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(12) Patent Application Publication (10) Pub. No.: US 2007/0287641 A1 Cassidy Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2007/0287641 A1 Cassidy Et Al US 20070287641A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2007/0287641 A1 Cassidy et al. (43) Pub. Date: Dec. 13, 2007 (54) ACIDIC TREATMENT FLUIDS AND Publication Classification ASSOCATED METHODS (51) Int. Cl. (75) Inventors: Juanita M. Cassidy, Duncan, OK CO2F 5/10 (2006.01) (US); Jim L. Lane, Duncan, OK (US); Chad E. Kiser, Comanche, (52) U.S. Cl. ....................................................... 507/235 OK (US) Correspondence Address: (57) ABSTRACT Halliburton Energy Services, Inc. 2600 S. 2nd Street Treatment fluids that comprise a phosphorus component Duncan, OK 73536-0440 useful for inhibiting metal corrosion in acidic environments 9 and associated methods of use are provided. An example of (73) Assignee: Halliburton Energy Services, Inc. a method of using Such treatment fluids may comprise providing a treatment fluid that comprises: an aqueous base (21) Appl. No.: 11/448,945 fluid, a weak acid or salt thereof, and a phosphorus compo nent, and introducing the treatment fluid into a Subterranean (22) Filed: Jun. 7, 2006 formation. US 2007/0287641 A1 Dec. 13, 2007 ACDIC TREATMENT FLUIDS AND lems, resort to using corrosion inhibitor formulations that ASSOCATED METHODS may be less effective, or forego the use of certain acidic treatment fluids entirely. BACKGROUND SUMMARY 0001. The present invention relates to methods and com 0006. The present invention relates to methods and com positions for treating Subterranean formations. More par positions for treating Subterranean formations. More par ticularly, the present invention relates to treatment fluids that ticularly, the present invention relates to treatment fluids that comprise a phosphorus component useful, inter alia, for comprise a phosphorus component useful, inter alia, for inhibiting metal corrosion in acidic environments, and asso inhibiting metal corrosion in acidic environments, and asso ciated methods of use. ciated methods of use. 0002 Acidic fluids may be present in a multitude of 0007. In one embodiment, the present invention provides operations in the oil and chemical industry. In these opera a method that comprises: providing a treatment fluid that tions, metal Surfaces in piping, tubing, heat exchangers, and comprises an aqueous base fluid, a weak acid or salt thereof, reactors may be exposed to acidic fluids. Acidic fluids are and a phosphorus component, and introducing the treatment often used as a treating fluid in wells penetrating Subterra fluid into a subterranean formation. nean formations. Such acidic treatment fluids may be used 0008. In another embodiment, the present invention pro in, for example, clean-up operations or stimulation opera vides a method that comprises: providing a treatment fluid tions for oil and gas wells. Acidic stimulation operations that comprises an aqueous base fluid, a weak acid or salt may use these treatment fluids in hydraulic fracturing and thereof, and a phosphorus component, introducing the treat matrix acidizing treatments. As used herein, the term “treat ment fluid into at least a portion of a Subterranean formation, ment fluid refers to any fluid that may be used in an contacting a surface in the Subterranean formation with the application in conjunction with a desired function and/or for treatment fluid, and allowing the treatment fluid to interact a desired purpose. The term “treatment” does not imply any with the surface in the subterranean formation so as to particular action by the fluid or any component thereof. inhibit corrosion of the surface. 0003) Acidic treatment fluids may include a variety of 0009. In another embodiment, the present invention pro acids such as, for example, hydrochloric acid, formic acid, vides a method that comprises: providing a treatment fluid hydrofluoric acid, and the like. While acidic treatment fluids that comprises an aqueous base fluid, a weak acid or salt may be useful for a variety of downhole operations, acidic thereof, and a phosphorus component, providing a surface treatment fluids can be problematic in that they can cause wherein an undesirable Substance resides on the Surface, and corrosion to downhole production tubing, downhole tools, allowing the treatment fluid to contact the surface so that at and other Surfaces in a Subterranean formation. As used least a portion of the undesirable substance is removed. herein, the term “corrosion” refers to any reaction between 0010. The features and advantages of the present inven a material and its environment that causes some deteriora tion will be readily apparent to those skilled in the art. While tion of the material or its properties. Examples of common numerous changes may be made by those skilled in the art, types of corrosion include, but are not limited to, the rusting Such changes are within the spirit of the invention. of metal, the dissolution of a metal in an acidic Solution, and patina development on the Surface of a metal. As used DESCRIPTION OF PREFERRED herein, the term “inhibit” refers to lessening the tendency of EMBODIMENTS a phenomenon to occur and/or the degree to which that phenomenon occurs. The term “inhibit does not imply any 0011. The present invention relates to methods and com particular degree or amount of inhibition. positions for treating Subterranean formations. More par 0004 To combat this potential corrosion problem, an ticularly, the present invention relates to treatment fluids that assortment of corrosion inhibitors have been used to reduce comprise a phosphorus component useful, inter alia, for or prevent corrosion to downhole metals and metal alloys inhibiting metal corrosion in acidic environments, and asso with varying levels of success. A difficulty encountered with ciated methods of use. the use of some corrosion inhibitors is the limited tempera 0012. One of the advantages of the treatment fluids of the ture range over which they may function effectively. For present invention is that they may be more effective than instance, certain conventional antimony-based inhibitor for corrosion inhibitors heretofore used and/or may possess mulations have been limited to temperatures above 270° F. desirable environmental properties for use in downhole and do not appear to function effectively below this tem environments, especially those that may be subject to more perature. stringent environmental regulations. Another advantageous 0005. Another drawback of some conventional corrosion feature of the present invention is that the phosphorus inhibitors is that certain corrosion inhibitors’ components components of the present invention may not require a high may not be compatible with the environmental standards in pH range. For example, in certain embodiments of the Some regions of the world. For example, quaternary ammo present invention, the treatment fluid may have a pH of less nium compounds and "Mannich condensation compounds than about 7. have been used as corrosion inhibitors. However, these 0013 The treatment fluids of the present invention gen compounds generally are not acceptable under stricter envi erally comprise an aqueous base fluid, a weak acid, and a ronmental regulations, such as those applicable in the North phosphorus component. The term “weak acid' is defined Sea region or other regions. Consequently, operators in some herein to include any acidic compound with a pH greater regions may be forced to Suffer increased corrosion prob than 1 that does not dissociate completely in an aqueous US 2007/0287641 A1 Dec. 13, 2007 fluid. The term "phosphorus component' is defined herein to treatment fluid, and/or other factors that will be recognized include anything containing a phosphorus atom or ion or by one of ordinary skill in the art with the benefit of this combination thereof. disclosure. 0014. The aqueous base fluids used in the treatment fluids 0016. The phosphorus component may comprise a phos of the present invention may comprise fresh water, saltwater phorus atom or ion, and a cation (e.g., an antimony, bismuth, (e.g., water containing one or more salts dissolved therein), potassium, Sodium, calcium, magnesium, cesium, or Zinc brine, seawater, or combinations thereof. Generally, the cation). Examples of Suitable phosphorus components water may be from any source, provided that it does not include, but are not limited to, antimony phosphate, bismuth contain components that might adversely affect the stability phosphate, potassium phosphate, sodium phosphate, cal and/or performance of the treatment fluids of the present cium phosphate, magnesium phosphate, cesium phosphate, invention. One of ordinary skill in the art, with the benefit of Zinc phosphate, antimony pyrophosphate, bismuth pyro this disclosure, will recognize what components might phosphate, potassium pyrophosphate, Sodium pyrophos adversely affect the stability and/or performance of the phate, calcium pyrophosphate, magnesium pyrophosphate, treatment fluids of the present invention. cesium pyrophosphate, Zinc pyrophosphate, antimony hypo 0015. A variety of weak acids can be used in conjunction phosphite, bismuth hypophosphite, potassium hypophos with the methods and compositions of the present invention. phite, Sodium hypophosphite, calcium hypophosphite, mag Examples of suitable weak acids include, but are not limited nesium hypophosphite, cesium hypophosphite, Zinc to, formic acid, acetic acid, citric acid, glycolic acid, hypophosphite, antimony polyphosphate, bismuth poly hydroxyacetic acid, lactic acid, hydrofluoric acid, 3-hydrox phosphate, potassium polyphosphate,
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