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(12) Patent Application Publication (10) Pub. No.: US 2007/0010404 A1 Welton Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2007/0010404 A1 Welton Et Al US 200700 10404A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2007/0010404 A1 Welton et al. (43) Pub. Date: Jan. 11, 2007 (54) CORROSION INHIBITOR OR INTENSIFIER Publication Classification FOR USE IN ACIDZING TREATMENT FLUIDS (51) Int. Cl. C09K 8/60 (2006.01) (52) U.S. Cl. .............................................................. 507/267 (75) Inventors: Thomas D. Welton, Duncan, OK (US); Juanita M. Cassidy, Duncan, OK (US) (57) ABSTRACT The invention also provides a composition for treating a subterranean formation penetrated by a wellbore. The com Correspondence Address: position is especially useful in acidizing treatments, which Robert A. Kent when combined with a corrosive aqueous fluid, inhibits the 2600 S. 2nd Street corrosion of metal Surfaces, most especially, “duplex Duncan, OK 73536-0440 (US) chrome steel Surfaces. An advantageous embodiment of the invention comprises at least 0.01% by weight of 3-hydrox ypropionic acid and at least 1% by weight of an acid or acid (73) Assignee: Halliburton Energy Services, Inc. precursor that different from 3-hydroxypropionic acid. The invention also provides a method for treating a Subterranean formation penetrated by a wellbore. The method comprises (21) Appl. No.: 11/177,512 the steps of forming the composition and introducing the composition into the Subterranean formation through the (22) Filed: Jul. 8, 2005 wellbore. US 2007/001 0404 A1 Jan. 11, 2007 CORROSION INHIBITOR OR INTENSIFIER FOR 0008 Various inhibitors for preventing the attack of acids USE IN ACIDZING TREATMENT FLUIDS on high chromium content steels have been proposed. Of the many inhibitors especially designed to prevent acid attack CROSS-REFERENCE TO RELATED on well casings, very few provide satisfactory protection, APPLICATIONS especially at higher temperatures. Usually inhibitor intensi fiers such as potassium iodide and formic acid are used to 0001. Not applicable assist the corrosion inhibitor. STATEMENT REGARDING FEDERALLY 0009. Accordingly, there is a need for the development of SPONSORED RESEARCH OR DEVELOPMENT a corrosion inhibitor or inhibitor intensifier, especially for high chromium or duplex steels, that perform satisfactorily 0002) Not applicable at higher temperatures. REFERENCE TO MICROFICHEAPPENDIX SUMMARY OF THE INVENTION 0003) Not applicable 0010. The invention provides a composition for treating a subterranean formation penetrated by a wellbore, the FIELD OF THE INVENTION composition comprising at least 0.01% by weight of a 0004 The invention generally relates to compositions compound according to a formula: and methods for treating a Subterranean formation. More specifically, the invention relates to compositions and meth ods using a corrosion inhibitor or inhibitor intensifier in acidizing treatment fluids. RC ukulsOR4 BACKGROUND OF THE INVENTION 0005 Acid treatments are used to stimulate and increase the production of hydrocarbons in a Subterranean formation. 0011 where each of R. R. R. and R is indepen This is commonly referred to as acidizing. One Such aqueous dently: acid treatment, referred to as "matrix-acidizing, involves 0012 a hydrogen; the introduction of an acid into a subterranean formation under pressure so that the acid flows through the pore spaces 0013 a straight, branched, cyclic, or heterocyclic alkyl of the formation. The acid of the aqueous acid treatment functional group; reacts with acid soluble materials contained in the formation 0014 a straight, branched, cyclic, or heterocyclic aryl to increase the size of the pore spaces and increase the functional group; or permeability of the formation. Another similar treatment known as “fracture-acidizing involves the formation of one 0015 a straight, branched, cyclic, or heterocyclic alky or more fractures in the formation and the introduction of an laryl functional group; and acid into the fractures to etch the fracture faces and form The composition also comprises at least 1% by weight of channels. Acid treatments are also utilized to do other an acid or acid precursor that is different from the functions such as wellbore and perforation cleanouts, scale compound according to the formula. removal, filter cake removal, and fluid loss "pill removal. 0006 A problem that often accompanies the acidizing 0016. The invention also provides a method for treating treatments described above is the corrosion of metal in a subterranean formation penetrated by a wellbore. The pumps, well tubular and casing equipment, and equipment method comprises the steps of forming the composition and that is used to introduce the acid treatments into the subter introducing the composition into the Subterranean formation ranean formation to be treated. It is expensive to repair or through the wellbore. replace the corroded equipment. The corrosion of equipment 0017. These and other aspects of the invention will be is increased by elevated temperatures encountered in deep apparent to one skilled in the art upon reading the following formations. Also, the corrosion results in at least the partial detailed description. While the invention is susceptible to neutralization of the acid in the acidizing treatment before it various modifications and alternative forms, specific reacts with the acid-soluble materials in the formation. embodiments thereof will be described in detail and shown 0007 To resist corrosive effects on metals that are by way of example. It should be understood, however, that employed in wells, more resistive alloys that contain high it is different from intended to limit the invention to the concentrations of chromium and nickel have been devel particular forms disclosed, but, on the contrary, the invention oped. Increasingly, “duplex’ chrome steels are being is to cover all modifications and alternatives falling within employed in wells that contain high concentrations of hydro the spirit and scope of the invention as expressed in the gen sulfide because they are much more resistant to corro appended claims. sion than are the 13% chromium and low alloy steels. These metals are called “duplex” because they contain ferritic and DETAILED DESCRIPTION OF THE austenitic phases. Although more resistant to acid gas cor PREFERRED EMBODIMENTS rosion, duplex alloys are more Susceptible to hydrochloric 0018. The invention provides a composition for treating acid and hydrochloric/hydrofluoric acid corrosion than 13% a subterranean formation penetrated by a wellbore. The chromium and low alloy steels due to high energy sites at composition advantageously inhibits corrosion on metal their austenite-ferrite microstructural boundaries. surfaces used in wells of a subterranean formation. The US 2007/001 0404 A1 Jan. 11, 2007 composition is especially useful in acidizing treatments, which when combined with a corrosive aqueous fluid, inhibits the corrosion of metal Surfaces, most especially, “duplex’ chrome steel surfaces. 0019. In accordance with the methods of the invention, a Subterranean formation is treated with a composition of the invention, and the corrosive effects of the acidizing compo 0028 where each of R. R. R. and R is indepen sition on metal in contact with the composition are reduced, dently: thereby reducing the damage to the well that penetrates the 0029 a hydrogen: Subterranean formation. The method comprises the steps of forming the composition and introducing the composition 0030) a straight, branched, cyclic, or heterocyclic alkyl into the wellbore. The method can further comprise the step functional group; of recovering the composition from the wellbore after the 0031 a straight, branched, cyclic, or heterocyclic aryl composition is introduced into the wellbore. The composi functional group; or tions and methods of the invention are based on the discov ery that alpha, beta-unsaturated carboxylic acids and deriva 0032 a straight, branched, cyclic, or heterocyclic alky tives thereof provide unexpected increased corrosion laryl functional group; inhibition against corrosive aqueous fluids as compared to 0033 (C) a precursor of the chemical; prior art corrosion-inhibiting compositions. 0034) (B) a derivative of the chemical; 0020. In one embodiment, the composition relates to 0035 (D) a precursor of a derivative of the chemi aqueous conformance control fluids and treatments. The cal; and any mixtures of the foregoing in any pro water that can be used for the composition can be of any portion. convenient or desired source. Such as fresh water, seawater, natural brine, formulated brine, 2% KCl solution, and other As used herein, a “precursor of another chemical is a water that does not undesirably interact with the composi chemical related structurally to the other chemical tion of the invention. Formulated brine is manufactured by and that theoretically reacts to form the other chemi dissolving one or more soluble salts in water, natural brine, cal. As used herein, a "derivative' of another chemi or seawater. Representative soluble salts are the chloride, cal is a chemical related structurally to the other bromide, acetate and formate salts of potassium, Sodium, chemical and that is theoretically derivable from it. calcium, magnesium, and Zinc. 0036). In one aspect of this invention, the compound is further selected from the group consisting of arabinaric 0021 According to one embodiment of the invention, the acid, glucaric acid, tartaric acid, 11-cyclobutanedicarboxy composition for inhibiting corrosion on metal according to lic acid, 2-(2-propynyl)malonic acid, 2.2-bis(hydroxymeth the invention
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