WO2006106298A1 - Fluides comprenant des agents de reticulation d'isopropylamine de zirconium et procedes associes - Google Patents

Fluides comprenant des agents de reticulation d'isopropylamine de zirconium et procedes associes Download PDF

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WO2006106298A1
WO2006106298A1 PCT/GB2006/001075 GB2006001075W WO2006106298A1 WO 2006106298 A1 WO2006106298 A1 WO 2006106298A1 GB 2006001075 W GB2006001075 W GB 2006001075W WO 2006106298 A1 WO2006106298 A1 WO 2006106298A1
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fluid
treatment fluid
zirconium
crosslinking
gelling agent
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Philip C. Harris
Stanley J. Heath
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Halliburton Energy Services Inc
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Halliburton Energy Services Inc
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Priority claimed from US11/101,006 external-priority patent/US7297665B2/en
Priority claimed from US11/100,973 external-priority patent/US7264054B2/en
Application filed by Halliburton Energy Services Inc filed Critical Halliburton Energy Services Inc
Priority to EP06726493A priority Critical patent/EP1885816A1/fr
Publication of WO2006106298A1 publication Critical patent/WO2006106298A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents

Definitions

  • the present invention relates generally to the treatment of subterranean formations with crosslinked treatment fluids, and more particularly to treatment fluids that comprise a zirconium isopropylamine crosslinking agent and associated methods.
  • Fracturing treatments generally involve pumping a crosslinked treatment fluid (e.g., a fracturing fluid) into a subterranean formation at a pressure sufficient to create or enhance one or more fractures in the subterranean formation.
  • the fracturing fluid generally has a viscosity that is sufficient to suspend proppant particulates and to place the proppant particulates in fractures, inter alia, to maintain the integrity of those fractures once the hydraulic pressure is released.
  • the viscosity of the fracturing fluid usually is reduced, and the fluid may be recovered from the formation.
  • Other treatments that use crosslinked treatment fluids include, but are not limited to, sand control treatments (e.g., gravel packing), drilling operations, polymer floods, and forming temporary plugs or blocks in subterranean formations, and the like.
  • Crosslinked treatment fluids generally comprise an aqueous fluid and a crosslinked gelling agent, wherein the crosslinked gelling agent may be the reaction product of a reaction that comprises a gelling agent and a crosslinking agent. This reaction between the gelling agent and the crosslinking agent is commonly referred to as "crosslinking.”
  • Preparation of these crosslinked treatment fluids typically involves combining the aqueous fluid with the gelling agent.
  • An optional buffer also may be included to provide an appropriate pH for hydration of the gelling agent and crosslinking.
  • a crosslinking agent may added for crosslinking one or more gelling agent molecules. Generally, the crosslinking may occur very slowly and/or not at all while the treatment fluid is at or below ambient temperature.
  • ambient temperature refers to a moderate temperature range normally encountered on the surface.
  • certain crosslinking agents such as zirconium lactate, may require temperatures greater than about 85°F to about 9O 0 F to initiate crosslinking.
  • the treatment fluid may be placed into a subterranean formation through a well bore. Because most subterranean formations are relatively hot, e.g., having temperatures in the range of from about 100°F to about 400 0 F, the treatment fluid may be heated as it passes through the well bore and into the subterranean formation.
  • Treatment fluids such as those described above, may be described as delayed crosslinking aqueous gels because crosslinking does not occur or occurs very slowly prior to introduction of the treatment fluid into the well bore.
  • An example of a delayed crosslinking aqueous gel comprises an organic carboxylated gelling agent, an aqueous fluid, a buffer (capable of maintaining the pH of the fluid at about 5 or above), and a zirconium IV-containing crosslinking agent.
  • the aqueous fluid used to form the gelled treatment fluids may be relatively cool (e.g., below about 70°F) and may even have temperatures as low as about 35 0 F. Where these relatively cool aqueous fluids are used, the formation temperatures may not be sufficient to heat the gelled treatment fluids to temperatures suitable for crosslinking while the gelled treatment fluids are resident in the well bore. If these temperatures are not reached, the gelled treatment fluids may be introduced into the subterranean formation with little or no crosslinking, and thus the gelled treatment fluids may not have viscosities sufficient for the particular applications. This problem may be particularly apparent in relatively shallow wells where the time the gelled treatment fluid is resident in the well bore may be short when compared to deeper wells.
  • the present invention relates generally to the treatment of subterranean formations with crosslinked treatment fluids, and more particularly to treatment fluids that comprise a zirconium isopropylamine crosslinking agent and associated methods.
  • An embodiment of the present invention provides a treatment fluid and a method of treating a subterranean formation.
  • the method may comprise providing a fluid having a temperature of less than about 7O 0 F, the fluid comprising an aqueous fluid, a gelling agent, and a zirconium isopropylamine crosslinking agent; allowing at least one crosslink to form in the gelling agent while the fluid has a temperature of less than about 70°F through a reaction that comprises at least a portion of the gelling agent and at least a portion of the zirconium isopropylamine crosslinking agent; and introducing the fluid into a well bore that penetrates the subterranean formation.
  • Another example of such a method may comprise providing a fluid comprising an aqueous fluid, a gelling agent, and a zirconium triisopropylamine crosslinking agent; and introducing the fluid into a well bore that penetrates the subterranean formation.
  • the method may comprise providing a fluid having a temperature of less than about 70 0 F, the fluid comprising an aqueous fluid, a gelling agent, and a zirconium isopropylamine crosslinking agent; allowing at least one crosslink to form in the gelling agent while the fluid has a temperature of less than about 70°F through a reaction that comprises at least a portion of the gelling agent and at least a portion of the zirconium isopropylamine crosslinking agent; and contacting the subterranean formation with the fluid at or above a pressure sufficient to create or enhance one or more fractures in at least a portion of the subterranean formation.
  • Figure 1 is a plot of temperature and viscosity versus time as measured using a Fann® Model 50 viscometer for sample fluids in accordance with one embodiment of the present invention and control sample fluids.
  • Figure 2 is a plot of temperature and viscosity versus time as measured using a Fann® Model 50 viscometer for a sample fluid in accordance with one embodiment of the present invention and a control sample fluid.
  • the present invention relates generally to the treatment of subterranean formations with crosslinked treatment fluids, and more particularly to treatment fluids that comprise a zirconium isopropylamine crosslinking agent and associated methods.
  • the treatment fluids of the present invention generally comprise an aqueous fluid, a gelling agent, and a zirconium isopropylamine crosslinking agent. Under the appropriate conditions ⁇ e.g., pH, temperature, etc.), crosslinking may occur between at least a portion of the gelling agent and at least a portion of the zirconium isopropylamine crosslinking agent to form an at least partially crosslinked gelling agent.
  • a second crosslinking agent may be included in the treatment fluids of the present invention in addition to the zirconium isopropylamine crosslinking agent.
  • Additional additives may be included in the treatment fluid as desired by one skilled in the art, with the benefit of this disclosure, dependent on the particular application. Such additives may include, but are not limited to, buffers, clay control agents, gases, foaming agents, delayed gel breakers, and a variety of other suitable additives.
  • Suitable aqueous fluids used to form the treatment fluids of the present invention include, but are not limited to, saltwater, brines, seawater, freshwater.
  • the aqueous fluid may be from any source, provided that it does not contain components that may adversely affect other components in the treatment fluids of the present invention.
  • gelling agents can be used in conjunction with the methods and compositions of the present invention, including, but not limited to, hydratable polymers that contain one or more functional groups such as hydroxyl, cis-hydroxyl, carboxylic acids, derivatives of carboxylic acids, sulfate, sulfonate, phosphate, phosphonate, amino, or amide.
  • Suitable gelling agents may comprise polymers, synthetic polymers, or a combination thereof.
  • suitable gelling agents may comprise polysaccharides, and derivatives thereof that contain one or more of these monosaccharide units: galactose, mannose, glucoside, glucose, xylose, arabinose, fructose, glucuronic acid, or pyranosyl sulfate.
  • Suitable polysaccharides include, but are not limited to, guar gum and derivatives thereof, such as hydroxyethyl guar, hydroxypropyl guar, carboxymethyl guar, carboxymethylhydroxyethyl guar, and carboxymethylhydroxypropyl guar ("CMHPG"); and a cellulose or a derivative thereof, such as hydroxyethyl cellulose, carboxyethylcellulose, carboxymethylcellulose, and carboxymethylhydroxyethylcellulose; and combinations thereof.
  • the gelling agents comprise an organic carboxylated gelling agent, such as CMHPG.
  • the derivatized cellulose is a cellulose grafted with an allyl or a vinyl monomer, such as those disclosed in United States Patent Nos. 4,982,793; 5,067,565; and 5,122,549, the relevant disclosures of which are incorporated herein by reference.
  • synthetic polymers and copolymers that contain the above- mentioned functional groups may be used. Examples of such synthetic polymers include, but are not limited to, polyacrylate, polymethacrylate, polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone, and derivatives thereof.
  • the gelling agents listed above may be included in the treatments fluids of the present invention separately or in combination.
  • Suitable gelling agents may be present in the treatment fluids of the present invention in an amount sufficient to provide the desired viscosity. In some embodiments, the gelling agents may be present in the treatment fluids of the present invention in an amount in the range of from about 0.01% to about 5% by weight of the aqueous fluid. In certain embodiments, the gelling agents may be present in the treatment fluids of the present invention in an amount in the range of from about 0.01% to about 2% by weight of the aqueous fluid.
  • the zirconium isopropylamine crosslinking agents useful in the present invention may be capable of initiating crosslinking of the gelling agent in the treatment fluids of the present invention at temperatures below about 70°F. In certain embodiments, the zirconium isopropylamine crosslinking agents may be capable of initiating crosslinking at temperatures below about 60 0 F. And in certain embodiments, the zirconium isopropylamine crosslinking agents may be capable of initiating crosslinking at temperatures down to about 35°F.
  • the zirconium isopropylamine crosslinking agents contain at least one zirconium IV ion that is capable of crosslinking at least two gelling agent molecules.
  • Suitable isopropylamine crosslinking agents include, but are not limited to, zirconium triisopropylamine, zirconium triisopropylamine lactate, zirconium diisopropylamine, and zirconium diisopropylamine lactate, and derivatives thereof and combinations thereof. It has been found that the use of zirconium triisopropylamine as a crosslinking agent can initiate crosslinking at low temperatures (e.g., down to about 35 0 F).
  • zirconium isopropylamine crosslinking agents useful in the present invention may be capable of initiating crosslinking under relatively high salt concentrations.
  • a zirconium isopropylamine crosslinking agent useful in the present invention has been show to produce a crosslinked treatment fluid at a pH between about 4 and about 6 while at 50 0 F and in the presence of about 7% KCl.
  • the zirconium isopropylamine crosslinking agents generally are present in the treatment fluids of the present invention, among other things, to provide the desired degree of crosslinking between gelling agent molecules.
  • the zirconium isopropylamine crosslinking agents generally may be present in an amount in the range of from about 0.001% to about 10% by weight of the aqueous fluid.
  • the zirconium isopropylamine crosslinking agents may be present in the treatment fluids of the present invention in an amount in the range of from about 0.01% to about 2% by weight of the aqueous fluid.
  • the treatment fluids of the present invention optionally may comprise a buffer.
  • Buffers may be included in the treatment fluids of the present invention to provide a desired pH, for example, a pH suitable for crosslinking and/or hydration of the gelling agent.
  • the buffer should be capable of maintaining the treatment fluids of the present invention at a pH of between about 4 and about 12. And in certain embodiments, the buffer should be capable of maintaining the pH between about 4 and about 6.
  • buffers may be used to accomplish this task, such as sodium acetate, ammonium acetate, acetic acid, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium or potassium diacetate, sodium hydroxide, potassium hydroxide, and h ' thium hydroxide, and combinations thereof and derivatives thereof.
  • the buffer comprises a mixture of acetic acid and sodium carbonate.
  • the buffer comprises a mixture of acetic acid and ammonium acetate.
  • the buffer may be present in the treatment fluids of the present invention in an amount sufficient to maintain the pH in, or adjust the pH to, a desired value or range. In certain embodiments, the buffer may be present in the treatment fluids of the present invention in an amount in the range of from about 0.001% to about 1% by weight of the aqueous fluid.
  • a second crosslinking agent may be included in the treatment fluids of the present invention in addition to the zirconium isopropylamine crosslinking agent.
  • the second crosslinking agent generally comprises at least one ion that is capable of crosslinking at least two gelling agent molecules.
  • suitable crosslinking agents include, but are not limited to, compounds that can supply boron ions (such as, for example, boric acid, disodium octaborate tetrahydrate, sodium diborate, pentaborates, ulexite and colemanite); compounds that can supply zirconium IV ions (such as, for example, zirconium lactate, zirconium lactate triethanolamine, zirconium carbonate, zirconium acetylacetonate, zirconium malate, zirconium citrate, and polyhydroxy complexes of zirconium); compounds that can supply titanium IV ions (such as, for example, titanium lactate, titanium malate, titanium citrate, titanium ammonium lactate, polyhydroxy complexes of titanium, titanium triethanolamine, and titanium acetylacetonate); aluminum compounds (such as, for example, aluminum lactate or aluminum citrate); antimony compounds; chromium compounds; iron compounds; copper compounds; or zinc compounds; or a combination thereof or
  • the second crosslinking agent comprises a compound that can supply zirconium IV ions, such as a zirconium IV-containing crosslinking agent.
  • zirconium IV ions such as a zirconium IV-containing crosslinking agent.
  • a zirconium IV-containing crosslinking agent An example of a suitable polyhydroxy complex of zirconium is described in U.S. Pat. No. 4,460,751, the relevant disclosure of which is incorporated herein by reference.
  • the zirconium isopropylamine crosslinking may be used, in some embodiments, as an accelerant, for example, if the aqueous fluid is at relatively low temperatures (e.g. , less than about 70 0 F), so that the zirconium isopropylamine crosslinking agent initiates crosslinking at temperatures less than 70 0 F.
  • the second crosslinking agent generally may be present in the treatment fluids of the present invention in an amount sufficient to provide, among other things, the desired degree of crosslinking between gelling agent molecules.
  • the second crosslinking agent may be present in an amount in the range from about 0.001% to about 10% by weight of the aqueous fluid.
  • the second crosslinking agent may be present in the treatment fluids of the present invention in an amount in the range from about 0.01% to about 1% by weight of the aqueous fluid.
  • the treatment fluids of the present invention optionally may be foamed using a suitable gas (such as carbon dioxide, air, or nitrogen, or a combination thereof) and a foaming agent.
  • suitable foaming agents include, but are not limited to, cationic, anionic, nonionic, or amphoteric surfactants, such as, for example, betaines, sulfated or sulfonated alkoxylates, alkyl quaternary amines, alkoxylated linear alcohols, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl alkoxylates, amine oxides, and C 10 -C 20 alkyldiphenyl ether sulfonates, and combinations thereof.
  • foaming agent employed will depend upon the type of formation which is to be fractured, the treatment fluid chosen, and the percentage of gas in the final foam.
  • the foaming agent may be mixed with the treatment fluid of the present invention before the gas is added to facilitate uniform mixing and to assist in stabilizing the two phase structure of the foam.
  • One of ordinary skill in the art, with the benefit of this disclosure, will be able to select the appropriate amount and type of foaming agent and gas for a particular application.
  • the treatment fluids of the present invention may further comprise a delayed gel breaker such as enzyme, oxidizing, acid, or temperature-activated gel breakers.
  • Gel breakers may be used to reduce the viscosity of an aqueous gel once a subterranean treatment is substantially complete.
  • the gel breaker used may be present in the treatment fluids of the present invention in an amount in the range of from about 0.05% to about 10% by weight of the gelling agent.
  • additives may be included in the treatment fluids of the present invention as desired for a particular application.
  • Such additives may include, but are not limited to, proppant particulates, clay control agents, corrosion inhibitors, biocides, friction reducers, gel stabilizers, fluid loss control additives, bactericides, and surfactants, and combinations thereof.
  • Suitable clay control agents include, but are not limited to, potassium chloride, sodium chloride, and tetramethyl ammonium chloride, and combinations thereof and derivatives thereof.
  • An example of a treatment fluid of the present invention comprises an aqueous fluid having a temperature of less than about 7O 0 F, CMHPG in an amount in the range of from about 0.1% to about 1% by weight of the aqueous fluid, a zirconium triisopropylamine crosslinking agent in an amount in the range of from about 0.01% to about 2% by weight of the aqueous fluid, a polyhydroxy complex of zirconium in an amount in the range of from about 0.005% to about 0.5% by weight of the aqueous fluid, a mixture of acetic acid and ammonium acetate in an amount in the range of from about 0.005% to about 0.1% by weight of the aqueous fluid, and potassium chloride in an amount of about 7% by weight of the aqueous fluid, wherein the treatment fluid has pH in the range of from about 4 to about 6.
  • the treatment fluids of the present invention may be prepared using any suitable methodology.
  • preparation of a particular treatment fluid may comprise admixing a gelling agent with an aqueous fluid, combining a buffer with the resulting fluid to adjust and/or maintain the pH at a desired level for crosslinking and/or hydration of the gelling agent, and then combining a zirconium isopropylamine crosslinking agent with the resulting fluid.
  • the mixing of the zirconium isopropylamine crosslinking agent and/or the second crosslinking agent into the treatment fluid may be performed using any suitable methodology.
  • the zirconium isopropylamine crosslinking agent and/or the second crosslinking agent may be combined into the treatment fluid "on the fly," for example the crosslinking agents may be injected into a stream of the treatment fluid comprising the aqueous fluid and the gelling agent during pumping.
  • Other additives, such as those described above, may combined with the treatment fluid of the present invention as desired for a particular application.
  • the treatment fluids may be used for carrying out a variety of subterranean treatments, where a crosslmked treatment fluid may be used, including, but not limited to, fracturing treatments, sand control treatments (e.g., gravel packing), polymer floods, and forming temporary plugs or blocks in subterranean formations, and the like.
  • fracturing treatments e.g., gravel packing
  • polymer floods e.g., polymer floods
  • temporary plugs or blocks in subterranean formations e.g., gravel packing
  • the treatment fluids of the present invention may be used in treating a subterranean formation.
  • An example of such a subterranean treating method comprises: providing a treatment fluid of the present invention that comprises an aqueous fluid, a gelling agent, and a zirconium isopropylamine crosslinking agent; and introducing the treatment fluid into a well bore that penetrates a subterranean formation.
  • Crosslinking may occur between at least a portion of the gelling agent and at least a portion of the zirconium isopropylamine crosslinking agent to form at least one crosslink in the gelling agent.
  • the treatment fluid may contact the subterranean formation at or above a pressure sufficient to create or enhance one or more fractures in at least a portion of the subterranean formation.
  • the treatment fluids of the present invention may be used in subterranean treatments, wherein the aqueous fluid available for use is relatively cool (e.g., less than about 70 0 F).
  • An example of such a subterranean treatment method comprises: providing a treatment fluid having a temperature of less than about 7O 0 F, the treatment fluid comprising an aqueous fluid, a gelling agent, and a zirconium isopropylamine crosslinking agent; allowing at least one crosslink to form in the gelling agent while the treatment fluid has a temperature of less than about 7O 0 F through a reaction that comprises at least a portion of the gelling agent and at least a portion of the zirconium isopropylamine crosslinking agent; and introducing the treatment fluid into a well bore that penetrates a subterranean formation.
  • the crosslinking may occur, under the appropriate conditions (e.g., pH, temperature, etc.), between at least a portion of the gelling agent and at least a portion of the zirconium isopropylamine crosslinking agent to form at least one crosslink in the gelling agent.
  • the crosslinking begins within a few seconds after preparation of the treatment fluid.
  • the crosslinking begins after the treatment fluid has been introduced into the well bore.
  • the crosslinking may begin shortly after preparation of a particular treatment fluid of the present invention and continue after the treatment fluid has been introduced into the well bore.
  • the treatment fluid may comprise a second crosslinking agent so that additional crosslinking may occur, for example, crosslinking may occur between at least a portion of the second crosslinking agent and additional portions of the gelling agent to form additional crosslinked gelling agent.
  • This crosslinking comprising the gelling agent and the second crosslinking agent may occur after the treatment fluid, in certain embodiments, is heated above about 70 0 F by formation temperatures.
  • sample fluids prepared as follows. Four sample fluids (Nos. 1-4) were prepared in a Waring Blendor by dissolving a CMHPG gelling agent in tap water containing 2% KCl by weight. The pH of each sample was adjusted to a pH of about 5 using a mixture of acetic acid and ammonium acetate. One or more crosslinking agents were added to each sample just prior to testing.
  • Viscosity measurements were made using a Farm® Model 50 viscometer equipped with a 420 spring, a 316SS cup, and a B2X bob. Once prepared, 60 ml of the sample fluid at about 75 0 F were transferred to the cup and immersed in the preheated bath on the viscometer. The bath was preheated to 125°F. The cup was set in motion at 106 rpm providing a shear rate of 40 sec "1 on the sample. The viscometer was programmed to maintain a constant shear rate of 40 sec "1 except when performing a shear rate scan. Shear rate scans were measured at 150, 106, 75, 53, 37, 26, and 18 sec “1 with 3 minutes at 40 sec "1 between scans. A plot of temperature ( 0 F) and viscosity (cP at 40 sec "1 ) versus time (min) for each sample is provided in Figure 1.
  • Sample Fluid No. 1 (control) comprised 25 pounds per thousand gallons (lb/Mgal) of a CMHPG gelling agent, 0.5 gallons per thousand gallons (gal/Mgal) of a zirconium lactate crosslinking agent, 1 gal/Mgal of a mixture of acetic acid and ammonium acetate, and 2% KCl by weight. This sample showed no crosslinking until about 90°F.
  • Sample Fluid No. 2 (control) comprised 25 lb/Mgal of a CMHPG gelling agent, 0.85 gal/Mgal of a polyhydroxy complex of zirconium, 1 gal/Mgal of a mixture of acetic acid and ammonium acetate, and 2% KCl by weight. This sample showed only a minor degree of crosslinking below 90°F.
  • Sample Fluid No. 3 comprised 25 lb/Mgal of a CMHPG gelling agent, 0.85 gal/Mgal of a polyhydroxy complex of zirconium, 0.1 gal/Mgal of a zirconium triisopropylamine crosslinking agent, 1 gal/Mgal of a mixture of acetic acid and ammonium acetate, and 2% KCl by weight.
  • the zirconium triisopropylamine was added to the fluid, the initial viscosity at 73 °F increased from about 200 cP to about 400 cP, indicating crosslinking below 90 0 F.
  • Sample Fluid No. 4 comprised 25 lb/Mgal of a CMHPG gelling agent, 0.5 gal/Mgal of a zirconium triisopropylamine crosslinking agent, 1 gal/Mgal of a mixture of acetic acid and ammonium acetate, and 2% KCl by weight.
  • the initial viscosity of this sample was 1300 cP at 74°F, indicating crosslinking below 90 0 F.
  • Sample Fluid No. 4 showed more shear sensitivity than Sample Fluid Nos. 1-3.
  • Example 1 indicates that zirconium isopropylamine crosslinking agents may initiate crosslinking at relatively lower temperatures than in fluids that do not contain the zirconium isopropylamine crosslinking agents.
  • sample fluids were prepared in a Waring Blendor by dissolving 25 lbs/Mgal of a CMHPG gelling agent in tap water containing either 2% KCl by weight, 7% KCl by weight, or 2 gal/Mgal of a tetramethyl ammonium chloride ("TMAC") clay control agent.
  • TMAC tetramethyl ammonium chloride
  • Example 2 indicates that sample fluids containing both a zirconium isopropylamine crosslinking agent and a polyhydroxy complex of zirconium achieve a higher viscosity at stable temperature conditions when compared to sample fluids containing only a polyhydroxy complex of zirconium.
  • EXAMPLE 3
  • sample fluids were prepared as follows. Two sample fluids (Nos. 5 and 6) were prepared in a Waring Blendor by dissolving 25 lbs/Mgal of a CMHPG gelling agent in tap water containing 2 gal/Mgal of a tetramethyl ammonium chloride clay control agent. The pH of each sample was adjusted to a pH of about 5 using 1 gal/Mgal of a mixture of acetic acid and ammonium acetate. Just prior to testing 0.5 gal/Mgal of either a zirconium lactate crosslinking agent or a zirconium triisopropylamine crosslinking agent was added to the sample fluid.
  • Viscosity measurements were made using a Farm® Model 50 viscometer equipped with a 420 spring, a 316SS cup, and a B2X bob. Prior to testing, the blender jar, sample fluid, bob, and cup were chilled in an ice bath at 32°F. 60 ml of the chilled sample fluid were transferred to the cup and immersed in the ice bath on the viscometer. The temperature of the cup was allowed to slowly rise. The cup was set in motion at 106 rpm providing a shear rate of 40 sec "1 on the sample. The viscometer was programmed to maintain a constant shear rate of 40 sec "1 . At about 90 minutes and 115 minutes, the ice bath was exchanged for a warm water bath. A plot of temperature ( 0 F) and viscosity (cP at 40 sec "1 ) versus time (min) for each sample is provided in Figure 2.
  • Sample Fluid No. 5 (control) comprised 25 lb/Mgal of a CMHPG gelling agent, 0.5 gal/Mgal of a zirconium lactate crosslinking agent, 1 gal/Mgal of a mixture of acetic acid and ammonium acetate, and 2 gal/Mgal of a tetramethyl ammonium chloride. This sample showed no crosslinking until the sample temperature reached about 9O 0 F.
  • Sample Fluid No. 6 comprised 25 lb/Mgal of a CMHPG gelling agent, 0.5 gal/Mgal of a zirconium triisopropylamine crosslinking agent, 1 gal/Mgal of a mixture of acetic acid and ammonium acetate, and 2 gal/Mgal of a tetramethyl ammonium chloride. This sample showed crosslinking below 40 0 F.
  • Example 3 indicates that zirconium isopropylamine crosslinking agents may initiate crosslinking at relatively lower temperatures than in fluids that do not contain the zirconium isopropylamine crosslinking agents.
  • sample fluids were prepared as follows. For this series of tests, sample fluids were prepared in a Waring Blendor by dissolving 40 lbs/Mgal of a CMHPG gelling agent in tap water containing 7% KCl by weight. The pH of each sample was adjusted to a pH of about 5 using a mixture of acetic acid and ammonium acetate in an amount of 1 gal/Mgal. Thereafter, 250 ml of the sample fluid were transferred to a 500 ml glass blender jar that was placed on a Chandler blender base, set to turn at 2,200 rpm. The temperature of the jar and the sample was adjusted as indicated in Table 2 for the vortex closure tests.
  • crosslinking agents were added to each sample, and the time to close the vortex and to achieve a static dome, also referred to as rollover, was measured.
  • the type and amount of crosslinking agent included each sample were varied.
  • the crosslinking agents tested included those that supply zirconium IV ions and those that supply titanium ions.
  • the sample fluid was transferred to a beaker and heated to 90°F in a water bath while stirring.
  • the qualitative elastic (lipping) character of the sample fluid was observed as the temperature of the sample fluid increased.
  • the lipping character of each sample fluid was observed at temperature.
  • TlIe Zirconium Lactate used in this sample fluid was CL-23TM crosslinking agent, a product of Halliburton Energy Services.
  • the Zirconium Lactate used in this sample fluid was Tyzor® 217 organic titanate, commercially available from Dupont Specialty Chemicals.
  • Example 4 indicates that zirconium isopropylamine crosslinking agents may initiate crosslinking at relatively lower temperatures than in fluids that do not contain the zirconium isopropylamine crosslinking agents.

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Abstract

La présente invention propose un procédé de traitement d'une formation souterraine. Le procédé peut inclure l'utilisation d'un fluide comprenant un fluide aqueux, un agent gélifiant et un agent de réticulation de triisopropylamine de zirconium et l'introduction de ce fluide dans un trou de sondage qui pénètre dans la formation souterraine. L'invention propose également des procédés de fracturation d'une formation souterraine.
PCT/GB2006/001075 2005-04-07 2006-03-23 Fluides comprenant des agents de reticulation d'isopropylamine de zirconium et procedes associes Ceased WO2006106298A1 (fr)

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EP06726493A EP1885816A1 (fr) 2005-04-07 2006-03-23 Fluides comprenant des agents de reticulation d'isopropylamine de zirconium et procedes associes

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US11/101,006 US7297665B2 (en) 2005-04-07 2005-04-07 Fluids comprising zirconium isopropylamine crosslinking agents and associated methods
US11/100,973 US7264054B2 (en) 2005-04-07 2005-04-07 Fluids comprising zirconium isopropylamine crosslinking agents and associated methods
US11/100,973 2005-04-07
US11/101,006 2005-04-07

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250044A (en) * 1978-06-26 1981-02-10 The Dow Chemical Company Breaker system for high viscosity fluids
US4477360A (en) * 1983-06-13 1984-10-16 Halliburton Company Method and compositions for fracturing subterranean formations
US4664713A (en) * 1984-05-04 1987-05-12 Halliburton Company Composition for and method of altering the permeability of a subterranean formation
EP0302544A2 (fr) * 1987-08-03 1989-02-08 Pumptech N.V. Fluide de fracturation à haute température à base de guar
US5182408A (en) * 1991-04-25 1993-01-26 Zirconium Technology Corporation Process for preparation of stable aqueous solutions of zirconium chelates
WO2002055843A1 (fr) * 2001-01-09 2002-07-18 Bj Services Company Compositions fluides de traitement de puits et procedes d'utilisation de celles-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250044A (en) * 1978-06-26 1981-02-10 The Dow Chemical Company Breaker system for high viscosity fluids
US4477360A (en) * 1983-06-13 1984-10-16 Halliburton Company Method and compositions for fracturing subterranean formations
US4664713A (en) * 1984-05-04 1987-05-12 Halliburton Company Composition for and method of altering the permeability of a subterranean formation
EP0302544A2 (fr) * 1987-08-03 1989-02-08 Pumptech N.V. Fluide de fracturation à haute température à base de guar
US5182408A (en) * 1991-04-25 1993-01-26 Zirconium Technology Corporation Process for preparation of stable aqueous solutions of zirconium chelates
WO2002055843A1 (fr) * 2001-01-09 2002-07-18 Bj Services Company Compositions fluides de traitement de puits et procedes d'utilisation de celles-ci

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Title
See also references of EP1885816A1 *

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