WO2006111703A2 - Compositions and methods of using a polymeric precipitate to reduce the loss of fluid to a subterranean formation - Google Patents

Compositions and methods of using a polymeric precipitate to reduce the loss of fluid to a subterranean formation Download PDF

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Publication number
WO2006111703A2
WO2006111703A2 PCT/GB2006/001244 GB2006001244W WO2006111703A2 WO 2006111703 A2 WO2006111703 A2 WO 2006111703A2 GB 2006001244 W GB2006001244 W GB 2006001244W WO 2006111703 A2 WO2006111703 A2 WO 2006111703A2
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WO
WIPO (PCT)
Prior art keywords
wellbore
activator
polymeric solution
precipitate
subterranean formation
Prior art date
Application number
PCT/GB2006/001244
Other languages
French (fr)
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WO2006111703A3 (en
Inventor
Kenneth W. Oyler
Carl J. Thaemilz
Original Assignee
Halliburton Energy Services, Inc
Curtis, Philip, Anthony
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US11/109,150 external-priority patent/US7943555B2/en
Priority claimed from US11/109,354 external-priority patent/US7905287B2/en
Application filed by Halliburton Energy Services, Inc, Curtis, Philip, Anthony filed Critical Halliburton Energy Services, Inc
Priority to EP06726648A priority Critical patent/EP1891177A2/en
Publication of WO2006111703A2 publication Critical patent/WO2006111703A2/en
Publication of WO2006111703A3 publication Critical patent/WO2006111703A3/en
Priority to NO20075890A priority patent/NO20075890L/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/426Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2652Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02Well-drilling compositions
    • C09K8/04Aqueous well-drilling compositions
    • C09K8/14Clay-containing compositions
    • C09K8/18Clay-containing compositions characterised by the organic compounds
    • C09K8/22Synthetic organic compounds
    • C09K8/24Polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C09K8/487Fluid loss control additives; Additives for reducing or preventing circulation loss
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/50Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
    • C09K8/504Compositions based on water or polar solvents
    • C09K8/506Compositions based on water or polar solvents containing organic compounds
    • C09K8/508Compositions based on water or polar solvents containing organic compounds macromolecular compounds

Definitions

  • the present invention generally relates to downhole operations, and more particularly to methods of forming a polymeric precipitate in a subterranean formation to reduce the loss of fluid to the formation.
  • Natural resources such as oil or gas residing in a subterranean formation can be recovered via the formation of wells that penetrate the formation.
  • a wellbore is typically drilled down to the formation while circulating a drilling fluid (also known as a drilling mud) through the wellbore.
  • a drilling fluid also known as a drilling mud
  • the drilling fluid carries the drill cuttings in a return flow stream back to the well drilling platform.
  • a string of pipe e.g., casing
  • the drilling fluid is then usually circulated downwardly through the interior of the pipe and upwardly through the annulus, which is located between the exterior of the pipe and the walls of the well bore.
  • Primary cementing is then usually performed whereby a cement slurry is pumped down through the string of pipe and into the annulus between the string of pipe and the walls of the wellbore to allow the cement slurry to set into an impermeable cement column and thereby seal the annulus.
  • Secondary cementing operations i.e., cementing operations occurring after the primary cementing operation, may also be performed.
  • One example of a secondary cementing operation is squeeze cementing whereby a cement slurry is forced under pressure to areas of lost integrity in the annulus to seal off those areas.
  • the fluids used in such downhole operations may be lost to the subterranean formation while circulating the fluids in the wellbore.
  • the fluids may enter the subterranean formation via depleted zones, zones of relatively low pressure, naturally occurring fractures, weak zones having fracture gradients exceeded by the hydrostatic pressure of the drilling fluid, and so forth.
  • lost circulation may occur in which the circulation of the drilling fluid in the wellbore drops due to it being lost to the formation. Its circulation may eventually become too low to allow for further drilling of the wellbore.
  • a cement slurry may be lost to the formation as it is being placed in the annulus, thereby rendering it ineffective in isolating the adjacent subterranean formation.
  • the amount of cement slurry may be insufficient to fill the annulus from top to bottom during primary cementing or to fill areas of lost integrity in a pre-existing cement column during secondary cementing. Further, dehydration of the cement slurry may result, compromising the strength of the cement that forms in the annulus.
  • methods of treating a subterranean formation comprise contacting a polymeric solution and an activator in the subterranean formation, thereby forming a precipitate to at least partially block a flow of a wellbore servicing fluid further into the formation.
  • the wellbore servicing fluid may be, for example, a drilling fluid, a cement composition, a workover fluid, or combinations thereof.
  • the polymeric solution may comprise, for example, a poly vinyl pyrrolidone aqueous solution
  • the activator may comprise, for example, a formate brine.
  • the polymeric solution and the activator are contacted before completing a drilling operation in the wellbore.
  • they are contacted before completing a primary cementing operation in the wellbore.
  • they are contacted before completing a secondary cementing operation in the wellbore.
  • the precipitate may be easily and quickly removed from the subterranean formation by dissolving it in fresh water.
  • methods of treating a wellbore that penetrates a subterranean formation comprise: introducing an activator to the wellbore; introducing a polymeric solution in situ with the activator, thereby forming a hard precipitate to at least partially block a flow pathway into the subterranean formation; circulating a wellbore servicing fluid through the wellbore; and dissolving the precipitate to prepare for hydrocarbon production.
  • methods of drilling a wellbore at least partially through a subterranean formation comprise: introducing an activator to the wellbore; introducing a polymeric solution in situ with the activator, thereby forming a hard precipitate to at least partially block a flow pathway into the subterranean formation; and applying torque to a bit within the wellbore while applying force to urge the bit to extend through the wellbore; and circulating a drilling fluid past the bit to remove cuttings therefrom.
  • FIG. IA is a side plan view of a drilling rig and a wellbore in the earth for recovering oil from a subterranean formation.
  • FIG. IB is a detailed view of a section of the wellbore depicted in FIG. IA 5 showing a precipitate blocking a flow pathway into the subterranean formation.
  • a polymeric solution and an activator may be contacted in a subterranean formation in such a manner as to form a hard precipitate in the formation.
  • a "polymeric solution” is defined as a solution comprising a polymer, an oligomer, or combinations thereof.
  • an "activator” is defined as a material that, when present in a sufficient amount, can cause the polymer and/or oligomer to precipitate out of the solution, wherein the activator may be a liquid in which the polymer and/or oligomer is insoluble. It is understood that "subterranean formation” encompasses both areas below exposed earth or areas below earth covered by water such as sea or ocean water.
  • the resulting polymeric precipitate is typically impermeable to fluid and thus may form a barrier in the formation that at least partially blocks one or more flow pathways through which a fluid could undesirably migrate into the formation.
  • flow pathways include natural or induced fractures, depleted zones, zones of relatively low pressure, weak zones having fracture gradients exceeded by the hydrostatic pressure of the fluid being used to service the wellbore, perforations formed by a perforating gun, and combinations thereof.
  • FIGS. IA and IB illustrate how the precipitate forms a barrier to at least partially reduce the flow of fluid far into a subterranean formation.
  • FIG. IA depicts a wellbore 10 that has been drilled in the earth such that it penetrates a subterranean formation.
  • An oil rig 30 positioned near the surface of the earth 20 may be used to recover oil from the formation.
  • a pipe 40 e.g., a drill pipe or tubing, may extend down through wellbore 10 for delivering fluid to and/or from the wellbore.
  • FIG. IB illustrates a section 50 of wellbore 10 in detail.
  • a precipitate 60 forms a solid coating across a flow pathway 70 such as a crack within wellbore 10 and thereby seals flow pathway 70.
  • the coating may have a thickness ranging from about 1 millimeter to about 10 millimeters.
  • precipitate 60 may extend across flow pathway 70.
  • Precipitate 60 is desirably impermeable to fluid and thus inhibits fluid from passing through pathway 70 and deeper into the adjacent subterranean formation.
  • precipitate 60 serves to reduce the loss of such fluid to the formation, allowing it to be primarily retained within wellbore 10 as it is pumped therethrough.
  • the coating formed by the precipitate will be effective in cracks that are both larger and smaller than the coating thickness near the wall of the wellbore. That is, cracks within the subterranean formation usually decrease in size at greater depths within the formation. Thus, the polymer solution may be pumped into cracks larger than the ensuing coating thickness to a depth where the cracks become sufficiently narrow to allow the coating to plug the entire crack.
  • a spacer separates the polymeric solution and the activator as they are being pumped downhole.
  • spacer is defined as a fluid that prevents the polymeric solution and the activator from interacting with each other as they pass down the wellbore and that is inert with respect to the polymeric solution and the activator.
  • suitable fluids to use as spacers include natural hydrocarbons, synthetic hydrocarbons, surfactants, glycols, fresh water, and combinations thereof.
  • the amount of the spacer employed in this embodiment may range from about 1 to about 5 barrels or alternatively may be about 2 barrels.
  • the polymeric solution, the spacer, and the activator are sequentially pumped to the formation.
  • the activator is pumped first and the polymeric solution is pumped behind the spacer. Within the subterranean formation, the polymeric solution and the activator are no longer separated and thus contact each other, resulting in the formation of the precipitate.
  • the polymeric solution and the activator may be displaced into the wellbore before or during the circulation/squeezing of a wellbore servicing fluid in the wellbore. hi an embodiment, they may be pumped downhole after the discovery that at least a portion of the wellbore servicing fluid is being lost to the subterranean formation. At this point, the circulation/squeezing of the wellbore servicing fluid in the wellbore may be terminated to allow for the formation of the precipitate within the formation. Once the precipitate has been formed, the circulation/squeezing of the fluid in the wellbore may then be resumed. The formation of the precipitate may occur within 1 minute of the initial contact between the polymeric solution and the activator. However, typically one waits for a period of in a range of from about 30 minutes to about 4 hours before passing the wellbore servicing fluid into the wellbore again.
  • the precipitate may be used to reduce a pre-completion loss to a subterranean formation.
  • a "pre-completion loss" refers to a loss of fluid to a subterranean formation that occurs before the wellbore is completed, i.e., before the annulus of the wellbore has been sealed by a sealant composition, e.g., a cement composition.
  • the pre-completion loss is the loss of a drilling fluid during its circulation through a wellbore both during and after the drilling of the wellbore.
  • the pre- completion loss is the loss of a cement slurry (or other type of sealant composition) during primary cementing.
  • the precipitate may be used to prevent a post-completion loss to the subterranean formation.
  • a post-completion loss refers to a loss of fluid to a subterranean formation that occurs after the wellbore is completed, i.e., after the annulus of the wellbore has been sealed by a sealant composition, e.g., a cement composition.
  • the post-completion loss may be that of a secondary sealant composition such as a cement composition.
  • the secondary sealant composition may be placed in one or more permeable zones present in the wellbore using a squeeze technique known in the art.
  • the permeable zones may extend, for example, through the wall of a conduit positioned in the wellbore, a sealant/cement column in the annulus of the wellbore, a microannulus of the wellbore, or combinations thereof.
  • Examples of those permeable zones include a fissure, a crack, a fracture, a streak, a flow channel, a void, and combinations thereof.
  • the post-completion loss may be the loss of a fluid, e.g., a workover fluid, during a production enhancement operation, e.g., a workover operation.
  • the precipitate may be removed to prepare the formation for the production of oil, gas, and/or water. That is, the precipitate may be removed to prevent it from blocking the flow of such natural resources from the formation. It may also be removed to avoid contaminating any water produced by the formation.
  • the precipitate may be removed by dissolving it in a fluid in which it is soluble such as fresh water, thereby providing a simple and inexpensive way to eliminate the precipitate.
  • the precipitate may be removed by water that is initially produced by the formation, or alternatively, it may be removed by water that is intentionally pumped into the wellbore. Examples of compounds that may be employed to dissolve the precipitate include but are not limited to fresh water and brines such as halide brines, e.g., sodium chloride brine.
  • the methods described above for reducing the loss of a wellbore servicing fluid to the subterranean formation utilize a polymeric solution and an activator.
  • the volume ratio of the polymeric solution to the activator may be in a range of from about 50:50 to about 70:30.
  • the polymeric solution comprises a polymer and a fluid in which the polymer has a relatively high solubility.
  • the polymeric solution may also include but is not limited to lost circulation materials, weighting agents such as barite, acid soluble particles, and combinations thereof.
  • An example of a suitable polymeric solution includes polyvinylpyrrolidone (PVP) in water, which is commercially available from ISP Technologies, Lie.
  • VTVTPRINT 540 solution (10% PVP by weight of the aqueous solution) and from Halliburton Energy Services, Inc. under the tradename of PERFORMATROL polymer (10% PVP by weight of the aqueous solution).
  • the amount of the polymer in the polymeric solution may be a range of from about 1% to about 90%, alternatively from about 5% to about 50 %, by weight of the polymeric solution.
  • Suitable activators include formate brines (e.g., potassium formate, sodium formate, and cesium formate), acetate brines (e.g., potassium acetate, sodium acetate, and cesium acetate), oxalate brines (e.g., potassium oxalate, sodium oxalate, and cesium oxalate), halide brines (e.g., zinc bromide), and combinations thereof.
  • the amount of the potassium formate in the activator may be in a range of from about 10% to about 78%, or alternatively from about 50% to about 78%, by weight of the total formate brine. Modifications to the Foregoing Embodiments
  • the activator may also serve as the solvent in which the polymer is dissolved.
  • the polymer may be coated with a material that prevents it from initially contacting the activator/solvent.
  • the polymer and the activator may be concurrently pumped downhole without forming a precipitate.
  • the coating may eventually dissolve such that the activator/solvent contacts the polymer and thus forms the precipitate.
  • the period of time required for the coating to completely dissolve may be sufficient to allow the polymer to be pumped into a crack or void in a subterranean formation. As a result, the formation of the precipitate is time delayed.
  • PERFORMATROL solution i.e., the PVP solution
  • PVP solution a PERFORMATROL solution
  • 16 lbs/gal of barite weighting agent were added to each PERFORMATROL solution sample.
  • the PERFORMATROL solution samples remained pumpable after the addition of the barite weighting agent.
  • the precipitate withstood a 500 psi differential such that no mud could pass through the precipitate at this pressure.
  • the thickness of the seal was measured as 1/8 inch.
  • the precipitate was also heated on a hotplate to determine the temperatures at which it is stable. The precipitate exhibited no apparent decomposition at temperatures less than or equal to 250 0 F.
  • the precipitate can be dissolved relatively quickly with freshwater or sodium chloride brine. Further, it may also be removed at a relatively slow rate with calcium chloride brine or calcium bromide brine. It is desirably insoluble in the ACCOLADE drilling mud.
  • Example 1 The procedure followed in Example 1 was repeated with different activators. More specifically, the potassium formate brines were replaced with sodium formate brines, cesium formate brines, and zinc bromide brines. AU of those brines caused the PVP to precipitate out of solution.

Abstract

Methods are provided for reducing the loss of a wellbore servicing fluid to a subterranean formation. A polymeric solution and an activator may be contacted in the formation, thereby forming a precipitate to at least partially block fluid from flowing further into the formation. The fluid may be, for example, a drilling fluid, a cement composition, a workover fluid, or combinations thereof. The polymeric solution may comprise a polyvinylpyrrolidone aqueous solution, and the activator may comprise a formate brine. In one embodiment, the polymeric solution and the activator are contacted before completing a drilling operation in the wellbore. hi another embodiment, they are contacted before completing a primary cementing operation in the wellbore. In yet another embodiment, they are contacted before completing a secondary cementing operation in the wellbore. When desirable, the precipitate may be easily and quickly removed from the subterranean formation by dissolving it in fresh water.

Description

COMPOSITIONS AND METHODS OF USING A POLYMERIC PRECIPITATE TO REDUCE TBDE LOSS OF FLUID TO A SUBTERRANEAN FORMATION
FIELD OF THE INVENTION
The present invention generally relates to downhole operations, and more particularly to methods of forming a polymeric precipitate in a subterranean formation to reduce the loss of fluid to the formation.
BACKGROUND OF THE INVENTION
The following paragraphs contain some discussion, which is illuminated by the innovations disclosed in this application, and any discussion of actual or proposed or possible approaches in this Background section does not imply that those approaches are prior art.
Natural resources such as oil or gas residing in a subterranean formation can be recovered via the formation of wells that penetrate the formation. In particular, a wellbore is typically drilled down to the formation while circulating a drilling fluid (also known as a drilling mud) through the wellbore. During the drilling process, the drill bit generates drill cuttings that consist of small pieces of shale and rock. The drilling fluid carries the drill cuttings in a return flow stream back to the well drilling platform. After terminating the circulation of the drilling fluid, a string of pipe, e.g., casing, is run into the wellbore. The drilling fluid is then usually circulated downwardly through the interior of the pipe and upwardly through the annulus, which is located between the exterior of the pipe and the walls of the well bore.
Primary cementing is then usually performed whereby a cement slurry is pumped down through the string of pipe and into the annulus between the string of pipe and the walls of the wellbore to allow the cement slurry to set into an impermeable cement column and thereby seal the annulus. Subsequent secondary cementing operations, i.e., cementing operations occurring after the primary cementing operation, may also be performed. One example of a secondary cementing operation is squeeze cementing whereby a cement slurry is forced under pressure to areas of lost integrity in the annulus to seal off those areas.
Unfortunately, the fluids used in such downhole operations may be lost to the subterranean formation while circulating the fluids in the wellbore. In particular, the fluids may enter the subterranean formation via depleted zones, zones of relatively low pressure, naturally occurring fractures, weak zones having fracture gradients exceeded by the hydrostatic pressure of the drilling fluid, and so forth. As a result, the services provided by the fluids are more difficult to achieve. For example, a problem known as lost circulation may occur in which the circulation of the drilling fluid in the wellbore drops due to it being lost to the formation. Its circulation may eventually become too low to allow for further drilling of the wellbore. Also, a cement slurry may be lost to the formation as it is being placed in the annulus, thereby rendering it ineffective in isolating the adjacent subterranean formation. In particular, the amount of cement slurry may be insufficient to fill the annulus from top to bottom during primary cementing or to fill areas of lost integrity in a pre-existing cement column during secondary cementing. Further, dehydration of the cement slurry may result, compromising the strength of the cement that forms in the annulus.
Traditional methods of overcoming the problems described above include sealing the zones through which the fluids can enter the subterranean formation with thixotropic cements, non-aqueous dispersions of clays, sodium silicate solutions in combination with calcium salt sweeps, and fluids containing inert platelets such as mica. However, the presence of such sealants in the formation may block the flow of oil or gas into the wellbore when it is desirable to begin production. Further, those materials may contaminate fresh water produced by the formation ahead of the oil or gas. Unfortunately, the sealants typically cannot be easily removed from the formation before production. A need therefore exists to develop a way to prevent the loss of fluid to the subterranean formation without adversely affecting the production of water, oil, or gas by the formation.
SUMMARY OF THE INVENTION
Some teachings and advantages found in the present application are summarized briefly below. However, note that the present application may disclose multiple embodiments, and not all of the statements in this Summary section necessarily relate to all of those embodiments. Moreover, none of these statements limit the claims in any way.
In embodiments, methods of treating a subterranean formation comprise contacting a polymeric solution and an activator in the subterranean formation, thereby forming a precipitate to at least partially block a flow of a wellbore servicing fluid further into the formation. The wellbore servicing fluid may be, for example, a drilling fluid, a cement composition, a workover fluid, or combinations thereof. The polymeric solution may comprise, for example, a poly vinyl pyrrolidone aqueous solution, and the activator may comprise, for example, a formate brine. In one embodiment, the polymeric solution and the activator are contacted before completing a drilling operation in the wellbore. In another embodiment, they are contacted before completing a primary cementing operation in the wellbore. In yet another embodiment, they are contacted before completing a secondary cementing operation in the wellbore. When desirable, the precipitate may be easily and quickly removed from the subterranean formation by dissolving it in fresh water.
In additional embodiments, methods of treating a wellbore that penetrates a subterranean formation comprise: introducing an activator to the wellbore; introducing a polymeric solution in situ with the activator, thereby forming a hard precipitate to at least partially block a flow pathway into the subterranean formation; circulating a wellbore servicing fluid through the wellbore; and dissolving the precipitate to prepare for hydrocarbon production.
In more embodiments, methods of drilling a wellbore at least partially through a subterranean formation comprise: introducing an activator to the wellbore; introducing a polymeric solution in situ with the activator, thereby forming a hard precipitate to at least partially block a flow pathway into the subterranean formation; and applying torque to a bit within the wellbore while applying force to urge the bit to extend through the wellbore; and circulating a drilling fluid past the bit to remove cuttings therefrom.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. IA is a side plan view of a drilling rig and a wellbore in the earth for recovering oil from a subterranean formation.
FIG. IB is a detailed view of a section of the wellbore depicted in FIG. IA5 showing a precipitate blocking a flow pathway into the subterranean formation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A polymeric solution and an activator may be contacted in a subterranean formation in such a manner as to form a hard precipitate in the formation. As used herein, a "polymeric solution" is defined as a solution comprising a polymer, an oligomer, or combinations thereof. As used herein, an "activator" is defined as a material that, when present in a sufficient amount, can cause the polymer and/or oligomer to precipitate out of the solution, wherein the activator may be a liquid in which the polymer and/or oligomer is insoluble. It is understood that "subterranean formation" encompasses both areas below exposed earth or areas below earth covered by water such as sea or ocean water. The resulting polymeric precipitate is typically impermeable to fluid and thus may form a barrier in the formation that at least partially blocks one or more flow pathways through which a fluid could undesirably migrate into the formation. Examples of such flow pathways include natural or induced fractures, depleted zones, zones of relatively low pressure, weak zones having fracture gradients exceeded by the hydrostatic pressure of the fluid being used to service the wellbore, perforations formed by a perforating gun, and combinations thereof.
The polymeric solution and the activator typically reach the subterranean formation by pumping them down a wellbore that penetrates the formation. The presence of the precipitate barrier in the formation allows fluids (known as wellbore servicing fluids) to be circulated or squeezed in the wellbore for the purpose of servicing the wellbore without being concerned that a substantial amount of the fluid could flow into and be lost to the formation. FIGS. IA and IB illustrate how the precipitate forms a barrier to at least partially reduce the flow of fluid far into a subterranean formation. FIG. IA depicts a wellbore 10 that has been drilled in the earth such that it penetrates a subterranean formation. An oil rig 30 positioned near the surface of the earth 20 may be used to recover oil from the formation. A pipe 40, e.g., a drill pipe or tubing, may extend down through wellbore 10 for delivering fluid to and/or from the wellbore. FIG. IB illustrates a section 50 of wellbore 10 in detail. As illustrated in FIG. IB, a precipitate 60 forms a solid coating across a flow pathway 70 such as a crack within wellbore 10 and thereby seals flow pathway 70. The larger the quantity of polymer solution pumped into wellbore 10, the thicker the coating formed therein. In an embodiment, the coating may have a thickness ranging from about 1 millimeter to about 10 millimeters. Also, from about 0.25 to about 0.5 gram/cubic centimeter of precipitate 60 may extend across flow pathway 70. Precipitate 60 is desirably impermeable to fluid and thus inhibits fluid from passing through pathway 70 and deeper into the adjacent subterranean formation. Thus, precipitate 60 serves to reduce the loss of such fluid to the formation, allowing it to be primarily retained within wellbore 10 as it is pumped therethrough.
It is believed that the coating formed by the precipitate will be effective in cracks that are both larger and smaller than the coating thickness near the wall of the wellbore. That is, cracks within the subterranean formation usually decrease in size at greater depths within the formation. Thus, the polymer solution may be pumped into cracks larger than the ensuing coating thickness to a depth where the cracks become sufficiently narrow to allow the coating to plug the entire crack.
In an embodiment, a spacer separates the polymeric solution and the activator as they are being pumped downhole. As used herein, "spacer" is defined as a fluid that prevents the polymeric solution and the activator from interacting with each other as they pass down the wellbore and that is inert with respect to the polymeric solution and the activator. Examples of suitable fluids to use as spacers include natural hydrocarbons, synthetic hydrocarbons, surfactants, glycols, fresh water, and combinations thereof. The amount of the spacer employed in this embodiment may range from about 1 to about 5 barrels or alternatively may be about 2 barrels. In one embodiment, the polymeric solution, the spacer, and the activator are sequentially pumped to the formation. In another embodiment, the activator is pumped first and the polymeric solution is pumped behind the spacer. Within the subterranean formation, the polymeric solution and the activator are no longer separated and thus contact each other, resulting in the formation of the precipitate.
The polymeric solution and the activator may be displaced into the wellbore before or during the circulation/squeezing of a wellbore servicing fluid in the wellbore. hi an embodiment, they may be pumped downhole after the discovery that at least a portion of the wellbore servicing fluid is being lost to the subterranean formation. At this point, the circulation/squeezing of the wellbore servicing fluid in the wellbore may be terminated to allow for the formation of the precipitate within the formation. Once the precipitate has been formed, the circulation/squeezing of the fluid in the wellbore may then be resumed. The formation of the precipitate may occur within 1 minute of the initial contact between the polymeric solution and the activator. However, typically one waits for a period of in a range of from about 30 minutes to about 4 hours before passing the wellbore servicing fluid into the wellbore again.
In one embodiment, the precipitate may be used to reduce a pre-completion loss to a subterranean formation. As used herein, a "pre-completion loss" refers to a loss of fluid to a subterranean formation that occurs before the wellbore is completed, i.e., before the annulus of the wellbore has been sealed by a sealant composition, e.g., a cement composition. In an embodiment, the pre-completion loss is the loss of a drilling fluid during its circulation through a wellbore both during and after the drilling of the wellbore. In another embodiment, the pre- completion loss is the loss of a cement slurry (or other type of sealant composition) during primary cementing.
In another embodiment, the precipitate may be used to prevent a post-completion loss to the subterranean formation. As used herein, a "post-completion" loss refers to a loss of fluid to a subterranean formation that occurs after the wellbore is completed, i.e., after the annulus of the wellbore has been sealed by a sealant composition, e.g., a cement composition. In an embodiment, the post-completion loss may be that of a secondary sealant composition such as a cement composition. By way of example, the secondary sealant composition may be placed in one or more permeable zones present in the wellbore using a squeeze technique known in the art. The permeable zones may extend, for example, through the wall of a conduit positioned in the wellbore, a sealant/cement column in the annulus of the wellbore, a microannulus of the wellbore, or combinations thereof. Examples of those permeable zones include a fissure, a crack, a fracture, a streak, a flow channel, a void, and combinations thereof. In yet another embodiment, the post-completion loss may be the loss of a fluid, e.g., a workover fluid, during a production enhancement operation, e.g., a workover operation.
In certain situations, it may be desirable to remove the polymeric precipitate from the subterranean formation. For instance, the precipitate may be removed to prepare the formation for the production of oil, gas, and/or water. That is, the precipitate may be removed to prevent it from blocking the flow of such natural resources from the formation. It may also be removed to avoid contaminating any water produced by the formation. In an embodiment, the precipitate may be removed by dissolving it in a fluid in which it is soluble such as fresh water, thereby providing a simple and inexpensive way to eliminate the precipitate. For example, the precipitate may be removed by water that is initially produced by the formation, or alternatively, it may be removed by water that is intentionally pumped into the wellbore. Examples of compounds that may be employed to dissolve the precipitate include but are not limited to fresh water and brines such as halide brines, e.g., sodium chloride brine.
The methods described above for reducing the loss of a wellbore servicing fluid to the subterranean formation utilize a polymeric solution and an activator. The volume ratio of the polymeric solution to the activator may be in a range of from about 50:50 to about 70:30. The polymeric solution comprises a polymer and a fluid in which the polymer has a relatively high solubility. In embodiments, the polymeric solution may also include but is not limited to lost circulation materials, weighting agents such as barite, acid soluble particles, and combinations thereof. An example of a suitable polymeric solution includes polyvinylpyrrolidone (PVP) in water, which is commercially available from ISP Technologies, Lie. under the tradename of VTVTPRINT 540 solution (10% PVP by weight of the aqueous solution) and from Halliburton Energy Services, Inc. under the tradename of PERFORMATROL polymer (10% PVP by weight of the aqueous solution). The amount of the polymer in the polymeric solution may be a range of from about 1% to about 90%, alternatively from about 5% to about 50 %, by weight of the polymeric solution. Examples of suitable activators include formate brines (e.g., potassium formate, sodium formate, and cesium formate), acetate brines (e.g., potassium acetate, sodium acetate, and cesium acetate), oxalate brines (e.g., potassium oxalate, sodium oxalate, and cesium oxalate), halide brines (e.g., zinc bromide), and combinations thereof. In an embodiment, the amount of the potassium formate in the activator may be in a range of from about 10% to about 78%, or alternatively from about 50% to about 78%, by weight of the total formate brine. Modifications to the Foregoing Embodiments
In an alternative embodiment, the activator may also serve as the solvent in which the polymer is dissolved. The polymer may be coated with a material that prevents it from initially contacting the activator/solvent. Thus, the polymer and the activator may be concurrently pumped downhole without forming a precipitate. The coating may eventually dissolve such that the activator/solvent contacts the polymer and thus forms the precipitate. The period of time required for the coating to completely dissolve may be sufficient to allow the polymer to be pumped into a crack or void in a subterranean formation. As a result, the formation of the precipitate is time delayed.
EXAMPLES
The invention having been generally described, the following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification or the claims to follow in any manner.
Example 1
Several samples of a PERFORMATROL solution (i.e., the PVP solution) were used in this example. About 16 lbs/gal of barite weighting agent were added to each PERFORMATROL solution sample. The PERFORMATROL solution samples remained pumpable after the addition of the barite weighting agent.
Various potassium formate brines (i.e., the activator) having different densities were combined with respective PERFORMATROL solution samples. The volume ratio of the potassium formate to the PERFORMATROL solution in each sample was 50:50. The densities of the potassium formate brine were 9.8 lb/gal, 10.3 lb/gal, 10.8 lb/gal, 11.7 lb/gal, and 12.2 lb/gal. These particular densities of the potassium formate brines caused a relatively hard PVP precipitate to form. It is believed that potassium formate brines having densities lower than 9.5 lb/gal will not form such a precipitate.
As shown in Table 1 below, various properties of the precipitate formed using the 13.2 lb/gal potassium formate brine were determined. For each mL of PERFORMATROL solution used, approximately 0.4 mL of the potassium formate brine was required to precipitate all of the PVP. The precipitate formed within 1 minute of contacting the PERFORMATROL solution with the formate brine. The sealing capability of the precipitate was determined by placing it on a slotted disk and then placing the disk in a filtration apparatus. A drilling mud was then placed on the disk and an attempt was made to filter the mud through the precipitate by applying a pressure of 500 psi across the disk. The precipitate withstood a 500 psi differential such that no mud could pass through the precipitate at this pressure. The thickness of the seal was measured as 1/8 inch. The precipitate was also heated on a hotplate to determine the temperatures at which it is stable. The precipitate exhibited no apparent decomposition at temperatures less than or equal to 2500F.
Table 1
Figure imgf000009_0001
In addition, the lengths of time required to dissolve the precipitate by contacting it with fresh water (placing it in about 100 mL), non-aqueous drilling muds, and halide brines were compared, as presented in Table 2 below. It is noted that ACCOLADE drilling mud is commercially available from Halliburton Energy Services, Inc. Table 2
Figure imgf000010_0001
Based on Table 2, the precipitate can be dissolved relatively quickly with freshwater or sodium chloride brine. Further, it may also be removed at a relatively slow rate with calcium chloride brine or calcium bromide brine. It is desirably insoluble in the ACCOLADE drilling mud.
Example 2
The procedure followed in Example 1 was repeated with different activators. More specifically, the potassium formate brines were replaced with sodium formate brines, cesium formate brines, and zinc bromide brines. AU of those brines caused the PVP to precipitate out of solution.
While preferred embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are possible and are within the scope of the invention.
Accordingly, the scope of protection is not limited by the description set out above but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each and every claim is incorporated into the specification as an embodiment of the present invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention. The discussion of a reference herein is not an admission that it is prior art to the present invention, especially any reference that may have a publication date after the priority date of this application. The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated by reference, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein.

Claims

What is claimed is:
1. A method of treating a subterranean formation, comprising contacting a polymeric solution and an activator in the subterranean formation, thereby forming a precipitate to at least partially block a flow of a wellbore servicing fluid further into the subterranean formation.
2. The method of claim 1, wherein the wellbore servicing fluid comprises a drilling fluid, a cement composition, a workover fluid, or combinations thereof.
3. The method of claim 1, wherein the contacting is performed before completing a drilling operation in the wellbore.
4. The method of claim 1, wherein the contacting is performed before completing a primary cementing operation in the wellbore.
5. The method of claim 1, wherein the contacting is performed before completing a secondary cementing operation in the wellbore.
6. The method of claim 1, wherein the contacting is performed during a workover operation.
7. The method of claim 1, wherein the polymeric solution comprises polyvinylpyrrolidone in water.
8. The method of claiml, wherein the activator comprises a formate brine, an acetate brine, an oxalate brine, a halide brine, or combinations thereof.
9. The method of claim 1, wherein the contacting comprises sequentially pumping the polymeric solution, a spacer, and the activator into the subterranean formation.
10. The method of claim 9, wherein the spacer comprises a natural hydrocarbon, a synthetic hydrocarbon, a glycol, a surfactant, fresh water, or combinations thereof.
11. The method of claim 1, wherein the contacting comprises sequentially pumping the activator, a spacer, and the polymeric solution into the subterranean formation.
12. The method of claim 1, wherein a solvent of the polymer comprises the activator such that the activator and the polymer are concurrently pumped in the wellbore, and wherein the polymer is coated with a material that dissolves as it passes down the welibore such that the contacting between the activator and the polymer is time delayed.
13. The method of claim 1, wherein a volume ratio of the polymeric solution to the activator is in a range of from about 50:50 to about 70:30.
14. The method of claim 1, wherein an amount of the polymer in the polymeric solution is in a range of from about 1 to about 90 by weight of the polymeric solution.
15. The method of claim 1, wherein an amount of the formate in the formate brine is in a range of from about 10% to about 78% by weight of the total formate brine.
16. The method of claim 1, further comprising removing the precipitate from the subterranean formation by dissolving the precipitate in water.
17. A method of treating a wellbore that penetrates a subterranean formation, comprising: introducing an activator to the wellbore; introducing a polymeric solution in situ with the activator, thereby forming a hard precipitate to at least partially block a flow pathway into the subterranean formation; circulating a wellbore servicing fluid through the wellbore; and dissolving the precipitate to prepare for hydrocarbon production.
18. The method of claim 17, further comprising introducing a spacer fluid to the wellbore in between the activator and the polymeric solution.
19. The method of claim 17, wherein the polymeric solution comprises polyvinylpyrrolidone in water.
20. A method of drilling a wellbore at least partially through a subterranean formation, comprising: introducing an activator to the wellbore; introducing a polymeric solution in situ with the activator, thereby forming a hard precipitate to at least partially block a flow pathway into the subterranean formation; applying torque to a bit within the wellbore while applying force to urge the bit to extend through the wellbore; and circulating a drilling fluid past the bit to remove cuttings therefrom.
21. A wellbore treatment kit comprising: a polymeric solution for placement in a wellbore that penetrates a subterranean formation; and an activator for causing a polymer to precipitate out of the polymeric solution when it contacts the polymeric solution, wherein the resulting precipitate is capable of at least partially blocking a flow of a wellbore servicing fluid into the subterranean formation.
22. The wellbore treatment kit of claim 21, wherein the wellbore servicing fluid comprises a drilling fluid, a cement composition, a workover fluid, or combinations thereof.
23. The wellbore treatment kit of claim 21, wherein the polymeric solution comprises polyvinylpyrrolidone in water.
24. The wellbore treatment kit of claim 21, wherein the activator comprises a formate brine, an acetate brine, an oxalate brine, a halide brine, or combinations thereof.
25. The wellbore treatment kit of claim 21, wherein a volume ratio of the polymeric solution to the activator is in a range of from about 50:50 to about 70:30.
26. The wellbore treatment kit of claim 21, wherein an amount of the polymer in the polymeric solution is in a range of from about 1 to about 90 by weight of the polymeric solution.
27. The wellbore treatment kit of claim 24, wherein an amount of formate in the formate brine is in a range of from about 10% to about 78% by weight of the total formate brine.
28. The wellbore treatment kit of claim 21, wherein the precipitate is capable of being dissolved in water for removing the precipitate from the subterranean formation.
29. The wellbore treatment kit of claim 21 , being disposed in the wellbore.
30. The wellbore treatment kit of claim 21, being disposed on a truck.
31. The wellbore treatment kit of claim 21, being stored in a warehouse.
32. The wellbore treatment kit of claim 21, wherein a solvent of the polymer comprises the activator, and wherein the polymer is coated with a material that is capable of dissolving as it passes down the wellbore such that contact between the activator and the polymer is time delayed.
33. A wellbore treatment kit comprising: a polymeric solution for placement in a wellbore that penetrates a subterranean formation; an activator for causing a polymer to precipitate out of the polymeric solution when it contacts the polymeric solution, wherein the resulting precipitate is capable of at least partially blocking a flow of a wellbore servicing fluid into the subterranean formation; and a spacer for separating the polymeric solution and the activator when they are pumped into the wellbore.
34. The wellbore treatment kit of claim 33, wherein the polymeric solution comprises polyvinylpyrrolidone in water.
35. The wellbore treatment kit of claim 33, wherein the activator comprises a formate brine, an acetate brine, an oxalate brine, a halide brine, or combinations thereof.
36. The wellbore treatment kit of claim 33, wherein the spacer comprises a natural hydrocarbon, a synthetic hydrocarbon, a glycol, a surfactant, fresh water, or combinations thereof.
37. A subterranean well comprising a precipitate disposed therein for at least partially blocking a flow of a wellbore servicing fluid into a subterranean formation penetrated by the well.
38. The subterranean well of claim 37, wherein the precipitate comprises polyvinylpyrrolidone that has been precipitated out of water.
39. The subterranean well of claim 37, wherein the precipitate is capable of being dissolved in water for removing the precipitate from the subterranean well.
40. The subterranean well of claim 37, wherein the wellbore servicing fluid comprises a drilling fluid, a cement composition, a workover fluid, or combinations thereof.
PCT/GB2006/001244 2005-04-19 2006-04-05 Compositions and methods of using a polymeric precipitate to reduce the loss of fluid to a subterranean formation WO2006111703A2 (en)

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