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United States Patent (19) 11 Patent Number: 4,865,129 Ryles 45 Date of Patent: Sep

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United States Patent (19) 11 Patent Number: 4,865,129 Ryles 45 Date of Patent: Sep United States Patent (19) 11 Patent Number: 4,865,129 Ryles 45 Date of Patent: Sep. 12, 1989 (54) HIGH TEMPERATURE PROFILE Attorney, Agent, or Firm-Frank M. Van Riet MODIFICATION AGENTS AND METHODS 57 ABSTRACT FOR USING SAME A new and improved composition and method for pro 75) Inventor: Roderick G. Ryles, Milford, Conn. file modification of subterranean formations character 73) Assignee: American Cyanamid Company, ized by high reservoir temperatures and/or harsh brine conditions are disclosed. The new and improved profile Stamford, Conn. modification agents comprise a gelable composition (21) Appl. No.: 226,713 comprising: (22 Filed: Aug. 1, 1988 (a) water; (b) a water-thickening and crosslinkable amount of a water-dispersible copolymer comprising from Related U.S. Application Data about 1 to about 99 mol % of units derived from an 62 Division of Ser. No. 946,265, Dec. 24, 1986, Pat. No. N,N-dialkylacrylamide monomer copolymerized 4,788,228. with from about 1 to about 99 mol % of units de 51 Int. Cl." .......................... E21B33/138; E21B 43; rived from acrylic acid or a salt thereof; and E21B 20 (c) an amount of a polyvalent metal sufficient to 52 U.S.C. .................................... 166/295; 166/274; crosslink the copolymer to form a stable gel. The 252/8.551; 252/8.554; 523/130 profile modification agents are effective to alter the 58 Field of Search ....... 252/8.551 APS, 8.554 APS; permeability of preselected portions of an under 523/130; 166/274, 295 ground formation by forming strong gels which are stable in harsh brine attemperatures of up to about 56 References Cited 120° C. The composition and method are particu U.S. PATENT DOCUMENTS larly adapted for use in enhanced oil recovery operations. 3,502,149 3/1970 Pence, Jr. .................... ... 166/295 3,727,689 4/1973 Clampitt. 252/8.551 Additionally, component (b) can be a water-dispersible 3,762,476 10/1973 Gall ................. ... 166/273 X terpolymer comprising from about 5 to about 75 mol 3,785,437 1/1974 Clampitt et al. ... ... 166/295 X percent of units derived fron an N,N-dialkylacryla 3,981,363 9/1976 Gall ..................................... 166/270 mide, from about 5 to about 35 mol percent of units 4,563,290 1/1986 Okada et al. 252/8.554 derived from acrylic acid or salts thereof and from 4,669,920 6/1987 Dymond .......................... 252/8.551 about 10 to about 90 mol percent of units derived from 4,799,548 1/1989 Mumallah et al. ............. 166/295 X 2-acrylamido-2-methylpropanesulfonic acid or salts 4,814,096 3/1989 Evani ............................... 252/8.554 thereof. Primary Examiner-John F. Terapane Assistant Examiner-Gary Geist 13 Claims, No Drawings 4,865,129 1. 2 zones. The mobility of a fluid in a permeable geological HIGH TEMPERATURE PROF LE formation is the effective permeability of the formation MODIFICATION AGENTS AND METHODS FOR to that fluid divided by the viscosity of the fluid. In the USING SAME past, a conventional method for reducing the mobility of drive fluids through permeable formations has been This is a division of application, Ser. No. 06/946,265, to increase the drive fluids viscosity. Such an increase in filed Dec. 24, 1986 now U.S. Pat. No. 4,788,228. viscosity is generally accomplished by using viscous solutions of high molecular weight polymers such as BACKGROUND OF THE INVENTION polyacrylamides, cellulose ethers, polysaccarides and The present invention relates to profile modification 10 the like. Such polymeric solutions have been found agents for altering the permeability of preselected por effective for reducing the water:oil ratio in the total tions of a subterranean formation. In preferred embodi producing well effluent and for increasing the daily ments, the present invention relates to a new and im production of hydrocarbonaceous fluids. proved composition and method for profile modifica In actual field practice, however, such mobility alter tion of a subterranean hydrocarbon-containing forma 5 ing polymers elute out of producing wells quickly and tion to reduce water:oil ratios and improved petroleum the water:oil ratios rapidly rise back to an undesirable recovery during enhanced oil recovery operations. level necessitating retreatment of the producing interval More particularly, it relates to new and improved aque with the viscous polymer solutions. These viscosity ous gelable compositions exhibiting high temperature increasing polymers are relatively expensive materials gel stability at temperatures up to about 150 C. and in 20 and a one time treatment would be particularly desir harsh brines and methods for using same. able. The enhanced secondary recovery of oil from oil More recently, reduction in the permeability of the bearing or containing subterranean formations by fluid pre-selected portions of various subterranean oil bear drive processes, wherein a fluid is injected into the ing formations has been accomplished with gelable formation by one or more injection wells to drive the oil 25 solutions of polymeric materials. The formation of gels through the formation to one or more production wells by the cross-linking of polymers is well known in the art is a known process, commonly referred to as enhanced for this purpose. A great deal of literature has been oil recovery. Fluids used in such processes include liq generated concerning the formation of gels in situ in uids such as water and various hydrocarbons, and gases underground formations for the purpose of treating the such as hydrocarbon gases, carbon dioxide, steam, etc. 30 formations to better produce oil and gas from bore holes Many oil reservoirs comprise layers or zones of porous drilled into the formations and to decrease undesired rock which can vary in permeability from zone to zone. water output. It is well recognized that polymer gels In all fluid drive processes, a recognized problem is the and processes incorporating same facilitate the plugging predilection of the drive fluid to channel along or of underground formations in desired areas e.g. by mod through the more permeable zones of the formation. 35 ifying the fluid flow profile, and in particular by de This is commonly referred to as channeling. Another creasing the relative permeability of the most permeable problem is viscous fingering which occurs, for example, portions of the formations. by the over-ride of a viscous fluid by a less viscous fluid. Prior art gelling compostions for use in profile modi The more conductive zones after the oil has been fication applications generally comprise water, poly largely displaced therefrom function as "thief zones' 40 mers capable of being cross-linked by polyvalent metal which permit the drive fluid to channel directly from cations and polyvalent metalion crosslinker. Prior art injection to production wells. In many instances, such crosslinkable polymers have included polyacrylamides, channeling or fingering results in leaving substantial carboxymethylcelluloses and polysaccharides, gener quantities of oil in the less permeable zones of the for ally of high molecular weight in excess of one million. mation which are bypassed. Such channeling or finger 45 A commonly used system for generating polyvalent ing can occur when the mobility i.e. the quotient of the metal ions has been to provide them in the form of reservoir's permeability to the drive fluid divided by the chelated metal ion complexes or as part of a redox sys viscosity of the drive fluid becomes large relative to the tem. The redox system will generally comprise redox mobility of the reservoir oil. couples wherein oxidizing agent is selected from water One of the significant problems, therefore, attendant 50 soluble compounds of polyvalent metals wherein the to the production of oil and gas from subterranean hy metal is present in a valence state which is capable of drocarbon containing formations, is the concomitant being reduced to a lower polyvalent state as exemplified production of water. Such produced water can be reser by potassium permanganate, sodium permanganate, voir water occasioned by coning or a similar phenom ammonium chromate, ammonium dichromate, the alkali ena of the aquifier, or it can be injection water from 55 metal chromates, the alkali metal dichromates and chro secondary or tertiary recovery treatments being applied mium trioxide. Sodium dichromate and potassium di to the formation. Whatever the source, there is an upper chromate because of low cost and ready availability are limit beyond which water production can no longer be the most widely used of the oxidizing agents. The re tolerated and its further entry into the producing well ducing agents in the redox couples have included sulfur bore must at least be reduced if further production of 60 containing compounds such as sodium or potassium hydrocarbon resources at that location is to be contin sulfide, sodium or potassium hydrosulfide, sodium or ued. potassium metabisulfite, sodium or potassium bisulfite, Regardless of whether the undesired water is a natu hydrogen sulfide, sodium or potassium thiosulfate, thi ral drive fluid or an artificial drive fluid such as from oacetamide and others, as well as non-sulfur containing secondary or tertiary recovery projects, the problem is 65 compounds, such as hydroquinone, perahydrazinoben primarily occasioned by the predilection of the drive zoic acid, hydrazine phosphite, hydrazine dichloride fluid to preferentially seek the higher permeability and others. Illustrative prior art profile modification zones and to more or less bypass the lower permeability compositions and methods are disclosed in U.S. Pat. 4,865,129 3 4. Nos. 2,718,497; 3,502,149; 3,727,689; 3,749,172; In commonly assigned copending application, Ser. 3,762,476; 3,785,437; 3,795,276; 3,952,806; 3,964,923; No. 729,512, now U.S. Pat. No. 4,746,687 there is dis 3,981,363; 4,018,286; 4,039,029; 4,040,484; 4,043,921; closed copolymers of 1) 2-acrylamido-2-methylpro 4,055,502; 4,110,230; 4,120,361; and 4,498,539 to list but a few.
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