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US 20120264660Al (19) United States (12) Patent Application Publication (10) Pub. N0.2 US 2012/0264660 A1 Nguyen et al. (43) Pub. Date: Oct. 18, 2012 (54) METHOD OF TRACKING FLUIDS C07C 65/10 (2006.01) PRODUCED FROM VARIOUS ZONES IN C07C 63/08 (2006.01) SUBTERRANEAN WELL C07C 57/48 (2006.01) C07C 53/126 (2006.01) (75) Inventors: Philip D. Nguyen, Duncan, OK C07C 57/03 (2006.01) (US); Jimmie D. Weaver, Duncan, OK (US); Johnny A. Barton, (52) us. c1. ........... .. 507/203; 562/606; 554/1; 554/230; Marlow, OK (US) 562/601; 562/598; 562/477; 562/493; 562/495; 562/476 (73) Assignee: Halliburton Energy Seervices, Inc., Houston, TX (US) (57) ABSTRACT (21) Appl. No.: 13/534,282 A traceable treatment composition for treating a subterranean formation having multiple Zones penetrated by a Well bore (22) Filed: Jun. 27, 2012 comprising a homogenous blend of a tracking composition and a resin composition. The tracking composition comprises Related US. Application Data a substantially non-radioactive tracking material selected from the group consisting of a metal salt. The metal portion of (60) Division of application No. 10/777,412, ?led on Feb. the metal salt may be selected from the group consisting of 12, 2004, Which is a division of application No. gold, silver, lithium, molybdenum, and vanadium. The metal 10/298,825, ?led on Nov. 18, 2002, noW Pat. No. salt may also be selected from the group consisting of: barium 6,725,926, Which is a continuation-in-part of applica bromide, barium iodide, beryllium ?uoride, beryllium bro tion No. 10/125,171, ?led on Apr. 18, 2002, noW Pat. mide, beryllium chloride, cadmium bromide, cadmium No. 6,691,780. iodide, chromium bromide, chromium chloride, chromium iodide, cesium bromide, cesium chloride, sodium bromide, Publication Classi?cation sodium iodide, sodium nitrate, sodium nitrite, potassium (51) Int. Cl. iodide, potassium nitrate, manganese bromide, Zinc bromide, C09K 8/80 (2006.01) Zinc iodide, sodium mono?uoroacetate, sodium tri?uoroac C07C 57/12 (2006.01) etate, sodium 3-?uoropropionate, potassium mono?uoroac C07C 57/10 (2006.01) etate, potassium tri?uoroacetate, and potassium 3-?uoropro C07C 65/03 (2006.01) pionate. US 2012/0264660 A1 Oct. 18, 2012 METHOD OF TRACKING FLUIDS agents or deformable particulates (See eg US. Pat. No. PRODUCED FROM VARIOUS ZONES IN 6,328,105 to BetZold, US. Pat. No. 6,172,011 to Card et al. SUBTERRANEAN WELL and US. Pat. No. 6,047,772 to Weaver et al.) For a multi-Zone Well that has been fractured With proppant and is plagued With CROSS-REFERENCE TO RELATED proppant ?oWback problems, it is quite di?icult to identify the APPLICATIONS Zone from Which the proppant is emanating unless the prop pant is tagged With a tracer. Radioactive materials have been [0001] This application is a divisional application of co commonly used in the logging or tagging of sand or proppant pending US. patent application Ser. No. 10/298,825, ?led placement, hoWever, such radioactive materials are haZard Nov. 18, 2002, the entire disclosure of Which is incorporated ous to the environment and the techniques for utiliZing such herein by reference, and Which itself is a continuation-in-part radioactive materials are complex, expensive and time con ofU.S. patent application Ser. No. 10/125,171, ?led Apr. 18, suming. Therefore, there is a need for simple compositions 2002, the entire disclosure of Which is incorporated herein by and methods for tracking the ?oWback of proppant in subter reference. ranean Wells to avoid the above problems. BACKGROUND DETAILED DESCRIPTION [0002] The present embodiment relates generally to the [0007] According to one embodiment, to determine from recovery of hydrocarbons from a subterranean formation pen Which Zone(s) a ?uid is being produced, a Water soluble etrated by a Well bore and more particularly to non-radioac inorganic or organic salt is dissolved in the base treatment tive compositions and methods of utilizing the non-radioac ?uid as the ?uid is being pumped doWnhole during the treat tive compositions for determining the source of treatment ment. Such treatment ?uids include but are not limited to ?uids being produced from a production formation having fracturing ?uids, drilling ?uids, disposal ?uids and injection multiple Zones. For example, the compositions and methods ?uids used as displacement ?uids in hydrocarbon recovery can be utiliZed for tracking the transport of particulate solids processes. Acting as a ?uid tracer agent, a salt is tagged into during the production of hydrocarbons from a subterranean the ?uid that is unique for each treatment job such as a formation penetrated by a Well bore. fracturing job treatment. Suitable Water soluble salts for this [0003] Transport of particulate solids during the production purpose are metal salts in Which the metal is selected from of hydrocarbons from a subterranean formation penetrated by Groups Ito VIII of the Periodic Table of the Elements as Well a Well bore is a continuing problem. The transported solids as the lanthanide series of rare earth metals so long as the can erode or cause signi?cant Wear in the hydrocarbon pro metal salts do not constitute a component of ?uids naturally duction equipment used in the recovery process. The solids present in the formation and are compatible With the ?uids also can clog or plug the Well bore thereby limiting or com injected into the formation. Preferred metals include barium, pletely stopping ?uid production. Further, the transported beryllium, cadmium, chromium, cesium, sodium, potassium, particulates must be separated from the recovered hydrocar manganese and Zinc. Particularly preferred Water soluble bons adding further expense to the processing. The particu salts include barium bromide, barium iodide, beryllium ?uo lates Which are available for transport may be present due to ride, beryllium bromide, beryllium chloride, cadmium bro an unconsolidated nature of a subterranean formation and/or mide, cadmium chloride, cadmium iodide, cadmium nitrate, as a result of Well treatments placing particulates in a Well chromium bromide, chromium chloride, chromium iodide, bore or formation, such as, by gravel packing or propped cesium bromide, cesium chloride, sodium bromide, sodium fracturing. iodide, sodium nitrate, sodium nitrite, potassium iodide, [0004] In the treatment of subterranean formations, it is potassium nitrate, manganese bromide, manganese chloride, common to place particulate materials as a ?lter medium Zinc bromide, Zinc chloride, Zinc iodide, sodium mono?uo and/ or a proppant in the near Well bore area and in fractures roacetate, sodium tri?uoroacetate, sodium 3-?uoropropi extending outWardly from the Well bore. In fracturing opera onate, potassium mono?uoroacetate, potassium tri?uoroac tions, proppant is carried into fractures created When hydrau etate, potassium 3-?uoropropionate. lic pressure is applied to these subterranean rock formations [0008] The ?uid tracer agents used in the method of this to a point Where fractures are developed. Proppant suspended embodiment must meet a number of requirements. They in a viscosi?ed fracturing ?uid is carried outWardly aWay should be relatively inexpensive, must be compatible With from the Well bore Within the fractures as they are created and ?uids naturally present in the reservoir and Within the rock extended With continued pumping. Upon release of pumping itself, as Well as be compatible With the ?uids injected into the pressure, the proppant materials remain in the fractures hold reservoir as part of the formation treatment. The ?uid tracer ing the separated rock faces in an open position forming a agents must be susceptible to being readily detected qualita channel for ?oW of formation ?uids back to the Well bore. tively and analyZed quantitatively in the presence of the mate [0005] Proppant ?oWback is the transport of proppants rials naturally occurring in the formation ?uids. For example, back into the Well bore With the production of formation ?uids an aqueous sodium chloride solution could be utiliZed as a folloWing fracturing. This undesirable result causes undue ?uid tracer agent but for the fact that mo st ?eld brines contain Wear on production equipment, the need for separation of sodium chloride in substantial quantities, and so detection solids from the produced hydrocarbons and occasionally also and analysis to differentiate the presence of sodium chloride decreases the e?iciency of the fracturing operation since the used as tracer in the presence of naturally-occurring sodium proppant does not remain Within the fracture and may limit chloride Would be dif?cult. the Width or conductivity of the created ?oW channel. [0009] In ?eld application, a knoWn amount of a selected [0006] Current techniques for controlling the ?oWback of Water soluble salt based on a knoWn concentration (i.e. 100 proppants include coating the proppants With curable resin, or parts per million) is dissolved in a volume of Water Which is blending the proppants With ?brous materials, tackifying l/1,ooo of the total actual volume of base ?uid required for the US 2012/0264660 A1 Oct. 18, 2012 treatment. The mixed solution is then metered to the base ?uid mixing the metal With a curable resin prior to coating the line at a rate of one gallon per 1,000 gallons of the base ?uid. curable resin onto the proppant. Preferably, the metal is To handle multiple Zones, various salts can be used provided selected from the Group VIB metals, the Group VIIB metals, that the interest cations or anions of selected compounds are and the lanthanide series of rare earth metals. Speci?cally, the unique to prevent any interference betWeen Zones. metal according to this embodiment may be chromium, [0010] According to another embodiment, metals are molybdenum, tungsten, manganese, technetium, rhenium, tagged onto proppant material or materials to be blended With lanthanum, cerium, praseodymium, neodymium, prome proppant material to provide for the ready identi?cation of thium, samarium, europium, gadolinium, terbium, dyspro ?oWback proppant from different stages or Zones of the Well.