7,8-diepoxydecanedioate; dibutyl
3,4,5,6-diepoxycyclohexane-1,2-carboxylate; dioctyl
3,4,7,8-diepoxyhexadecanedioate; diethyl
5,6,9,10-diepoxytetradecanedioate or similar anhydrides. In other
embodiments the epoxy resin is DURA COAT.TM. 1A available from
JACAM Chemicals, LLC, of Sterling, Kans. Other epoxy resins are
available from JACAM Chemicals, LLC, of Sterling, Kans. or may be
found in U.S. Pat. Nos. 5,936,059; 7,557,169; 7,547,373; 7,267,782;
6,943,219; and 6,277,903.
[0071] Suitable curing agents for the epoxy resins include, without
limitation, polyamine curing agents, alkoxylated polyamine curing
agents, heterocylic amine curing agents, or similar compounds
including a plurality of amino groups, or mixtures and combinations
thereof. Exemplary alkoxylated polyamine curing agents include,
without limitation, alkoxylated aliphatic polyamines, alkoxylated
cycloaliphatic polyamines, alkoxylated aromatic polyamines,
alkoxylated heterocyclic polyamines or mixtures and combinations
thereof. In certain embodiments, the alkoxylated polyamines are
alkoxylated N-alkyl- and N-alkylenyl-substituted
1,3-diaminopropanes or mixtures and combinations thereof. In other
embodiments, the alkoxylated polyamines include alkoxylated
N-hexadecyl-1,3-diaminopropane, N-tetradecyl-1,3-diaminopropane,
N-octadecyl-1,3-diaminopropane, N-pentadecyl-1,3-diaminopropane,
N-heptadecyl-1,3-diaminopropane, N-nonadecyl-1,3-diaminopropane,
N-octadecnyl-1,3-diaminopropane or mixtures and combinations
thereof. In other embodiments, the alkoxylated polyamines include
commercially available mixtures of ethoxylated N-alkylated and
N-alkenylated diamines. In other embodiments, the polyamine is a
commercial product, ethoxylated N-tallow-1,3-diaminopropane, where
the degree of ethoxylation is approximately 10 moles ethoxylate per
mole of tallow diamine. In other embodiments the epoxy resin is
DURA COAT.TM. 2B available from JACAM Chemicals, LLC, of Sterling,
Kans. Other epoxy curing agents are available from JACAM Chemicals,
LLC, of Sterling, Kans. or may be found in U.S. Pat. Nos.
5,936,059; 7,557,169; 7,547,373; 7,267,782; 6,943,219; and
6,277,903. Exemplary aromatic heterocyclic amine curing agents
include, without limitation, pyrrolidine, alkyl pyrrolidines,
oxazoline, alkyl oxazolines, triazoles, alkyl triazoles,
pyrazolidine, alkyl pyrazolidine, piperidine, alkyl piperidines,
piperazine, alkyl piperazines, imidazoline, imidazolidine, alkyl
imidazolidines, azepane, alkyl azepane, azepine, alkyl azepines,
morpholine, alkyl morpholines, diazapines, alkyl diazapines, or
mixtures and combinations thereof. In certain embodiments, the
curing agents are a mixture of alkyl pyridines such as
AKOLIDINE.TM. 11, available from Lonza Group Ltd, Joseph
Colleluori, Muenchensteinerstrasse 38, CH-4002 Basel, Switzerland
and DURA COAT.TM. 2B, available from JACAM Chemicals, LLC, of
Sterling, Kans. In other embodiments, the diluent is pyrrolidine.
In other embodiments, the diluent is imodazoline.
[0072] Suitable diluent, solubilizing agents or solvent systems for
use in the present invention include, without limitation, aromatic
solvents and heterocyclic aromatic solvents or mixtures and
combinations thereof. Exemplary examples include, without
limitation, benzene, toluene, xylene, aromatic oils, aromatic
naphtha, pyrrole, alkyl pyrrols, imidazole, alkyl imidazole,
pyridine, alkyl pyridines, pyrazole, alkyl pyrazoles, oxazole,
alkyl oxazoles, or mixtures and combinations thereof.
[0073] Suitable blowing agents for use in the practice of this
invention include, without limitation, arylsulphonyl hydrazides
including benzene sulphonyl hydrazides, alkylated benzene sulphonyl
hydrazides, e.g., 4-methyl benzene sulphonyl hydrazide, and dimeric
arylsulphonyl hydrazides including p,p'-oxybis(benzene sulphonyl
hydrazide), other similar blowing agents that decompose to generate
either nitrogen, carbon dioxide or another inert or substantially
inert gas, or mixtures and combinations thereof.
DETAILED DESCRIPTION OF THE DRAWINGS
[0074] Referring now to FIGS. 1A-D, an embodiment of a zonal
isolation procedure of this invention, generally 100, is shown to
include well borehole 102 having a wall 104. Inserted into the
borehole 102 is a casing string 106, which has a distal end 108
disposed near a bottom 110 of the well 102. Looking at FIG. 1B, a
supply conduit 112 including a packer 114 is inserted into the
borehole 102 and an epoxy-based zonal isolation composition 116 of
this invention is pumped into the borehole 102 through the conduit
112 and into an annular space 118 between the wall 104 of the
borehole 102 and an outer wall 120 of the casing 106. Looking at
FIG. 1C, pumping is continued until the composition 116 fills the
annular space 118 to a desired level 122 in the borehole 102 and
the conduit 112 and packer 114 are removed (shown after equipment
removal). Looking at FIG. 1D, the composition 116 cures to form a
cured, epoxy-based zone isolation structure 124.
[0075] Referring now to FIGS. 2A-D, another embodiment of a zonal
isolation procedure of this invention, generally 200, is shown to
include well borehole section 202 having a wall 204 and including a
casing string 206 extending through the section 202. Looking at
FIG. 2B, the section 202 is shown equipped with a bottom zone
isolation sealing member 208, outlets 210, and a supply conduit 212
including packers 214. An epoxy-based zonal isolation composition
216 of this invention is then pumped through the conduit 212 into
an annular space 218 between the wall 204 of the section 202 above
the member 208. Looking at FIG. 2C, pumping is continued until the
composition 216 fills the annular space 218 to a desired level 220
in the section 202. The conduit 212 and packers 214 are then
removed (shown after equipment removal). Looking at FIG. 2D, the
composition 216 cures to form a cured, epoxy-based zone isolation
structure 222 within the section 202.
[0076] Referring now to FIGS. 3A-D, an embodiment of an expansion
tubing procedure of this invention, generally 300, is shown to
include well borehole 302 having a wall 304 and including a casing
string 306 extending through the borehole 302, where the casing 306
has a distal end 308 disposed near a bottom 310 of the borehole
302. The casing 306 also includes an expandable section 312.
Looking at FIG. 3B, the borehole 302 is shown equipped with a
supply conduit 314 including a packer 316. An epoxy-based zonal
isolation composition 318 of this invention is then pumped through
the conduit 314 into an annular space 320 between the wall 304 of
the borehole 302. Pumping is continued until the composition 318
fills the annular space 320 to a desired level 322 in the borehole
302. The conduit 314 and packer 316 are then removed (not shown)
and the composition 318 allowed to cure to form a cured,
epoxy-based zone isolation structure 324 within the borehole 302.
An expansion member 326 is then inserted into the casing 306 and
the tubing is expanded by pulling the expansion member 326 through
the expansion section 312 of the casing 306 to expand the expansion
section 312. The expansion operation results in a compression of
the cured, epoxy-based zone isolation structure 324 to form a
compressed, cured, epoxy-based zone isolation structure 328 as
shown in FIG. 3D. Additional details on expansion tubing, how it is
expanded and used in downhole applications may be found in,
published Apr. 1, 2010 and U.S. Pat. Nos. 3,049,752, 3,678,560,
3,905,227, 4,204,426, 4,616,987, 5,271,469, 5,271,472, 5,947,213,
6,112,809, 6,296,057, 6,843,317, 6,880,632, 7,182,141, 7,215,125,
7,500,389, 7,634,942, and United States Published Application No.
20030111234, 20040099424, 20040154797, 20040163819, 20040216925,
20050173109, 20050173130, 20050279514, 20050279515, 20060027376,
20070151360, 20080083533 and 20100078166.
[0077] Referring now to FIGS. 4A-D, an embodiment of a squeeze out
procedure of this invention, generally 400, is shown to include
well borehole section 402 having a wall 404 and including a casing
string 406 extending through the section 402. The section 402
includes a region 408 through which fluid flow into and out of the
casing 406. This region 408 may result in contamination of
production fluids, treating fluids, or other fluids typically used
in downhole operations. To reduce or eliminate the flow of fluid
through the region 408, a sealant of this invention can be pumped
into the region 408, and after curing, the sealant will form a seal
reducing or eliminating fluid flow into and out of the casing 406.
Looking at FIG. 4B, the section 402 is shown equipped with a supply
conduit 410 including packers 412. An epoxy-based zonal isolation
composition 414 of this invention is then pumped through the
conduit 410 into an annular space 416 between the wall 404 of the
section 402 and an outer wall 418 of the casing 406. Looking at
FIG. 4C, pumping is continued until the composition fills the
annular space 416 to a desired level 420 in the section 402. The
conduit 410 and packers 412 are then removed (shown after equipment
removal). Looking at FIG. 4D, the composition 414 cures to form a
cured, epoxy-based zone isolation structure 422 within the section
402 reducing or eliminating flow through the case 406 at the region
408.
EXPERIMENTS OF THE INVENTION
Example 1
[0078] This example illustrates the formulation of epoxy foam zonal
isolation compositions for high temperature applications, where the
composition has a set temperature in a high-temperature range
between about 150.degree. F. to about 300.degree. F. and the
compositions including 1 wt. %, 3 wt. %, 5 wt. %, 10 wt. %, 15 wt.
% and 20 wt. % added of p-toluenesulfohydrazide (TSH) or
4-methylbenzene p-toluenesulfohydrazide.
[0079] 22.6 grams of DURA COAT.TM. 1A, available from JACAM
Chemicals, LLC, of Sterling, Kans., was added to 2.6 grams of
AKOLIDINE.TM. 11, available from Lonza Group Ltd, Joseph
Colleluori, Muenchensteinerstrasse 38, CH-4002 Basel, Switzerl and
an indicated amount of p-toluenesulfohydrazide with mixing. To this
solution was added 2.0 grams of DURA COAT.TM. 2B, available from
JACAM Chemicals, LLC, of Sterling, Kans., and placed in an oven @
250.degree. F. for 24 hr to form a high-temperature foam zonal
isolation composition (HTFZIC) of this invention. Table I tabulates
the components, the amount and weight percentages of the HTFZI
compositions of this invention.
TABLE-US-00001 TABLE I High-Temperature Zone Isolation Composition
DURA DURA Foams COAT .TM. 1A COAT .TM. 2B Akolidine .TM. 11 TSH* F1
22.6 grams 2.0 grams 2.6 grams 1 wt. % F2 22.6 grams 2.0 grams 2.6
grams 3 wt. % F3 22.6 grams 2.0 grams 2.6 grams 5 wt. % F4 22.6
grams 2.0 grams 2.6 grams 10 wt. % F5 22.6 grams 2.0 grams 2.6
grams 20 wt. % *p-toluenesulfohydrazide
[0080] The experimental data showed that F4 had the best foam
properties of the tested compositions having a compressive strength
between 3.318 and 5.704 psi. F5 was too exothermic and had reduced
foam properties.
Example 2
[0081] This example illustrates the formulation of epoxy foam zonal
isolation compositions for high temperature applications, where the
composition has a set temperature in a high-temperature range
between about 150.degree. F. to about 300.degree. F. and the
compositions including 1 wt. %, 3 wt. %, 5 wt. %, 10 wt. %, 15 wt.
% and 20 wt. % added of p-toluenesulfohydrazide (TSH) or
4-methylbenzene p-toluenesulfohydrazide.
[0082] 5 wt. % and 10 wt. % of p-toluenesulfohydrazide were added
to the formula of Example 1 base sample above and the final
composition was placed in oven rolling cell at 250.degree. F. under
a pressure of 300 psi using a gas mixture including 96% nitrogen
and 4% oxygen. After 24 hr of pressurization, the sample with 10
wt. % TSH showed better foam properties than the sample with 5 wt.
% TSH. FIG. 5 illustrates the cured and foamed seal of this
invention.
[0083] All references cited herein are incorporated by reference
for every purpose permitted by controlling United States Laws.
Although the invention has been disclosed with reference to its
preferred embodiments, from reading this description those of skill
in the art may appreciate changes and modification that may be made
which do not depart from the scope and spirit of the invention as
described above and claimed hereafter.
* * * * *