MX339949B

Resin sealant for zonal isolation and methods for making and using same.

Abstract

Epoxy-based, temperature specific zonal isolation compositions are disclosed and methods for isolating zones in borehole of oil and gas wells using the compositions, where the composition is adjusted for use in high-temperature, mid-temperature and low-temperature applications.

MX339949B, drawing sheet 1 — Sheet 1 of 72

Term

4.7 yearsleft in the term

Expires 20 May 2031.

28 claims: 14 independent, 14 dependent

1
NOVEDAD DE LA INVENCIÓN NOVELTY OF THE INVENTION Habiendo descrito la presente considera como novedad, y por lo tanto propiedad lo contenido en las siguientes:Having described this, it considers as novelty, and therefore property, the content of the following: CLAIMS REIVINDICACIONES 1. Un método para aislamiento de zonas caracterizado porque comprende: one. A method for isolation of zones characterized in that it comprises: variar una composición de una composición de base vary a composition from a base composition 10 epoxy depending on a borehole temperature to form a temperature specific epoxy base composition, wherein the epoxy base composition comprises an epoxy resin or a plurality of epoxy resins and a temperature specific curing system, 10 epóxica dependiendo de una temperatura de pozo de perforación para formar una composición de base epóxica específica de la temperatura, en donde la composición de base epóxica comprende una resina epóxica o una pluralidad de resinas epóxicas y un sistema de curado específico de la temperatura, 15 en donde el sistema de curado específico de la temperatura comprende: fifteen where the specific temperature curing system comprises: a) a high temperature curing system that includes an alkoxylated polyamine or a mixture of alkoxylated polyamines for high borehole temperatures a) un sistema de curado de alta temperatura que incluye una poliamina alcoxilada o una mezcla de poliaminas alcoxiladas para temperaturas de pozo de perforación altas 20 que tienen un valor entre 66°C hasta 149°C (150°F hasta twenty having a value between 66 ° C to 149 ° C (150 ° F to 300 ° F) to form a high temperature epoxy based composition;300°F) para formar una composición de base epóxica de alta temperatura;invención, se se reclama como invention, it is claimed as b) a medium temperature curing system that b) un sistema de curado de temperatura media que IMPÍ includes imidazoline or a mixture of imidazolines for moderate borehole temperatures ranging from 32.2 ° C to 66 ° C (between 90 ° F to 150 ° F) to form a medium temperature epoxy base composition, and IMPÍ incluye imidazolina o una mezcla de imidazolinas para temperaturas de pozo de perforación moderadas que tienen un valor entre 32.2°C y 66°C (entre 90°F y 150°F) para formar una composición de base epóxica de temperatura media, y c) a low temperature curing system including pyrrole, pyridine, piperidine, or mixtures thereof, for moderate drilling well temperatures ranging from 10 ° C to 32.2 ° C (between 50 ° F and 90 ° F) to form a low temperature epoxy base composition, pump the temperature specific epoxy base composition into a ring between a drill hole and a pipe string, and allowing the composition to cure to form a zone isolation structure, where the zone isolation structure is compressible. c) un sistema de curado de baja temperatura que incluye pirrol, piridina, piperidina, o mezclas de los mismos, para temperaturas de pozo de perforación moderadas que tienen un valor entre 10°C y 32.2°C (entre 50°F y 90°F) para formar una composición de base epóxica de baja temperatura, bombear la composición de base epóxica específica de la temperatura en un anillo entre un pozo de perforación y una sarta de tubería, y permitir que la composición se cure para formar una estructura de aislamiento de zonas, donde la estructura de aislamiento de zonas es comprimible.
15
Una composición para aislamiento de zonas dependiente de temperatura, caracterizada porque comprende:fifteen. A composition for temperature-dependent insulation of zones, characterized in that it comprises: an epoxy based composition including: una composición de base epóxica que incluye: an epoxy resin or a plurality of epoxy resins. una resina epóxica o una pluralidad de resinas epóxicas. a specific temperature curing system comprising: un sistema de curado específico de la temperatura que comprende: a) a high-temperature curing system that includes an alkoxylated polyamine or a mixture of alkoxylated polyamines for high borehole temperatures that are between 66 ° C to 149 ° C (150 ° F to a) un sistema de curado de alta temperatura que incluye una poliamina alcoxilada o una mezcla de poliaminas alcoxiladas para temperaturas altas de pozo de perforación que tienen un valor entre 66°C hasta 149°C (150°F hasta 300 ° F) to form a high temperature epoxy based composition;300°F) para formar una composición de base epóxica de alta temperatura;b) a medium temperature curing system that includes imidazoline or a mixture of imidazolines for moderate borehole temperatures that are between 32.2 ° C and 66 ° C (between 90 ° F and 150 ° F) to form b) un sistema de curado de temperatura media que incluye imidazolina o una mezcla de imidazolinas para temperaturas de pozo de perforación moderadas que tienen un valor entre 32.2°C y 66°C (entre 90°F y 150°F) para formar IMPI a medium temperature epoxy based composition;or IMPI una composición de base epóxica de temperatura media;o c) a low temperature curing system that includes pyrrole, pyridine, piperidine, or mixtures thereof, for low borehole temperatures that are between 10 ° C and 32.2 ° C (between 50 ° F and 90 ° F) to form a low temperature epoxy based composition, wherein the composition cures at the designated temperature to form a compressible zone insulation structure. c) un sistema de curado de baja temperatura que incluye pirrol, piridina, piperidina, o mezclas de los mismos, para temperaturas bajas de pozo de perforación que tienen un valor entre 10°C y 32.2°C (entre 50°F y 90°F) para formar una composición de base epóxica de baja temperatura, en donde la composición cura a la temperatura designada para formar una estructura de aislamiento de zona comprimible.
16
The composition according to claim 16. La composición de conformidad con la reivindicación 15, caracterizada porque la estructura de aislamiento de zonas se localiza en una sección del anillo entre el pozo de perforación y una sarta de tubería, de manera que la estructura de aislamiento de zonas se localice a lo largo de un tramo de la sarta de tubería. 15, characterized in that the zone isolation structure is located in a section of the ring between the drill hole and a pipe string, so that the zone isolation structure is located along a section of the pipe string .
17
The composition according to claim 17. La composición de conformidad con la reivindicación 15, caracterizada porque la estructura de aislamiento de zonas se comprime durante o después del curado, cuando una sección de la sarta de tubería se expande y en donde la estructura de aislamiento de zonas es suficientemente comprimible para aislar la sección de tubería sin pérdida sustancial en integridad del sello o aislamiento de zonas. 15, characterized in that the zone insulation structure is compressed during or after curing, when a section of the pipe string expands and wherein the zone isolation structure is compressible enough to insulate the pipe section without substantial loss in seal integrity or zone isolation.
19
The composition according to claim 19. La composición de conformidad con la reivindicación 15, caracterizada porque la estructura de aislamiento de zonas tiene suficientes propiedades de compresibilidad y resiliencia para permitir la compresión de la estructura sin pérdida sustancial en integridad del sello o aislamiento de zonas. 15, characterized in that the zone insulation structure has sufficient compressibility and resilience properties to allow compression of the structure without substantial loss in seal integrity or zone isolation.
20
La composición de conformidad con la reivindicación twenty. The composition according to claim 15, caracterizada porque además comprende un diluyente seleccionado del grupo que consiste de solventes aromáticos, solventes aromáticos heterocíclicos y mezclas y combinaciones de los mismos. 15, characterized in that it further comprises a diluent selected from the group consisting of aromatic solvents, heterocyclic aromatic solvents, and mixtures and combinations thereof.
21
La composición de conformidad con la reivindicación twenty-one. The composition according to claim 15, caracterizada porque la resina epóxica o las resinas epóxicas se seleccionan del grupo que consiste de:(a) resina epóxica de éteres de glicidilo preparada por la reacción de epiclorhidrina con un compuesto que contiene un grupo hidroxilo llevada a cabo bajo condiciones alcalinas de reacción;(b) resinas epóxicas preparadas por la reacción de epiclorhidrina con compuestos mononucleares di- y tri-hidroxi fenólicos;(c) derivados epoxidados de aceites naturales con ácidos saturados e insaturados mixtos de cadena larga que tienen entre alrededor de 14 y 20 átomos de carbono;(d) 15, characterized in that the epoxy resin or epoxy resins are selected from the group consisting of: (a) glycidyl ether epoxy resin prepared by the reaction of epichlorohydrin with a hydroxyl group-containing compound carried out under alkaline reaction conditions ;(b) epoxy resins prepared by the reaction of epichlorohydrin with di- and tri-hydroxy phenolic mononuclear compounds;(c) epoxidized derivatives of natural oils with long chain mixed saturated and unsaturated acids having between about 14 and 20 carbon atoms;(d) IMPI poliepóxidos derivados de ésteres de ácidos policarboxílicos con alcoholes insaturados;(e) poliepóxidos derivados de ésteres preparados a partir de alcoholes insaturados y ácidos carboxílicos insaturados;(f) polímeros epoxidados de base butadieno;(g) derivados epoxidados de dímeros de dienos, y (h) mezclas o combinaciones de los mismos. IMPI polyepoxides derived from esters of polycarboxylic acids with unsaturated alcohols;(e) polyepoxides derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids;(f) butadiene-based epoxidized polymers;(g) epoxidized derivatives of diene dimers, and (h) mixtures or combinations thereof.
22
The composition according to claim 22. La composición de conformidad con la reivindicación 21, caracterizada porque las resinas epóxicas tienen un peso molecular entre 50 y 10,000. 21, characterized in that epoxy resins have a molecular weight between 50 and 10,000.
23
2. 3. The composition according to claim 23. La composición de conformidad con la reivindicación 15, caracterizada porque la composición de base epóxica comprende desde 60 % en peso hasta 85 % en peso de una resina epóxica de éteres de glicidilo o mezcla de resinas epóxicas de éteres de glicidilo, desde 1 % en peso hasta 15 % en peso del sistema de curado de alta temperatura que comprende un agente de curado N-sebo-1,3-diaminopropano etoxilado, y desde 15, characterized in that the epoxy base composition comprises from 60% by weight to 85% by weight of a glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins, from 1% by weight to 15% by weight of the system temperature curing agent comprising an ethoxylated N-tallow-1,3-diaminopropane curing agent, and from 39 Weight% to 0% by weight of a mixture of alkyl pyridine diluents or solvents, where the diluents or solvents are used to reduce the viscosity of the high temperature composition. 39 % en peso hasta 0 % en peso de una mezcla de diluyentes o solventes de alquil piridina, donde los diluyentes o solventes se usan para reducir la viscosidad de la composición de alta temperatura.
24
The composition according to claim 24. La composición de conformidad con la reivindicación 23, caracterizada porque las resinas epóxicas de éteres de glicidilo se preparan por la reacción de epiclorhidrina con un compuesto que contiene un grupo hidroxilo llevada a cabo 23, characterized in that the glycidyl ether epoxy resins are prepared by the reaction of epichlorohydrin with a hydroxyl group-containing compound carried out IMPI ίίΛΤΤΠΓΓΟ MEXICANO or la tftorwoAo IMPI ίίΛΤΤΠΓΓΟ MEXICANO or la tftorwoAo WOMSTWAL bajo condiciones de reacción alcalinas. WOMSTWAL under alkaline reaction conditions.
25
The composition according to claim 25. La composición de conformidad con la reivindicación 15, caracterizada porque la composición de base epóxica de temperatura moderada comprende desde 70 % en peso hasta 50 % en peso de una resina epóxica de éteres de glicidilo o una mezcla de resinas epóxicas de éteres de glicidilo y desde 30 % en peso hasta 50 % en peso del sistema de curado de temperatura media. 15, characterized in that the moderate temperature epoxy base composition comprises from 70% by weight to 50% by weight of a glycidyl ether epoxy resin or a mixture of glycidyl ether epoxy resins and from 30% by weight to 50% by weight of the medium temperature curing system.
26
The composition according to claim 26. La composición de conformidad con la reivindicación 25, caracterizada porque las resinas epóxicas de éteres de glicidilo se preparan por la reacción de epiclorhidrina con un compuesto que contiene un grupo hidroxilo llevada a cabo bajo condiciones de reacción alcalinas y el agente de curado es imidazolina o una mezcla de imidazolinas. 25, characterized in that the glycidyl ether epoxy resins are prepared by the reaction of epichlorohydrin with a hydroxyl group-containing compound carried out under alkaline reaction conditions and the curing agent is imidazoline or a mixture of imidazolines.
27
The composition according to claim 27. La composición de conformidad con la reivindicación 15, caracterizada porque la composición de base epóxica de baja temperatura comprende desde 75 % en peso hasta 99 % en peso de una resina epóxica de éteres de glicidilo o una mezcla de resinas epóxicas de éteres de glicidilo y desde 25 % en peso hasta 1 % en peso del sistema de curado de baja temperatura. 15, characterized in that the low temperature epoxy base composition comprises from 75% by weight to 99% by weight of a glycidyl ether epoxy resin or a mixture of glycidyl ether epoxy resins and from 25% by weight to 1% by weight of the low temperature curing system.
28
The composition according to claim 28. La composición de conformidad con la reivindicación 27, caracterizada porque caracterizada porque las resinas epóxicas de éteres de glicidilo se preparan por la reacción V9 IMPI^ 27, characterized in that characterized in that the glycidyl ether epoxy resins are prepared by the reaction V9 IMPI ^ INSTITUTO MEXICANO MEXICAN INSTITUTE Di LA PROPIEDAD Λ«induítrial de epiclorhidrina con un compuesto que contiene un grupo hidroxilo llevada a cabo bajo condiciones de reacción alcalinas. Say THE í «inductive property of epichlorohydrin with a hydroxyl group-containing compound carried out under alkaline reaction conditions. IMPI IMPI INSTITUTO MEXICANO Df m RRORIfDAO MEXICAN INSTITUTE Df m RRORIfDAO INDUSTRIAL INDUSTRIAL

Independent claims14

484 paragraphs in 85 sections, as filed

(54) Title: RESIN AND FOAM RESIN SEALANTS FOR ISOLATION OF AREAS AND METHODS FOR THE PREPARATION AND USE OF THEM.

(54) Title: RESIN SEALANT FOR ZONAL ISOLATION AND METHODS FOR MAKING AND USING SAME.

(57) Summary

Epoxy based temperature specific zone isolation compositions and methods for zone isolation in crude oil and gas drilling wells are described when using the compositions, where the composition is adjusted for use in high temperature, medium temperature applications. and low temperature. Sealing compositions for foam-forming epoxy-based zone isolation are also described and methods for isolation of crude oil and gas wellbore zones using the compositions. The foam nature of cured seals provides sufficient compressibility and resilience to be used with expandable tubing without substantial loss in sealant integrity and in injection operations.

(57) Abstract

PATENT TITLE NO. 339949

Yes.

Mexican Institute of Industrial Property

Owner (s): CLEARWATER INTERNATIONAL, LLC.

Address: 515 Post Oak Blvd, Suite 600, Houston, Texas, 77027, USA

Name: RESIN AND FOAM RESIN SEALANTS FOR ISOLATION OF AREAS AND METHODS FOR THE PREPARATION AND USE OF THEM

Classification: IC.8: C08G59 / 68; E21B33 / 12

Inventor (s): FRANK ZAMORA; SARKIS R. KAKADJIAN; TINA GARZA

<td></td><td colspan="2">SOUCITUD '</td><td></td><td>lljljl</td>

<td>Numbers</td><td>there</td><td>Date of presentation:</td><td>Hour:</td><td>One thousand</td>

<td>s</td><td></td><td>PRIORITY</td><td></td><td> &</td>

<td>'Ii !. 'S Country: .i</td><td>TO</td><td>Date:</td><td>Number:</td><td></td>

<td>US</td><td></td><td>March 22, 2011</td><td> 13/053,975</td><td></td>

<td>Validity: Twenty years</td><td>s ·</td><td></td><td></td><td>jr s</td>

The reference patent is filed with fiflidamento nn i

Expiration Date: May 20, 2031

Disagreement with Article 23 of the Proprietary Law ccftada from the date of submission of the request

QPíen subscribes the present title has been given by Industnal (Official Dlano of i 304, 06/16/2005, 25 / ®1 / 2006, OÍ i), 4th and 12th sections I and III d |

7/2002, 07/15/2004, 28/87/2004 and Option I

1st, 2nd fraction V, 6th fraction III, and 59 of the Industrial Property Law.

(niiet «This patent has a validity of twenty non-renewable years, I will be subject to payment of the * arifa to keep the rights in force:

based on the provisions of articles 6, sections III and 7, bis 2 of the Law of the

Federation (DOF) 2? ®6 / ti91. Reformed on 08/02/1994 25Ί0 / 1996, 12/26/1997, # 05/1999, 5 / 2009.06 / 01/2010, Ιδ / ΟΜΟ'Ρ '8AÍ R. 7.01 / 2012 and ΓΑ®4 / 2012); Articles 1, 3 / fraction V Regulations of the Mexican Institute cMk la f * iupihd «l Industrial (DOF 12/14/1999, re-signed on 9/2007); Articles 1, 3, 4, 5, section V, Subsection a), 16 sections I and II and 30 of the 1st, 3rd, Brazilian Statute

and 5th Clause a) of the Agreement that delegates powers to the Deputy Directors General, Coordinator, Divisional Directors, Regional Office Holders, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

Issue Date: June 16, 2016

MX / 2016/47450

33W

RESIN AND FOAM RESIN SEALANTS FOR AI§E & táfc ^ ®Oi

ZONES AND METHODS FOR THE PREPARATION AND USE OF THE SAME

FIELD THE INVENTION

Modalities of the present invention relate to zone isolation methods and systems, where a zone isolation composition is pumped into a ring between a drill hole and a tubular member that is allowed to set to form an isolation seal, where The seal is compressible enough for the expandable pipe to expand without loss of seal integrity. The cured compositions are ideally suited for use with. expansion pipe, where the composition for zone isolation must be compressible, while the isolation of the zones is continued.

IMPI

Mexican INSTITUTE

OF THE PROPERTY

INDUSTRIAL absence of a solvent or solubilizing agent. The invention contemplates a different combination of resins, hardening agents and solubilizing agents for different temperature application: a low temperature zone insulation composition, a moderate temperature insulation composition and a high temperature insulation composition, where the low temperature composition sets at a low temperature range, the moderate temperature composition sets at an interval moderate temperature and high temperature composition sets at a high temperature range. All compositions cure to form a compressible epoxy zone isolation seal that can be used with expansion piping.

Modalities of the present invention relate to zone isolation methods and systems, where a zone isolation composition is pumped into a ring between a drill hole and a tubular member and allowed to set to form a foamed insulation seal. , where the seal has sufficient compressibility for the expandable pipe to expand without loss in seal integrity. The cured compositions are ideally suited for use with expansion pipe, where the composition for zone insulation should be

IMPI

VTTiyroMeucANo

M INDUSTRIAL PROPERTY compressible, while continuing to isolate areas.

More particularly, embodiments of the present invention relate to zone isolation methods and systems, where the zone isolation composition is pumped into a ring between a drill hole and a tubular member that is allowed to test to form a seal. Foamed insulation, where the seal has sufficient compressibility for the expandable pipe to expand without loss of 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 the optional solubilizing agents for different temperature applications. A low temperature zone insulation composition sets at a low temperature range. A moderate temperature insulation composition sets at a moderate temperature range. A temperature insulation composition is set at a high temperature range.

All compositions cure to form a compressible epoxy foam seal for zone insulation, for use in any application where compressibility is needed such as with expansion piping.

IMPI

BACKGROUND OF THE INVENTION

Conventional zone insulation sealers are cements, foam fluids, or resins. In expandable pipe applications, the zone insulation sealant must be able to compress and continue the seal after the sealant is pumped behind the pipe and sets. Conventional zone insulation systems do not offer the compressible and / or resilient properties necessary to allow the expandable tube to expand without fracturing the system due to its hardness making zone isolation obvious. Using such compositions requires that the expandable tube must expand prior to setting of the sealant.

This requires delaying the setting of the sealant for a sufficient time to allow the expandable tube to expand prior to the setting of the sealant. Once the pipe expands, the sealant sets. Problems arise when the expansion of the expandable pipe cannot occur within the retarding window once the sealant sets, the expandable pipe cannot expand due to the incompresibility of the cured sealant.

Thus, there is a need in the art for a sealant that is compressible and / or resilient that allows the expandable pipe to expand before, during, and / or after the sealant cures. The solution to these problems is a sealant

IMPI

which is compressible and / or resilient enough to allow expansion of the expandable tube before, during, or after the material has hardened, while maintaining an effective zone insulation seal.

SUMMARY OF THE INVENTION

Modalities of the present invention provide an epoxy composition for zone isolation that includes an epoxy resin or a plurality of epoxy resins and a curing agent or a plurality of curing agents in the presence or absence of a diluent or solvent, where the composition is cured to form an epoxy cured composition for zone insulation that has sufficient compressibility and / or resilience properties to allow compression of the composition without substantial loss in seal integrity or zone isolation. In certain embodiments, compressibility is sufficient to allow expansion of the expansion pipe during or especially after hardening or curing of the composition. The sealing compositions are designed to have sufficient strength and bond characteristics so that the short casing, expandable pipe, or other pipe inserted into the drill hole is held in place in the drill hole and borehole.

MEXICAN INSTITUTE

OF IA MONEDAD Α ».. Τ3 ;? * INDUSTRIAL drilling is sealed so there is no .. my fluid prayer from one area to another area. The term substantial loss of seal integrity means that the integrity of the seal after compression is applied is at least 75% of the integrity of the seal before compression.

In other embodiments, the term means that the integrity of the seal after compression is applied is at least 85% of the integrity of the seal before compression. In other embodiments, the term means that the integrity of the seal after compression is applied is at least 90% of the integrity of the seal before compression. In other embodiments, the term means that the integrity of the seal after compression is applied is at least 95% of the integrity of the seal before compression.

Modalities of the present invention provide an epoxy resin system that has desired mechanical properties that allow the epoxy resin system to have improved compressibility and / or resilience properties.

Modalities of the present invention provide an elastic sealing composition for use as an injection material to shut off annular gas migration and / or zone insulation during superior insulation of the primary casing pipe or short

IMPI

MEXICAN INSTITUTE »and THE INDUSTRIAL RRONtDAO

coating. The sealant composition is unique in that the mechanical properties are set to allow the composition to be ductile and offer long lasting insulation.

Modalities of the present invention provide methods for isolation of zones that include inserting a pipeline into a drill hole. After laying the pipe, pump a composition of this invention into a ring between the wall of the drill hole and an outer wall of the pipe. Allow sufficient time for the composition to cure by sealing the ring. The composition can be pumped in two parts, the resins and hardening agents are pumped separately into the well and mixed in a static mixing chamber inside the well prior to being pumped into the ring. In the case of expansion pipe, methods may also include expanding the pipe, where expansion of the pipe results in compression of the composition, where the composition maintains insulation after expansion.

Modalities of the present invention provide methods for injection operations that include pumping the composition into the ring or region, where fluid migration occurs (gas, liquid, or mixture of the

INSTITUTO MEXICANO DE LA FRORIgriAD industrial themselves) to form a seal to reduce or eliminate such migration. Methods may also include isolating the region such that the composition locally reduces or prevents the migration of fluids (gas, liquid, or mixture thereof). Methods may also include maintaining insulation until the composition is fully cured.

Modalities of the present invention provide a method for zone isolation that includes pumping an epoxy based composition into a ring between a drill hole and a string of pipe. The composition is then allowed to cure to form a zone isolation structure comprising the cured composition. The cured composition is compressible and cures at a temperature range of between about 10 ° and about 149 ° C (50 ° and about

300 ° F). The method may also include pre-pumping, isolating a section of a ring between the drill hole and the pipe string so that the zone isolation structure is located along a length of the pipe string. The method may also include during or after curing, expanding a section of the pipe string, where the compressibility of the cure is sufficient to allow pipe expansion without substantial loss in seal integrity or zone isolation. The zone isolation structure is located at a distal end of the

IMPI

drilling well. The composition comprises an epoxy resin or a plurality of epoxy resins and a curing agent or a plurality of curing agents in the presence or absence of a diluent or solvent, where the composition cures to form a cured epoxy composition having sufficient compressibility properties and / or resilience to allow compression of the composition without substantial loss in seal integrity or zone isolation. Diluents comprise aromatic solvents and heterocyclic aromatic solvents or mixtures and combinations thereof. Epoxy resins can comprise a) glycidyl ether epoxy resin prepared by the reaction of epichlorohydrin with a hydroxyl group-containing compound carried out under alkaline reaction conditions; (b) epoxy resins prepared by the reaction of epichlorohydrin with di- and tri-hydroxy phenolic mononuclear compounds; (c) epoxidized derivatives of natural oils with long chain mixed 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) butadiene-based epoxidized polymers; (g) epoxidized derivatives of diene dimers, and

IMPI

(h) mixtures or combinations thereof. Epoxy resins can have a molecular weight between about 50 and about 10,000. Curing agents may comprise polyamine curing agents, alkoxylated polyamine curing agents, heterocyclic amine curing agents, or the like including a plurality of amino groups, or mixtures and combinations thereof. Curing agents may comprise alkoxylated aliphatic polyamines, alkoxylated cycloaliphatic polyamines, alkoxylated aromatic polyamines, alkoxylated heterocyclic polyamines, or mixtures and combinations thereof. Curing agents may comprise alkoxylated 1,3-diaminopropanes substituted by N-allyl and N-alkenyl or mixtures and combinations thereof. Aromatic heterocyclic amine curing agents may comprise pyrrolidine, some pyrrolidines, oxazoline, some oxazolines, triazoles, some triazoles, pyrazolidine, some pyrazolidine, piperidine, some alkyl piperidines, piperazine, some piperazines, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazine, imidazoline, imidazoline azepane, azepine, alkyl azepines, morpholine, alkyl morpholines, diazapins, alkyl diazapins, or mixtures and combinations thereof.

Curing agents include alkyl pyridines and DURA COAT

2B.

IMPI

In certain embodiments, the temperature range is from about 66 ° C to about 149 ° C (150 ° F to about 300 ° F) and the composition ranges from about 60 wt% to about 85 wt% of an epoxy resin or epoxy resin mixture, from about 1% by weight to about 15% by weight of curing agents, and from about 39% by weight to about 0% by weight of a diluent or solvent, where the diluent or solvent is used to reduce the viscosity of the composition. Epoxy resins are glycidyl ether epoxy resins or glycidyl ether epoxy resin blends, the curing agent is an alkoxylated polyamine or alkoxylated polyamine mixture, and the diluent is an aromatic heterocyclic solvent or aromatic heterocyclic solvent mixture. Epoxy resin is DURA COAT

IA, the curing agent is DURA COAT 2B and the diluent is

AKOLIDINE 11.

IMPI

glycidyl ether epoxy or mixture of raei ^ ag opAyjpaft of glycidyl ethers and the curing agent may be a heterocyclic amine. The epoxy resin can be DURA COAT IA and the curing agent can be an imidazoline or mixture or imidazolines.

In certain embodiments, the temperature range is between about 10 ° C and around 32.2 ° C (50 ° F and around 90 ° F) and the composition ranges from about 75% by weight to about 99% by weight of an epoxy resin or mixture of epoxy resins and from about 25% by weight to about 1% by weight of curing agents. The epoxy resins can be glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins and the curing agent is an imidazoline, pyrrolidine, pyrrole, pyridine, piperidine or mixtures thereof. The epoxy resin can be DURA COAT IA and the curing agent can be an imidazoline, pyrrolidine, pyrrole, pyridine, piperidine, or mixtures thereof.

Modalities of the present invention provide methods and systems for zone isolation, where the zone isolation compositions are pumped into a ring between a drill hole and a tubular member that is allowed to set and form a foam insulation seal, where the seal has- properties of resilience and / or

Sufficient compressibility to maintain the casing and to allow expansion of the pipe without substantial loss in seal integrity. Modalities of the present invention also provide methods and systems for injection work, where a composition of this invention is injected or pumped into an area to form an airtight foam seal in situ that has the desired properties of resilience and / or compressibility. , where the foam composition expands into cavities and cracks and continues to expand after curing. Modalities of the compositions of this invention include an epoxy resin, a hardening agent, a blowing agent, and optionally a solvent or solubilizing agent, where the foam composition expands within cavities and cracks and continues to expand after curing. Blowing agents generate gases at a desired decomposition temperature to create open-cell, and / or closed-cell foams in situ, where the cured composition has a Poisson ratio of less than about 0.5.

Modalities of the present invention provide foamable epoxy seal insulation compositions comprising an epoxy resin or a plurality of epoxy resins, a hardening agent or a

IMPI

plurality of hardening agents, a blowing agent or a plurality of blowing agents and optionally a diluent, solvent, solubilizing system, where the compositions cure to form insulating structures or seals of epoxy foam zones having compressibility and / or properties Sufficient resilience to allow compression of structures or seals without substantial loss in seal integrity or zone isolation.

In certain embodiments, compressibility is sufficient to allow expansion of the expansion 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 bond characteristics so that short casing, expandable pipe, or other pipe inserted into the drill hole is held in place in the drill hole.

<td colspan="2">drilling. Then</td><td>of</td><td>forge the</td><td>Well of</td><td>drilling</td><td>I know</td>

<td>seals so</td><td>than</td><td>not</td><td colspan="2">there is substantially</td><td>migration</td><td>of</td>

<td>fluids from a</td><td>zone</td><td colspan="2">to another area</td><td> •</td><td></td><td></td>

<td>Modalities</td><td>of</td><td>the</td><td>Present</td><td>invention</td><td colspan="2">provide</td>

Epoxy foamable resin systems that have desired mechanical properties, while having improved compressibility and / or resilience properties.

Modalities of the present invention provide

MEXICAN INSTITUTE OF PROPERTY

INDUSTRIAL

Foamable sealant compositions for use as injection material to shut off gas and / or annular liquid migration and / or to isolate areas during insulating of short top casing or primary casing. The sealing compositions are unique in that the mechanical properties are set to allow the compositions to be ductile and to offer long-lasting insulation. The sealing compositions are also foams, which have higher compressibility and / or resilience properties and better flow properties during curing and foaming so that the compositions form superior seals by getting into cavities and surface cracks in the drill hole, while adhere to the outer surface of the pipe lining or cover. Due to the foam nature of the sealing compositions, the compositions have a Poisson ratio of less than or equal to about 0.5. However, the epoxy foam sealants of this invention continue to expand after setting allowing the compositions to sink deeper into formations and provide improved sealing and long lasting seal integrity. This expansion continues to ensure effective zone isolation even after expansion of expandable pipe or after setting of tubular members

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in its final configuration. Without affecting Milestone they love sealing properties.

Modalities of the present invention provide methods for zone isolation that include inserting a pipeline into a drill hole. After laying the pipe, pump a composition of this invention into a ring between the wall of the drill hole and an outer wall of the pipe. Allow sufficient time for the composition to cure and foam to form a foamed seal to seal the ring.

The compositions can be pumped into parts, the resins, blowing agents and hardening agents can all be pumped separately into the well and mixed in a static mixing chamber within the well before the components are pumped into the ring. In the case of expansion pipe, methods may also include expanding the pipe, where expansion of the pipe results in compression of the foam seals, where the seals lie insulating after expansion. Expansion can take place after cure and / or during cure.

In certain embodiments, expansion takes place during curing and foaming.

Modalities of the present invention provide methods for injection operations that include pumping

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INDUSTRIAL the composition within the ring or a τ-ρςρ-όη. same.

where fluid migration occurs (gas, liquid, or mixtures thereof), to form a seal to reduce or eliminate such migration. The methods may also include isolating the region or regions such that the composition locally reduces or prevents the migration of fluids (gas, liquid, or mixture thereof). Methods may also include maintaining insulation until the composition is fully cured and foamy.

Modalities of the present invention provide methods for zone isolation including pumping foamable epoxy-based compositions into a ring between a drill hole and a string of pipe. The compositions are then allowed to cure to form zone or seal insulation structures comprising the cured foamed compositions of this invention. The cured / foamed seals cure at a temperature range between about 10 ° and about 14 9 ° C (50 ° and about 300 ° F) and the blowing agents are selected to decompose at the cure temperature. Methods may also include pre-pumping, isolating a section of a ring between the drill hole and the pipe string so that the zone isolation structure is located along a length of the pipe string.

rlocpuóg Hol

The methods may also include during curing, expanding a section of the pipe string, where the compressibility of the cured and foamed seals is sufficient to allow expansion of expandable pipe without substantial loss in seal integrity or zone insulation. The zone isolation structure can also be located at a distal end of the drill hole. The foamable compositions comprise an epoxy resin or a plurality of epoxy resins, a blowing agent or a plurality of blowing agents, a hardening agent or a plurality of hardening agents and optionally a diluent, solubilizing or solvent system, where the compositions are cured and the blowing agents are decomposed to form a cured foamable epoxy sealing composition having sufficient compressibility and / or resilience properties to allow compression of the composition without substantial loss in seal integrity or zone isolation.

BRIEF DESCRIPTION OF THE FIGURES

The invention may be better understood with reference to the following detailed description together with the accompanying illustrative figures in which like elements are numbered the same:

Figure IA details a ring between a drill hole and a pipe inserted into the drill hole.

Figure IB details the ring in Figure IA that has a sealant supply conduit inserted into the drill hole with a plug to prevent the sealant from filling the casing showing the ring to be filled with zone or composition insulation epoxy sealant of this invention.

Figure 1C details the ring of Figure IA after a zone of the drill hole has been filled with the epoxy composition for zone isolation.

Figure ID details the area of the Figure IA ring filled with a cured, compressible composition for isolation of epoxy zones after cure.

Figure 2A details a ring between a drill hole and a pipe inserted into the drill hole.

Figure 2B details the ring of Figure 2A having a sealant supply conduit inserted into the drill hole with seals and an insulation member to isolate a section of the ring showing the section to be filled with zone insulation or epoxy sealant composition of this invention.

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MEXICAN INSTITUTE '

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Figure 2C details the ring of Figure 9A after the section has been filled with the epoxy composition for zone isolation.

Figure 2D details the ring area of Figure 2A filled with a cured, compressible composition for isolation of epoxy zones after cure.

Figure 3A details a ring between a drill hole and an expandable pipe, where the ring is filled with an epoxy composition for isolation of areas of this invention.

Figure 3B details the ring of Figure 3A after curing and after expansion of the expandable pipe, where the composition has been compressed.

Figure 4A details a drilling well that includes a structure within the well that has a ring through which production fluids or other fluids can flow into the structure from a formation or into the formation from the structure, where the ring is filled with an epoxy sealing composition of this invention.

Figure 4B details the ring of Figure 4A after the ring has cured sealing.

Figure 5 details a viscosity versus temperature graph of one embodiment of a high temperature zone isolation composition of this invention.

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compared to its components.

<td>The figure</td><td>IA '</td><td>detailing</td><td>a ring between a</td><td>water well</td><td>of</td>

<td>drilling and</td><td>a</td><td>pipeline</td><td>inserted inside the</td><td>water well</td><td>of</td>

<td>drilling.</td><td></td><td></td><td></td><td></td><td></td>

<td>The figure</td><td>IB '</td><td>detailing</td><td>the figure ring</td><td>IA '</td><td>than</td>

It has a sealant supply conduit inserted into the drill hole with a plug to prevent the sealant from filling the casing showing the ring to be filled with a zone insulation or epoxy sealant composition of this invention.

Figure 1C 'details the ring of Figure IA' after a zone of the drill hole has been filled with the epoxy composition for zone isolation.

Figure ID 'details the area of the ring in Figure

IA 'filled with a cured, compressible composition for isolation of epoxy zones after curing.

<td>The figure</td><td>2A '</td><td>detailing</td><td>a ring between a</td><td>water well</td><td>of</td>

<td>drilling and</td><td>a</td><td>pipeline</td><td>inserted inside the</td><td>water well</td><td>of</td>

<td>drilling.</td><td></td><td></td><td></td><td></td><td></td>

<td>The figure</td><td>2B '</td><td>detailing</td><td>the figure ring</td><td>2A '</td><td>than</td>

has a sealant supply conduit inserted into the borehole with seals and an isolation member to isolate a section of the ring showing the section to be filled with zone insulation

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epoxy sealant composition of this invention.

Figure 2C 'details the ring of Figure 2A' after the section has been filled with the epoxy composition for zone isolation.

Figure 2D 'details the area of the ring in Figure

2A 'filled with a cured, compressible composition for isolation of epoxy zones after curing.

Figure 3A 'details a ring between a drill hole and an expandable pipe, where the ring is filled with an epoxy composition for isolation of areas of this invention.

Figure 3B 'details the ring of Figure 3A' after curing and after expansion of the expandable pipe, where the composition has been compressed.

Figure 4A 'details a drill hole including an in-hole structure that has a ring through which production fluids or other fluids can flow into the structure from a formation or into the formation from the structure, where the ring is filled with an epoxy sealing composition of this invention.

Figure 4B 'details the ring of Figure 4A' after curing that seals the ring.

Figure 5 'details a photograph of a composition "IMPIOS

4-3 MEXICAN INSTITUTE J?

OF THE PROPERTY

INB'JSTHIAL> »« * O> * Cured / Foamed Seal of this invention.

DETAILED DESCRIPTION OF THE INVENTION

Definitions of the Invention

The term "substantially no fluid migration" means that there is less than or equal to 5% fluid migration from one zone to another zone. In other modalities, the term means that there is less than or equal to 2.5% of fluid migration from one zone to another zone. In other embodiments, the term means there is less than or equal to

1% fluid migration from one area to another area. In other embodiments, the term means that there is no migration of fluids from one zone to another zone.

The term without substantial loss of seal integrity means that the integrity of the seal after compression is at least 75% of the integrity of the seal before compression. In other embodiments, the term means that the integrity of the seal after compression is applied is at least 80% of the integrity of the seal before compression. In other embodiments, the term means that the integrity of the seal after compression is applied is at least 85% of the integrity of the seal before compression.

In other embodiments, the term .means that the integrity of the seal after compression is applied is at least 90% of

ΙΜΡΙ

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

the integrity of the seal before compression. In other embodiments, the term means that the integrity of the seal after compression is applied is at least 95% of the integrity of the seal before compression. In other embodiments, the term means that the integrity of the seal after compression is applied is at least 99% of the integrity of the seal before compression. In other embodiments, the term means that the integrity of the seal after compression is applied is equal to the integrity of the seal before compression.

The term gpt means gallons for thousands of gallons.

The term gptg means gallons for thousands of gallons.

The term pptg means pounds per thousand gallons.

The term "% by weight" means percent by weight.

The term w / w means weight for weight.

The inventors have found that a settable epoxy based resin thermal system can be used as a zone isolation sealer in zone isolation operations within the well. The epoxy based resin system cures to form a composition for insulating areas that have sufficient compressibility for use in expansion piping applications, where the composition is compressed during expansion of

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pipe without substantial loss in seal integrity, where the term substantial means that the integrity of the seal after expansion is at least 80% of the integrity of the seal prior to expansion and after setting. In other embodiments, the integrity of the seal after expansion is at least 85% of the integrity of the seal prior to expansion and after setting. In other embodiments, the integrity of the seal after expansion is at least 90% of the integrity of the seal prior to expansion and after setting. In other embodiments, the integrity of the seal after expansion is at least 95% of the integrity of the seal prior to expansion and after setting. The inventors have found that the composition can be pumped into a ring between the well enclosure and the expansion pipe, and the pipe expand while the composition cures. The compositions of this invention are designed to cure after the composition has been pumped into an area, where isolation is required or desired. In certain embodiments, hardening agents have delayed the onset of cure. In other embodiments, the hardening agent is added to the resins within the well, just before the composition is pumped into the area. In these latter modalities, the resin and hardening agents can

IMPIO® *

MEXICAN INSTITUTE

OF OWN AGE On »

INDUSTRIAL pass through a static mixer, mechanical mixer, mechanical electromixer or other type of mixer to ensure adequate dispersion of the curing agent in the resin.

Modalities of the present invention broadly relate to an epoxy base zone isolation composition that includes an epoxy resin or a plurality of epoxy resins and a hardening agent or a plurality of hardening agents in the presence or absence of a diluent or solvent. The composition cures to form a cured composition for epoxy base zone insulation that has sufficient compressibility and / or resilience properties to allow compression of the composition without substantial loss in seal integrity or zone isolation. In certain embodiments, compressibility is sufficient to allow expansion of the expansion line tube during or especially after the composition hardens or cures. The sealing compositions are designed to have sufficient strength and bond characteristics so that the short casing, expandable pipe, or other pipe inserted into the drill hole is held in place in the drill hole and the drill hole is seal so there is no migration of fluids from one area to

IMPI

O 7 MEXICAN INSTITUTE

Dt THE PROPERTY

INDUSTRIAL another area.

Modalities of the present invention specifically refer to a high temperature epoxy base zone isolation composition including an epoxy resin or a plurality of epoxy resins and a hardening agent or a plurality of hardening agents in the presence or absence of a diluent or solvent. The composition is designed to thermally adjust a temperature between about 66 ° C to around 149 ° C (150 ° F to around 300 ° F). In certain embodiments, the high temperature zone insulation composition includes from about 60% by weight to about 85% by weight of an epoxy resin or epoxy resin blend, from about 1% by weight to about 15% by weight of curing agents, and from about 39% by weight to about 0% by weight of a diluent or solvent. The diluent or solvent is used to reduce the viscosity of the composition. In other embodiments, the high temperature zone insulation composition includes from about 65% by weight to about 85% by weight of an epoxy resin or epoxy resin blend, from about 5% by weight to about 10% by weight of curing agents, and from about 30% by weight to about 5% by weight of

a diluent or solvent. In other embodiments, the high temperature zone insulation composition includes from about 75% by weight to about 85% by weight of an epoxy resin or epoxy resin blend, from about 5% by weight to about 10% by weight of curing agents, and from about 20% by weight to about 5% 'by weight of a diluent or solvent.

In other embodiments, the high temperature zone insulation composition includes from about 80% by weight to about 85% by weight of an epoxy resin or epoxy resin blend, from about 5% by weight to about 10% by weight of curing agents, and from about 15% by weight to about 5% by weight of a diluent or solvent. In certain embodiments, the epoxy resin is a glycidyl ether epoxy resin or mixture of glycidyl ether 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 solvents. aromatic heterocyclics.

In other embodiments, the epoxy resin is DURA COAT IA available from JACAM Chemicals, LLC, of Sterling, KS, the curing agent is DURA COAT 2B available from JACAM

Chemicals, LLC, of Sterling, KS and the diluent is AKOLIDINE available from Lonza Group Ltd, Joseph Colleluori,

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Muenchensteinerstrasse 38, CH-4002 Basel, Switzerland.

Modalities of the present invention specifically refer to compositions for isolation of medium temperature epoxy base zones including an epoxy resin or a plurality of epoxy resins and a hardening agent or a plurality of hardening agents in the presence or absence of a diluent or solvent. The composition is designed to thermally adjust a temperature between around 32.2 ° C and around 66 ° C (90 ° F and around 150 ° F). In certain embodiments, the medium temperature zone insulation composition includes from about 70% by weight to about 50% by weight of an epoxy resin or epoxy resin blend and from about 30% by weight to about 50% by weight of curing agents. In other embodiments, the composition for insulation of medium temperature zones includes from about 60% by weight to about 50% by weight of an epoxy resin or epoxy resin blend and from about 40% by weight to about 50% by weight of curing agents. In other embodiments, the medium temperature composition for zone isolation includes from about 55% by weight to about 50% by weight of an epoxy resin or epoxy resin blend and from about 45% by weight to about 50% in

IMPI

weight of curing agents. Compositions for insulation of medium temperature zones can be diluted with up to about 20% by weight of a diluent or solvent, where the diluent or solvent is used to reduce the viscosity of the composition. In other embodiments, the epoxy resin is glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins and the curing agent is a heterocyclic amine. In certain embodiments, the epoxy resin is DURA COAT IA available from JACAM Chemicals, LLC, of Steriing, KS, and the curing agent is an imidazoline or mixture or imidazolines.

Modalities of the present invention specifically refer to compositions for isolation of low temperature epoxy based zones including an epoxy resin or a plurality of epoxy resins and a hardening agent or a plurality of hardening agents in the presence or absence of a diluent or solvent. The composition is designed to thermally adjust a temperature between around 10 ° C and around 32.2 ° C (50 ° F and around 9 ° F). In certain embodiments, the low temperature zone insulation composition includes from about 75% by weight to about 99% by weight of an epoxy resin or epoxy resin blend and from about 25% by weight to about 1% in

weight of curing agents.

In other embodiments, the low temperature composition for zone insulation includes from about 85% by weight to about

97.5% by weight of an epoxy resin or epoxy resin blend and from about 15% by weight to about

2.5% by weight of curing agents. In other embodiments, the low temperature zone insulation composition includes from about 90% by weight to about 95% by weight of an epoxy resin or epoxy resin blend and from about 10% by weight to about 5% by weight of curing agents. Low temperature zone insulation compositions can be diluted with up to about 20% by weight of a diluent or solvent, where the diluent or solvent is used to reduce the viscosity of the composition. In other embodiments, the epoxy resin is glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins and the curing agent is a heterocyclic amine. In certain embodiments, the epoxy resin is DURA COAT IA available from JACAM Chemicals, LLC, of Sterling, KS, and the curing agent is an imidazoline, pyrrolidine, pyrrole, pyridine, piperidine, or mixtures thereof.

Modalities of the present invention also broadly relate to methods for isolation of zones including

IMPI

--5 MEXICAN INSTITUTE

FROM INDUSTRIAL PROPERTY insert a pipe into a drill hole.

After laying the pipe, pump a composition of this invention into a ring between the wall of the drill hole and an outer wall of the pipe.

The method also includes allowing sufficient time for the composition to cure by sealing the ring. The composition can be pumped in two parts, the resins and hardening agents are pumped by .separate inside the well and mixed in a static mixing chamber inside the well

<td colspan="2">prior to pumping into the</td><td>ring.</td><td></td>

<td>Modalities of</td><td>the</td><td>Present</td><td>invention too</td>

<td>provide methods</td><td>for</td><td>operat ions</td><td>injection that</td>

<td>include pumping</td><td>of the</td><td>composition</td><td>within spaces</td>

<td>ringtones, regions or</td><td colspan="2">locations in a</td><td>full well where</td>

<td colspan="3">gas or oil migration occurs to reduce or eliminate such migration.</td><td>to form a seal</td>

The inventors have found that thermal setting epoxy based resin systems can be used as a zone isolation seal in zone isolation operations within the well. The epoxy based resin system cures and foams at an elevated temperature to form zone insulation structures or foam seals that have sufficient compressibility for use in expansion, injection or other piping.

IMPI «ST1TUTO MEXICANO Dt LA PROPIEDAD INDUSTRIAL

operations that require a compressible and resilient seal.

During pipe expansion, foamed and cured seal compositions compress without substantial loss in seal integrity. The inventors have found that the compositions can be pumped into a ring between the well enclosure and the expansion pipe, and the pipe expand while the compositions cure. The compositions of this invention are designed to cure and foam after the compositions have been pumped into an area, where isolation is required or desired. In certain embodiments, curing or hardening agents and blowing agents have delayed the onset of curing. In other embodiments, the curing agents and blowing agents are added to the resins within the well, just before the compositions are pumped into the zone. In these latter embodiments, the resins and curing or hardening agents can be passed through a static mixer, mechanical mixer, mechanical electromixer, or other type of mixer to ensure adequate dispersion of the curing or hardening agents into the resin. In certain embodiments, curing agents and blowing agents are temperature sensitive such that curing and blowing only occurs when the composition reaches a given elevated temperature.

IMPI

Modalities of the present invention broadly relate to foamable epoxy base zone insulation compositions including an epoxy resin or a plurality of epoxy resins, a curing agent or a plurality of curing agents, and a blowing agent or a plurality of blowing agents, and optionally a solvent system in the presence or absence of a diluent or solvent system. The compositions cure and foam to form seals or zone isolation structures based on cured and foamed epoxies having sufficient compressibility and / or resilience properties to allow compression of the composition without substantial loss in seal integrity or zone isolation. .

In certain modalities, the compressibility is sufficient

<td>to allow the</td><td>expansion of</td><td>tube of</td><td>the</td><td>pipeline</td><td>of</td>

<td>expansion during</td><td>or especially</td><td>then</td><td>of</td><td>toughen</td><td>or</td>

<td colspan="3">cure composition. The compositions</td><td>of</td><td>sealed</td><td>I know</td>

<td>designed to have</td><td>characteristics</td><td colspan="2">enough of</td><td colspan="2">resistance</td>

and union so that the short casing, expandable pipe, or other pipe inserted into the drill hole is held in place in the drill hole and the drill hole is sealed so that there is no migration of fluids from an area to another area.

In certain modalities, the compositions of this

Invention are low temperature foamable zone insulation compositions that settle and foam at a low temperature range between about 10 ° C and about 32.2 ° C (50 ° F and about 90 ° F). In other embodiments, the compositions of this invention are compositions for insulation. foaming zones, of moderate temperature, that settle to a moderate temperature range between around 32.2 ° C and around 66 ° C (90 ° F and around 150 ° F). In certain embodiments, the compositions of this invention are high temperature foamable zone insulation compositions that sit at a high temperature range between about 66 ° C to about 149 ° C (150 ° F to about 300 ° F). All compositions cure and foam to form compressible zone insulation epoxy foam seals capable of use in any application, where compressibility and / or resilience properties are required or desired such as with expansion piping operations and injection.

High Temperature Compositions

Modalities of the present invention specifically refer to compositions for isolation of areas of

IMPI

MEXICAN INSTITUTE of the property A ^ - ^ Industrial high temperature foamable epoxy based base including an epoxy resin or a plurality of epoxy resins, a curing agent or a plurality of curing agents, and a blowing agent with a plurality of blowing agents in the presence or absence of a diluent or solvent system. The composition is designed to thermally adjust a temperature between about 66 ° C to around 149 ° C [150 ° F to around 300 ° F).

In certain embodiments, high temperature foamable zone insulation compositions include from about 60% by weight to about 85% by weight of an epoxy resin or epoxy resin blend, from about 1% by weight to about 15 % by weight of a curing agent or mixture of curing agents, from about 5% by weight to about 15% by weight of a blowing agent or mixture of blowing agents and optionally from about 0% by weight to about 39% by weight of a diluent or solvent system, with based on the weight of the other components. The diluent or solvent system is used to reduce the viscosity of the composition.

In other embodiments, high temperature foamable zone insulation compositions include from about 65% by weight to about 85% by weight of an epoxy resin or epoxy resin blend,

from about 5% by weight to about 10% by weight of a curing agent or mixture of curing agents, from about 5% by weight to about 15% by weight of a blowing agent or mixture of agents blowing and from about 5% by weight to about 30% by weight of a diluent or solvent system, based on the weight of the other components.

In other embodiments, the high temperature zone insulation composition includes from about 75% by weight to about 85% by weight of an epoxy resin or epoxy resin blend, from about 5% by weight to about 10% by weight of curing agent or mixture of curing agents, from about 5% by weight to about 15% by weight of a blowing agent or mixture of blowing agents and from about 5% by weight to about 20% by weight of a diluent or solvent system, based in the weight of the other components.

a blowing agent or mixing agent

IMPI

INSTITITO MEXICANO DE AI «ΟΡΙΕΠΑΡ industrial blown, and from about 5% by weight to about 15% by weight of a diluent or solvent system based on the weight of the other components.

In certain embodiments, the epoxy resin is a glycidyl ether epoxy resin or mixture of glycidyl ether 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 solvents. aromatic heterocyclics.

In other embodiments, the epoxy resin is DURA COAT IA available from JACAM Chemicals, LLC, of Sterling, KS, the curing agent is DURA COAT 2B available from JACAM

Chemicals, LLC, of Sterling, KS and the diluent is AKCLIDINE available from Lonza Group Ltd, Joseph Colleluori,

Muenchensteinerstrasse 38, CH-4002 Basel, Switzerland.

Medium Temperature Compositions

Modalities of the present invention specifically relate to medium temperature foamable epoxy base zone isolation compositions including an epoxy resin or a plurality of epoxy resins, a curing agent or a plurality of curing agents, and a blowing or a plurality of blowing agents in

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MEXICAN INSTITUTE

Γ> € i A DB.iuirrv.i, - /-¼ _ 11 · '^^ · of industrial property the presence or absence of a system of diluents or solvents. The compositions are designed to thermally adjust a temperature between about 32.2 ° C and around 66 ° C (90 ° F and around 150 ° F).

In certain embodiments, medium temperature foamable zone insulation compositions include from about 70 wt% to about wt% of one. epoxy resin or epoxy resin blend, from about 30% by weight to about% by weight of a curing or curing agent or a mixture of curing agents and from about 5% by weight to about 15% by weight weight of a blowing agent or mixture of blowing agents based on the weight of the other components.

In other embodiments, the medium temperature zone insulation composition includes from about 60% by weight to about 50% by weight of an epoxy resin or epoxy resin blend, from about 40% by weight to about 50% by weight of a curing or curing agent or a mixture of curing agents and from about 5% by weight to about 15% by weight of a blowing agent or mixture of blowing agents based on the weight of the other components.

In other modalities, the insulation composition of

Medium temperature zones include from about 55% by weight to about 50% by weight of an epoxy resin or epoxy resin blend and from about 45% by weight to about 50% by weight of a hardening or curing or a mixture of curing agents and from about 5% by weight to about 15% by weight of a blowing agent or mixture of blowing agents based on the weight of the other components. Compositions for insulation of medium temperature zones can be diluted with up to about 20% by weight of a diluent or solvent, where the diluent or solvent is used to reduce the viscosity of the composition.

In other embodiments, the epoxy resin is glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins and the curing agent is a heterocyclic amine.

In certain modalities, the epoxy resin is HARD

COAT IA available from JACAM Chemicals, LLC, of Sterling, KS, and the curing agent is an imidazoline or mixture or imidazolines.

Low Temperature Compositions

Modalities of the present invention specifically refer to compositions for isolation of areas of

low temperature epoxy base including an epoxy resin or a plurality of epoxy resins, a curing agent or a plurality of curing agents, and a blowing agent or a plurality of blowing agents in the presence or absence of a thinners or solvents.

The composition is designed to thermally adjust a temperature between around 10 ° C and around 32.2 ° C (50 ° F and around 90 ° F).

In certain embodiments, the low temperature zone insulation composition includes from about 75% by weight to about 99% by weight of an epoxy resin or a mixture of epoxy resins, from about% by weight to about 1% by weight of a hardening or curing agent or a mixture of curing agents and from about 5% by weight to about 20% by weight blowing agents based on the weight of the other components.

In other embodiments, the low temperature zone insulation composition includes from about 85% by weight to about 97.5% by weight of an epoxy resin or a mixture of epoxy resins, from about 15% by weight to about 2.5 % by weight of a curing agent or a mixture of curing agents and from about 5% by weight to about 20% by weight blowing agents

IMPI

based on the weight of the other components.

In other embodiments, the low temperature zone insulation composition includes from about 90% by weight to about 95% by weight of an epoxy resin or epoxy resin blend, from about 10% by weight to about 5% by weight of a curing agent or mixture of curing agents, and from about 5% by weight to about 20% by weight of a blowing agent or mixture of blowing agents based on the weight of the other components . Low temperature zone insulation compositions can be diluted with up to about 20% by weight of a diluent or solvent, where the diluent or solvent is used to reduce the viscosity of the composition.

In other embodiments, the epoxy resin is glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins and the curing agent is a heterocyclic amine.

In certain modalities, the epoxy resin is HARD

COAT IA available from JACAM Chemicals, LLC, of Sterling, KS, and the curing agent is an imidazoline, pyrrolidine, pyrrole, pyridine, piperidine, or mixtures thereof.

Methods

Modalities of the present invention also relate

broadly to methods for zone isolation that include inserting a pipe into a drill hole.

After laying the pipe, pump a foamable composition of this invention into a ring between the wall of the drill hole and an outer wall of the pipe. The methods also include allowing sufficient time for the compositions to cure and foam by sealing the ring. The compositions can be pumped in parts. In certain embodiments, resins and blowing agents and curing or hardening agents can be pumped separately into the well and mixed in a static mixing chamber within the well prior to being pumped into the ring. In other embodiments, the resins and the curing or hardening agents and the blowing agent are pumped separately into the well and mixed in a static mixing chamber within the well prior to being pumped into the ring.

Modalities of the present invention also provide methods for injection operations that include pumping a composition of this invention into annular spaces, regions, or locations in an entire well, where fluid migration occurs to form a seal to reduce or eliminate such migration.

In certain modalities, the diluent system

ΜΡΙ

4 'ΤΟυΤΟ MEXICAN

Dt THE PROPERTY

INDUSTRIAL comprises aromatic solvents and heterocyclic aromatic solvents or mixtures and combinations thereof.

Epoxy resins can comprise: (a) glycidyl ether epoxy resin prepared by the reaction of epichlorohydrin with a hydroxyl group-containing compound carried out under alkaline reaction conditions; (b) epoxy resins prepared by the reaction of epichlorohydrin with di- and tri-hydroxy phenolic mononuclear compounds; (c) epoxidized derivatives of natural oils with long chain mixed saturated and unsaturated acids having between about 14 and 20 carbon atoms; (d) polyepoxides derived from polycarboxylic acid esters with unsaturated alcohols; (e) polyepoxides derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids; (f) butadiene-based epoxidized polymers; (g) epoxidized derivatives of diene dimers, and (h) mixtures or combinations thereof. Epoxy resins can have a molecular weight between about 50 and about 10,000.

Curing agents may comprise polyamine curing agents, alkoxylated polyamine curing agents, heterocyclic amine curing agents, or the like including a plurality of amino groups, or mixtures and combinations thereof. The agents

IMPI

/. C MEXICAN INSTITUTE4 · £ THE PROPERTY

INDUSTRIAL curing may comprise alkoxylated aliphatic polyamines, alkoxylated cycloaliphatic polyamines, alkoxylated aromatic polyamines, alkoxylated heterocyclic polyamines, or mixtures and combinations thereof.

In certain embodiments, the temperature range is from about 66 ° C to about 149 ° C (150 ° F to about 300 ° F) and the composition ranges from about 60 wt% to about 85 wt% of an epoxy resin or a mixture of epoxy resins, from about 1% by weight to about 15% by weight of a curing agent or a mixture of curing agents, and from about 5% by weight to about 15% by weight of the blowing agent a mixture or blowing agents and from about 39% by weight to about 0% by weight 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. Epoxy resins are glycidyl ether epoxy resins or glycidyl ether epoxy resin blends, the curing agent is an alkoxylated polyamine or alkoxylated polyamine mixture and the diluent is an aromatic heterocyclic solvent or aromatic heterocyclic solvent mixture.

The epoxy resin is DURA COAT IA, the curing agent is

DURA COAT 2B and the diluent is AKOLIDINE 11.

Üt LA ΡΚΟΓΙΑΒΛΙ. INDUSTRIAL

In certain embodiments the temperature range is between about 32.2 ° C and around 66 ° C (90 ° F and around 150 ° F) and the composition ranges from about 70% by weight to about 50% by weight of an epoxy resin or a mixture of epoxy resins, from about 30% by weight to about 50% by weight of curing or hardening agents or a mixture of curing acids and from about 5% by weight to about 20% by weight of a blowing agent or mixture of blowing agents based on the weight of the other components. The epoxy resins can be glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins and the curing agent can be a heterocyclic amine. The epoxy resin can be DURA COAT 1A and the curing agent can be an imidazoline or mixture or imidazolines.

IMPI

7 MEXICAN INSTITUTE

OF THE PROPERTY

INDUSTRIAL blown based on the weight of the other components, epoxy resins can be glycidyl ether epoxy resin or mixture of glycidyl ether epoxy resins and the curing agent is an imidazoline, pyrrolidine, pyrrole, pyridine, piperidine or mixtures of the same. The epoxy resin can be DURA COAT IA and the curing agent can be an imidazoline, pyrrolidine, pyrrole, pyridine, piperidine, or mixtures thereof.

In certain embodiments, the composition comprises from about 60% by weight to about 85% by weight of an epoxy resin or a mixture of epoxy resins, from about 1% by weight to about 15% by weight of a hardening agent or curing or a mixture of curing agents, from about 5% by weight to about 15% by weight of blowing agent or a mixture of blowing agents and from about 39% by weight to about 0% by weight of a solvent system, based on the weight of the other components.

Materials Appropriate for Use in the Invention

The appropriate epoxy resin includes, without limitation, (a) glycidyl ether epoxy resin prepared by the reaction of epichlorohydrin with a hydroxyl group-containing compound (eg, bisphenol A) carried out under

ΙΜΡΙ

alkaline reaction conditions; (b) epoxy resins prepared by the reaction of epichlorohydrin with di- and tri-hydroxy phenolic mononuclear compounds such as resorcinol and floroglucinol, selected polynuclear polyhydroxy phenolic compounds such as bis (phidroxyphenyl) methane and 4,4'-dihydroxy biphenyl, or polyols aliphatics such as 1,4-butanediol and glycerol; (c) epoxidized derivatives of natural oils such as long chain mixed saturated and unsaturated acid glycerol triesters having between about 14 and 20 carbon atoms (eg, 16, 18 and 20 carbon atoms) (the oil soybean is a typical triglyceride that can be converted to polyepoxide); (d) polyepoxides derived from polycarboxylic acid esters such as maleic acid, terephthalic acid, oxalic acid, succinic acid, azelaic acid, maionic acid, tartaric acid, adipic acid or the like, with unsaturated alcohols; (e) polyepoxides derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids; (f) butadiene-based epoxy 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 unsaturated polycarboxylic acid esters; (g) derivatives

IMPI Mexican Institute R

Γ * Τ I a H / 'xeicnin u L ·., *** “i: ··· í'. ijC

INDUSTRIAL epoxides of diene dimers such as butadiene 4-vinyl cyclohexene-1 and cyclopentadiene dicyclopentadiene, and (h) mixtures or combinations thereof.

Appropriate epoxy resins for use in the invention have molecular weights generally within the range of about 50 to about 10,000. In other modalities, the interval is between around 2000 and around 1500. In other embodiments, the epoxy resin is a commercially available Epon 828 epoxy resin, a reaction product of epichlorohydrin and 2,2-bis (4hydroxyphenyl) propane (bisphenol A) and having a molecular weight of about 400, an epoxy equivalent ( ASTM

D-1652) of about 185-192. Exemplary examples of some epoxy resins include, without limitation: 2,3-epoxypentyl-3,4-epoxybutyrate epoxy esters; 2,3-epoxybutyl-3,4-epoxyhexanoate; 3,4-epoxyoctyl-2,3-epoxycyclohexane carboxylate; 2,3-epoxidedecyl-4,5epoxyoctanoate; 2,3-epoxyisobutyl-4,5-epoxidedecanoate; 2,3-epoxycyclododecyl-3,4-epoxy-pentanoate; 3,4-epoxyocti1-2,3epoxycyclododecane carboxylate or the like; and polyepoxides derived from the latter include the following: dimethyl 3,4,7,8-diepoxidecanedioate; dibutyl 3,4,5,6 diepoxycyclohexane-1,2-carboxylate; dioctii 3,4,7,8diepoxyhexadecanedioate;

money

5,6,9,10IMPI

MEXICAN INSTITUTE OF PROPERTY

INDUSTRIAL

diepoxytetradecanedioate or similar anhydrides. In other modalities the epoxy resin is DURA COAT IA available from

JACAM Chemicals, LLC, of Sterling, KS. Other epoxy resins are available from JACAM Chemicals, LLC, of Sterling, KS or can be found in United States Patents of

America Nos. 5,936,059; 7,557,169; 7,547,373; 7,267,782;

6,943,219; and 6,277,903.

Suitable curing agents for epoxy resins include, without limitation, polyamine curing agents, alkoxylated polyamine curing agents, heterocyclic amine curing agents, or similar compounds including a plurality of amino groups, or mixtures and combinations of the same. 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 1,3-diaminopropanes substituted by N-alkyl and N-alkylenyl 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-nonadecyl1,3-diaminopropane, N-octadecyl-1,3-diaminopropane or mixtures and combinations thereof. In other embodiments, the alkoxylated polyamines include commercially available mixtures of N-alkylated and Nalkenyl ethoxylated diamines. In other embodiments, the polyamine is a commercial product, N-tallow-1,3-diaminopropane ethoxylated, where the degree of ethoxylation is approximately 10 moles ethoxylated per mole of diamine bait. In other embodiments, the epoxy resin is DURA COAT 2B available from JACAM Chemicals,

LLC, of Sterling, KS. Other epoxy curing agents are available from JACAM Chemicals, LLC, of Sterling, KS or can be found in US Patent 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, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline, imidazoline , azepane, alkyl azepane, azepine, alkyl azepines, morpholine, alkyl morpholines, diazapine, alkyl diazapine, or mixtures and combinations thereof. In certain embodiments, the curing agents are a mixture of alkyl pyridines

IMPI

such as Akolidine 11, available from Lonza Group Ltd,

Joseph Colleluori, Muenchensteinerstrasse 38, CH-4002

Basel, Switzerland and DURA COAT 2B. In other embodiments, the diluent is pyrrolidine. In other embodiments, the diluent is imodazoline.

The appropriate 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 pyrroles, imidazole, alkyl imidazole, pyridine, alkyl pyridines, pyrazole, alkyl pyrazoles, oxazole, alkyl oxazoles, or mixtures and combinations of the same.

Appropriate blowing agents for use in the practice of this invention include, without limitation, arylsulfonyl hydrazides including. benzene sulfonyl hydrazides, alkylated benzene sulfonyl hydrazides, for example 4-methyl benzene sulfonyl hydrazide, and arylsulfonyl hydrazides dimeric including p, p'-oxybis (benzene sulfonyl hydrazide), other similar blowing agents which decompose to generate either nitrogen , carbon dioxide or other inert or substantially inert gas, or mixtures and

IMPI

MEXICAN INSTITUTE OF IROPIEDAD

INDUSTRIAL

combinations thereof.

Referring now to Figures 1A-1D, one embodiment of a zone isolation procedure of this invention, generally 100, is shown to include drill hole 102 having a wall 104. Inserted within drill hole 102 is a string. of casing pipe 106, having a distal end 108 arranged near the bottom 110 of well 102. Referring to Figure IB, a supply conduit 112 including a plug 114 is inserted into drill hole 102 and an epoxy base zone isolation composition 116 of this invention is pumped into drill hole 102 through the conduit 112 and in annular space 118 between wall 104 of drill hole 102 and an outer wall

120 of the casing 106. As for the

Figure 1C, pumping is continued until composition 116 fills annular space 118 to a desired level 122 in borehole 102 and conduit 112 and plug 114 are removed (shown after removal of equipment). Referring to Figure ID, composition 116 is cured to form a cured epoxy base zone isolate structure

124.

Referring now to Figures 2A-2D, another embodiment

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4 MEXICAN INSTITUTE

FROM THE FWHEOAP

INDUSTRIAL of a zone isolation method of this invention, generally 200, is shown to include a borehole section 202 having a wall 204 and to include a string of casing pipe 206 extending through section 202 Regarding the Figure

2B, section 202 is shown equipped with a bottom zone insulation seal member 208, outlets 210, and a supply conduit 212 including shutters 214. An epoxy base zone insulation composition 216 of this invention is then it pumps through conduit 212 into an annular space 218 between wall 204 of section 202 above member 208. Referring to Figure 2C, pumping is continued until composition 216 fills annular space 218 to a desired level 220 in section 202. Duct 212 and plugs 214 are then removed (shown after removal of equipment). Regarding the Figure

2D, composition 216 is cured to form a cured epoxy base zone isolate structure 222 within section 202.

Referring now to Figures 3A-3D, one embodiment of an expansion pipe method of this invention, generally 300, is shown to include a borehole 302 having a wall 304 and to include a string of casing pipe 306 which extends to

MEXICAN INSTITUTE C? * MONTH £ Yes3>

OF THE FOPOPIEUAD C

INDUSTRIAL through drill hole 302, where casing 306 has a distal end 308 disposed near the bottom 310 of drill hole 302. Casing 306 also includes an expanded section 312.

Referring to Figure 3B, drill hole 302 is shown equipped with a supply conduit 314 that includes a plug 316. An epoxy base zone insulation composition 318 of this invention is then pumped through conduit 314 into a annular space 320 between wall 304 of drill hole 302. Pumping is continued until composition 318 fills the annular space

320 to a desired level 322 in drill hole 302.

Conduit 314 and plug 316 are then removed (not shown) and composition 318 allowed to cure to form a cured epoxy base zone isolate structure 324 within drill hole 302. An expansion member

326 it is then inserted into the liner pipe 306 and the pipe expands by pulling the expansion member 326 through the expansion section 312 of the liner pipe 306 to expand the expansion section 312. The expansion operation results in a compression of the cured epoxy base zone isolate structure 324 to form a compressed, cured epoxy base zone isolate structure 328 as shown in Figure

IMPI

N ITfTUTO MEXICANO

PE LA PAOHEOAD Ό

INDUSTRIAL

3D. Additional details on the expansion pipe, how it expands and uses in-well applications can be found in, 01/04/2010 Publications and

United States Nos. 3049752, 3678560, 3905227, 4204426,

4616987, 5271469, 5271472, 5947213, 6112809, 6296057,

6843317, 6880632, 7182141, 7215125, 7500389, 7634942, and

United States Publication Request No.

20030111234,

20040216925,

20050279515,

20100078166.

20040099424,

20050173109,

20040154797,

20050173130,

20060027376, 20070151360,

20040163819,

20050279514,

20080083533 and

Referring now to Figures 4A-4D, one embodiment of an injection method of this invention, generally 400, is shown to include a borehole section 402 having a wall 404 and to include a string of casing pipe 406 that extends through section 402. Section 402 includes a region

408 through which fluid flows into and out of casing 406. This region 408 can result in contamination of production fluids, treatment fluids, or other fluids typically used in in-well operations. To reduce or eliminate fluid flow through region 408, a sealant of this invention can be pumped into region 408, and then

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MEXICAN INSTITUTE OF THE ERORIEOAD

INDUSTRIAL

Upon curing, the sealant will form a seal that reduces or eliminates fluid flow into and out of casing pipe 406. Referring to Figure 4B, section 402 is shown equipped with supply duct 410 including shutters 412. An epoxy base zone insulation composition 414 of this invention is then pumped through conduit 410 into an annular space 416 between wall 404 of section 402 and an outer wall 418 of casing 406. As for the Figure 4C, pumping is continued until the composition fills annular space 416 to a desired level 420 in section 402. Duct 410 and plugs 412 are then removed (shown after removal of equipment). Referring to Figure 4D, composition 414 is cured to form a cured epoxy base zone isolate structure 422 within section 402 by reducing or eliminating flow through liner 406 in region 408.

EXPERIMENTS OF THE INVENTION

Example 1

This example illustrates the formulation of a zone isolation epoxy composition for high temperature applications, where the composition has a setting temperature in a high temperature range between about (150 F to about 66 ° C to about 149 ° C

300 ° F).

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MEXICAN INSTITUTE OF THE INDUSTRIAL PRONEBAD

22.6 grams of DURA COAT IA were added to 2.6 grams of

Akolidine 11 with mixed. 2.0 grams of DURA COAT 2B was added to this solution to form a high temperature zone insulation composition (HTZIC) of this invention. Table I tabulates the components, quantity, and weight percentages of the HTZI composition of this invention, while Table II tabulates properties of the components.

TABLE I

Composition for insulation of high temperature areas

<td>Component</td><td>Weight (g)</td><td>Percentage (p / p)</td>

<td>Akolidine 11</td><td> ' 2.6</td><td> 9.6</td>

<td>Total</td><td> 27.2</td><td> 100</td>

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XSTITUTü MEXICANO DE LA FRONEDAC INDUSTRIAL

Table II

Component Properties and HTZIC

<td>Component</td><td>Colour</td><td>pH</td><td>r @ 25 ° C (g / cm3)</td><td>SG @ 25 ° C</td>

<td>DURA COAT IA</td><td>Colorless</td><td> 9.02</td><td> 1.16094</td><td> 1.16473</td>

<td>DURA COAT 2B</td><td>Coffee</td><td> 10.92</td><td> 0.93827</td><td> 0.94105</td>

<td>Akolidine 11</td><td>Dark coffee</td><td> 3.14</td><td> 0.93394</td><td> 0.93685</td>

<td>HTZI</td><td>Dark coffee</td><td> 8.40</td><td> 1.11433</td><td> 1.11763</td>

Referring now to Figure 5, a viscosity versus temperature graph is shown for the components used in making the HTZI composition and the composition.

Example 2

This example illustrates the formulation of an epoxy composition for zone isolation for medium temperature applications, where the composition has a temperature

<td>of</td><td>setting</td><td>in</td><td>an interval</td><td>Of temperature</td><td>average between</td>

<td colspan="2">about</td><td> 32.2</td><td>° C and around</td><td>66 ° C (90 ° F and</td><td>about</td>

<td></td><td colspan="2">Added</td><td>50 grams of</td><td>DURA COAT IA a</td><td>50 grams of</td>

imodaziline to form an insulation composition of

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INSTITUTO MEXICANO DF LA PROPERTY INtUSTRlAL

medium temperature zones (MTZI) of this invention. The

Table III tabulates the components, amount, and weight percentages of the MTZI composition of this invention.

TABLE III

Composition for Isolation of Medium Temperature Zones

<td>Component</td><td>Percentage (p / p)</td><td>r (g / cm3)</td>

<td>Imodazoline</td><td> 50</td><td></td>

<td>Total</td><td> 100</td><td></td>

Example 3

This example illustrates the formulation of a zone isolation epoxy composition for low temperature applications, where the composition has a setting temperature in a low temperature range between about 10 ° C and about 32.2 ° C (50 ° F and around 90 ° F).

92.5 grams of DURA COAT 1A were added to 7.5 grams of pyrrolidine to form a low temperature zone insulation (LTZI) composition of this invention. The board

IV tabulates the components, amount, and weight percentages of the LTZI composition of this invention.

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TABLE IV

Composition for Isolation of Low Temperature Zones

<td>Component</td><td>Percentage (p / p)</td><td>r (g / cm3)</td>

<td>Pyrrolidine</td><td> 7.5'</td><td> 0.86</td>

<td>Total</td><td> 100</td><td></td>

Referring now to Figures IA'-ID ', one embodiment of a zone isolation method of this invention, generally 100', is shown to include a borehole 102 'having a wall 104'. Inserted into drill hole 102 'is a string of casing pipe 106' ', which has a distal end

108 'arranged near the bottom 110' of the well 102 '. Referring to Figure IB ', a supply conduit 112' including a plug 114 'is inserted into the drill hole

102 'and an epoxy base zone insulation composition 116' of this invention is pumped into borehole 102 'through conduit 112' and into an annular space 118 'between wall 104' of borehole 102 ' and an outer wall 120 'of the casing pipe 106'. Referring to Figure 1C ', pumping is continued until composition 116' fills annular space 118 'to a

IMPI

desired level 122 'in drill hole 102' and conduit 112 'and plug 114' are removed (shown after removal of equipment). Referring to Figure ID ', composition 116' is cured to form a cured epoxy base zone isolate structure 124 '.

Referring now to Figures 2A'-2D ', another embodiment of a zone isolation procedure of this invention, generally 200', is shown to include borehole section 202 'having a wall 204' and including a string. of casing pipe 206 'extending through section 202'. Regarding the Figure

2B ', 1st section 202' is shown equipped with a bottom zone isolation seal member 208 ', outlets 210', and a supply conduit 212 'including shutters 214'.

A composition for insulation of epoxy based areas

216 'of this invention is then pumped through the conduit

212 'in an annular space 218' between wall 204 'of section 202' above member 208 '. Regarding the Figure

2C ', pumping is continued until composition 216' fills annular space 218 'to a desired level 220' in section 202 '. The conduit 212 'and plugs 214' are then removed (shown after removal of the kit). Referring to Figure 2D ', composition 216' is cured to form a base zone isolate structure

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epoxy, cured 222 'within section 202'.

Referring now to Figures 3A'-3D ', one embodiment of an expansion pipe method of this invention, generally 300', is shown to include a borehole 302 'having a wall 304' and to include a string of casing 306 'extending through bore 302', where casing 306 'has a distal end 308' arranged near the bottom 310 'of bore 302'. The

<td>pipeline</td><td colspan="2">lining 306 '</td><td>it also includes</td><td>a</td><td colspan="2">section</td>

<td>expandable</td><td> 312' .</td><td>As to</td><td>Figure 3B ',</td><td>the</td><td>water well</td><td>of</td>

<td>drilling</td><td> 302'</td><td colspan="2">shown equipped with a</td><td colspan="2">conduit</td><td>of</td>

<td>supply</td><td> 314'</td><td>including</td><td>a shutter</td><td> 316'</td><td></td><td>A</td>

<td>composition</td><td>for</td><td>isolation of</td><td colspan="2">epoxy based areas</td><td> 318'</td><td>of</td>

<td colspan="3">this invention is then pumped.</td><td colspan="2">through the duct</td><td> 314'</td><td>in</td>

<td>a space</td><td colspan="2">cancel 320 'between</td><td>wall 304 '</td><td>of the</td><td>water well</td><td>of</td>

<td>drilling</td><td> 302'</td><td>Pumping</td><td colspan="2">it continues until</td><td>than</td><td>the</td>

<td>composition</td><td> 318'</td><td colspan="3">fill the annular space 320 'up</td><td colspan="2">a level</td>

<td>desired 322</td><td>' in</td><td colspan="2">drill hole 302 '.</td><td>The</td><td colspan="2">conduit</td>

314 'and plug 316' are then removed (not shown) and composition 318 'allowing cure to form a cured epoxy base zone isolate structure 324' within drill hole 302 '. An expansion member 326' is then inserted into the casing 306 'and the

IMPI

MEXICAN INSTITUTE

Dr LA rROrlEDAD _ INDUSTRIAL pipe expands by pulling expansion member 326 'through expansion section 312' of casing 306 'to expand expansion section

312 '. The expansion operation results in compression of the cured epoxy base zone isolate structure 324 'to form a compressed, cured epoxy base zone isolate structure 328' as shown in Figure

3D '. Additional details on expansion pipe, how it expands and uses in-well applications can

<td> 10</td><td>Meet in,</td><td>publications</td><td>from 01/04/2010</td><td>and Patents of</td>

<td></td><td>United States</td><td>No. 3049752</td><td colspan="2"> , 3678560, 3905227, 4204426,</td>

<td></td><td>Application</td><td>Publication</td><td>of the states</td><td>United No.</td>

<td></td><td colspan="2">With reference now</td><td>to the Figures</td><td>4A'-4D ', a</td>

An injecting method embodiment of this invention, generally 400 ', is shown to include borehole section 402' having a wall 404 'and to include a string of casing pipe 406' which extends through the section 402 '. Section 402 'includes a

IMPI

region 408 'through which fluid flows into and out of casing pipe 406'. This region 408 'can result in contamination of production fluids, treatment fluids, or other fluids typically used in operations within the wellbore. To reduce or eliminate fluid flow through region 408 ', a sealant of this invention can be pumped into region 408', and after curing, the sealant will form a seal that reduces or eliminates fluid flowing into and out of casing pipe

406 '. Referring to Figure 4B ', section 402' is shown equipped with a supply conduit 410 'including shutters 412'. An epoxy base zone insulation composition 414 'of this invention is then pumped through conduit 410' into an annular space 416 'between wall 404' of section 402 'and an outer wall 418' of the casing 406 '. Referring to Figure 4C ', pumping is continued until the composition fills annular space 416' to a desired level 420 'in section 402'.

Duct 410 'and plugs 412' are then removed (shown after removal of equipment). Referring to Figure 4D ', composition 414' is cured to form a cured epoxy base zone isolate structure 422 'within section 402' by reducing or eliminating flow through coating 406 'in region 408 '.

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MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

EXPERIMENTS OF THE INVENTION

Example 1'

This example illustrates the formulation of epoxy foam composition for zone insulation for high temperature applications, where the composition has a setting temperature in a high temperature range between

<td>around</td><td>of</td><td>66 ° C</td><td>until</td><td>about</td><td> 1493C (</td><td>150 ° F</td><td>until</td>

<td>around</td><td>of</td><td>300 ° F)</td><td>and the</td><td>compositions</td><td colspan="2">which include 1</td><td>% in</td>

<td>weight, 3%</td><td>in</td><td>weight,</td><td>5% in</td><td>weight, 10% in</td><td>weight, 15</td><td colspan="2">% by weight and</td>

<td>20% in</td><td>weight</td><td colspan="2">aggregate of</td><td colspan="2">p-toluenesulfohydrazide</td><td>(TSH)</td><td>or 4-</td>

methylbenzene p-toluenesulfohydrazide.

Added 22.6 grams of DURA COAT IA to 2.6 grams of

Akolidine 11 and an indicated amount of ptoluensulfohydrazide with mixing. 2.0 grams of DURA COAT 2B was added to this solution and placed in an oven @ 250 ° F (121 ° C) for 24 hr to form a high temperature foam zone insulation composition (HTFZIC) of this invention. Table I 'tabulates the components, quantity, and weight percentages of the HTFZI compositions of this invention.

IΜ ΡI

7 MEXICAN INSTITUTE

Κ PROPERTY O * »s ^

INDUSTRIAL

TABLE 1'

Composition for insulation of high temperature areas

<td>Foams</td><td>DURA COAT IA</td><td>DURA COAT 2B</td><td>Akolidine 11</td><td>TSH *</td>

<td>F1</td><td>22.6 grams</td><td>2.0 grams</td><td>2.6 grams</td><td>1% by weight</td>

<td>F2</td><td>22.6 grams</td><td>2.0 grams</td><td>2.6 grams</td><td>3% by weight</td>

<td>F3</td><td>22.6 grams</td><td>2.0 grams</td><td>2.6 grams</td><td>5% by weight</td>

<td>F4</td><td>22.6 grams</td><td>2.0 grams</td><td>2.6 grams</td><td>10 wt%</td>

<td>F5</td><td>22.6 grams</td><td>2.0 grams</td><td>2.6 grams</td><td>20% by weight</td>

p-toluenesulfohydrazide

Experimental data shows that F4 has the best foaming properties of proven compositions that have a compressive strength between 0.233 and 0.400 kg / cm.2 (3,318 and 5,704 psi). F5 was highly exothermic and has low foaming properties.

Example 2 '

This example illustrates the epoxy foam composition formulation for zone insulation for high temperature applications, where the composition has a setting temperature in a high temperature range between about 66 ° C to about 149 ° C (150 ° F up to about 300 ° F) and compositions including 1% by weight, 3% by weight, 5% by weight, 10% by weight, 15% by weight and% by weight added p-toluensulfohydrazide (TSH) or 468

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MEXICAN INSTITUTE DtLA INDUSTRIAL PROPERTY

methylbenzene p-toluenesulfohydrazide.

5% by weight and 10% by weight of ptoluensulfohydrazide were added to the base sample formula of the

Example 1 above and the final composition was placed in a corrugated cell furnace at 121 ° C (250 ° F) under a pressure of

21.09 kg / cm2 (300 psi) using a gas mixture that includes 96% nitrogen and 4% oxygen. After 24 hr of pressurization, the 10 wt% TSH sample shows better foaming properties than the 5 wt% TSH sample. Figure 5 'illustrates the foamed and cured seal of this invention.

All references cited herein are incorporated for reference for each permitted purpose controlled by the Laws of the United States. Although the invention has been described with reference to its preferred embodiments, upon reading this description those of skill in the art can appreciate the changes and modifications that can be made without departing from the scope and spirit of the invention as described above and later claimed.

IMPI

MEXICAN INSTITUTE

OF THE VVINDUSTRIAL PROPERTY

Contents85

14 members in 4 offices

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Priority claims
Document	Office	Kind	Date
12784479	United States of America	–	2010-05-20
78447910	United States of America	A	2010-05-20
78447910	United States of America	A	2010-05-20
13053975	United States of America	–	2011-03-22
201113053975	United States of America	A	2011-03-22
201113053975	United States of America	A	2011-03-22
12784479	–	–	–
13053975	–	–	–
US20100784479	–	–	–
US201113053975	–	–	–

Members14

Family members, oldest first
Document	Office	Kind
GB201108332D0	United Kingdom	D0	2011-06-29
CA2740453A1	Canada	A1	2011-11-20
MX2011005373A	Mexico	A	2011-11-21
GB2480546A	United Kingdom	A	2011-11-23
US2011284247A1	United States of America	A1	2011-11-24
US2011284248A1	United States of America	A1	2011-11-24
GB2480546B	United Kingdom	B	2013-06-26
CA2740453C	Canada	C	2013-10-22
US8851174B2	United States of America	B2	2014-10-07
US8899328B2	United States of America	B2	2014-12-02
US2015011440A1	United States of America	A1	2015-01-08
US2015051311A1	United States of America	A1	2015-02-19
MX339949BThis record	Mexico	B	2016-06-16
US10301526B2	United States of America	B2	2019-05-28