Title of Invention

A METHOD OF CEMENTING A SUBTERRANEAN FORMATION

Abstract Settable compositions that comprise water, CKD, and microspheres, wherein the lightweight settable composition has a density less than about 13 pounds per gallon. Methods of cementing that comprise providing a lightweight settable composition having a density less than about 13 pounds per gallon, the lightweight settable composition comprising water, CKD, and microspheres, introducing the lightweight settable composition into a location to be cemented and allowing the lightweight settable composition to set therein.
Full Text FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(See section 10, rule 13)
"LIGHTWEIGHT SETT ABLE COMPOSITIONS COMPRISING CEMENT KBLN DUST AND METHODS
OF USING THEM"


HALLIBURTON ENERGY SERVICES, INC., of P.O. Box 1431, Duncan, Oklahoma 73533, United States of America
The following specification particularly describes the invention and the manner in which it is to be performed.


WO 2007/128945

PCT7GB2006/003694


LIGHTWEIGHT SETTABLE COMPOSITIONS COMPRISING
CEMENT KILN DUST AND METHODS OF USING THEM
BACKGROUND
The present invention relates to cementing operations and, more particularly, 5 to lightweight settable compositions comprising water, cement kiln dust ("CKD"), and microspheres, and associated methods of use.
Settable compositions may be used in a variety of above ground (e.g., in the construction industry) and subterranean applications. As used herein, the term "settable composition" refers to any composition that over time will set to form a hardened mass. One
10 example of a settable composition comprises hydraulic cement and water. Subterranean applications that may involve settable compositions include, but are not limited to, primary and remedial cementing. For example, settable compositions may be used in primary cementing operations whereby pipe strings, such as casing and liners, are cemented in well bores. In performing primary cementing, a settable composition may be pumped into an
15 annular space between the subterranean formation and the pipe string disposed therein. The settable composition sets in the annular space, thereby forming an annular sheath of hardened cement (e.g., a cement sheath) that supports and positions the pipe string in the well bore and bonds the exterior surface of the pipe string to the walls of the well bore. Settable compositions also are used in remedial cementing operations such as plugging highly
20 permeable zones or fractures in well bores, plugging cracks and holes in pipe strings, and the like.
In some instances, settable compositions utilized in subterranean operations may be lightweight, for example, to prevent excessive hydrostatic pressure from being exerted on subterranean formations penetrated by the well bore, whereby the formations may
25 be unintentionally fractured or the hole may collapse. One type of lightweight settable composition is a foamed cement composition, e.g., a cement composition that comprises a surfactant and a gas. Additionally, lightweight additives {e.g., microspheres) also may be added to settable compositions to reduce the density thereof.
During the manufacture of cement, a waste material commonly referred to as
30 "CKD" is generated. "CKD," as that term is used herein, refers to a partially calcined kiln feed which is typically removed from the gas stream and collected in a dust collector during

WO 2007/128945 PCT/GB2006/003694

the manufacture of cement. Usually, large quantities of CKD are collected in the production of cement that are commonly disposed of as waste. Disposal of the waste CKD can add undesirable costs to the manufacture of the cement, as well as the environmental concerns associated with its disposal. The chemical analysis of CKD from various cement 5 manufactures varies depending on a number of factors, including the particular kiln feed, the efficiencies of the cement production operation, and the associated dust collection systems. CKD generally may comprise a variety of oxides, such as Si02, Al203, Fe203, CaO, MgO, S03, Na20, and K20.
SUMMARY
10 The present invention relates to cementing operations and, more particularly,
to lightweight settable compositions comprising water, CKD, and microspheres, and associated methods of use.
According to one aspect of the invention there is provided a lightweight settable composition that comprises water, CKD, and microspheres, wherein the hghtweight
15 settable composition has a density of less than about 13 pounds per gallon.
According to another aspect of the invention there is provided a lightweight settable composition that comprises water, CKD, microspheres, vitrified shale, and hydrated lime, wherein the lightweight settable composition has a density of less than about 13 pounds per gallon.
20 According to another aspect of the invention there is provided a lightweight
settable composition that comprises water, CKD, and microspheres comprising soda lime borosilicate glass, wherein the lightweight settable composition has a density of less than about 13 pounds per gallon.
According to another aspect of the invention there is provided a method of
25 cementing that comprises providing a Hghtweight settable composition having a density of less than about 13 pounds per gallon, the lightweight settable composition comprising water, CKD, and microspheres, introducing the lightweight settable composition into a location to be cemented, and allowing the lightweight settable composition to set therein.
According to another aspect of the invention there is provided method of
30 primary cementing that comprises providing a Hghtweight settable composition having a density of less than about 13 pounds per gallon, the lightweight settable composition

WO 2007/128945 PCT/GB2006/003694
comprising water, CKD, and microspheres, introducing the lightweight settable composition
into an annulus between a subterranean formation and a pipe string located in the
subterranean formation, and allowing the lightweight settable composition to set in the
' annulus.
5 The features and advantages of the present invention will be apparent to those
skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention relates to cementing operations and, more particularly,
10 to lightweight settable compositions comprising water, CKD, and microspheres, and associated methods of use. The lightweight settable compositions of the present invention may be used in a variety of subterranean applications, including primary cementing, and remedial cementing. The lightweight settable compositions of the present invention also may be used in surface applications, for example, construction cementing.
15 In one embodiment, a lightweight settable composition of the present
invention comprises water, CKD, and microspheres. The lightweight settable compositions of the present invention should have a density suitable for a particular application as desired by those of ordinary skill in the art, with the benefit of this disclosure. Lightweight settable compositions generally have a density of less than about 13 pounds per gallon ("ppg")- In
20 some embodiments, the lightweight settable compositions of the present invention may have a density in the range of from about 4 ppg to about 13 ppg. In the some embodiments, the lightweight settable composition may be foamed to further reduce the density thereof, for example, in the range of from about 4 ppg to about 11 ppg.
The water used in the lightweight settable compositions of the present
25 invention may include freshwater, saltwater (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated saltwater produced from subterranean formations), seawater, or combinations thereof. Generally, the water may be from any source, provided that it does not contain an excess of compounds that may adversely affect other components in the lightweight settable composition. In some embodiments, the water may be included in
30 an amount sufficient to form a pumpable slurry,In some embodiments, the water may be included in the lightweight settable compositions of the present invention in an amount in the

WO 2007/128945 PCT/GB2006/003694
range of from about 20% to about 80% by weight of the lightweight settable composition. In some embodiments, the water may be included in an amount in the range of from about 30% to about 70% by weight of the lightweight settable composition.
The CKD should be included in the lightweight settable compositions in an 5 amount sufficient to provide the desired compressive strength, density, and/or cost reduction. In some embodiments, the CKD may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 0.01% to about 80% by weight of the lightweight settable composition. In some embodiments, the CKD may be present in the lightweight settable compositions of the present invention in an amount in the range of
10 from about 2.5% to about 80% by weight of settable materials. In some embodiments, the CKD may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 2.5% to about 60% by weight of the lightweight settable composition. In some embodiments, the CKD may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 5% to about
15 50% by weight of the lightweight settable compositioa
The microspheres used in the lightweight settable compositions of the present invention may be any microsphere suitable for use in subterranean applications to, inter alia, reduce the density of the settable composition. Suitable microspheres generally have a density of less than about 8.345 ppg (1.0 gram per cubic centimeter ("g/cc")). A variety of
20 microspheres may be utilized in accordance with the present invention, including hollow, solid, and/or porous microspheres. Generally, the microspheres should have a crush strength greater than about 100 psi. Suitable microspheres may comprise a variety of materials, including, but not limited to, microspheres that comprise glass, soda lime borosilicate glass, fly ash, ceramic, polystyrene, other polymeric materials, and mixtures thereof. In some
25 embodiments of the lightweight settable compositions of the present invention, the microspheres are hollow, glass microspheres. In some embodiments, the microspheres may comprise a crosslinked polymeric material, such as polystyrene crosslinked with divinyl benzene {e.g., plastic beads). The microspheres may be obtained from any suitable source. Examples of suitable fly ash microspheres are commercially available from Halliburton
30 Energy Services, Inc., Duncan, Oklahoma, under the tradename SPHERELITE microspheres. Suitable hollow, soda lime borosilicate glass microspheres include 3M SCOTCHLITE™ glass bubbles.

WO 2007/128945 PCT/GB2006/003fi94
Generally, suitable microspheres have a size of less than about 150 microns.
In some embodiments, the microspheres have a size in the range of from about 5 microns to
about 150 microns, alternatively from about 20 microns to about 105 microns, and
alternatively from about 15 microns to about 80 microns.
5 The microspheres should be included in the lightweight settable compositions
in an amount sufficient to provide the desired density, for example, less than about 13 ppg of the lightweight settable composition. In some embodiments, the microspheres may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 1% to about 30% by weight of the lightweight settable composition. In
10 some embodiments, the microspheres may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 3% to about 25% by weight of the lightweight settable composition. In other embodiments, the microspheres may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 5% to about 20% by weight of the lightweight settable composition.
15 The lightweight settable compositions of the present invention may optionally
comprise a hydraulic cement. A variety of hydraulic cements may be utilized in accordance with the present invention, including, but not limited to, those comprising calcium, aluminum, silicon, oxygen, iron, and/or sulfur, which set and harden by reaction with water. Suitable hydraulic cements include, but are not limited to, Portland cements, pozzolana
20 cements, gypsum cements, high alumina content cements, slag cements, silica cements, and combinations thereof. In certain embodiments, the hydraulic cement may comprise a Portland cement. In some embodiments, the Portland cements that are suited for use in the present invention are classified as Classes A, C, H, and G cements according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API
25 Specification 10, Fifth Ed., July 1,1990.
Where present, the hydraulic cement generally may be included in the lightweight settable compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the hydraulic cement may be present in the lightweight settable compositions of the present invention in an amount up to about 75%
30 by weight of the lightweight settable composition. In some embodiments, the hydraulic cement may be present in the lightweight settable compositions of the present invention in an amount up to about 70% by weight of the lightweight settable composition. In some

WO 2007/128945 PCT/GB200fi/003694
embodiments, the hydraulic cement may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 10% to about 70% by weight of the lightweight settable composition. In some embodiments, the hydraulic cement may be present in the lightweight settable compositions of the present invention in an amount in the 5 range of from about 20% to about 65% by weight of the lightweight settable composition.
In some embodiments, a pozzolana cement that may be suitable for use comprises fly ash. "Fly ash," as that term is used herein, refers to the residue from the combustion of powdered or ground coal, wherein the fly ash carried by the flue gases may be recovered, for example, by electrostatic precipitation. A variety of fly ashes may be suitable,
10 including fly ash classified as Class C and Class F fly ash according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Ed., July 1, 1990. Class C fly ash comprises both silica and lime so that, when mixed with water, it sets to form a hardened mass. Class F fly ash generally does not contain sufficient lime, so an additional source of calcium ions is required for the Class F fly ash to
15 form a settable composition with water. In some embodiments, lime may be mixed with Class F fly ash in an amount in the range of from about 15% to about 25% by weight of the fly ash. In some instances, the lime may be hydrated lime. Suitable examples of fly ash include, but are not limited to, POZMIX® A cement additive, commercially available from Halliburton Energy Services, Inc., Duncan, Oklahoma.
20 Where present, the fly ash generally may be included in the lightweight
settable compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the fly ash may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 5% to about 40% by weight of the lightweight settable composition. In some embodiments, the fly
25 ash may be present in the lightweight settable compositions of the present invention in an amount in the range of from about 7% to about 30% by weight of the lightweight settable composition.
In some embodiments, a slag cement that may be suitable for use may comprise slag. "Slag," as that term is used herein, refers to a granulated, blast furnace by-
30 product formed in the production of cast iron and generally comprises the oxidized impurities found in iron ore. Slag generally does not contain sufficient basic material, so slag cement further may comprise a base to produce a settable composition that may react with water to

WO 2(107/128945 PCT/GB2006/003694


set to form a hardened mass. Examples of suitable sources of bases include, but are not limited to, sodium hydroxide, sodium bicarbonate, sodium carbonate, lime, and combinations thereof.
Where present, the slag cement generally may be included in the lightweight 5 settable compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the slag cement may be present in the lightweight settable compositions of the present invention in an amount up to about 60% by weight of the lightweight settable composition. In some embodiments, the slag cement may be present in the lightweight settable compositions of the present invention in an amount in
10 the range of from about 5% to about 40% by weight of the lightweight settable composition.
In certain embodiments, the lightweight settable compositions of the present
invention further may comprise metakaolin. Generally, metakaolin may be prepared by
heating kaolin clay, for example, to temperatures in the range of from about 600° C to about
800°C. In some embodiments, the metakaolin may be present in the lightweight settable
15 compositions of the present invention in an amount in the range of from about 2.5% to about 40% by weight of the lightweight settable composition. In some embodiments, the metakaolin may be present in an amount in the range of from about 5% to about 30% by weight of the lightweight settable composition.
In certain embodiments, the lightweight settable compositions of the present
20 invention further may comprise vitrified shale. Among other things, vitrified shale included in the lightweight settable compositions may react with excess lime to form a suitable cementing material, for example, calcium silicate hydrate. A variety of vitrified shales are suitable, including those comprising silicon, aluminum, calcium, and/or magnesium. Suitable examples of vitrified shale include, but are not limited to, PRESSUR-SEAL® FINE LCM
25 material and PRESSUR-SEAL® COARSE LCM material, which are commercially available from TXI Energy Services, Inc., Houston, Texas. Generally, the vitrified shale may have any particle size distribution as desired for a particular application. In certain embodiments, the vitrified shale may have a particle size distribution in the range of from about 37 micrometers to about 4,750 micrometers.
30 Where present, the vitrified shale may be included in the lightweight settable
compositions of the present invention in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the vitrified shale and

WO 2(107/128945 PCT/GB2006/003694

necessary amount of lime for setting may be present in an amount up to about 50% by weight of the lightweight settable composition. In some embodiments, the vitrified shale may be present in an amount in the range of from about 5% to about 30% by weight of the lightweight settable composition. One of ordinary skill in the art, with the benefit of this 5 disclosure, will recognize the appropriate amount of the vitrified shale to include for a chosen application
In certain embodiments, the lightweight settable compositions of the present invention further may comprise zeolite. Zeolites generally are porous alumino-silicate minerals that may be either a natural or synthetic material. Synthetic zeolites are based on
10 the same type of structural cell as natural zeolites, and may comprise aluminosilicate hydrates. As used herein, the term "zeolite" refers to all natural and synthetic forms of zeolite. An example of a suitable source of zeolite is available from the C2C Zeolite Corporation of Calgary, Canada. In some embodiments, the zeolite may be present in the lightweight settable compositions of the present invention in an amount in the range of from
15 about 2.5% to about 2.5% by weight of the lightweight settable compositioa
In certain embodiments, the lightweight settable compositions of the present invention further may comprise a set retarding additive. Examples of suitable set retarding additives include, but are not limited to, ammonium, alkali metals, alkaline earth metals, metal salts of sulfoalkylated lignins, hydroxycarboxy acids, copolymers that comprise acrylic
20 acid or maleic acid, and combinations thereof. One example of a suitable sulfoalkylate lignin comprises a sulfomethylated lignin. Suitable set retarding additives are disclosed in more detail in United States Patent No. Re. 31,190, the entire disclosure of which is incorporated herein by reference. Suitable set retarding additives are commercially available from Halliburton Energy Services, Inc. under the tradenames HR® 4, HR® 5, HR® 7, HR® 12,
25 HR®15 HR® 25, SCR™ 100, and SCR™ 500. Generally, where used, the set retarding additive may be included in the lightweight settable compositions of the present invention in an amount sufficient to provide the desired set retardation. In some embodiments, the set retarding additive may be present in an amount in the range of from about 0.02% to about 2.5% by weight of the lightweight settable composition.
30 Optionally, other additional additives may be added to the lightweight settable
compositions of the present invention as deemed appropriate by one skilled in the art, with the benefit of this disclosure. Examples of such additives include, but are not limited to,

WO 2007/128945 PCT/GB 2006/00 3694
accelerators, lost circulation materials, filtration control additives, dispersants, and combinations thereof. Suitable examples of these additives include crystalline silica compounds, amorphous silica, salts, fibers, calcined clays, combinations thereof and the like. In certain embodiments, the lightweight settable compositions of the present 5 invention may be foamed with a gas. These foamed embodiments may comprise water, CKD, microspheres, a gas, and a surfactant. Other suitable additives, such as those discussed previously, also may be included in the foamed lightweight settable compositions of the present invention as desired by those of ordinary skill in the art, with the benefit of this disclosure. The gas used in the foamed lightweight settable compositions of the present
10 invention may be any gas suitable for foaming a settable composition, including, but not limited to, air, nitrogen, or combinations thereof. Generally, the gas should be present in the foamed lightweight settable compositions of the present invention in an amount sufficient to form the desired foam. In certain embodiments, the gas may be present in the foamed lightweight settable compositions of the present invention in an amount in the range of from
15 about 10% to about 80% by volume of the composition.
Generally, the surfactant may be present in the foamed lightweight settable compositions of the present invention in an amount sufficient to provide a suitable foam. In some embodiments, the surfactant may be present in an amount in the range of from about 0.5% and about 5% by volume of the water ("bvow").
20 The lightweight settable compositions of the present invention may be used in
a variety of subterranean applications, including, but not limited to, primary cementing, and remedial cementing. The lightweight settable compositions of the present invention also may be used in surface applications, for example, construction cementing.
An example of a method of the present invention comprises providing a
25 lightweight settable composition of the present invention having a density of less than about 13 ppg, the lightweight settable composition comprising water, CKD, and microspheres, placing the lightweight settable composition in a location to be cemented, and allowing the lightweight settable composition to set therein. In some embodiments, the location to be cemented may be above ground, for example, in construction cementing. In some
30 embodiments, the location to be cemented may be in a subterranean formation, for example, in subterranean applications. As desired by one of ordinary skill in the art, with the benefit of this disclosure, the lightweight settable compositions of the present invention useful in this

WO 2007/128945 PCT/GB2006/003694

method further may comprise any of the above-listed additives, as well any of a variety of other additives suitable for use in subterranean applications.
Another example of a method of the present invention is a method of primary cementing. An example of such a method may comprise providing a lightweight sellable 5 composition of the present invention having a density of less than about 13 ppg, the lightweight settable composition comprising water, CKD, and microspheres; introducing the lightweight settable composition into an annulus between a subterranean formation and a pipe string located in the subterranean formation; and allowing the lightweight settable composition to set in the annulus. Generally, in most instances, the lightweight settable
10 composition should set into hardened mass that fixes the pipe string to the subterranean formation. As desired by one of ordinary skill in the art, with the benefit of this disclosure, the lightweight settable compositions of the present invention useful in this method further may comprise any of the above-listed additives, as well any of a variety of other additives suitable for use in subterranean application.
15 To facilitate a better understanding of the present invention, the following
examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the scope of the invention.
EXAMPLE 1 A series of sample settable compositions were prepared at room temperature
20 and subjected to 96-hour compressive strength tests at I20°F in accordance with API Specification 10. The sample compositions comprised microspheres (3M' SCOTCHLITE' glass bubbles), and Class C Portland cement or Class A CKD in the amounts indicated in the table below. Sample No. 1 additionally comprised water (200% bwoc), SILICALITE™ cement additive (17.8% bwoc), CAL-SEAL® calcined gypsum plaster (8.9% bwoc), and
25 MICRO MATRIX® cement (17.8% bwoc). Sample No. 2 additionally comprised water (257.14% bwoc), SILICALITE™ cement additive (28.6% bwoc), CAL-SEAL® calcined gypsum plaster (17.1% bwoc), and MICRO MATRIX® cement (28.6% bwoc). In these examples, "bwoc" refers to by weight of cement, wherein the cement is the Portland cement and/or CKD included in the sample composition. SILICALITE cement additive is an
30 amorphous silica powder commercially available from Halliburton Energy Services, Inc. CAL-SEAL CAL-SEAL® calcined gypsum plaster is commercially available from U.S.

WO 2007/128945

PCT/GB2006/003694

Gypsum Company. MICRO MATRIX® cement is a fine hydraulic cement, commercially available from Halliburton Energy Services, Inc.
The results of the compressive strength tests are set forth in the table below.
TABLE 1 Compressive Strength Tests

EXAMPLE 2
10 A series of sample settable compositions were prepared at room temperature
and subjected to 24-hour compressive strength tests at 100°F in accordance with API Specification 10. The sample compositions comprised microspheres (3M' SCOTCHLITE glass bubbles), Class C Portland cement, and Class A CKD in the amounts indicated in Table 2 below. Each of the sample compositions also comprised water (180% bwoc), 15 SILICALITE™ cement additive (8% bwoc), CAL-SEAL® calcined gypsum plaster (4% bwoc), and MICRO MATRIX® cement (12% bwoc).
The results of the compressive strength tests are set forth in the table below,
TABLE 2 Compressive Strength Tests


WO 2007/128945 PCT/GB2006/003694

EXAMPLE 3
A series of sample sertable compositions were prepared at room temperature and subjected to 24-hour compressive strength tests at 100°F and 14Q°F in accordance with API Specification 10. The sample compositions comprised microspheres (3M™ 5 SCOTCHLITE™ glass bubbles), Class G CKD, and Class G Portland cement in the amounts indicated in the table below. Each of the sample compositions also comprised water (86.47% bwoc), SILICALITE™ cement additive (4% bwoc), CAL-SEAL® calcined gypsum plaster (2% bwoc), and MICRO MATRIX® cement (6% bwoc).
The results of the compressive strength tests are set forth in the table below.
10 TABLE 3
Compressive Strength Tests

Sample Density (PPg) Cement Class G
(% bwoc) CKD Class G
(% bwoc) SCOTCH-LITE™ Bead K25
(% bwoc) 24-Hour
Compressive
Strength at
100°F
(psi) 24-Hour
Compressive
Strength at
140°F
(psi)
No. 6 7.50 100 0 20 150 250
No. 7 7.50 70 30 20 85 238
No. 8 7.50 0 100 20 19 11.5

15
20

EXAMPLE 4
A series of sample sertable compositions were prepared at room temperature and subjected to 96-hour compressive strength tests at 140°F and 160°F in accordance with API Specification 10. The sample compositions comprised microspheres (3MTM SCOTCHLITE™ glass bubbles) and Class H CKD. Each of the sample compositions also comprised water, hydrated lime, vitrified shale (PRESSUR-SEAL® FINE LCM material), and CFR™-3 cement dispersant CFR -3 cement dispersant is commercially available from Halliburton Energy Services, Inc.
The results of the compressive strength tests are set forth in the table below.

TABLE 4 Compressive Strength Tests


WO 2007/128945 PCT/GB2006/003694
Accordingly, Examples 1-4 indicate that settable compositions comprising hydraulic cement, CKD, and microspheres may have suitable compressive strengths for a particular application.
Therefore, the present invention is well adapted to attain the ends and advantages
5 mentioned as well as those that are inherent therein. While numerous changes may be made
by those skilled in the art, such changes are encompassed within the spirit of this invention as
defined by the appended claims. The terms in the claims have their plain, ordinary meaning
unless otherwise explicitly and clearly defined by the patentee.

WO 2007/128945 PCT/GB20nfi/003(i94

CLAIMS:
I. A lightweight settable composition comprising water, cement kiln dust,
and microspheres, wherein the lightweight settable composition has a density less than about
13 pounds per gallon.
5 2. The lightweight settable composition of claim 1 wherein the cement
kiln dust is present in the lightweight settable composition in an amount in the range of from about 0.01% to about 80% by weight of the lightweight settable composition.
3. The lightweight settable composition of claim 1 wherein the
microspheres are present in the lightweight settable composition in an amount in the range of
10 from about 1% to 30% by weight of the lightweight settable composition.
4. The lightweight settable composition of claim 1 wherein the microspheres have a size less than about 150 microns.
5. The lightweight settable composition of claim 1 wherein the microspheres comprise at least one microsphere selected from the group consisting of hollow
15 microspheres, solid microspheres, porous microspheres, and combinations thereof.
6. The lightweight settable composition of claim 1 wherein the
microspheres comprise a material selected from the group consisting of glass, fly ash,
ceramic, polystyrene, other polymeric materials, and combinations thereof.
7. The lightweight settable composition of claim 1 wherein the
20 microspheres comprise sodium lime borosilicate glass.
8. The lightweight settable composition of claim 1 wherein the microspheres comprise polystyrene crosslinked with divinyl benzene.
9. The lightweight settable composition of claim 1 wherein the microspheres have a crush strength of greater than about 100 psi.
25 10. The lightweight settable composition of claim 1 wherein the
microspheres have a density of less than about 8.345 pounds per gallon.
11. The lightweight settable composition of claim 1 wherein the
lightweight settable composition further comprises a hydraulic cement.

WO 2(107/128945 PCT/GB2006/003fi94

12. The lightweight settable composition of claim 1 wherein the lightweight settable composition further comprises an additive selected from the group consisting of fly ash, vitrified shale, zeolite, hydrated lime, slag cement, metakaolin, and combinations thereof.
5 13. The lightweight settable composition of claim 1 wherein the
lightweight settable composition further comprises an additive selected from the group consisting of a set retarding additive, an accelerator, a lost circulation material, a filtration control additive, a dispersant, a gas, a foam stabilizing surfactant, and combinations thereof.
14. The lightweight settable composition of claim 1:
10 wherein the cement kiln dust is present in the lightweight settable
composition in an amount in the range of from about 2.5% to about 60% by weight of the lightweight settable composition;
wherein the microspheres are present in the lightweight settable composition in an amount in the range of from about 1% to 30% by weight of the lightweight 15 settable composition; and
wherein the lightweight settable composition further comprises Portland cement in an amount in the range of from about 20% to about 65% by weight of the lightweight settable composition.
15. A lightweight settable composition comprising water, CKD,
20 microspheres, vitrified shale, and hydrated lime, wherein the lightweight settable composition has a density less than about 13 pounds per gallon.
16. The lightweight settable composition of claim 15 wherein the
microspheres comprise at least one microsphere selected from the group consisting of hollow
microspheres, solid microspheres, porous microspheres, and combinations thereof.
25 17. The lightweight settable composition of claim 15 wherein the
microspheres comprise a material selected from the group consisting of glass, fly ash, ceramic, polystyrene, other polymeric materials, and combinations thereof.
18. A lightweight settable composition comprising water, CKD, and
microspheres comprising soda lime borosilicate glass, wherein the lightweight settable
30 composition has a density less than about 13 pounds per gallon.
19. The lightweight settable composition of claim 18 wherein the

WO 2(107/128945 PCT/GB2006/003694


microspheres comprise at least one microsphere selected from the group consisting of hollow microspheres, solid microspheres, porous microspheres, and combinations thereof.
20. The lightweight settable composition of claim 18 wherein the
microspheres comprise a material selected from the group consisting of glass, fly ash,
5 ceramic, polystyrene, other polymeric materials, and combinations thereof.
21. A method of cementing comprising:
providing a lightweight settable composition having a density less than
about 13 pounds per gallon, the lightweight settable composition comprising water, cement
kiln dust, and microspheres;
10 introducing the lightweight settable composition into a location to be
cemented; and
allowing the lightweight settable composition to set therein.
22. The method of claim 21 wherein the location to be cemented is in a
subterranean formation.
15 23. The method of claim 21 wherein the cement kiln dust is present in the
lightweight settable composition in an amount in the range of from about 0.01% to about 80% by weight of the lightweight settable composition.
24. The method of claim 21 wherein the microspheres are present in the
lightweight settable composition in an amount in the range of from about 1% to 30% by
20 weight of the lightweight settable compositioa
25. The method of claim 21 wherein the microspheres have a size less than about \50 microns.
26. The method of claim 21 wherein the microspheres comprise at least one microsphere selected from the group consisting of hollow microspheres, solid
25 microspheres, porous microspheres, and combinations thereof
27. The method of claim 21 wherein the microspheres comprise a material
selected from the group consisting of glass, fly ash, ceramic, polystyrene, other polymeric
materials, and combinations thereof.
28. The method of claim 21 wherein the microspheres comprise sodium
30 lime borosilicate glass.

WO 2007/128945 PCT/GB2006/003694
29, The method of claim 21 wherein the microspheres comprise
polystyrene crosslinked with divinyl benzene.
30. The method of claim 21 wherein the microspheres have a crush
strength of greater than about 100 psi.
5 31. The method of claim 21 wherein the microspheres have a density of
less than about 8.345 pounds per gallon.
32. The method of claim 21 wherein the lightweight settable composition
further comprises a hydraulic cement.
33. The method of claim 21 wherein the lightweight settable composition
10 further comprises an additive selected from the group consisting of fly ash, vitrified shale,
zeolite, hydrated lime, slag cement, metakaolin, and combinations thereof.
34. The method of claim 21 wherein the lightweight settabJe composition
further comprises an additive selected from the group consisting of at retarding additive,
an accelerator, a lost circulation material, a filtration control additive, a dispersant, a gas, a
15 foam stabilizing surfactant, and combinations thereof.
35. The method of claim 21:
wherein the cement kiln dust is present in the lightweight settable
composition in an amount in the range of from about 2.5% to about 60% by weight of the
lightweight settable composition;
20 wherein the microspheres are present in the lightweight settable
composition in an amount in the range of from about 1% to 30% by weight of the lightweight settable composition; and
wherein the lightweight settable composition further comprises Portland cement in an amount in the range of from about 20% to about 65% by weight of the 25 lightweight settable composition.
36. A method of primary cementing composing:
providing a lightweight settable composition having a density less than
about 13 pounds per gallon, the lightweight settable composition comprising water, cement
kiln dust, and microspheres;
30 introducing the lightweight settable composition into an annulus

WO 2007/128945

PCT/GB2006/003694


between a subterranean formation and a pipe string located in the subterranean formation; and
allowing the lightweight settable composition to set in the annulus.
37. The method of claim 36 wherein the microspheres have a size less than
5 about 150 microns.
38. The method of claim 36 wherein the microspheres comprise at least
one microsphere selected ftom the group consisting of hollow microspheres, solid
microspheres, porous microspheres, and combinations thereof.
39. The method of claim 36 wherein the microspheres comprise a material
10 selected from the group consisting of glass, fly ash, ceramic, polystyrene, other polymeric
materials, and combinations thereof.
40. The method of claim 36 wherein the microspheres comprise sodium
fi'me borosificate gfass.
Dated this 17th day of October, 2008
PRIYANKA CHOPRA OF K &S PARTNERS AGENT FR HE APPLICANT

Documents:

2267-MUMNP-2008-ABSTRACT(14-3-2012).pdf

2267-MUMNP-2008-ABSTRACT(23-10-2008).pdf

2267-MUMNP-2008-ABSTRACT(AMENDED)-(14-3-2012).pdf

2267-MUMNP-2008-ABSTRACT(GRANTED)-(29-5-2012).pdf

2267-mumnp-2008-abstract.doc

2267-mumnp-2008-abstract.pdf

2267-MUMNP-2008-ASSIGNMENT (14-3-2012).pdf

2267-MUMNP-2008-ASSIGNMENT(14-3-2012).pdf

2267-MUMNP-2008-CANCELLED PAGES(14-5-2012).pdf

2267-MUMNP-2008-CLAIMS(23-10-2008).pdf

2267-MUMNP-2008-CLAIMS(AMENDED)-(14-3-2012).pdf

2267-MUMNP-2008-CLAIMS(AMENDED)-(14-5-2012).pdf

2267-MUMNP-2008-CLAIMS(GRANTED)-(29-5-2012).pdf

2267-MUMNP-2008-CLAIMS(MARKED COPY)-(14-3-2012).pdf

2267-MUMNP-2008-CLAIMS(MARKED COPY)-(14-5-2012).pdf

2267-mumnp-2008-claims.doc

2267-mumnp-2008-claims.pdf

2267-mumnp-2008-correpondence.pdf

2267-MUMNP-2008-CORRESPONDENCE(1-1-2009).pdf

2267-MUMNP-2008-CORRESPONDENCE(11-2-2009).pdf

2267-MUMNP-2008-CORRESPONDENCE(14-5-2012).pdf

2267-MUMNP-2008-CORRESPONDENCE(17-5-2012).pdf

2267-mumnp-2008-correspondence(20-2-2009).pdf

2267-MUMNP-2008-CORRESPONDENCE(29-2-2012).pdf

2267-MUMNP-2008-CORRESPONDENCE(7-1-2009).pdf

2267-MUMNP-2008-CORRESPONDENCE(8-5-2012).pdf

2267-MUMNP-2008-CORRESPONDENCE(IPO)-(30-5-2012).pdf

2267-MUMNP-2008-DESCRIPTION(COMPLETE)-(23-10-2008).pdf

2267-mumnp-2008-description(complete).doc

2267-mumnp-2008-description(complete).pdf

2267-MUMNP-2008-DESCRIPTION(GRANTED)-(29-5-2012).pdf

2267-MUMNP-2008-EP DOCUMENT(29-2-2012).pdf

2267-MUMNP-2008-FORM 1(14-3-2012).pdf

2267-mumnp-2008-form 1.pdf

2267-MUMNP-2008-FORM 18(7-1-2009).pdf

2267-MUMNP-2008-FORM 2(COMPLETE)-(23-10-2008).pdf

2267-MUMNP-2008-FORM 2(GRANTED)-(29-5-2012).pdf

2267-MUMNP-2008-FORM 2(TITLE PAGE)-(14-3-2012).pdf

2267-MUMNP-2008-FORM 2(TITLE PAGE)-(23-10-2008).pdf

2267-MUMNP-2008-FORM 2(TITLE PAGE)-(GRANTED)-(29-5-2012).pdf

2267-mumnp-2008-form 2(title page).pdf

2267-mumnp-2008-form 2.doc

2267-mumnp-2008-form 2.pdf

2267-MUMNP-2008-FORM 26(11-2-2009).pdf

2267-MUMNP-2008-FORM 26(8-5-2012).pdf

2267-MUMNP-2008-FORM 3(1-1-2009).pdf

2267-MUMNP-2008-FORM 3(14-3-2012).pdf

2267-mumnp-2008-form 3(23-10-2008).pdf

2267-MUMNP-2008-FORM 3(29-2-2012).pdf

2267-mumnp-2008-form 3.pdf

2267-mumnp-2008-form 5.pdf

2267-mumnp-2008-pct-ib-304.pdf

2267-mumnp-2008-pct-isa-210.pdf

2267-MUMNP-2008-PETITION UNDER RULE 137(17-5-2012).pdf

2267-MUMNP-2008-REPLY TO EXAMINATION REPORT(14-3-2012).pdf

2267-MUMNP-2008-REPLY TO HEARING(14-5-2012).pdf

2267-MUMNP-2008-SPECIFICATION(AMENDED)-(14-3-2012).pdf

2267-MUMNP-2008-SPECIFICATION(MARKED COPY)-(14-3-2012).pdf

2267-MUMNP-2008-US DOCUMENT(14-5-2012).pdf

2267-MUMNP-2008-US DOCUMENT(29-2-2012).pdf

2267-mumnp-2008-wo international publication report a1.pdf


Patent Number 252734
Indian Patent Application Number 2267/MUMNP/2008
PG Journal Number 22/2012
Publication Date 01-Jun-2012
Grant Date 29-May-2012
Date of Filing 23-Oct-2008
Name of Patentee HALLIBURTON ENERGY SERVICES, INC.
Applicant Address P. O. BOX 1431, DUNCAN, OKLAHOMA 73533.
Inventors:
# Inventor's Name Inventor's Address
1 RODDY, CRAIG, W. 2906 TIMBER RIDGE DRIVE, DUNCAN, OKLAHOMA 73533.
2 CHATTERJI, JITEN 2213 SCOTT LANE, DUNCAN, OKLAHOMA 73533.
3 BRENNEIS, DARRELL, CHAD ROUTE 2, BOX 195, MARLOW, OKLAHOMA 73055.
4 KING, BOBBY, J. 2780 S. 27TH STREET, DUNCAN, OKLAHOMA 73533.
PCT International Classification Number C04B28/02
PCT International Application Number PCT/GB2006/003694
PCT International Filing date 2006-10-04
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 11/416,563 2006-05-03 U.S.A.
2 11/416,754 2006-05-03 U.S.A.