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(12) Patent Application Publication (10) Pub. No.: US 2006/0229213 A1 Harris Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2006/0229213 A1 Harris Et Al US 2006022921.3A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0229213 A1 Harris et al. (43) Pub. Date: Oct. 12, 2006 (54) FLUIDS COMPRISING ZIRCONUM Publication Classification ISOPROPYLAMINE CROSSLINKING AGENTS AND ASSOCATED METHODS (51) Int. Cl. C09K 8/68 (2006.01) (75) Inventors: Phillip C. Harris, Duncan, OK (US); C09K 8/56 (2006.01) Stanley J. Heath, Duncan, OK (US) (52) U.S. Cl. ............................................ 507/271; 507/209 Correspondence Address: Robert A. Kent (57) ABSTRACT 2600 S. 2nd Street Duncan, OK 73536-0440 (US)(US Treatment fluids that may comprise an aqueous fluid, a gelling agent, and a Zirconium triisopropylamine crosslink (73) Assignee: Halliburton Energy Services, Inc. ing agent are provided. Also provided are crosslinking (21) Appl. No.: 11/101,006 agents that may comprise a Zirconium triisopropylamine crosslinking agent, and a Zirconium IV-containing crosslink (22) Filed: Apr. 7, 2005 ing agent. US 2006/02292.13 A1 Oct. 12, 2006 FLUIDS COMPRISING ZRCONUM to about 400° F., the treatment fluid may be heated as it ISOPROPYLAMINE CROSSLINKING AGENTS passes through the well bore and into the Subterranean AND ASSOCATED METHODS formation. As the treatment fluid heats to temperatures greater than ambient temperatures, crosslinking may occur CROSS-REFERENCE TO RELATED to form a crosslinked treatment fluid that may have a desired APPLICATIONS Viscosity for a particular application (e.g., proppant trans port). Treatment fluids. Such as those described above, may 0001. The present invention is related to copending U.S. be described as delayed crosslinking aqueous gels because application Ser. No. Attorney Docket No. HES crosslinking does not occur or occurs very slowly prior to 2004-IP-015962U1 entitled “Fluids Comprising Zirconium introduction of the treatment fluid into the well bore. An Isopropylamine Crosslinking Agents and Associated Meth example of a delayed crosslinking aqueous gel comprises an ods, filed concurrently herewith, the entire disclosure of organic carboxylated gelling agent, an aqueous fluid, a which is incorporated herein by reference. buffer (capable of maintaining the pH of the fluid at about 5 BACKGROUND or above), and a Zirconium IV-containing crosslinking agent. 0006. However, in some instances, the aqueous fluid used 0002 The present invention relates generally to the treat to form the gelled treatment fluids may be relatively cool ment of subterranean formations with crosslinked treatment (e.g., below about 70° F.) and may even have temperatures fluids, and more particularly to treatment fluids that com as low as about 35° F. Where these relatively cool aqueous prise a Zirconium isopropylamine crosslinking agent and fluids are used, the formation temperatures may not be associated methods. sufficient to heat the gelled treatment fluids to temperatures 0003) A variety of subterranean treatments using suitable for crosslinking while the gelled treatment fluids are crosslinked treatment fluids have been developed. One sub resident in the well bore. If these temperatures are not terranean treatment that uses a crosslinked treatment fluid reached, the gelled treatment fluids may be introduced into for stimulating production from a subterranean formation is the Subterranean formation with little or no crosslinking, and a fracturing treatment. Fracturing treatments generally thus the gelled treatment fluids may not have viscosities involve pumping a crosslinked treatment fluid (e.g., a frac sufficient for the particular applications. This problem may turing fluid) into a subterranean formation at a pressure be particularly apparent in relatively shallow wells where Sufficient to create or enhance one or more fractures in the the time the gelled treatment fluid is resident in the well bore subterranean formation. The fracturing fluid generally has a may be short when compared to deeper wells. Viscosity that is sufficient to Suspend proppant particulates and to place the proppant particulates in fractures, interalia, SUMMARY to maintain the integrity of those fractures once the hydrau 0007. The present invention relates generally to the treat lic pressure is released. Once at least one fracture is created ment of subterranean formations with crosslinked treatment and the proppant particulates are substantially in place, the fluids, and more particularly to treatment fluids that com viscosity of the fracturing fluid usually is reduced, and the prise a Zirconium isopropylamine crosslinking agent and fluid may be recovered from the formation. Other treatments associated methods. that use crosslinked treatment fluids include, but are not 0008 An embodiment of the present invention provides limited to, sand control treatments (e.g., gravel packing), a treatment fluid. In an example of such a treatment fluid, the drilling operations, polymer floods, and forming temporary treatment fluid of the present invention may comprise an plugs or blocks in Subterranean formations, and the like. aqueous fluid, a gelling agent, and a Zirconium triisopropy 0004 Crosslinked treatment fluids generally comprise an lamine crosslinking agent. In another example of Such a aqueous fluid and a crosslinked gelling agent, wherein the treatment fluid, the treatment fluid of the present invention crosslinked gelling agent may be the reaction product of a may comprise an aqueous fluid; a buffer; a clay control reaction that comprises a gelling agent and a crosslinking agent; an organic carboxylated gelling agent, a Zirconium agent. This reaction between the gelling agent and the triisopropylamine crosslinking agent; and a Zirconium IV crosslinking agent is commonly referred to as “crosslink containing crosslinking agent; wherein the treatment fluid ing.” Preparation of these crosslinked treatment fluids typi has a pH in the range of from about 4 to about 6. cally involves combining the aqueous fluid with the gelling agent. An optional buffer also may be included to provide an 0009. Another embodiment of the present invention pro appropriate pH for hydration of the gelling agent and vides a crosslinking agent that may comprise a Zirconium crosslinking. Next, a crosslinking agent may added for triisopropylamine crosslinking agent, and a Zirconium IV crosslinking one or more gelling agent molecules. Generally, containing crosslinking agent. the crosslinking may occur very slowly and/or not at all 0010. The features and advantages of the present inven while the treatment fluid is at or below ambient temperature. tion will be apparent to those skilled in the art. While As used herein, “ambient temperature” refers to a moderate numerous changes may be made by those skilled in the art, temperature range normally encountered on the Surface. For Such changes are within the spirit of the invention. instance, certain crosslinking agents, such as Zirconium lactate, may require temperatures greater than about 85° F. BRIEF DESCRIPTION OF THE DRAWINGS to about 90°F. to initiate crosslinking. 0011. These drawings illustrate certain aspects of some of 0005. After preparation, the treatment fluid may be the embodiments of the present invention and should not be placed into a subterranean formation through a well bore. used to limit or define the invention. Because most Subterranean formations are relatively hot, 0012 FIG. 1 is a plot of temperature and viscosity versus e.g., having temperatures in the range of from about 100°F. time as measured using a Fann R. Model 50 viscometer for US 2006/02292.13 A1 Oct. 12, 2006 sample fluids in accordance with one embodiment of the and 5,122,549, the relevant disclosures of which are incor present invention and control sample fluids. porated herein by reference. Additionally, synthetic poly mers and copolymers that contain the above-mentioned 0013 FIG. 2 is a plot of temperature and viscosity versus functional groups may be used. Examples of Such synthetic time as measured using a Fann R. Model 50 viscometer for a polymers include, but are not limited to, polyacrylate, poly sample fluid in accordance with one embodiment of the methacrylate, polyacrylamide, polyvinyl alcohol, and poly present invention and a control sample fluid. vinylpyrrolidone, and derivatives thereof. The gelling agents DESCRIPTION OF PREFERRED listed above may be included in the treatments fluids of the EMBODIMENTS present invention separately or in combination. 0018 Suitable gelling agents may be present in the 0014. The present invention relates generally to the treat treatment fluids of the present invention in an amount ment of subterranean formations with crosslinked treatment sufficient to provide the desired viscosity. In some embodi fluids, and more particularly to treatment fluids that com ments, the gelling agents may be present in the treatment prise a Zirconium isopropylamine crosslinking agent and fluids of the present invention in an amount in the range of associated methods. from about 0.01% to about 5% by weight of the aqueous 0.015 The treatment fluids of the present invention gen fluid. In certain embodiments, the gelling agents may be erally comprise an aqueous fluid, a gelling agent, and a present in the treatment fluids of the present invention in an Zirconium isopropylamine crosslinking agent. Under the amount in the range of from about 0.01% to about 2% by appropriate conditions (e.g., pH, temperature, etc.), weight of the aqueous fluid. crosslinking may occur between at least a portion of the 0019. The zirconium isopropylamine crosslinking agents gelling agent
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