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WO 2007/034155 Al (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date PCT (10) International Publication Number 29 March 2007 (29.03.2007) WO 2007/034155 Al (51) International Patent Classification: 11th Street, Duncan, OK 73533 (US). FROST, Keith, A. C23F 11/04 (2006.01) C23F 11/10 (2006.01) [US/US]; Rt. 2, Box 82, Duncan, OK 73533 (US). C23F 11/08 (2006.01) E21B 41/02 (2006.01) C23F 11/18 (2006.01) (74) Agents: CURTIS, Philip, Anthony et al.; A A Thornton & Co., 235 High Holborn, London WClV 7LE (GB). (21) International Application Number: PCT/GB2006/003454 (81) Designated States (unless otherwise indicated, for every kind of national protection available): AE, AG, AL, AM, (22) International Filing Date: AT,AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN, 18 September 2006 (18.09.2006) CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, HN, HR, HU, ID, IL, IN, IS, JP, (25) Filing Language: English KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT, LU, LV,LY,MA, MD, MG, MK, MN, MW, MX, MY, MZ, (26) Publication Language: English NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, TN, TR, (30) Priority Data: TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW 11/235,397 26 September 2005 (26.09.2005) US 11/234,997 26 September 2005 (26.09.2005) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant (for all designated States except US): HAL¬ GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, LIBURTON ENERGY SERVICES, INC. [US/US]; P O ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), Box 1431, Ducanon, OK 73533 (US). European (AT,BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HU, IE, IS, IT, LT, LU, LV,MC, NL, PL, PT, (71) Applicant (for M W only): CURTIS, Philip, Anthony RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, [GB/GB] ; A A Thornton & Co, 235 High Holborn, London GN, GQ, GW, ML, MR, NE, SN, TD, TG). WClV 7LE (GB). Published: (72) Inventors; and — with international search report (75) Inventors/Applicants (for US only): CASSIDY, Juanita, M. [US/US]; 930 Woodside Drive, Duncan, OK 73533 For two-letter codes and other abbreviations, refer to the "G uid (US). KISER, Chad, E. [US/US]; Rt 2 Box 535, Co- ance Notes on Codes and Abbreviations" appearing at the beg in manche OK 73529 (US). LANE, Jim, L. [US/US] ; 511N. ning of each regular issue of the PCT Gazette. (54) Title: CORROSION INHIBITOR COMPOSITIONS AND ASSOCIATED METHODS (57) Abstract: Corrosion inhibitor compositions may include certain combinations of the following components: a group 15 metal source, a cinnamaldehyde compound, an additional aldehyde compound, an acetylenic compound, a surfactant, an iodide source, and a solvent. Certain embodiments may omit one or more of these components. The inhibitor corrosion compositions may possess desirable environmental properties particularly for use in downhole environments. The corrosion inhibitor compositions herein do not require the presence of quaternary ammonium compounds or "Mannich" condensation compounds. CORROSION INHIBITOR COMPOSITIONS AND ASSOCIATED METHODS BACKGROUND The present invention relates to corrosion inhibitor compositions for inhibiting the corrosion of metals and more particularly, to corrosion inhibitor compositions useful for inhibiting metal corrosion in acidic environments and associated methods. Acidic treatment fluids may be used for a multitude of operations in the oil and chemical industry. Metal surfaces exposed to acidic treatment fluids include piping and tubing used in industrial chemical equipment such as, for example, in heat exchangers and reactors. Acidic treatment fluids are also often used as a treating fluid in wells penetrating subterranean formations. Such acidic treatment fluids may include, for example, acidic clean-up fluids or stimulation fluids for oil and gas wells. Acidic stimulation fluids may include, for example, fluids used in hydraulic fracturing and matrix acidizing treatments. As used herein, the term "treatment fluid" refers to any fluid that may be used in a subterranean application in conjunction with a desired function and/or for a desired purpose. The term "treatment fluid" does not imply any particular action by the fluid or any component thereof. Acidic treatment fluids may include a variety of acids such as, for example, hydrochloric acid, formic acid, hydrofluoric acid, and the like. While acidic treatment fluids may be useful for a variety of downhole operations, acidic treatment fluids can be problematic in that they can cause corrosion to downhole production tubing and downhole tools. To combat this potential corrosion problem, an assortment of corrosion inhibitors have been used to reduce or prevent corrosion to downhole metals and metal alloys with varying levels of success. A difficulty encountered with the use of some corrosion inhibitors is the limited temperature range over which they may function effectively. For instance, certain conventional antimony-based inhibitor formulations have been limited to temperatures above 270°F, because they do not appear to function effectively below this temperature. Another drawback of some conventional corrosion inhibitors is that certain corrosion inhibitors components may not be compatible with the higher environmental standards of some regions. One illustrative example relates to use quaternary ammonium compounds or "Mannich" condensation compounds. These compounds are generally not acceptable under stricter environmental regulations, such as those applicable in the North Sea region or other regions. Consequently, operators in some regions may be forced to suffer increased corrosion problems, to resort to using less desirable corrosion inhibitor formulations that may be less effective, or to forego the use of certain acidic treatment fluids entirely. SUMMARY The present invention relates to corrosion inhibitor compositions for inhibiting the corrosion of metals and more particularly, to corrosion inhibitor compositions useful for inhibiting metal corrosion in acidic environments and associated methods. An example of a corrosion inhibitor composition comprises a group 15 metal source; and a cinnamaldehyde compound. Another example of a corrosion inhibitor composition comprises a group 15 metal source; a cinnamaldehyde compound; and an acetylenic compound. An example of a method of inhibiting corrosion of a metal surface comprises providing a corrosion inhibitor composition, the corrosion inhibitor composition comprising a group 15 metal source, a cinnamaldehyde compound, and an acetylenic compound; contacting the metal surface with the corrosion inhibitor composition; and allowing the corrosion inhibitor composition to interact with the metal surface so as to inhibit corrosion of the metal surface. Another example of a method of inhibiting corrosion of a metal surface comprises providing a corrosion inhibitor composition, the corrosion inhibitor composition comprising a group 15 metal source and a cinnamaldehyde compound; contacting the metal surface with the corrosion inhibitor composition; and allowing the corrosion inhibitor composition to interact with the metal surface so as to inhibit corrosion of the metal surface. Corrosion inhibitor compositions of the present invention may further comprise one or more of the following components: an additional aldehyde compound, an acetylenic compound, a surfactant, an iodide source, and a solvent. The features and advantages of the present invention will be apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention. DESCRIPTION OF PREFERRED EMBODIMENTS The present invention relates to corrosion inhibitor compositions for inhibiting the corrosion of metals and more particularly, to corrosion inhibitor compositions useful for inhibiting metal corrosion in acidic environments and associated methods. In certain embodiments, the corrosion inhibitor compositions may comprise a group 15 metal source, a cinnarnaldehyde compound, an additional aldehyde compound, an acetylenic compound, a surfactant, an iodide source, and a solvent. Not all of these components are essential elements of the inhibitor corrosion composition. One or more of these components may be omitted in specific embodiments. As will be more clear throughout this disclosure and the claims, some of the components are optional in certain embodiments. One of the advantages of the inhibitor corrosion compositions of the present invention is that they may be more effective than corrosion inhibitors heretofore used and/or may possess desirable environmental properties for use in downhole environments, especially those that may be subject to more stringent environmental regulations. Another advantageous feature of the present invention is that the corrosion inhibitors of the present invention do not require the presence of quaternary ammonium compounds or "Mannich" condensation compounds to function. Environments in which corrosion inhibitor compositions of the present invention may be particularly effective include any downhole application in which the environment is relatively acidic. Such acidity may pose a problem for any metal surfaces present therein. In some embodiments, the corrosion inhibitor compositions of the present invention may be used as
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