Well treatment compositions and methods utilizing nano-particles.

(54) Title: COMPOSITIONS AND METHODS OF WELL TREATMENT USING NANOPARTICLES. (54) Title: WELL TREATMENT COMPOSITIONS AND METHODS UTILIZING NANO-PARTICLES.

(57) Summary

The present invention relates to well treatment compositions and methods using nanoparticles, more particularly, in one or more embodiments, to well cement compositions and / or well completion fluids comprising nanoparticles. In a preferred embodiment, the present invention provides a leaching method that includes the inclusion of nanoparticles ranging from about 1 nanometer to about 100 nanometers in termination fluids, where the nanoparticles comprise at least a nanoparticle selected from the group consisting of nanoalumina, zinc nanoxide, nanoboro, iron nanoxide, nanosilice, and any of their combinations; and the use of completion fluid in the completion of the well.

(57) Abstract

Disclosed performances relate to well treatment fluids and methods that use nano-particles. Exemplary nanoparticles are selected from the group consisting of particulate nano-silica, nano-alumina, nano-zinc oxide, nano-boron, nano-iron oxide, and combinations thereof. Embodiments also relate to methods of cementing that inelude the use of nanoparticles. An exemplary method of cementing comprises introducing a cement composition into a subterranean formation, where the cement composition comprises cement, water and a particulate nano-silica. Embodiments also relate to use of nano-particles in drilling fluids, completion fluids, simulation fluids, and well clean-up fluids.

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PATENT TITLE No. 355755

Headlines):

Home:

Denomination:

Classification:

HALLIBURTON ENERGY SERVICES INC.

10200 Bellaire Blvd, Houston, Texas, 77072, USA

COMPOSITIONS AND METHODS OF TREATMENT OF WELLS USING NANOPARTICLES.

CIP: CO4B2O / 0O; C04B2ty (»; PQ9K8 / Q3; C09K8 / 46; C09K8 / 48; C09K8 / 487;

C09K8 / 5Íte; C0eKÍ / 504íC09Kfc / 516 '.

CPC: B82Y30 / 00; C04B28 / 02; C09K8 / 032; C09K8 / 46; C09K8 / 502; C09K8 / 516;

Inventor (s):

, 009 ^ 5/5045; C04B21-M CSetl: C04B28 / 02, C04B14,

CARL J. THA6MLIT,

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ífHWY L. COVINGT; JITEN CHATTERJI; D.

Number:

MX / a / 2014/012972 ^{&gt; λ}'\ · Λ' 'V?&gt;'

Country:

US

Validity: Twenty years Expiration Date April 26, 2033 Expyftitttqton Date:

Reference patent granted with Andamento

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Number:

4/13 &lt;112 j,_:y '&gt; -^Λ'. -: í || ilos ti, 2 · freccÓB Y. ί⁶ Μοοιφη W. / 59 deértey de la é / $&gt; i «lad1 ndustrial.

In accordance with article O. of the Law ¿fcHaJ'reptpdJO lndustnaíl a'pfedkit · ratawMéene4HB &amp; M0 «fea de venté andifMtf extendable, counted from the date of filing of 1 * fcolicitud inténgacídnalYestetli« yak | j paid tariffs to keep tgigent.

Who subscribes the present title or hade Q0n fundamento erijo dispongoÚós, articul · (Official Gazette of the Federation (5flte.&gt; Jsp / W19ad »&gt; -« imimAi el ¢ ^ / 06 /), 994, 01/25/2006, 06 / 05 / 2009,06 / 01/2010, tS / WSWje, 'dS / oerJÓTO, 2770 &lt;U2 &lt;y¿ and Θ9Α04Ζ2Ο:' Regulations of the Mexican Institute of &amp; i articles 1st, 3rd, 4th, 5th fraction V Subparagraph a), 12/27/1999, amended on 10/10/2002, 07/29/20:

Deputy Generals, Coordinator, Divisioi Departmental Directors and other subordinates of the Mexican Institute of 04/08/2004 and 09/13/2007).

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^ eja Industrial Property Law * * 1999, 01/26/2004, 06/16/2005, so a), 4th and 12th sections I and III of refog | ii «eSÍif- 01 / f ¥ 50t5? M5 / 07/2004, 07/28/2004 and 09/07/2007); stfltsáóAe ^ H ^ Vdenj ^ tutd ^ Mexican Industrial Property (DOF) Jlíl »^ y ^ ejÍ8g¿u * &lt;05 |₍Agreement that delegates powers to the nJbficinaqiflPSfijfíales Directors, Divisional Deputy Directors, Coordinators (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004,

6th Mc) aons 5 / J £ * l | 3t articles 1 °. 3'

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This letter is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TÉR of the Agreement establishing the guidelines for the use of the Electronic Payment and Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.

THE DIVISIONAL DIRECTOR OF PATENTS

NAHANNY CANAL REYES

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(55) 53340700 www.gob.mx/impi

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MX / 2018/36482

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COMPOSITIONS AND METHODS OF TREATMENT OF WELLS USING

NANOPARTICLES

FIELD OF THE INVENTION

The present invention relates to well treatment compositions and methods using nanoparticles, more particularly, in one or more embodiments, to well cement compositions and / or well completion fluids comprising nanoparticles.

REFERENCE TO RELATED REQUESTS

This application is a continuation in part of the

United States of America Patent Application No.

12 / 567,782, filed on September 27, 2009, titled

Cement Compositions and Methods Using Nanoclay, which is a continuation in part of United States of America Patent Application No. 12 / 263,954, filed on November 3, 2008, titled Cement Compositions and Methods Using Nanohydraulic Cement, which is a continuation in part of the Patent Application of the

United States of America No. 11 / 747,002, now, United States of America Patent No. 7,559,369, filed May 2007, entitled Well Treatment Compositions and Methods Using Nanoparticles. The descriptions

OF OWN OWNERSHIP ·

INDUSTRIAL '^ U. * 7 - of these applications are incorporated in the present application by way of reference, in their entirety.

BACKGROUND OF THE INVENTION

In general, well treatments include a wide variety of methods that can be carried out in oil, gas, water, and / or geothermal wells, such as drilling, completion, and maintenance and cleaning for recovery ( workover). Drilling, termination, and maintenance and cleaning methods for recovery may include, without limitation, drilling, fracturing, acidification, profiling, cementing, gravel packing, puncture, and compliance methods. Many of these well treatments are designed to improve and / or facilitate the recovery of desirable fluids from an underground well.

In cementing methods, such as well construction and repair cementing, cementitious well compositions are commonly used.

For example, in underground well construction, a string of pipe (for example, casing and casing) can be lowered into a well, and can be cemented in place using a cementitious composition. The cementing process of the pipe string in place

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INDUSTRIAL is commonly called primary cementing. In a typical primary cementing method, a cement composition can be pumped into a ring between the well walls and the outside surface of the pipe string arranged there. The cement composition is established in the annular space, so as to form a substantially waterproof hardened cement annular sheath, which supports and positions the pipe string in the wellbore, and bonds the outer surface of the pipe string to the formation underground. Among other things, the established cement annular sheath that surrounds the pipe string works to prevent the migration of fluids in the ring, as well as to protect the pipe string from corrosion.

The cement compositions can also be used in methods of repair cementation, such as compression cementation and placement of cement plugs.

In operation, the cement annular sleeve formed between the well and the pipe string often suffers structural failure due to pipe movements causing shear stresses exerted on the established cement.

Such stress conditions are commonly a consequence of relatively high fluid temperatures and / or pressures within the cemented pipe string during testing, puncture, fluid injection, or fluid production.

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For example, such stress can occur in wells subjected to steam production or recovery of hot formation fluids from high temperature formations. The high temperature and / or pressure of the internal piping can produce the expansion of the piping string, both radially and longitudinally, which exerts stresses on the cement sheath, causing failure of the cement bond between the outer surfaces of the pipe or the walls of the well, or both, and consequently, allow the spillage of formation fluids, etc. Therefore, it may be desirable for the cement composition used for cementing well pipe strings to develop high strength after establishment, and have sufficient resilience (eg, elasticity and ductility) to resist loss of cement bond between the exterior surfaces of the pipe or the well walls, or both. Furthermore, it may be desirable that the cement composition can resist cracking and / or breaks that can result from other forces on the cement sleeve. For example, it may be desirable for the cement sheath to include structural features that protect its structural integrity against forces associated with formation displacement, overburden pressure, subsidence, plate drag

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INDUSTRIAL ^ * ¿· __ tectonics, pipe movements, impacts and shocks subsequently generated by drilling and other well operations.

In addition to including components that improve the mechanical properties of cement, in a number of cementing methods, it may also be desirable to include one or more set-up accelerators in cementitious well compositions to counteract certain constituents and / or environmental characteristics. that excessively decrease establishment times. For example, among other things, low temperatures and cement additives (eg, additives to control fluid loss and dispersants) can cause or contribute excessive settling time for a cement composition. Therefore, in certain situations, it may be desirable to reduce settling time, by including a settling accelerator in the cement composition. That is, the set-up accelerator can be included in a cement composition in order to counteract the components of the cement composition or the conditions surrounding the cement composition that cause excessive set-up time.

Completion fluids are another type of fluid that can be used in well treatment. A fluid of

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IMPI completion is typically a solids free liquid that is used, in part, to control well pressure while the well is being completed. Completion fluid is typically placed in the well after drilling, although prior to the start of production, in order to facilitate completion of the well, which typically involves preparing the bottom of the well to the required specifications, the lowering of the production pipeline and its associated equipment inside the well, and optionally, if desired, carrying out production improvement operations. The completion fluid, in general, must be chemically compatible with the reservoir formation and fluid, and must not damage the permeability of the formation or other equipment placed inside the well, such as production sieves. In order to avoid any damage, the completion fluid is usually filtered to a high degree, to remove any solids that may be introduced into the region near the well or into the equipment inside the well.

Typically, brines, such as chlorides, bromides, and formates, have been used as finishing fluids. However, these metal brines can be expensive, corrosive, and difficult to handle. For example, brines can have a tendency to corrosion and

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Orí: / damage to equipment inside the well, in many cases, especially those equipment of a delicate nature such as production screens. The brines can also cause unwanted precipitation reactions that can damage the permeability of the production formation. Additionally, the disposal of brines can be difficult and expensive, especially on land where environmental regulations prohibit the placement of high concentrations of chlorides and other ions in landfills.

SUMMARY OF THE INVENTION

The present invention relates to well treatment compositions and methods using nanoparticles, and more particularly, in one or more embodiments, to well cement compositions and / or well completion fluids comprising nanoparticles.

An embodiment of the present invention provides a method of completion of a well, comprising: the inclusion of nanoparticles in a completion fluid; and the use of completion fluid in the completion of the well.

Another embodiment of the present invention provides a well completion method comprising: providing a completion fluid comprising nanoparticles; and the introduction of the termination fluid

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PE. INDUSTRIAL PROPERTY in a well.

Another embodiment of the present invention provides a well completion method comprising: the inclusion of nanoparticles having a particle size of from about 1 nanometer to about 100 nanometers in a completion fluid, where the nanoparticles comprise by at least one nanoparticle selected from the group consisting of nanoalumina, zinc nanoxide, nanoboro, iron nanoxide, nanosilica, and any combination thereof; and the use of completion fluid in the completion of the well.

The features and advantages of the present invention will be apparent to those skilled in the art, upon reading the following description of the specific embodiments.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to well treatment compositions and methods using nanoparticles, and more particularly, in one or more embodiments, to well cement compositions and / or well completion fluids comprising nanoparticles.

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Ways of realizing cement compositions

An exemplary embodiment of the cement compositions of the present invention comprises cement, water, and nanosilica particles. Those skilled in the art will appreciate that exemplary cement compositions, in general, should have a density suitable for a particular application. As an example, the cement composition may have a density in the range of about

479 kg / m3 (4 pounds per gallon (lb / gal)) to about 2396 kg / m3 (20 lb / gal). In exemplary embodiments, the cement compositions can have a density in the range of from about 959 kg / m3 (8 lb / gal) to about

2037 kg / m3 (17 lb / gal). Exemplary embodiments of the cement compositions may be foamed or non-foamed, or may comprise other means of reducing their density, such as hollow microspheres, low density elastic beads, or other density reducing additives known in the art. Those of skill in the art, with the benefit of this disclosure, will recognize the appropriate density for a particular application.

Examples of embodiments of the cement compositions of the present invention comprise a cement.

Any of a variety of cements suitable for use in cementing operations can be used.

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I

INSTITUTO MEXICANC DE IA PROPIEDAD INDI.JSTPIAI.

underground, in accordance with the exemplary embodiments of the present invention. Suitable examples include hydraulic cements comprising calcium, aluminum, silicon, oxygen and / or sulfur, which are established and cured by reaction with water. Such hydraulic cements include, without limitation, Portland cements, pozzolanic cements, gypsum cements, high alumina cements, slag cements, silica cements, and combinations thereof. In certain embodiments, the hydraulic cement can comprise a Portland cement. Portland cements that may be suitable for use in the exemplary embodiments of the present invention are classified as Class A, C, H, and G cements according to the North American Petroleum Institute (American

Petroleum Institute), API Specification for Materials and

Testing for Well Cements, API Specification 10, Fifth Ed., July 1, 1990.

The water used in the exemplary embodiments of the cement compositions of the present invention may be fresh water or salt water (for example, water containing one or more salts dissolved therein, sea water, brines, saturated salt water, etc. .). In general, the water can be present in an amount sufficient to form a pumped suspension.

In embodiments

Ml.AlCANG INSTITUTE

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In exemplary terms, water can be present in cement compositions in an amount in the range of about 33% to about 200% by weight of cement (bwoc), on a dry basis. In exemplary embodiments, the water can be present in an amount in the range of about 35% to about 70% bwoc.

Furthermore, exemplary embodiments of the cement compositions comprise nanosilica. Nanosilica can be described as nanosilica particles. That is, the nanosilica may have a particulate nature, and is not, for example, a colloidal silica or a suspension of solution silica. In fact, in one embodiment, the nanosilica particles can be added to the cement composition as a dry nanosilica powder. In general, nanosilica particles can be defined as nanosilica having a particle size less than or equal to about

100 nm. For example, nanosilica particles can have a particle size in the range of about 1nm to about 100nm (about 1 χ 10-9m around

100 x 10-9 m). In certain exemplary embodiments, the nanosilica particles can have a particle size of less than or equal to about 50 nm. For example, nanosilica particles can have a particle size in the range of about 5nm to about 50

IMPI

ÍNlTTiVIU MEXICANO OE '.AM®? IEDAP INtMJSTRIAL nm. In other exemplary embodiments, the nanosilica particles can have a particle size of less than or equal to about 30 nm. For example, nanosilica particles can have a particle size in the range of from about 5nm to about 30nm. However, it should be noted that the nanosilica particles can be used in combination with silica particles of different sizes, according to the present embodiments.

For example, a quantity of silica particles with particle sizes greater than 100 nm can be included in a cement composition according to the present embodiments.

It is now recognized that the nanosilica particles used with the present embodiments, which may include silicon dioxide, may have an effect on certain physical characteristics of the resulting cements. For example, in relation to the inclusion of colloidal silica or larger silica particles in a cement suspension, the inclusion of nanosilica particles in the cement suspension can provide improved mechanical properties, such as compressive strength, resistance to tensile, Young's modulus and Poísson's ratio. Furthermore, nanosilica particles can also be included in the cement composition

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as an establishment accelerator, in order to accelerate establishment time of the resulting cement composition. Consequently, a cement composition according to the present embodiments can comprise a sufficient amount of nanosilica particles to provide the desired characteristics in a resulting cement. In exemplary embodiments, the nanosilica particles can be present in the cement composition in an amount in the range of from about 1% to about 25% bwoc. In exemplary embodiments, the nanosilica particles can be present in the cement composition in an amount in the range of from about 5% to about 15% bwoc.

Other additives suitable for use in underground cementing operations may also be added to exemplary embodiments of the cement compositions.

Examples of such additives include resistance to retrogression additives, establishment accelerators, ballasting agents, weight reducing additives, heavy weight additives, lost circulation materials, filtration control additives, dispersants, defoaming agents, foaming agents, and combinations thereof. .

Specific examples of these and other additives include crystalline silica, amorphous silica, salts, fibers, clays, el

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flying, lime, latex, thixotropic additives, their combinations and the like. The person skilled in the art, with the benefit of this description, will be able to easily determine the type and amount of additive useful for a particular application and a desired result.

As will be appreciated by those skilled in the art, exemplary embodiments of the cement compositions of the present invention can be used in a variety of underground applications, including primary and repair cementation. Exemplary embodiments of the cement compositions can be introduced into an underground formation and allowed to settle. Exemplary embodiments of the cement compositions can comprise cement, water, and the nanosilica particles. By way of example, in exemplary primary cementation embodiments, a cement composition may be introduced into a space between an underground formation and a pipe string located in the underground formation. The cement composition can be allowed to set, to form a hardened mass in the space between the underground formation and the pipe string.

In addition, in exemplary repair cementation embodiments, a cement composition may be used, for

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IND'JSTFJAL example, in compression cementation operations, or in the placement of cement plugs. One or more hydrocarbons (eg oil, gas, etc.) can be produced from a well that penetrates the underground formation.

While the foregoing description is directed to the use of nanosilica particles, those skilled in the art will also appreciate that it may be desirable to use other types of nanoparticles, in accordance with the embodiments of the present invention. Examples of such nanoparticles include nanoalumina, zinc nanoxide, nanoboro, iron nano oxide, and combinations thereof. In certain exemplary embodiments, the nanoparticles may be particulate in nature, and not, for example, a colloidal nanoparticle or a suspension of the nanoparticle in solution.

Furthermore, while the foregoing description is directed to the use of nanosilica particles in well cementing methods, those skilled in the art will appreciate that the present technique further contemplates the use of nanoparticles in any of a variety of different underground treatments. For example, nanoparticles can be included in any of a number of well treatment fluids that can be used in underground treatments, including drilling fluids, completion fluids, stimulation fluids, and well cleaning fluids. According to another embodiment, the nanoparticles can be included as shingles.

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THE FRCP'U.AI · V INnnSTklAC '· ».,« Λ in a well treatment fluid. For example, a well treatment fluid containing the nanoparticles can be introduced into an underground formation at a pressure sufficient or higher to create or increase one or more fractures in the underground formation. Augmentation of a fracture includes the enlargement of a pre-existing fracture in the formation. At least a portion of the nanoparticles can be deposited in one or more fractures, so that the closure of the fractures is avoided completely with the release of pressure, so as to form conductive channels through which fluids can flow to the well (or from the well).

In addition to the use of nanoparticles without encapsulation, embodiments of the present invention may include encapsulation of the nanoparticles to facilitate transport and incorporation of the nanoparticles into well treatment fluids (eg, cement compositions). . Specifically, encapsulation of the nanoparticles in accordance with the present embodiments may comprise enclosing the nanoparticles within a container or external particulate coating. Examples of encapsulation methods are set forth in the United States Patents.

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United of America Nros. 5,373,901; 6,444,316; 6,527,051;

6,554,071; 7,156,174; and 7,204,312, the pertinent descriptions of which are incorporated by reference in this application.

Various types of encapsulation can be employed so that the nanoparticles (for example, the nanosilica particles) are contained, while retaining their particle nature and consequently retaining their corresponding effect on the physical properties of cement suspensions. For example, nanoparticles can be encapsulated within a bag, capsule, layer, liner, or the like. Furthermore, the material used for the encapsulation of the nanoparticles can be selected so as to facilitate the transport and / or the incorporation of the nanoparticles in a well treatment fluid. For example, in order to facilitate manipulation of the nanoparticles and / or to facilitate controlled release of the nanoparticles, the encapsulating material may be degradable. This can facilitate manipulation of the nanoparticles by allowing the encapsulated nanoparticles to be included in a well treatment fluid without the need for the nanoparticles to be first removed from the encapsulating material. Furthermore, the encapsulating material can be designed to degrade with a

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certain index when in contact with certain materials (for example, water), so that nanoparticles are released into the well treatment fluid at a desired time. Examples of materials that dissolve in water, which can be used to encapsulate the nanoparticles, are described in US Patent Nos.

United States of America Nos. 4,961,790 and 5,783,541, the pertinent descriptions of which are incorporated by reference in this application.

In accordance with exemplary embodiments, the cement compositions of the present invention can utilize a suitable packing volume fraction for a particular application, as desired. In accordance with this application, the term "packing volume fraction" refers to the volume of the particulate materials in a fluid, divided by the total volume of the fluid. The size ranges of the preferred particulate materials are selected, as well as their respective proportions, to provide a maximized packing volume fraction, such that the fluid is in a hindered state of establishment. In such a state, the particulate materials are known to behave collectively as a porous solid material. The state of impaired establishment is believed to correspond, in practice, to a

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IWUTUTü MEXICANO Dt THE INDUSTRIAL PROPERTY much higher concentration of solid material in the fluid, than that present in some traditional cement compositions.

The present embodiments can include a combination of at least three features in order to obtain a maximum fraction of packaging volume. One is the use of at least three particulate materials, where at least the three particulate materials have disunited size ranges from one another. In some embodiments, each of the three particle materials may include a different particle size selected from the following

<td colspan="3">ranges: around</td><td>from 7 nm to</td><td>about</td><td> 50</td><td>nm,</td><td>around</td><td>of</td>

<td colspan="2">0.05 micron</td><td colspan="2">around</td><td colspan="2">0.5 micron,</td><td> 0,</td><td>5 micron</td><td>to</td>

<td>around</td><td>of</td><td> 10</td><td>microns</td><td>, around</td><td>of</td><td> 10</td><td>microns</td><td>to</td>

<td>around</td><td>of</td><td> 20</td><td>microns</td><td>, around</td><td>of</td><td> 20</td><td>microns</td><td>to</td>

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about 800 microns, and more than about 1 millimeter.

For example, a first particle material can include particles from about 7nm to about nm in size, a second particle material can include particles from about 0.05 micron to about 0.5 micron in size, and a third particulate material may include particles with a size of from about 10 microns to about 20 microns. According to

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In present embodiments, the first particulate material includes at least one of nanosilica, nanoalumina, zinc nanoxide, nanoboro, iron nanoxide, or combinations thereof. Another feature of the present embodiments may comprise the choice of the proportions of the three particulate materials in relation to the mixing, so that the fluid, when mixed, is in an impeded state of establishment. Another feature may comprise choosing the ratios of the three particulate materials to each other, and according to their respective size ranges, so that the maximum fraction of packing volume is at least substantially achieved for the sum total of all the particulate materials in the fluid system. The packaging volume fraction is described in greater detail in the US Patents.

United of America Nros. 5,518,996 and 7,213,646, the relevant portions of which are incorporated by reference in the present application.

Ways of carrying out determination fluids

As mentioned above, nanoparticles can be included in termination fluids in accordance with embodiments of the present invention. Nanoparticles can be included in termination fluids to provide a number of benefits

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MEXICAN INSTITUTE

OF THE WOFIEL'ALJ í different. For example, nanoparticles can be used to enhance or otherwise improve the rheological properties of termination fluids. As a further example, nanoparticles can be included in termination fluids as ballast materials in order to increase fluid density. Because the nanoparticles are nanometric, it is believed that they should not undesirably plug the permeability of the formation, or other equipment inside the well, such as production screens, and consequently, they can be included in the completion fluids. Furthermore, the inclusion of nanoparticles in finishing fluids can have additional beneficial effects, especially in slate formations. For example, it is believed that nanoparticles can prevent the influx of fluids from the well into the nanoporosity often found within shale formations, such as oily shales, by sealing these pores, which isolates and stabilizes the shale formation. against the destabilizing hydraulic forces of the well.

An exemplary embodiment of the termination fluids can comprise nanoparticles.

In general, nanoparticles can be defined to have an average particle size of less than 1 micron. For example, nanoparticles can have a

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INSTITUTO MEXICANO OF LA PROPIEDAD INDUSTRIAL has an average particle size range from around 1____ nm to less than 1 micron. In some embodiments, the nanoparticles can have an average particle size in a range of from about 1nm to about 800nm, and alternatively from about 1nm to about

100 nm. In a particular embodiment, the nanoparticles can have an average particle size in a range from about 20nm to about 100nm. In specific embodiments, the nanoparticles can have a particle size of about 1nm, about 10nm, about 50nm, about 100nm, about 200nm, about 400nm, about 600nm, or around 800nm. In some embodiments, the nanoparticles can be provided in colloidal form, for example, a colloidal nanoparticle or a suspension of the nanoparticle in a fluid. In some embodiments, the nanoparticle can be a nanoparticle in the form of particles. The nanoparticles can be encapsulated or otherwise contained, as described above.

Examples of suitable nanoparticles include nanoalumina, zinc nanoxide, nanoboro, iron nano oxide, and nanosilica. Additional examples of suitable nanoparticles include other nanometer-sized materials, including barium nanosulfate, manganese nanotetraoxide, nanoxide

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3 MEXICAN INSTITUTE

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INDUSTRIAL magnesium, calcium nanocarbonate, nanograph, barium nanoxide, cerium nanoxide, lanthanum nanoxide, titanium nanodioxide, nano clay, and nanoaluminosilicates.

Combinations of different nanoparticles can also be used. In some embodiments, the nanoparticle is not acid soluble.

The nanoparticles can be included in a termination fluid in an amount sufficient for a desired application. For example, nanoparticles can be included in a termination fluid in an amount sufficient to ballast the fluid to a desired density. In some embodiments, the nanoparticles can be present in the termination fluid in an amount in the range of about 0.1% to about 70% by volume of the termination fluid. In specific embodiments, the nanoparticles can be presented in an amount that varies

<td colspan="2">from anyone</td><td>and / or including any</td><td>from around</td><td>of</td><td> 0,1%,</td>

<td>around</td><td>of</td><td>1%, about 10%,</td><td>around</td><td>of</td><td> 20%,</td>

<td>around</td><td>of</td><td>30%, about 40%,</td><td>around</td><td>of</td><td> 50%,</td>

<td>20 around</td><td>of</td><td>60%, or about 70% in</td><td>volume of</td><td colspan="2">fluid</td>

termination. The person skilled in the art, with the benefit of this invention, will be able to select an appropriate amount of the nanoparticles for use in a particular application.

In some embodiments, the termination fluids

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they can comprise a base fluid, such a ctnricr ^ 'iir'r ·· ^ iurete «oil base or a water-based fluid. Oil-based fluids can comprise definas, internal olefins, alkanes, aromatic solvents, cycloalkanes, liquefied petroleum gas, kerosene, diesel oils, crude oils, heavy oils, gas oils, fuel oils, paraffin oil, mineral oils, oils. low toxicity minerals, esters, amides, synthetic oils (eg polyolefins), polydiorganosiloxanes, siloxanes, organosiloxanes, ethers, acetals, dialkylcarbonates, hydrocarbons, and combinations thereof. Water-based fluids can comprise fresh or salt water, such as brine or sea water. The base fluid can be present in an amount in the range of about 25% to about 99% by volume of the completion fluid.

Other additives suitable for use in termination operations may also be included in termination fluids in the embodiments of the present invention. Examples of such additives include salts, surfactants, additives for the control of fluid loss, gases such as nitrogen or carbon dioxide, surface modifying agents, foaming agents, corrosion inhibitors, oxide scale inhibitors, agents for control of clay, biocides,

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friction reducers, antifoaming agents, dispersants, flocculants, H2S scrubbers,

CO2, oxygen scavengers, lubricants, viscosifiers, breakers, wetting agents, and their combinations. The person skilled in the art, with the benefit of this invention, will be able to easily determine the type and amount of additive useful for a particular application.

Finishing fluids can have a density as desired for a particular application. In general, the termination fluid should be of sufficient density to, for example, control formation pressures.

As described above, the nanoparticles can be used, in some embodiments, as ballasting agents in order to increase the density of the termination fluid. By way of example, the nanoparticles can be included in the termination fluid in an amount sufficient to ballast the termination fluid. In some embodiments, the termination fluid may have a density in the range of from about 899 kg / m3 (7.5 pounds per gallon) to about 2636 kg / m3 (22 pounds per gallon), and alternatively, from about 1238 kg / m3 (12 lb / gal) to about 2157 kg / m3 (18 lb / gal). The person skilled in the art, with the benefit of this invention, will be able to determine without difficulty an appropriate fluid density.

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termination for a particular application.

As will be appreciated by those skilled in the art, for the benefit of this invention, the embodiments of the termination fluids of the present invention can be used in a variety of termination operations. For example, completion fluids can be used in post-drilling operations, albeit prior to the start of production. In some embodiments, the completion operation may comprise preparing the bottom of the well to the required specifications, lowering the production pipeline and its associated interior well equipment, or performing production improvement operations.

By way of example, the completion fluid may be presented in the well while equipment, such as sieves, production liners and / or borehole valves, is lowered into the borehole. In one embodiment, the termination fluid may be present in the well while punctures are formed in the casing pipe disposed in the well. Among other functions, the terminating fluid must act to control formation pressures.

An embodiment of the present invention may comprise a well completion method comprising the provision of a completion fluid comprising

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nanoparticles and the introduction of the completion fluid into a well. In some embodiments, interior well equipment can be lowered into the well, while the completion fluid is in the well. Inside well equipment can include, for example, screens, production liners and / or inside well valves. A particular example of a type of downhole equipment that is sensitive to plugging by solids-laden fluids, such as drilling fluids, comprises wire-wrapped screens. Wire-wrapped screens can be used, for example, when a well casing having a porous screen is required to mechanically retain the formation sand. Because the nanoparticles are nanometer-sized, the nanoparticles should not undesirably seal off wellbore equipment. In contrast, if micron-sized or larger particles are included in the completion fluids, the wellbore equipment, as well as formation permeability, will be sensitive to plugging events.

In order to facilitate a better understanding of the present technique, the following examples of some specific embodiments are provided. The following examples are not to be interpreted in any way to limit or

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Example 1

Five different cement suspensions were prepared (i.e. Suspension A, Suspension B, Suspension C,

Suspension D and Suspension E). The resulting established suspensions and cements were then evaluated to determine the establishment or thickening times and other physical properties of each of the five different suspensions. As set out below, the respective test results for the five different suspensions demonstrate that the inclusion of nanosilica particles in the suspension reduces the establishment time and increases the strength of the resulting cement, in relation to cements resulting from the inclusion of the other evaluated silica components.

Suspensions A, B, C and D were prepared by combining the dry components with cement, before adding water to form the respective suspension. Suspension E was prepared by dry blending the components dry with cement, before adding water and then adding colloidal silica to form the respective suspension. Additionally, each of the five suspensions included a different type of silica. Two of the five suspensions included nanosilica particles from

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according to the present embodiments, and the other three included silica in different shapes and sizes (eg, colloidal silica and microsilica). Although the silica included in each of the five suspensions was different, the other components used in each of the five suspensions were similar. Specifically, in addition to a specific type of silica, each of the five suspensions included 100% bwoc Class G cement, 0.5% bwoc retardant, and enough water to achieve a suspension density of approximately 1438 kg / m3 (12.00 lbs / gal). The specific retardant used in the suspensions was the HR-5 cement retarder, which is a sulfomethylated lignosulfonate. It should be noted that the cement retarder

HR5 can be obtained from Halliburton Energy Services, Inc., and is described in the United States of America Patent.

No. RE 31,190.

As stated above, each of the five suspensions included a different type of silica, and enough water to achieve a resulting suspension density of 1438 kg / m3 (12.00 lbs / gal). Suspensions A and B included nanosilica particles according to the present embodiments, and 0.0581483 m3 / bag (15.36 gal / sk (bag)) of water. Specifically, Suspension A included 15% bwoc of nanosilica particles that had a

At a particle size of approximately 30 nm, and Suspension

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B included nanosilica particles having a particle size of approximately 10nm. Suspension C included

15% bwoc of SILICALITE cement additive and 0.0593598 m3 / bag (15.68 gal / sk) of water. SILICALITE (compacted) cement additive, available from Halliburton Energy

Services, Inc., Duncan, Oklahoma, is an amorphous silica that generally ranges in size from about 2.5 microns to about 50 microns. Suspension D included

15% bwoc of MICROSAND cement additive and 0.0597005 m3 / bag (15.77 gal / sk) of water. MICROSAND Cement Additive, available from Halliburton Energy Services, Inc., Duncan,

Oklahoma is a crystalline silica ground to a substantially uniform particle size distribution of about 5 to 10 microns. Suspension E included

0.0193828 m3 / bag (5.12 gal / sk) of lightweight cement additive

GasCon 469 ™ and 0.0381977 m3 / bag (10.09 gal / sk) of water. GASCOND 469 Lightweight Cement Additive can be obtained from

Halliburton Energy Services, Inc., Duncan, Oklahoma, and can be defined as a colloidal silicic acid suspension containing suspended silicic acid particles that generally have a particle size of less than about 20nm.

After the preparation of the five suspensions, tests were carried out to determine various ·

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physical characteristics associated with the inclusion of the different silica components in each of the associated cement compositions. One of these tests was carried out with the aim of measuring the thickening time associated with each of the five suspensions.

Specifically, the total thickening time (TTT) associated with each cement suspension was determined by performing a thickening time test in accordance with API Recommended Practice (Institute

North American Petroleum) 10, API Specification for

Materials and Testing for Well Cements. The TTT measurement for each suspension was based on the achievement, of the respective suspension, of a consistency of 70 units.

Bearden (Be) at 27 ° C (80 ° F). The results of these measurements are set forth, for each of the five suspensions, in Table 1 below.

Additional tests were carried out on the cement suspensions, in order to determine the properties of resistance to force (for example, compressive strength, shear bond strength, and tensile strength) for each of the suspensions. . Each of the strength resistance property tests was carried out

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carried out on the respective cement suspensions at a temperature of 27 ° C (80 ° F) and after the establishment of the suspensions for 72 hours. The tests of strength resistance properties included tests of non-destructive and destructive ultrasonic resistance, a compression resistance test, a shear bond test, and a tensile strength test. Nondestructive and destructive ultrasonic analyzer tests were conducted using a UCA ultrasonic cement analyzer in order to determine a 72 hour UCA value and a crowded UCA value, respectively. Compressive strength tests and UCA analyzer tests were carried out in accordance with API 10B Recommended Practice. In addition, Brazilian shear bond and tensile strength tests were carried out to determine the values ​​of shear strength and tensile strength, respectively, for the different cement compositions. Shear bond strength tests were performed as described in SPE 7 64 entitled A Cement Bond Study

Pipe, of LG Carter and GW Evans. Brazilian tensile strength tests were carried out in accordance with ASTM C 496-96. The results of the tests carried out on each of the five compositions are shown in

Table 1 below.

Table 1

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<td>Suspension</td><td>Silica type</td><td>TTT at 70 Be (H: Min)</td><td>UCA_72hMPa (psi)</td><td>UCAjipiñado MPa (psi)</td><td>Resist. buy. MPa (psi)</td><td>Resist. Link from cut MPa (psi)</td><td>Resist. traction Brazil. MPa (psi)</td>

<td>Suspension TO</td><td>particles of nanosilica 30nm</td><td> 2:43</td><td> 2,26 (328)</td><td> 2,88 (419)</td><td> 2,95 (428)</td><td> 1,16 (169)</td><td> 1,02 (148,28)</td>

<td>Suspension B</td><td>particles of nanosilica 10nm</td><td> 5:00</td><td> 3,44 (500)</td><td> 3,31 (481)</td><td> 2,77 (402)</td><td> 0,35 (51)</td><td> 0,10 (14,72)</td>

<td>Suspension C</td><td>Silica amorphous</td><td> 14:32</td><td> 1,83 (266)</td><td> 1,42 (206)</td><td> 1,45 (211)</td><td> 0,67 (98)</td><td> (0,65 95,5)</td>

<td>Suspension D</td><td>Silica crystalline</td><td> 20:00+</td><td> 1,79 (260)</td><td> 1,96 (285)</td><td> 1,73 (252)</td><td> 0,25 (37,2)</td><td> (0,70 102,16)</td>

<td>Suspension AND</td><td>Silica colloidal</td><td> 20:00+</td><td> 1,55 (225)</td><td> 1,50 (219)</td><td> 2,57 (374)</td><td> 0,29 (42,4)</td><td> (0,58 84,71)</td>

Example 2

Samples of Suspensions A, C, were also evaluated.

D and E described above, in order to determine various additional physical properties associated with the resulting established cements and to confirm the relative differences previously demonstrated. Although different instruments and calibration parameters were used in the further evaluation of the suspensions, the test information

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INF * 'TRIAL indicates that the relative differences between the different suspensions are similar to those differences illustrated in Example 1. In fact, as indicated above in Example 1, the respective test results in the

Example 2 for the five different cements demonstrate that the inclusion of nanosilica particles in the cement composition increases the strength of the resulting cement in relation to the cements resulting from the inclusion of the other evaluated silica components.

Three samples were evaluated for each of the three conventional cement suspensions (Suspension C,

Suspension D and Suspension E) and four samples of Suspension

A, in order to determine the compressive strength, Young's modulus and Poisson's ratio. The compressive strength tests were carried out in accordance with the

API Specification 10. It should be noted that the compressive strength measurements in Example 1 are different from those in Example 2, because different equipment and different calibrations were used. However, the relative differences between the compressive strengths for each of the five suspensions are similar. Young's modulus and Poisson's ratio were statistically determined by means of the compression test using a load frame. Young's modulus o

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The modulus of elasticity for each sample was obtained from a ratio of a simple tensile force applied to each sample, to a resulting deformation under load parallel to the stress in said sample. The Poisson ratio for each sample was determined by calculating a ratio of deformation under transverse load to a corresponding deformation under axial load, resulting from uniformly distributed axial stresses below a proportional limit of each sample. The values ​​determined for the three samples from each of the five different cement suspensions are set forth below in Table 2.

Table 2

<td>Suspension</td><td>Shows</td><td>Silica type</td><td>Compressive strength MPa (psi)</td><td>Young's modulus</td><td>Relation of Poisson</td>

<td>Suspension A</td><td>Sample 1</td><td>nanosilica particles 30nm</td><td> 8,66 (1257)</td><td>2.26E + 05</td><td> **</td>

<td>Suspension A</td><td>Sample 2</td><td>nanosilica particles 30nm</td><td> 8,19 (1189)</td><td>2,12E + 05</td><td> 0,109</td>

<td>Suspension A</td><td>Sample 3</td><td>nanosilica particles 30nm</td><td> 8,61 (1249)</td><td>2.04E + 05</td><td> 0,092</td>

<td>Suspension A</td><td>Sample 4</td><td>nanosilica particles 30nm</td><td> 8,79 (1275)</td><td>2,13E + 05</td><td> 0,110</td>

<td>Suspension C</td><td>Sample 1</td><td>Silica amorphous</td><td> 3,21 (466)</td><td>2,53E + 05</td><td> 0,064</td>

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<td rowspan="2">Suspension C</td><td rowspan="2">Sample 2</td><td rowspan="2">Silica amorphous</td><td rowspan="2"> 3,33 (483)</td><td></td><td></td>

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<td>Suspension C</td><td>Sample 3</td><td>Silica amorphous</td><td> 3,48 (506)</td><td>2.40E + 05</td><td> 0,053</td>

<td>Suspension D</td><td>Sample 1</td><td>Silica crystalline</td><td> 2,41 (350)</td><td>l, 42E + 05</td><td> 0,068</td>

<td>Suspension D</td><td>Sample 2</td><td>Silica crystalline</td><td> 2,73 (397)</td><td>l, 50E + 05</td><td> 0,063</td>

<td>Suspension D</td><td>Sample 3</td><td>Silica crystalline</td><td> 2,60 (378)</td><td>l, 46E + 05</td><td> 0,060</td>

<td>Suspension E</td><td>Sample 1</td><td>Silica colloidal</td><td> 3,54 (514)</td><td>1.03E + 05</td><td> 0,063</td>

<td>Suspension E</td><td>Sample 2</td><td>Silica colloidal</td><td> 4,12 (598)</td><td>l, 15E + 05</td><td> 0,072</td>

<td>Suspension E</td><td>Sample 3</td><td>Silica colloidal</td><td> 4,32 (627)</td><td>l, 23E + 05</td><td> 0,071</td>

The particular embodiments disclosed above are illustrative only, as the present invention may be subject to various modifications and alternative forms. However, it should be understood that the invention is not intended to be limited to the particular disclosed embodiments. Rather, the present invention should cover all modifications, equivalents, and alternatives within the scope and spirit of the present invention, as defined

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in the following appended claims. In addition, each range of values ​​(in the form of about / about a to about / about b, or, equivalently, about / about a to b, or, equivalently, about / about ab) disclosed in the present description of specific embodiments is to be understood as the reference to the power set (the set of all subsets) of the respective range of values, and the set for each range contemplated within the widest range of values.

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