Drill-in fluids and associated methods

Information

  • Patent Grant
  • 7678742
  • Patent Number
    7,678,742
  • Date Filed
    Wednesday, September 20, 2006
    18 years ago
  • Date Issued
    Tuesday, March 16, 2010
    14 years ago
Abstract
Of the many methods provided herein, the present invention provides a method comprising: providing a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; placing the drill-in fluid in a subterranean formation; and allowing the relative permeability modifier fluid loss control additive to reduce fluid loss from the drill-in fluid to the subterranean formation. Another example is a method of degrading a filter cake in a subterranean formation comprising: providing a filter cake produced by a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; and allowing the degradable bridging agent to degrade.
Description
BACKGROUND OF THE INVENTION

The present invention relates to fluid loss control for drill-in fluids for use in subterranean formations, and more particularly to fluid loss control for drill-in fluids and filter cakes comprising degradable bridging agents, and to methods of using such fluids in subterranean drilling operations.


Many oil and gas wells in unconsolidated or poorly consolidated sandstone formations are completed “open hole,” meaning that the well bores do not contain casing or liners. Although this type of completion allows the produced fluids to flow directly into the well bore, it suffers the disadvantage that the sandface is unsupported and may collapse. Also, selective treatments or remedial operations within the reservoir section may be more difficult.


Unconsolidated or poorly consolidated formations generally are high permeability production intervals and are drilled with specialized fluids referred to in the art as “drill-in fluids.” A drill-in fluid generally comprises two components: particulate solids (e.g., for bridging on the pore throats of the sandstone of the formation); and polymeric components (e.g., for providing viscosity and fluid loss control). Under pressurized downhole conditions, the drill-in fluid may form a filter cake that comprises an acid-soluble portion (e.g., calcium carbonate bridging solids) and a polymeric portion on the face of a portion of the subterranean formation. In most instances, once formed, the integrity of the filter cake should be maintained to provide the necessary fluid loss control and hole stability for subsequent operations. A common subsequent treatment is a gravel pack sand control operation that involves running a screen into the open hole interval, and pumping a gravel pack fluid comprising gravel into the annulus between the screen and open hole to form a gravel pack.


Generally, at some point after the gravel pack is placed, it is desirable to remove the filter cake from the formation face as it may act as an impediment to the production of desirable fluids from the formation. However, degrading the filter cake may be difficult since the screen and gravel pack tend to prevent the components designed to degrade the filter cake from interacting with it. Degrading the filter cake may be even more difficult, considering that the degradation is generally best when it is uniformly accomplished along what may be thousands of feet of open hole. Thus, because the gravel and gravel pack carrier fluid contact the filter cake uniformly across the entire interval, placing components with the gravel pack that are capable of ultimately degrading the filter cake would be desirable if such degradation could be delayed long enough to ensure that the placement of the gravel pack treatment is not jeopardized or high fluid loss rates are not incurred until the completion equipment is installed.


To degrade the acid-soluble particulate portion of the drill-in fluid filter cake, acids or delayed-release acid systems may be used. A common type of delayed-release acid system comprises acid precursors that slowly hydrolyze to form acids that may ultimately degrade the acid-soluble portion of the filter cake. These delayed-release acid systems, however, can be problematic if they degrade the acid-soluble component of the filter cake too slowly or too quickly. Removal of only 1% to 2% of the bridging solids in the filter cake can result in a significant loss of fluid to the surrounding formation. If a delayed-release acid system is designed not to dissolve more than 1% or 2% of the acid-soluble portion of the filter cake in a chosen period of time (e.g., a 12-hour period), then total removal may take days, if not weeks. This is undesirable. On the other hand, if a delayed-release acid system is designed to totally degrade the acid-soluble portion within an acceptable “total cleanup time” (e.g., 24 to 48 hours), it is likely to cause hole instability and potential fluid loss problems during gravel pack placement. To control such fast-acting delayed-release acid systems, buffers (which are mixtures of weak acids and their conjugate bases) may be considered to achieve a delayed interaction of the acid with the acid-soluble portion of the filter cake for a desired time period. However, such buffer systems have met with little success when used with these delayed-release acid systems, inter alia, because the esters may undergo acid- or base-catalyzed hydrolysis at pHs much below or above 7. Also, conventional buffers may suffer when exposed to components, such as calcium carbonate, in the filter cake and, as a result, the acid component of the buffer may be quickly consumed.


Oxidizers have been used to degrade the polymeric portions of filter cakes within desired delay and total cleanup times. Since these oxidizers are not able to degrade the acid-soluble portion of a filter cake, the usefulness of such oxidizer systems generally is limited to cases where the bridging particles that comprise the particulate portion of the filter cake are small enough to flow back through the screen.


High permeability sandstone can be problematic for drill-in fluids because of fluid loss into the formation. Fluid loss is undesirable as it results in more fluid needing to be pumped, which increases expense. Moreover, the fluid that leaks off into the formation can cause damage to the formation, which may decrease permeability and/or productivity.


SUMMARY OF THE INVENTION

The present invention relates to fluid loss control for drill-in fluids for use in subterranean formations, and more particularly to fluid loss control for drill-in fluids and filter cakes comprising degradable bridging agents, and to methods of using such fluids in subterranean drilling operations.


In one embodiment, the present invention provides a method comprising: providing a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; placing the drill-in fluid in a subterranean formation; and allowing the relative permeability modifier fluid loss control additive to reduce fluid loss from the drill-in fluid to the subterranean formation.


In one embodiment, the present invention provides a method of degrading a filter cake in a subterranean formation comprising: providing a filter cake produced by a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; and allowing the degradable bridging agent to degrade.


The features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of the preferred embodiments, which follows.





BRIEF DESCRIPTION OF THE DRAWINGS

These drawings illustrate certain aspects of some of the embodiments of the present invention, and should not be used to limit or define the invention.



FIG. 1 depicts a graphical representation of the results of experiments discussed in the Examples section.





DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention relates to fluid loss control for drill-in fluids for use in subterranean formations, and more particularly to fluid loss control for drill-in fluids and filter cakes comprising degradable bridging agents, and to methods of using such fluids in subterranean drilling operations.


The drill-in fluids of the present invention generally comprise an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole. Optionally, the drill-in fluids can comprise any additional additives suitable for use in such fluids. The term “irreversible” as used herein means that the degradable material once degraded should not recrystallize or reconsolidate while downhole, e.g., the degradable material should degrade in situ but should not recrystallize or reconsolidate in situ. The terms “degradation” or “degradable” refer to both the two relatively extreme cases of hydrolytic degradation that the degradable material may undergo, i.e., heterogeneous (or bulk erosion) and homogeneous (or surface erosion), and any stage of degradation in between these two. This degradation can be a result of, inter alia, a chemical or thermal reaction or a reaction induced by radiation.


The drill-in fluids of the present invention comprise an aqueous base fluid. The aqueous-base fluid component of the fluids of the present invention may include fresh water, saltwater, brine (e.g., saturated saltwater), or seawater. Generally, the water may be from any source provided that it does not contain components that may adversely affect other components in the fluid.


The drill-in fluids of the present invention comprise a viscosifier. A variety of viscosifiers may be included in the drill-in fluids of the present invention. Examples of suitable viscosifiers include, inter alia, biopolymers such as xanthan and succinoglycan, cellulose derivatives such as hydroxyethylcellulose, and guar and its derivatives such as hydroxypropyl guar. Combinations and derivatives of these are suitable as well. In certain preferred embodiments, the viscosifier is xanthan. The viscosifier is present in the drill-in fluids of the present invention in an amount sufficient to suspend the bridging agent and drill cuttings in the drill-in fluid. More particularly, the viscosifier may be present in the drill-in fluids of the present invention in an amount in the range of from about 0.01% to about 1% by weight. In certain preferred embodiments, the viscosifier is present in the drill-in fluid in an amount in the range of from about 0.13% to about 0.30% by weight.


The drill-in fluids of the present invention further comprise a relative permeability modifier fluid loss control additive, also referred to herein as a “relative permeability modifier.” Generally, the relative permeability modifiers useful in the present invention may be any relative permeability modifier that is suitable for use in subterranean operations. After introducing the relative permeability modifier into a portion of the subterranean formation, e.g., with a drill-in fluid of the present invention, it is believed that the relative permeability modifier attaches to surfaces within the porosity of the subterranean formation, so as to reduce the permeability of the portion of the subterranean formation to aqueous fluids without substantially changing its permeability to hydrocarbons. Additionally, in some embodiments, the relative permeability modifier may also facilitate suspension of the bridging agents in the drill-in fluids.


Examples of suitable relative permeability modifiers include water-soluble polymers, with or without hydrophobic or hydrophilic modification. A water-soluble polymer with hydrophobic modification is referred to herein as a “hydrophobically modified polymer.” As used herein, the term “hydrophobic modification,” or “hydrophobically modified,” refers to the incorporation into the hydrophilic polymer structure of hydrophobic groups, wherein the alkyl chain length is from about 4 to about 22 carbons. A water-soluble polymer with hydrophilic modification is referred to herein as a “hydrophilically modified polymer.” As used herein, the term “hydrophilic modification,” or “hydrophilically modified,” refers to the incorporation into the hydrophilic polymer structure of hydrophilic groups, such as to introduce branching or to increase the degree of branching in the hydrophilic polymer. Combinations of hydrophobically modified polymers, hydrophilically modified polymers, and water-soluble polymers without hydrophobic or hydrophilic modification may be included in the relative modifier fluids of the present invention.


The hydrophobically modified polymers useful in the present invention typically have molecular weights in the range of from about 100,000 to about 10,000,000. While these hydrophobically modified polymers have hydrophobic groups incorporated into the hydrophilic polymer structure, they should remain water-soluble. In some embodiments, a mole ratio of a hydrophilic monomer to the hydrophobic compound in the hydrophobically modified polymer is in the range of from about 99.98:0.02 to about 90:10, wherein the hydrophilic monomer is a calculated amount present in the hydrophilic polymer. In certain embodiments, the hydrophobically modified polymers may comprise a polymer backbone, the polymer backbone comprising polar heteroatoms. Generally, the polar heteroatoms present within the polymer backbone of the hydrophobically modified polymers include, but are not limited to, oxygen, nitrogen, sulfur, or phosphorous.


The hydrophobically modified polymers may be synthesized using any suitable method. In one example, the hydrophobically modified polymers may be a reaction product of a hydrophilic polymer and a hydrophobic compound. In another example, the hydrophobically modified polymers may be prepared from a polymerization reaction comprising a hydrophilic monomer and a hydrophobically modified hydrophilic monomer. Those of ordinary skill in the art, with the benefit of this disclosure, will be able to determine other suitable methods for the synthesis of suitable hydrophobically modified polymers.


In certain embodiments, suitable hydrophobically modified polymers may be synthesized by the hydrophobic modification of a hydrophilic polymer. The hydrophilic polymers suitable for forming hydrophobically modified polymers of the present invention should be capable of reacting with hydrophobic compounds. Suitable hydrophilic polymers include, homo-, co-, or terpolymers such as, but not limited to, polyacrylamides, polyvinylamines, poly(vinylamines/vinyl alcohols), alkyl acrylate polymers in general, and derivatives thereof. Additional examples of alkyl acrylate polymers include, but are not limited to, polydimethylaminoethyl methacrylate, polydimethylaminopropyl methacrylamide, poly(acrylamide/dimethylaminoethyl methacrylate), poly(methacrylic acid/dimethylaminoethyl methacrylate), poly(2-acrylamido-2-methyl propane sulfonic acid/dimethylaminoethyl methacrylate), poly(acrylamide/dimethylaminopropyl methacrylamide), poly (acrylic acid/dimethylaminopropyl methacrylamide), and poly(methacrylic acid/dimethylaminopropyl methacrylamide). Combinations and derivatives of these are suitable as well. In certain embodiments, the hydrophilic polymers comprise a polymer backbone and reactive amino groups in the polymer backbone or as pendant groups, the reactive amino groups capable of reacting with hydrophobic compounds. In some embodiments, the hydrophilic polymers comprise dialkyl amino pendant groups. In some embodiments, the hydrophilic polymers comprise a dimethyl amino pendant group and a monomer comprising dimethylaminoethyl methacrylate or dimethylaminopropyl methacrylamide. In certain embodiments of the present invention, the hydrophilic polymers comprise a polymer backbone, the polymer backbone comprising polar heteroatoms, wherein the polar heteroatoms present within the polymer backbone of the hydrophilic polymers include, but are not limited to, oxygen, nitrogen, sulfur, or phosphorous. Suitable hydrophilic polymers that comprise polar heteroatoms within the polymer backbone include homo-, co-, or terpolymers, such as, but not limited to, celluloses, chitosans, polyamides, polyetheramines, polyethyleneimines, polyhydroxyetheramines, polylysines, polysulfones, gums, starches, and derivatives thereof. In one embodiment, the starch is a cationic starch. A suitable cationic starch may be formed by reacting a starch, such as corn, maize, waxy maize, potato, and tapioca, and the like, with the reaction product of epichlorohydrin and trialkylamine. Combinations and derivatives of these are suitable as well.


The hydrophobic compounds that are capable of reacting with the hydrophilic polymers of the present invention include, but are not limited to, alkyl halides, sulfonates, sulfates, organic acids, and organic acid derivatives. Examples of suitable organic acids and derivatives thereof include, but are not limited to, octenyl succinic acid; dodecenyl succinic acid; and anhydrides, esters, imides, and amides of octenyl succinic acid or dodecenyl succinic acid. Combinations and derivatives of these are suitable as well. In certain embodiments, the hydrophobic compounds may have an alkyl chain length of from about 4 to about 22 carbons. In another embodiment, the hydrophobic compounds may have an alkyl chain length of from about 7 to about 22 carbons. In another embodiment, the hydrophobic compounds may have an alkyl chain length of from about 12 to about 18 carbons. For example, where the hydrophobic compound is an alkyl halide, the reaction between the hydrophobic compound and hydrophilic polymer may result in the quaternization of at least some of the hydrophilic polymer amino groups with an alkyl halide, wherein the alkyl chain length is from about 4 to about 22 carbons.


As previously mentioned, in certain embodiments, suitable hydrophobically modified polymers also may be prepared from a polymerization reaction comprising a hydrophilic monomer and a hydrophobically modified hydrophilic monomer. Examples of suitable methods of their preparation are described in U.S. Pat. No 6,476,169, the relevant disclosure of which is incorporated herein by reference. The hydrophobically modified polymers synthesized from the polymerization reactions may have estimated molecular weights in the range of from about 100,000 to about 10,000,000 and mole ratios of the hydrophilic monomer(s) to the hydrophobically modified hydrophilic monomer(s) in the range of from about 99.98:0.02 to about 90:10.


A variety of hydrophilic monomers may be used to form the hydrophobically modified polymers useful in the present invention. Examples of suitable hydrophilic monomers include, but are not limited to acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, vinyl pyrrolidone, dimethylaminoethyl methacrylate, acrylic acid, dimethylaminopropylmethacrylamide, vinyl amine, vinyl acetate, trimethylammoniumethyl methacrylate chloride, methacrylamide, hydroxyethyl acrylate, vinyl sulfonic acid, vinyl phosphonic acid, methacrylic acid, vinyl caprolactam, N-vinylformamide, N,N-diallylacetamide, dimethyldiallyl ammonium halide, itaconic acid, styrene sulfonic acid, methacrylamidoethyltrimethyl ammonium halide, quaternary salt derivatives of acrylamide, and quaternary salt derivatives of acrylic acid. Combinations and derivatives of these are suitable as well.


A variety of hydrophobically modified hydrophilic monomers also may be used to form the hydrophobically modified polymers useful in the present invention. Examples of suitable hydrophobically modified hydrophilic monomers include, but are not limited to, alkyl acrylates, alkyl methacrylates, alkyl acrylamides, alkyl methacrylamides alkyl dimethylammoniumethyl methacrylate halides, and alkyl dimethylammoniumpropyl methacrylamide halides, wherein the alkyl groups have from about 4 to about 22 carbon atoms. Combinations and derivatives of these are suitable as well. In another embodiment, the alkyl groups have from about 7 to about 22 carbons. In another embodiment, the alkyl groups have from about 12 to about 18 carbons. In certain embodiments, the hydrophobically modified hydrophilic monomer comprises octadecyldimethylammoniumethyl methacrylate bromide, hexadecyldimethylammoniumethyl methacrylate bromide, hexadecyldimethylammoniumpropyl methacrylamide bromide, 2-ethylhexyl methacrylate, or hexadecyl methacrylamide. Combinations and derivatives of these are suitable as well.


Suitable hydrophobically modified polymers that may be formed from the above-described reactions include, but are not limited to, acrylamide/octadecyldimethylammoniumethyl methacrylate bromide copolymer, dimethylaminoethyl methacrylate/vinyl pyrrolidone/hexadecyldimethylammoniumethyl methacrylate bromide terpolymer, and acrylamide/2-acrylamido-2-methyl propane sulfonic acid/2-ethylhexyl methacrylate terpolymer. Combinations and derivatives of these are suitable as well. Another suitable hydrophobically modified polymer formed from the above-described reaction is an amino methacrylate/alkyl amino methacrylate copolymer. A suitable dimethlyaminoethyl methacrylate/alkyl-dimethylammoniumethyl methacrylate copolymer is a dimethylaminoethyl methacrylate/hexadecyl-dimethylammoniumethyl methacrylate copolymer. As previously discussed, these copolymers may be formed by reactions with a variety of alkyl halides. For example, in some embodiments, the hydrophobically modified polymer may be a dimethylaminoethyl methacrylate/hexadecyl-dimethylammoniumethyl methacrylate bromide copolymer. Combinations and derivatives of these are suitable as well.


In another embodiment of the present invention, the relative permeability modifier may comprise a water-soluble hydrophilically modified polymer. The hydrophilically modified polymers of the present invention typically have molecular weights in the range of from about 100,000 to about 10,000,000. In certain embodiments, the hydrophilically modified polymers comprise a polymer backbone, the polymer backbone comprising polar heteroatoms. Generally, the polar heteroatoms present within the polymer backbone of the hydrophilically modified polymers include, but are not limited to, oxygen, nitrogen, sulfur, or phosphorous.


The hydrophilically modified polymers may be synthesized using any suitable method. In one example, the hydrophilically modified polymers may be a reaction product of a hydrophilic polymer and a hydrophilic compound. Those of ordinary skill in the art, with the benefit of this disclosure, will be able to determine other suitable methods for the preparation of suitable hydrophilically modified polymers.


In certain embodiments, suitable hydrophilically modified polymers may be formed by additional hydrophilic modification, for example, to introduce branching or to increase the degree of branching, of a hydrophilic polymer. The hydrophilic polymers suitable for forming the hydrophilically modified polymers used in the present invention should be capable of reacting with hydrophilic compounds. In certain embodiments, suitable hydrophilic polymers include, homo-, co-, or terpolymers, such as, but not limited to, polyacrylamides, polyvinylamines, poly(vinylamines/vinyl alcohols), and alkyl acrylate polymers in general. Additional examples of alkyl acrylate polymers include, but are not limited to, polydimethylaminoethyl methacrylate, polydimethylaminopropyl methacrylamide, poly(acrylamide/dimethylaminoethyl methacrylate), poly(methacrylic acid/dimethylaminoethyl methacrylate), poly(2-acrylamido-2-methyl propane sulfonic acid/dimethylaminoethyl methacrylate), poly(acrylamide/dimethylaminopropyl methacrylamide), poly (acrylic acid/dimethylaminopropyl methacrylamide), and poly(methacrylic acid/dimethylaminopropyl methacrylamide). Combinations and derivatives of these are suitable as well. In certain embodiments, the hydrophilic polymers comprise a polymer backbone and reactive amino groups in the polymer backbone or as pendant groups, the reactive amino groups capable of reacting with hydrophilic compounds. In some embodiments, the hydrophilic polymers comprise dialkyl amino pendant groups. In some embodiments, the hydrophilic polymers comprise a dimethyl amino pendant group and at least one monomer comprising dimethylaminoethyl methacrylate or dimethylaminopropyl methacrylamide. In other embodiments, the hydrophilic polymers comprise a polymer backbone comprising polar heteroatoms, wherein the polar heteroatoms present within the polymer backbone of the hydrophilic polymers include, but are not limited to, oxygen, nitrogen, sulfur, or phosphorous. Suitable hydrophilic polymers that comprise polar heteroatoms within the polymer backbone include homo-, co-, or terpolymers, such as, but not limited to, celluloses, chitosans, polyamides, polyetheramines, polyethyleneimines, polyhydroxyetheramines, polylysines, polysulfones, gums, starches, and derivatives thereof. In one embodiment, the starch is a cationic starch. Combinations and derivatives of these are suitable as well. A suitable cationic starch may be formed by reacting a starch, such as corn, maize, waxy maize, potato, tapioca, and the like, with the reaction product of epichlorohydrin and trialkylamine.


The hydrophilic compounds suitable for reaction with the hydrophilic polymers include polyethers that comprise halogens, sulfonates, sulfates, organic acids, and organic acid derivatives. Combinations and derivatives of these are suitable as well. Examples of suitable polyethers include, but are not limited to, polyethylene oxides, polypropylene oxides, and polybutylene oxides, and copolymers, terpolymers, and mixtures thereof. Combinations and derivatives of these are suitable as well. In some embodiments, the polyether comprises an epichlorohydrin-terminated polyethylene oxide methyl ether.


The hydrophilically modified polymers formed from the reaction of a hydrophilic polymer with a hydrophilic compound may have estimated molecular weights in the range of from about 100,000 to about 10,000,000 and may have weight ratios of the hydrophilic polymers to the polyethers in the range of from about 1:1 to about 10:1. Suitable hydrophilically modified polymers having molecular weights and weight ratios in the ranges set forth above include, but are not limited to, the reaction product of polydimethylaminoethyl methacrylate and epichlorohydrin-terminated polyethyleneoxide methyl ether; the reaction product of polydimethylaminopropyl methacrylamide and epichlorohydrin-terminated polyethyleneoxide methyl ether; and the reaction product of poly(acrylamide/dimethylaminopropyl methacrylamide) and epichlorohydrin-terminated polyethyleneoxide methyl ether. Combinations and derivatives of these are suitable as well. In some embodiments, the hydrophilically modified polymer comprises the reaction product of a polydimethylaminoethyl methacrylate and epichlorohydrin-terminated polyethyleneoxide methyl ether having a weight ratio of polydimethylaminoethyl methacrylate to epichlorohydrin-terminated polyethyleneoxide methyl ether of about 3:1.


Sufficient concentrations of a suitable relative permeability modifier should be present in the fluids of the present invention to provide the desired degree of fluid loss control, gravel suspension, and/or viscosity enhancement. In some embodiments, the relative permeability modifier should be included in the fluids of the present invention in an amount in the range of from about 0.02% to about 10% by weight of the fluid. In other embodiments, the relative permeability modifier should be present in the fluids of the present invention in an amount in the range of from about 0.01% to about 1.0% by weight of the fluid. In certain embodiments, the relative permeability modifier may be provided in a concentrated aqueous solution prior to its combination with the other components necessary to form the fluids of the present invention.


In other embodiments of the present invention, the relative permeability modifiers may comprise a water-soluble polymer without hydrophobic or hydrophilic modification. Examples of suitable water-soluble polymers include, but are not limited to, homo-, co-, and terpolymers of acrylamide, 2-acrylamido-2-methyl propane sulfonic acid, N,N-dimethylacrylamide, vinyl pyrrolidone, dimethylaminoethyl methacrylate, acrylic acid, dimethylaminopropylmethacrylamide, vinyl amine, vinyl acetate, trimethylammoniumethyl methacrylate chloride, methacrylamide, hydroxyethyl acrylate, vinyl sulfonic acid, vinyl phosphonic acid, methacrylic acid, vinyl caprolactam, N-vinylformamide, N,N-diallylacetamide, dimethyldiallyl ammonium halide, itaconic acid, styrene sulfonic acid, methacrylamidoethyltrimethyl ammonium halide, quaternary salt derivatives of acrylamide and quaternary salt derivatives of acrylic acid. Combinations and derivatives of these are suitable as well.


The drill-in fluids of the present invention further comprise a degradable bridging agent. The bridging agent becomes suspended in the drill-in fluid and, as the drill-in fluid begins to form a filter cake within the subterranean formation, the bridging agent becomes distributed in the resulting filter cake, most preferably uniformly. In certain preferred embodiments, the filter cake forms upon the face of the formation itself, upon a sand screen, upon a gravel pack, or upon another suitable surface within the subterranean formation or well bore. After the requisite time period dictated by the characteristics of the particular degradable bridging agent used, the degradable bridging agent degrades. This degradation, in effect, causes the degradable bridging agent to be removed from the filter cake, preferably substantially. As a result, voids are created in the filter cake. Removal of the degradable bridging agent from the filter cake should allow produced fluids to flow more freely.


Generally, the degradable bridging agent is present in the drill-in fluid in an amount sufficient to create an efficient filter cake. As referred to herein, the term “efficient filter cake” will be understood to mean a filter cake comprising no material beyond that required to provide a desired level of fluid loss control. In certain embodiments, the degradable bridging agents are present in the drill-in fluid in an amount ranging from about 0.1% to about 32% by weight. In certain preferred embodiments, the degradable bridging agents are present in the drill-in fluid in the range of from about 3% and about 10% by weight. In certain preferred embodiments, the bridging agent is present in the drill-in fluids in an amount sufficient to provide a fluid loss of less than about 15 mL in tests conducted according to the procedures set forth by API Recommended Practice (RP) 13. One of ordinary skill in the art with the benefit of this disclosure will recognize an optimum concentration of degradable material that provides desirable values in terms of enhanced ease of removal of the filter cake at the desired time without undermining the stability of the filter cake during its period of intended use.


The degradable bridging agents comprise a degradable material. Nonlimiting examples of suitable degradable materials that may be used in conjunction with the present invention include, but are not limited to, degradable polymers, dehydrated compounds, and/or mixtures of the two. Combinations and derivatives of these are suitable as well. In choosing the appropriate degradable material, one should consider the degradation products that will result. Also, these degradation products should not adversely affect other operations or components. For example, a boric acid derivative may not be included as a degradable material in the drill-in fluids of the present invention where such fluids utilize xanthan as the viscosifier, because boric acid and xanthan are generally incompatible. One of ordinary skill in the art, with the benefit of this disclosure, will be able to recognize when potential components of the drill-in fluids of the present invention would be incompatible or would produce degradation products that would adversely affect other operations or components.


As for degradable polymers, a polymer is considered to be “degradable” herein if the degradation is due to, inter alia, chemical and/or radical process such as hydrolysis, oxidation, enzymatic degradation, or UV radiation. The degradability of a polymer depends at least in part on its backbone structure. For instance, the presence of hydrolyzable and/or oxidizable linkages in the backbone often yields a material that will degrade as described herein. The rates at which such polymers degrade are dependent on the type of repetitive unit, composition, sequence, length, molecular geometry, molecular weight, morphology (e.g., crystallinity, size of spherulites, and orientation), hydrophilicity, hydrophobicity, surface area, and additives. Also, the environment to which the polymer is subjected may affect how the polymer degrades, e.g., temperature, presence of moisture, oxygen, microorganisms, enzymes, pH, and the like.


Suitable examples of degradable polymers that may be used in accordance with the present invention include but are not limited to those described in the publication of Advances in Polymer Science, Vol. 157 entitled “Degradable Aliphatic Polyesters” edited by A. C. Albertsson, the disclosure of which is hereby incorporated by reference. Specific examples include homopolymers, random, block, graft, and star- and hyper-branched aliphatic polyesters. Such suitable polymers may be prepared by polycondensation reactions, ring-opening polymerizations, free radical polymerizations, anionic polymerizations, carbocationic polymerizations, and coordinative ring-opening polymerization for, e.g., lactones, and any other suitable process. Specific examples of suitable polymers include polysaccharides such as dextrans or celluloses; chitins; chitosans; proteins; orthoesters; aliphatic polyesters; poly(lactides); poly(glycolides); poly(ε-caprolactones); poly(hydroxybutyrates); poly(anhydrides); aliphatic polycarbonates; poly(orthoesters); poly(amino acids); poly(ethylene oxides); and polyphosphazenes. Combinations and derivatives of these are suitable as well. Of these suitable polymers, aliphatic polyesters and polyanhydrides are preferred. Polyanhydrides are another type of particularly suitable degradable polymer useful in the present invention. Polyanhydride hydrolysis proceeds, inter alia, via free carboxylic acid chain-ends to yield carboxylic acids as final degradation products. The erosion time can be varied over a broad range of changes in the polymer backbone. Examples of suitable polyanhydrides include poly(adipic anhydride), poly(suberic anhydride), poly(sebacic anhydride), and poly(dodecanedioic anhydride). Other suitable examples include but are not limited to poly(maleic anhydride) and poly(benzoic anhydride).


Plasticizers may be present in the degradable materials of the present invention. The plasticizers may be present in an amount sufficient to provide the desired characteristics, for example, (a) more effective compatibilization of the melt blend components, (b) improved processing characteristics during the blending and processing steps, and (c) control and regulation of the sensitivity and degradation of the polymer by moisture. Suitable plasticizers include but are not limited to derivatives of oligomeric lactic acid, selected from the group defined by the formula:




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where R is a hydrogen, alkyl, aryl, alkylaryl, acetyl, heteroatom, or a mixture thereof and R is saturated, where R′ is a hydrogen, alkyl, aryl, alkylaryl, acetyl, heteroatom, or a mixture thereof and R′ is saturated, where R and R′ cannot both be hydrogen, where q is an integer: 2≦q≦75; and mixtures thereof. Preferably q is an integer; 2≦q≦10. As used herein the term “derivatives of oligomeric lactic acid” includes derivatives of oligomeric lactide.


Aliphatic polyesters useful in the present invention may be prepared by substantially any of the conventionally known manufacturing methods such as those described in U.S. Pat. Nos. 6,323,307; 5,216,050; 4,387,769; 3,912,692; and 2,703,316, the relevant disclosures of which are incorporated herein by reference. In addition to the other qualities above, the plasticizers may enhance the degradation rate of the degradable polymeric materials.


The physical properties of degradable polymers depend on several factors such as the composition of the repeat units, flexibility of the chain, presence of polar groups, molecular mass, degree of branching, crystallinity, orientation, etc. For example, short chain branches reduce the degree of crystallinity of polymers while long chain branches lower the melt viscosity and impart, inter alia, elongational viscosity with tension-stiffening behavior. The properties of the material utilized can be further tailored by blending, and copolymerizing it with another polymer, or by changing the macromolecular architecture (e.g., hyper-branched polymers, star-shaped, or dendrimers, etc.). The properties of any such suitable degradable polymers (e.g., hydrophobicity, hydrophilicity, rate of degradation, etc.) can be tailored by introducing select functional groups along the polymer chains. For example, poly(phenyllactide) will degrade at about ⅕th of the rate of racemic poly(lactide) at a pH of 7.4 at 55° C. One of ordinary skill in the art with the benefit of this disclosure will be able to determine the appropriate functional groups to introduce to the polymer chains to achieve the desired physical properties of the degradable polymers.


Dehydrated compounds may be used in accordance with the present invention as a degradable material. A dehydrated compound is suitable for use in the present invention if it will degrade over time as it is rehydrated. For example, a particulate solid anhydrous borate material that degrades over time may be suitable. Specific examples of particulate solid anhydrous borate materials that may be used include but are not limited to anhydrous sodium tetraborate (also known as anhydrous borax), and anhydrous boric acid. Combinations and derivatives of these are suitable as well. These anhydrous borate materials are only slightly soluble in water. However, with time and heat in a subterranean environment, the anhydrous borate materials react with the surrounding aqueous fluid and are hydrated. The resulting hydrated borate materials are substantially soluble in water as compared to anhydrous borate materials and as a result degrade in the aqueous fluid. In some instances, the total time required for the anhydrous borate materials to degrade in an aqueous fluid is in the range of from about 8 hours to about 72 hours depending upon the temperature of the subterranean zone in which they are placed.


Blends of certain degradable materials may also be suitable. One example of a suitable blend of materials is a mixture of poly(lactic acid) and sodium borate where the mixing of an acid and base could result in a neutral solution where this is desirable. Another example would include a blend of poly(lactic acid) and boric oxide, a blend of calcium carbonate and poly(lactic) acid, a blend of magnesium oxide and poly(lactic) acid, and the like. In certain preferred embodiments, the degradable material is calcium carbonate plus poly(lactic) acid. Where a mixture including poly(lactic) acid is used, in certain preferred embodiments the poly(lactic) acid is present in the mixture in a stoichiometric amount, e.g., where a mixture of calcium carbonate and poly(lactic) acid is used, the mixture comprises two poly(lactic) acid units for each calcium carbonate unit. Other blends that undergo an irreversible degradation may also be suitable, if the products of the degradation do not undesirably interfere with either the conductivity of the filter cake or with the production of any of the fluids from the subterranean formation.


The choice of degradable material can depend, at least in part, on the conditions of the well, e.g., well bore temperature. For instance, lactides have been found to be suitable for lower temperature wells, including those within the range of about 60° F. to about 150° F., and polylactides have been found to be suitable for well bore temperatures above this range. Dehydrated salts may also be suitable for higher temperature wells.


Also, we have found that a preferable result is achieved if the degradable material degrades slowly over time as opposed to instantaneously. The slow degradation of the degradable material helps, inter alia, to maintain the stability of the filter cake.


The specific features of the degradable material may be modified so as to maintain the filter cake's filtering capability when the filter cake is intact while easing the removal of the filter cake when such removal becomes desirable. In certain embodiments, the degradable material has a particle size distribution in the range of from about 0.1 micron to about 1.0 millimeters. Whichever degradable material is utilized, the bridging agents may have any shape, including but not limited to particles having the physical shape of platelets, shavings, flakes, ribbons, rods, strips, spheroids, toroids, pellets, tablets, or any other physical shape. One of ordinary skill in the art with the benefit of this disclosure will recognize the specific degradable material and the preferred size and shape for a given application.


The fluids of the present invention optionally may comprise gravel particulates suitable for use in subterranean applications. Suitable gravel particulates include, but are not limited to, gravel, natural sand, quartz sand, particulate garnet, glass, ground walnut hulls, nylon pellets, aluminum pellets, bauxite, ceramics, and polymeric materials, and combinations thereof. One having ordinary skill in the art, with the benefit of this disclosure, will recognize the particulate type, size, and amount to use in conjunction with the fluids of the present invention to achieve a desired result. In certain embodiments, the gravel particulates used may be included in the fluids to form a gravel pack downhole. In some embodiments, the gravel particulates may be coated with a resin or tackifying composition, wherein the gravel particulates may form hard, permeable masses in the formation, inter alia, to reduce the migration of formation particulates.


Additional additives may be added to the fluids of the present invention as deemed appropriate for a particular application by one skilled in the art with the benefit of this disclosure. Examples of such additives include, but are not limited to, weighting agents, surfactants, scale inhibitors, antifoaming agents, bactericides, salts, foaming agents, additional fluid loss control additives, gel breakers, shale swelling inhibitors, and combinations thereof.


The fluids of the present invention may be used in a variety of sand control operations where it is desirable to provide fluid loss control, gravel particulate suspension, and/or viscosity enhancement. In some embodiments, where the fluids of the present invention are used with gravel packing and frac packing operations, carrier fluids that comprise an aqueous component, a water-soluble relative permeability modifier, and gravel particulates may be introduced into a well bore so as to create a gravel pack. In certain embodiments, the carrier fluids of the present invention further may comprise a viscosifying agent. Examples of suitable viscosifying agents include, but are not limited to, xanthan, guar or guar derivatives, cellulose derivatives, a viscoelastic surfactant, etc. In other embodiments, no viscosifying agents may be included in the carrier fluids of the present invention and the relative permeability modifier may act to suspend the gravel particulates. In these embodiments, where no viscosifying agent is included in the carrier fluid, the pumping rates of the carrier fluid should be sufficient to place the gravel particulates into the desired location for the gravel pack without the use of viscosifying agents. In one embodiment, the carrier fluid does not comprise a viscosifying agent where the well bore is horizontal. Among other things, the water-soluble relative permeability modifiers present in the carrier fluid may act to provide gravel particulate suspension and/or reduce fluid loss from the carrier fluid into the subterranean formation. Furthermore, the water-soluble relative permeability modifiers may attach to the gravel particulates placed into the well bore, and to surfaces within the subterranean formation during normal leak off from the carrier fluid. In some embodiments, the presence of the water-soluble relative permeability modifiers on the gravel particulates and in the formation may reduce the permeability of those areas to aqueous-based fluids without substantially changing the permeability to hydrocarbons. This may reduce fluid loss into the formation from other fluids (e.g., completion fluids) that may be introduced into the well bore subsequent to the carrier fluid and reduce the subsequent problems associated with water flowing into the well bore from the subterranean formation.


In other embodiments, the fluids of the present invention may be placed into the well bore as a pill either prior to or after the stabilization of unconsolidated formation particulates in a section of the subterranean formation penetrated by the well bore. The formation particulates may be stabilized by any suitable technique, including gravel packing and frac packing. In these embodiments, fluids of the present invention that comprise an aqueous-based component and a relative permeability modifier may be introduced to the well bore that penetrates the section of the subterranean formation to be stabilized. The desired volume of the fluid of the present invention introduced into the well bore is based, inter alia, on several properties of the section to be treated, such as depth and volume of the section, as well as permeability and other physical properties of material in the section. Among other things, the relative permeability modifier included in the fluid of the present invention may attach to surfaces within the subterranean formation during normal leak off from the carrier fluid or to gravel particulates that may have been placed into the well bore. The presence of the water-soluble relative permeability modifiers on the gravel particulates and/or in the formation may reduce the permeability of those areas to aqueous-based fluids without substantially changing the permeability to hydrocarbons. This may reduce fluid loss into the formation from other fluids (e.g., carrier fluids or completion fluids) that may be introduced into the well bore subsequent to the fluid and reduce the subsequent problems associated with water flowing into the well bore from the subterranean formation.


The filter cake formed by the drill-in fluids of the present invention may be removed after a desired amount of time by being contacted with a degrading agent. In certain embodiments, the degrading agent comprises water. The source of the degrading agent may be, inter alia, a drill-in fluid, such as a gravel pack fluid or a completion brine, for instance. In certain embodiments, the source of the degrading agent may be the bridging agent itself. For example, the bridging agent may comprise a water-containing compound. Any compound containing releasable water may be used as the water-containing compound. As referred to herein, the term “releasable water” will be understood to mean water that may be released under desired downhole conditions, including, inter alia, temperature. In certain embodiments, the water-containing compound may be sodium acetate trihydrate, sodium borate decahydrate, sodium carbonate decahydrate, or the like. In certain preferred embodiments, the water-containing compound is sodium acetate trihydrate.


The filter cake formed by the drill-in fluids of the present invention is a “self-degrading” filter cake. As referred to herein, the term “self-degrading filter cake” will be understood to mean a filter cake that may be removed without the need to circulate a separate “clean up” solution or “breaker” through the well bore, such clean up solution or breaker having no purpose other than to degrade the filter cake. Though the filter cakes formed by the drill-in fluids of the present invention constitute “self-degrading” filter cakes, an operator may nevertheless occasionally elect to circulate a separate clean up solution through the well bore under certain circumstances, such as when the operator desires to hasten the rate of degradation of the filter cake. In certain embodiments, the bridging agents of the present invention are sufficiently acid-degradable as to be removed by such treatment.


An example of a method of the present invention comprises: placing a drill-in fluid in a subterranean formation, the drill-in fluid comprising an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; and forming a self-degrading filter cake comprising the bridging agent upon a surface within the formation whereby fluid loss through the self-degrading filter cake is reduced.


Another example of a method of the present invention is a method comprising: providing a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; placing the drill-in fluid in a subterranean formation; and allowing the relative permeability modifier fluid loss control additive to reduce fluid loss from the drill-in fluid to the subterranean formation.


Another example of a method of the present invention comprises a method of drilling an open hole in a subterranean formation, comprising the steps of: circulating through a drill pipe and drill bit a drill-in fluid comprising an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; forming a filter cake comprising the bridging agent upon a surface within the formation; and permitting the filter cake to degrade.


Another example of a method of the present invention is a method of degrading a filter cake in a subterranean formation comprising: providing a filter cake produced by a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole; and allowing the degradable bridging agent to degrade.


An example of a drill-in fluid of the present invention comprises an aqueous base fluid, a viscosifier, a relative permeability modifier fluid loss control additive, and a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole.


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 entire scope of the invention. To facilitate a better understanding of the present invention, the following examples of exemplary embodiments are given. In no way should such examples be read to limit the scope of the invention.


EXAMPLES

The drill-in fluids were made using a standard mud mixing and conditioning procedures. Tables 1 and list the components for each sample. “N-Vis” is a xanthan, and is available from Halliburton Energy Services, Duncan, Okla. “N-Dril HT Plus” is a starch, and is available from Halliburton Energy Services, Duncan, Okla. “Baracarb-50” is a calcium carbonate based bridging agent, and is available from Halliburton Energy Services, Duncan, Okla. “Baracarb-5” is a calcium carbonate bridging agent bridging agent, and is available from Halliburton Energy Services, Duncan, Okla. “HPT-1” is a relative permeability modifier fluid loss control additive, and is available from Halliburton Energy Services, Duncan, Okla. The water, salt, xanthan, and starch were mixed on a Hamilton-Beach blender at high speed for 20 minutes. The remaining ingredients were added at low speed and mixed for an additional five minutes. The mud samples were placed in sealed jars, and then in a 65° C. roller oven for approximately 16 hour.


The drill-in fluid mud recipe without HPT-1 is shown in Table 1.












TABLE 1







Component
Amount




















10% NaCl
336
mL



N-Vis
0.85
g



N Dril HT Plus
7.4
g



PLA Powder
28
g



(6250D, 160 um)



Baracarb-50
14
g



Baracarb-5
10
g










The drill-in fluid mud recipe with HPT-1 is shown in Table 2.












TABLE 2







Component
Amount




















10% NaCl
325
mL



N-Vis
0.85
g



N Dril HT Plus
7.4
g



PLA Powder
28
g



(6250D, 160 um)



Baracarb-50
14
g



Baracarb-5
10
g



HPT-1
11
mL










A standard Model 90B filtration test was performed on the samples at BHST and 500 PSI differential pressure (800 PSI system pressure). Once the system was up to temperature and pressure, the filtrate valve was opened for 60 minutes. The filtrate profile was monitored and analysis was performed on the data. Once the filter cakes were made, the excess mud was poured out of the Model 90B, breaker was added and shut in with the filter cake at temperature. The machine was then programmed to hold a 50 PSI differential pressure on the filter cake at 195° F., and fluid leak off was monitored. We viewed an increase in the fluid leak off rate as an indication of filter cake degradation. FIG. 1 shows the difference in fluid leak off between the samples, with and without HPT-1 added to the drill-in fluid. During the “filter cake making” step, as the bridging particles and polymers form a filter cake there is a “spurt” volume (initial volume measure as the vertical value at 0 minutes), then a filter cake deposition period (the curved part of the chart, from zero to about 20-30 minutes) then the period of cake equilibrium (30+ minutes, straight line part of chart) where the depositional forces equal the erosion forces from the shear shaft. The slope of the straight line portion of the graph is an indication of filter cake thickness and permeability.


Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood as referring to the power set (the set of all subsets) of the respective range of values, and set forth every range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Therefore, the present invention is well adapted to carry out the objects and attain the ends and advantages 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.

Claims
  • 1. A method comprising: providing a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole, and a relative permeability modifier fluid loss control additive, wherein the relative permeability modifier fluid loss control additive comprises a water-soluble hydrophobically modified polymer comprising a reaction product of a hydrophilic polymer and a hydrophobic compound, wherein the mole ratio of the hydrophilic polymer to the hydrophobic compound is in the range of from about 99.98:0.02 to about 90:10;placing the drill-in fluid in a subterranean formation; andallowing the relative permeability modifier fluid loss control additive to reduce fluid loss from the drill-in fluid to the subterranean formation.
  • 2. The method of claim 1 wherein the hydrophobically modified polymer comprises a polymer backbone, the polymer backbone comprising polar heteroatoms.
  • 3. The method of claim 1 wherein the hydrophilic polymer is selected from the group consisting of: polyacrylamide homopolymers; polyacrylamide copolymers; polyacrylamide terpolymers; polyacrylamides; polyvinylamines; poly(vinylamines/vinyl alcohols); alkyl acrylate polymers; polydimethylaminoethyl methacrylate; polydimethylaminopropyl methacrylamide; poly(acrylamide/dimethylaminoethyl methacrylate); poly(methacrylic acid/dimethylaminoethyl methacrylate); poly(2-acrylamido-2-methyl propane sulfonic acid/dimethylaminoethyl methacrylate); poly(acrylamide/dimethylaminopropyl methacrylamide); poly (acrylic acid/dimethylaminopropyl methacrylamide); poly(methacrylic acid/dimethylaminopropyl methacrylamide); celluloses; chitosans; polyamides; polyetheramines; polyethyleneimines; polyhydroxyetheramines; polylysines; polysulfones; gums; starches; cationic starches; and combinations and derivatives thereof.
  • 4. The method of claim 1 wherein the hydrophobic compound is selected from the group consisting of: alkyl halides; sulfonates; sulfates; organic acids; organic acid derivatives; octenyl succinic acid; dodecenyl succinic acid; anhydrides; esters; imides; amides of octenyl succinic acid; amides of dodecenyl succinic acid; and combinations and derivatives thereof.
  • 5. The method of claim 1 wherein the hydrophilic polymer is made from a reaction comprising a hydrophilic monomer selected from the group consisting of: acrylamide; 2-acrylamido-2-methyl propane sulfonic acid; N,N-dimethylacrylamide; vinyl pyrrolidone; dimethylaminoethyl methacrylate; acrylic acid; dimethylaminopropylmethacrylamide; vinyl amine; vinyl acetate; trimethylammoniumethyl methacrylate chloride; methacrylamide; hydroxyethyl acrylate; vinyl sulfonic acid; vinyl phosphonic acid; methacrylic acid; vinyl caprolactam; N-vinylformamide; N,N-diallylacetamide; dimethyldiallyl ammonium halide; itaconic acid; styrene sulfonic acid; methacrylamidoethyltrimethyl ammonium halide; quaternary salt derivatives of acrylamide; quaternary salt derivatives of acrylic acid; and combinations and derivatives thereof.
  • 6. The method of claim 1 wherein the hydrophilic polymer is made from a reaction comprising a hydrophobically modified hydrophilic monomer selected from the group consisting of: alkyl acrylates; alkyl methacrylates; alkyl acrylamides; alkyl methacrylamides alkyl dimethylammoniumethyl methacrylate halides; alkyl dimethylammoniumpropyl methacrylamide halides, wherein the alkyl groups have from about 4 to about 22 carbon atoms; octadecyldimethylammoniumethyl methacrylate bromide; hexadecyldimethylammoniumethyl methacrylate bromide; hexadecyldimethylammoniumpropyl methacrylamide bromide; 2-ethylhexyl methacrylate; hexadecyl methacrylamide; and combinations and derivatives thereof.
  • 7. The method of claim 1 wherein the hydrophobically modified polymer is selected from the group consisting of: acrylamide/octadecyldimethylammoniumethyl methacrylate bromide copolymers; dimethylaminoethyl methacrylate/vinyl pyrrolidonelhexadecyldimethylammoniumethyl methacrylate bromide terpolymers; and acrylamide/2-acrylamido-2-methyl propane sulfonic acid/2-ethylhexyl methacrylate terpolymers; amino methacrylate/alkyl amino methacrylate copolymers; dimethylaminoethyl methacrylatelhexadecyl-dimethylammoniumethyl methacrylate copolymers; and dimethylaminoethyl methacrylateihexadecyl-dimethylammoniumethyl methacrylate bromide copolymers.
  • 8. The method of claim 1 wherein the degradable material is selected from the group consisting of: degradable polymers, dehydrated compounds, and a blend thereof.
  • 9. The method of claim 1 wherein the degradable material is a degradable polymer selected from the group consisting of: aliphatic polyesters; polysaccharides; dextrans; celluloses; chitins; chitosans; proteins; orthoesters; aliphatic polyesters; poly(lactides); poly(glycolides); poly(ecaprolactones); poly(hydroxybutyrates); poly(anhydrides); aliphatic polycarbonates; poly(orthoesters); poly(amino acids); poly(ethylene oxides); polyphosphazenes; poly(adipic anhydride); poly(suberic anhydride); poly(sebacic anhydride); poly(dodecanedioic anhydride); poly(maleic anhydride); poly(benzoic anhydride); and combinations and derivatives thereof.
  • 10. The method of claim 1 wherein the degradable material is a dehydrated compound selected from the group consisting of: anhydrous compounds that degrade over time as they are rehydrated; anhydrous sodium tetraborate; and anhydrous boric acid.
  • 11. The method of claim 1 wherein the drill-in fluid further comprises an additive selected from the group consisting of: gravel particulates; natural sand; quartz sand; particulate garnet; glass; ground walnut hulls; nylon pellets; aluminum pellets; bauxite; ceramics; polymeric materials; weighting agents, surfactants, scale inhibitors, antifoaming agents, bactericides, salts, foaming agents, additional fluid loss control additives, gel breakers, shale swelling inhibitors, and combinations thereof.
  • 12. A method comprising: providing a drill-in fluid that comprises an aqueous base fluid, a viscosifier, a degradable bridging agent comprising a degradable material capable of undergoing an irreversible degradation downhole, and a relative permeability modifier fluid loss control additive, wherein the relative permeability modifier fluid loss control additive comprises a water-soluble hydrophobically modified polymer comprising a polymerization reaction product of a hydrophilic monomer and a hydrophobically modified hydrophilic monomer, wherein the mole ratio of the hydrophilic monomer to the hydrophobically modified hydrophilic monomer is in the range of from about 99.98:0.02 to about 90:10;placing the drill-in fluid in a subterranean formation; andallowing the relative permeability modifier fluid loss control additive to reduce fluid loss from the drill-in fluid to the subterranean formation.
  • 13. The method of claim 12 wherein the hydrophobically modified polymer comprises a polymer backbone, the polymer backbone comprising polar heteroatoms.
  • 14. The method of claim 12 wherein the hydrophilic monomer is selected from the group consisting of: acrylamide; 2-acrylamido-2-methyl propane sulfonic acid; N,N-dimethylacrylamide; vinyl pyrrolidone; dimethylaminoethyl methacrylate; acrylic acid; dimethylaminopropylmethacrylamide; vinyl amine; vinyl acetate; trimethylammoniumethyl methacrylate chloride; methacrylamide; hydroxyethyl acrylate; vinyl sulfonic acid; vinyl phosphonic acid; methacrylic acid; vinyl caprolactam; N-vinylformamide; N,N-diallylacetamide; dimethyldiallyl ammonium halide; itaconic acid; styrene sulfonic acid; methacrylamidoethyltrimethyl ammonium halide; quaternary salt derivatives of acrylamide; quaternary salt derivatives of acrylic acid; and combinations and derivatives thereof.
  • 15. The method of claim 12 wherein the hydrophobically modified hydrophilic monomer is selected from the group consisting of: alkyl acrylates; alkyl methacrylates; alkyl acrylamides; alkyl methacrylamides alkyl dimethylammoniumethyl methacrylate halides; alkyl dimethylammoniumpropyl methacrylamide halides, wherein the alkyl groups have from about 4 to about 22 carbon atoms; octadecyldimethylammoniumethyl methacrylate bromide; hexadecyldimethylammoniumethyl methacrylate bromide; hexadecyldimethylammoniumpropyl methacrylamide bromide; 2-ethylhexyl methacrylate; hexadecyl methacrylamide; combinations and derivatives thereof.
  • 16. The method of claim 12 wherein the hydrophobically modified polymer is selected from the group consisting of: acrylamide/octadecyldimethylammoniumethyl methacrylate bromide copolymers; dimethylaminoethyl methacrylate/vinyl pyrrolidonelhexadecyldimethylammoniumethyl methacrylate bromide terpolymers; and acrylamide/2-acrylamido-2-methyl propane sulfonic acid/2-ethylhexyl methacrylate terpolymers; amino methacrylate/alkyl amino methacrylate copolymers; dimethylaminoethyl methacrylatelhexadecyl-dimethylammoniumethyl methacrylate copolymers; and dimethylaminoethyl methacrylatelhexadecyl-dimethylammoniumethyl methacrylate bromide copolymers.
  • 17. The method of claim 12 wherein the degradable material is selected from the group consisting of: degradable polymers, dehydrated compounds, and/or blend thereof.
  • 18. The method of claim 12 wherein the degradable material is a degradable polymer selected from the group consisting of: aliphatic polyesters; polysaccharides; dextrans; celluloses; chitins; chitosans; proteins; orthoesters; aliphatic polyesters; poly(lactides); poly(glycolides); poly(ecaprolactones); poly(hydroxybutyrates); poly(anhydrides); aliphatic polycarbonates; poly(orthoesters); poly(amino acids); poly(ethylene oxides); polyphosphazenes; poly(adipic anhydride); poly(suberic anhydride); poly(sebacic anhydride); poly(dodecanedioic anhydride); poly(maleic anhydride); poly(benzoic anhydride); and combinations and derivatives thereof.
  • 19. The method of claim 12 wherein the degradable material is a dehydrated compound selected from the group consisting of: anhydrous compounds that degrade over time as they are rehydrated; anhydrous sodium tetraborate; and anhydrous boric acid.
  • 20. The method of claim 12 wherein the drill-in fluid further comprises an additive selected from the group consisting of: gravel particulates; natural sand; quartz sand; particulate garnet; glass; ground walnut hulls; nylon pellets; aluminum pellets; bauxite; ceramics; polymeric materials; weighting agents, surfactants, scale inhibitors, antifoaming agents, bactericides, salts, foaming agents, additional fluid loss control additives, gel breakers, shale swelling inhibitors, and combinations thereof.
  • 21. A method of degrading a filter cake in a subterranean formation comprising: providing a filter cake produced by a drill-in fluid that comprises: an aqueous base fluid;a viscosifier;a degradable bridging agent that comprises a degradable material selected from the group consisting of: a degradable polymer, a dehydrated compound, and a blend thereof; anda relative permeability modifier fluid loss control additive selected from the group consisting of: a water-soluble hydrophobically modified polymer comprising a reaction product of a hydrophilic polymer and a hydrophobic compound, wherein the mole ratio of the hydrophilic polymer to the hydrophobic compound is in the range of from about 99.98:0.02 to about 90:10, anda water-soluble hydrophobically modified polymer comprising a polymerization reaction product of a hydrophilic monomer and a hydrophobically modified hydrophilic monomer, wherein the mole ratio of the hydrophilic monomer to the hydrophobically modified hydrophilic monomer is in the range of from about 99.98:0.02 to about 90:10; andallowing the degradable bridging agent to degrade.
US Referenced Citations (326)
Number Name Date Kind
2239671 Woodhouse Apr 1941 A
2703316 Palmer Mar 1955 A
2863832 Perrine Dec 1958 A
2910436 Fall et al. Oct 1959 A
3015680 Isler et al. Jan 1962 A
3173484 Huitt et al. Mar 1965 A
3195635 Fast Jul 1965 A
3215199 Dilgren Nov 1965 A
3251415 Bombardieri et al. May 1966 A
3272650 Mac Vittie Sep 1966 A
3302719 Fischer Feb 1967 A
3307630 Dilgren et al. Mar 1967 A
3297090 Dilgren Oct 1967 A
3364995 Atkins et al. Jan 1968 A
3366178 Malone et al. Jan 1968 A
3382924 Veley et al. May 1968 A
3434971 Atkins Mar 1969 A
3441085 Gidley Apr 1969 A
3451818 Wareham Jun 1969 A
3455390 Gallus Jul 1969 A
3658832 Asato et al. Apr 1972 A
3744566 Szabo et al. Jul 1973 A
3784585 Schmitt et al. Jan 1974 A
3819525 Hatterbrun Jun 1974 A
3828854 Templeton et al. Aug 1974 A
3868998 Lybarger et al. Mar 1975 A
3910862 Barabas et al. Oct 1975 A
3912692 Casey et al. Oct 1975 A
3948672 Harnsberger Apr 1976 A
3955993 Curtice May 1976 A
3960736 Free et al. Jun 1976 A
3968840 Tate Jul 1976 A
3998272 Maly Dec 1976 A
3998744 Arnold et al. Dec 1976 A
4068718 Cooke, Jr. et al. Jan 1978 A
4129183 Kalfoglou Dec 1978 A
4142595 Anderson et al. Mar 1979 A
4152274 Phillips et al. May 1979 A
4158521 Anderson et al. Jun 1979 A
4158726 Kamada et al. Jun 1979 A
4169798 DeMartino Oct 1979 A
4172066 Zweigle et al. Oct 1979 A
4261421 Watanabe Apr 1981 A
4299710 Dupre et al. Nov 1981 A
4366071 McLaughlin et al. Dec 1982 A
4366072 McLaughlin et al. Dec 1982 A
4366073 McLaughlin et al. Dec 1982 A
4366074 McLaughlin et al. Dec 1982 A
4374739 McLaughlin et al. Feb 1983 A
4387769 Erbstoesser et al. Jun 1983 A
4393939 Smith et al. Jul 1983 A
4395340 McLaughlin Jul 1983 A
4401789 Gideon Aug 1983 A
4439334 Borchardt Mar 1984 A
4440649 Loftin et al. Apr 1984 A
4447342 Borchardt et al. May 1984 A
4460052 Gockel Jul 1984 A
4460627 Weaver et al. Jul 1984 A
4462718 McLaughlin et al. Jul 1984 A
4470915 Conway Sep 1984 A
4498995 Gockel Feb 1985 A
4526695 Erbstoesser et al. Jul 1985 A
4532052 Weaver et al. Jul 1985 A
4536297 Loftin et al. Aug 1985 A
4536303 Borchardt Aug 1985 A
4536305 Borchardt et al. Aug 1985 A
4552670 Lipowski et al. Nov 1985 A
4554081 Borchardt et al. Nov 1985 A
4563292 Borchardt Jan 1986 A
4604216 Irvin et al. Aug 1986 A
4627926 Peiffer et al. Dec 1986 A
4671883 Connell Jun 1987 A
4693639 Hollenbeak et al. Sep 1987 A
4694905 Armbruster Sep 1987 A
4699722 Dymond et al. Oct 1987 A
4715967 Bellis Dec 1987 A
4716964 Erbstoesser et al. Jan 1988 A
4730028 Bock et al. Mar 1988 A
4785884 Armbruster Nov 1988 A
4797262 Dewitz Jan 1989 A
4809783 Hollenbeck et al. Mar 1989 A
4817721 Pober Apr 1989 A
4828726 Himes et al. May 1989 A
4843118 Lai et al. Jun 1989 A
4848467 Cantu et al. Jul 1989 A
4886354 Welch et al. Dec 1989 A
4957165 Cantu et al. Sep 1990 A
4959432 Fan et al. Sep 1990 A
4961466 Himes et al. Oct 1990 A
4986353 Clark et al. Jan 1991 A
4986354 Cantu et al. Jan 1991 A
4986355 Casad et al. Jan 1991 A
5071934 Peiffer Dec 1991 A
5082056 Tackett, Jr. Jan 1992 A
5097904 Himes et al. Mar 1992 A
5142023 Gruber et al. Aug 1992 A
5146986 Dalrymple Sep 1992 A
5160642 Schield et al. Nov 1992 A
5197544 Himes Mar 1993 A
5208216 Williamson et al. May 1993 A
5211234 Floyd May 1993 A
5216050 Sinclair Jun 1993 A
5244042 Dovan et al. Sep 1993 A
5247059 Gruber et al. Sep 1993 A
5249628 Surjaatmadja Oct 1993 A
5271466 Harms Dec 1993 A
5295542 Cole et al. Mar 1994 A
5325923 Surjaatmadja et al. Jul 1994 A
5330005 Card et al. Jul 1994 A
5342530 Aften et al. Aug 1994 A
5359026 Gruber Oct 1994 A
5360068 Sprunt et al. Nov 1994 A
5363916 Himes et al. Nov 1994 A
5373901 Norman et al. Dec 1994 A
5379841 Pusch et al. Jan 1995 A
5382371 Szabo et al. Jan 1995 A
5386874 Laramay et al. Feb 1995 A
5396957 Surjaatmadja et al. Mar 1995 A
5402846 Jennings, Jr. et al. Apr 1995 A
5439055 Card et al. Aug 1995 A
5460226 Lawton et al. Oct 1995 A
5464060 Hale et al. Nov 1995 A
5475080 Gruber et al. Dec 1995 A
5484881 Gruber et al. Jan 1996 A
5497830 Boles et al. Mar 1996 A
5499678 Surjaatmadja et al. Mar 1996 A
5504235 Hirose et al. Apr 1996 A
5505787 Yamaguchi Apr 1996 A
5512071 Yam et al. Apr 1996 A
5536807 Gruber et al. Jul 1996 A
5591700 Harris et al. Jan 1997 A
5594095 Gruber et al. Jan 1997 A
5597783 Audibert et al. Jan 1997 A
5604186 Hunt et al. Feb 1997 A
5607902 Smith et al. Mar 1997 A
5607905 Dobson, Jr. et al. Mar 1997 A
5637556 Argillier et al. Jun 1997 A
5646093 Dino Jul 1997 A
5669456 Audibert et al. Sep 1997 A
5670473 Scepanski Sep 1997 A
5698322 Tsai et al. Dec 1997 A
5720347 Audibert et al. Feb 1998 A
5728653 Audibert et al. Mar 1998 A
5735349 Dawson et al. Apr 1998 A
5765642 Surjaatmadja Jun 1998 A
5791415 Nguyen et al. Aug 1998 A
5833000 Weaver et al. Nov 1998 A
5849401 El-Afandi et al. Dec 1998 A
5853048 Weaver et al. Dec 1998 A
5887653 Bishop et al. Mar 1999 A
5893416 Read Apr 1999 A
5908073 Nguyen et al. Jun 1999 A
5909774 Griffith et al. Jun 1999 A
5924488 Nguyen et al. Jul 1999 A
5944106 Dalrymple et al. Aug 1999 A
5964291 Bourne et al. Oct 1999 A
5972848 Audibert et al. Oct 1999 A
5979557 Card et al. Nov 1999 A
6004400 Bishop et al. Dec 1999 A
6020289 Dymond Feb 2000 A
6024170 McCabe et al. Feb 2000 A
6028113 Scepanski Feb 2000 A
6047772 Weaver et al. Apr 2000 A
6070664 Dalrymple et al. Jun 2000 A
6114410 Betzold Sep 2000 A
6123965 Jacob et al. Sep 2000 A
6124245 Patel Sep 2000 A
6131661 Conner et al. Oct 2000 A
6135987 Tsai et al. Oct 2000 A
6143698 Murphey et al. Nov 2000 A
6162766 Muir et al. Dec 2000 A
6169058 Le et al. Jan 2001 B1
6172011 Card et al. Jan 2001 B1
6187839 Eoff et al. Feb 2001 B1
6189615 Sydansk Feb 2001 B1
6202751 Chatterji et al. Mar 2001 B1
6209643 Nguyen et al. Apr 2001 B1
6209646 Reddy et al. Apr 2001 B1
6214773 Harris et al. Apr 2001 B1
6228812 Dawson et al. May 2001 B1
6237687 Barbee, Jr. et al. May 2001 B1
6242390 Mitchell et al. Jun 2001 B1
6253851 Schroeder, Jr. et al. Jul 2001 B1
6260622 Blok et al. Jul 2001 B1
6277900 Oswald et al. Aug 2001 B1
6283210 Soliman et al. Sep 2001 B1
6291013 Gibson et al. Sep 2001 B1
6311773 Todd et al. Nov 2001 B1
6323307 Bigg et al. Nov 2001 B1
6326458 Gruber et al. Dec 2001 B1
6328105 Betzold Dec 2001 B1
6357527 Norman et al. Mar 2002 B1
6359047 Thieu et al. Mar 2002 B1
6364016 Dalrymple et al. Apr 2002 B1
6364945 Chatterji et al. Apr 2002 B1
6380137 Heier et al. Apr 2002 B1
6380138 Ischy et al. Apr 2002 B1
6387986 Moradi-Araghi et al. May 2002 B1
6390195 Nguyen et al. May 2002 B1
6394185 Constien May 2002 B1
6422314 Todd et al. Jul 2002 B1
6454003 Chang et al. Sep 2002 B1
6476169 Eoff et al. Nov 2002 B1
6476283 Devore et al. Nov 2002 B1
6485947 Rajgarhia et al. Nov 2002 B1
6488763 Brothers et al. Dec 2002 B2
6494263 Todd Dec 2002 B2
6497283 Eoff et al. Dec 2002 B1
6508305 Brannon et al. Jan 2003 B1
6509301 Vollmer et al. Jan 2003 B1
6516885 Munday Feb 2003 B1
6527051 Reddy et al. Mar 2003 B1
6554071 Reddy et al. Apr 2003 B1
6569814 Brady et al. May 2003 B1
6569983 Treybig et al. May 2003 B1
6599863 Palmer et al. Jul 2003 B1
6609578 Patel et al. Aug 2003 B2
6627719 Whipple et al. Sep 2003 B2
6667279 Hessert et al. Dec 2003 B1
6669771 Tokiwa et al. Dec 2003 B2
6681856 Chatterji et al. Jan 2004 B1
6686328 Binder Feb 2004 B1
6702023 Harris et al. Mar 2004 B1
6710019 Sawdon et al. Mar 2004 B1
6710107 Audibert et al. Mar 2004 B2
6761218 Nguyen et al. Jul 2004 B2
6763888 Harris et al. Jul 2004 B1
6787506 Blair et al. Sep 2004 B2
6793018 Dawson et al. Sep 2004 B2
6803348 Jones et al. Oct 2004 B2
6817414 Lee Nov 2004 B2
6855672 Poelker et al. Feb 2005 B2
6896058 Munoz, Jr. et al. May 2005 B2
6949491 Cooke, Jr. Sep 2005 B2
6983801 Dawson et al. Jan 2006 B2
6997259 Nguyen et al. Feb 2006 B2
7021377 Todd et al. Apr 2006 B2
7036586 Roddy et al. May 2006 B2
7093664 Todd et al. Aug 2006 B2
7398825 Nguyen et al. Jul 2008 B2
20010016562 Muir et al. Aug 2001 A1
20020036088 Todd Mar 2002 A1
20020125012 Dawson et al. Sep 2002 A1
20030019627 Qu et al. Jan 2003 A1
20030060374 Cooke, Jr. Mar 2003 A1
20030104948 Poelker et al. Jun 2003 A1
20030114314 Ballard et al. Jun 2003 A1
20030130133 Vollmer Jul 2003 A1
20030188766 Banerjee et al. Oct 2003 A1
20030191030 Blair et al. Oct 2003 A1
20030234103 Lee et al. Dec 2003 A1
20040014607 Sinclair et al. Jan 2004 A1
20040040706 Hossaini et al. Mar 2004 A1
20040045712 Eoff et al. Mar 2004 A1
20040055747 Lee Mar 2004 A1
20040070093 Mathiowitz et al. Apr 2004 A1
20040094300 Sullivan et al. May 2004 A1
20040102331 Chan et al. May 2004 A1
20040106525 Willberg et al. Jun 2004 A1
20040138068 Rimmer et al. Jul 2004 A1
20040152601 Still et al. Aug 2004 A1
20040152602 Boles Aug 2004 A1
20040162386 Altes et al. Aug 2004 A1
20040171495 Zamora et al. Sep 2004 A1
20040214724 Todd et al. Oct 2004 A1
20040216876 Lee Nov 2004 A1
20040220058 Eoff et al. Nov 2004 A1
20040229756 Eoff et al. Nov 2004 A1
20040229757 Eoff et al. Nov 2004 A1
20040231845 Cooke, Jr. Nov 2004 A1
20040261993 Nguyen Dec 2004 A1
20040261995 Nguyen et al. Dec 2004 A1
20040261996 Munoz, Jr. et al. Dec 2004 A1
20040261999 Nguyen Dec 2004 A1
20050000694 Dalrymple et al. Jan 2005 A1
20050006095 Justus et al. Jan 2005 A1
20050028976 Nguyen Feb 2005 A1
20050034861 Saini et al. Feb 2005 A1
20050034865 Todd et al. Feb 2005 A1
20050034868 Frost et al. Feb 2005 A1
20050045328 Frost et al. Mar 2005 A1
20050059556 Munoz, Jr. et al. Mar 2005 A1
20050059557 Todd et al. Mar 2005 A1
20050059558 Blauch et al. Mar 2005 A1
20050103496 Todd et al. May 2005 A1
20050126780 Todd et al. Jun 2005 A1
20050126785 Todd Jun 2005 A1
20050130848 Todd et al. Jun 2005 A1
20050155796 Eoff et al. Jul 2005 A1
20050161220 Todd et al. Jul 2005 A1
20050164894 Eoff et al. Jul 2005 A1
20050167104 Roddy et al. Aug 2005 A1
20050167105 Roddy et al. Aug 2005 A1
20050178549 Eoff et al. Aug 2005 A1
20050183741 Surjaatmadja et al. Aug 2005 A1
20050199396 Sierra et al. Sep 2005 A1
20050205258 Reddy et al. Sep 2005 A1
20050205266 Todd et al. Sep 2005 A1
20050230114 Eoff et al. Oct 2005 A1
20050230116 Eoff et al. Oct 2005 A1
20050252659 Sullivan et al. Nov 2005 A1
20050272613 Cooke, Jr. Dec 2005 A1
20050274517 Blauch et al. Dec 2005 A1
20050277554 Blauch et al. Dec 2005 A1
20050279502 Eoff et al. Dec 2005 A1
20050284632 Dalrymple et al. Dec 2005 A1
20060016596 Pauls et al. Jan 2006 A1
20060032633 Nguyen Feb 2006 A1
20060046938 Harris et al. Mar 2006 A1
20060048938 Kalman Mar 2006 A1
20060065397 Nguyen et al. Mar 2006 A1
20060105917 Munoz, Jr. et al. May 2006 A1
20060105918 Munoz, Jr. et al. May 2006 A1
20060169182 Todd et al. Aug 2006 A1
20060169449 Mang et al. Aug 2006 A1
20060169450 Mang et al. Aug 2006 A1
20060172893 Todd et al. Aug 2006 A1
20060172894 Mang et al. Aug 2006 A1
20060172895 Mang et al. Aug 2006 A1
20060185847 Saini et al. Aug 2006 A1
20060185848 Surjaatmadja et al. Aug 2006 A1
20080070805 Munoz et al. Mar 2008 A1
20080070807 Munoz et al. Mar 2008 A1
20080139411 Harris et al. Jun 2008 A1
20080173448 Nguyen et al. Jul 2008 A1
20080196897 Nguyen Aug 2008 A1
Foreign Referenced Citations (37)
Number Date Country
2 250 552 Apr 1974 DE
0 510 762 Oct 1992 EP
0 383 337 Apr 1996 EP
0 879 935 Nov 1998 EP
0 879 935 Feb 1999 EP
0 896 122 Feb 1999 EP
1 033 378 Sep 2000 EP
1 193 365 Apr 2002 EP
1 312 753 May 2003 EP
1 413 710 Apr 2004 EP
2 221 940 Feb 1990 GB
2 335 428 Sep 1999 GB
2 412 389 Mar 2004 GB
WO 9315164 Aug 1993 WO
WO 9407949 Apr 1994 WO
WO 9408078 Apr 1994 WO
WO 9408090 Apr 1994 WO
WO 9509879 Apr 1995 WO
WO 9711845 Apr 1997 WO
WO 9927229 Jun 1999 WO
WO 9949183 Sep 1999 WO
WO 9950530 Oct 1999 WO
WO 0057022 Sep 2000 WO
WO 0078890 Dec 2000 WO
WO 0102698 Jan 2001 WO
WO 0187797 Nov 2001 WO
WO 02055843 Jan 2002 WO
WO 0212674 Feb 2002 WO
WO 02097236 Dec 2002 WO
WO 03027431 Apr 2003 WO
WO 03056130 Jul 2003 WO
WO 2004007905 Jan 2004 WO
WO 2004037946 May 2004 WO
WO 2004038176 May 2004 WO
WO 2004094781 Nov 2004 WO
WO 2004101706 Nov 2004 WO
WO 03027431 Apr 2006 WO
Related Publications (1)
Number Date Country
20080070805 A1 Mar 2008 US