Compositions and processes for fracturing subterranean formations

Abstract

The present invention is directed to novel additives packages, to fluid compositions including the additives, to methods of using the fluid compositions and the additives package, to methods of recovering hydrocarbons, and to petroleum products made from hydrocarbons derived from these methods. The novel additives packages may be used in a fluid composition for fracturing a subterranean. The additives package of the present invention include one or more gelling agents; one or more cross-linking agent; and one or more high temperature stabilizers; wherein the additives package further comprises one or more ingredients selected from the group consisting of a clay stabilizer, a metallic base, a cross-link retarded and a gel breaker, and any combination thereof; and wherein the additives package optionally includes a diluent.

1 . A process comprising the steps of:
 injecting a fluid composition into a subterranean formulation, wherein the subterranean formation has a temperature of 150° C. or more; and   recovering a hydrocarbon from the subterranean formation; wherein the fluid composition includes:   i) one or more gelling agents;   ii) 50 weight percent or more water; and   iii) a high temperature stabilizer including a thiosulfate, an amine compound, or both.   
     
     
         2 - 20 . (canceled) 
     
     
         21 . The process of  claim 1 , wherein the subterranean formation has a temperature of about 180° C. or more. 
     
     
         22 . The process or  claim 1 , wherein the high temperature stabilizer includes the thiosulfate and the amine compound. 
     
     
         23 . The process of  claim 1 , wherein the fluid composition includes one or more cross-linking agent. 
     
     
         24 . The process of  claim 1 , wherein the fluid composition includes a metallic Base. 
     
     
         25 . The process of  claim 1 , wherein the fluid composition includes a clay stabilizer, a metallic base, a cross-link retarder, a gel breaker, or any combination thereof. 
     
     
         26 . The process of  claim 1 , wherein the process induces a step of mixing an additives package with one or more fluids to form the fluid composition. 
     
     
         27 . The process of  claim 1 , wherein the composition includes one or more cross-linking agents, and the total concentration of any titanium and zirconium cross-linking agents is less than 20 weight percent based on the total concentration of the one or more cross-linking agents. 
     
     
         28 . The process of  claim 1 , wherein the fluid composition includes a boron containing compound; a metal halide salt; a gluconate salt; and a metal bromate. 
     
     
         29 . The process of  claim 1 , wherein the fluid composition additives package includes a diol selected from the group consisting of ethylene glycol, propylene glycol, a derivative thereof, and any combination thereof. 
     
     
         30 . The process of  claim 1 , wherein the fluid composition includes the amine compound at a concentration greater than about 2 pounds per thousand gallons of fluid and the thiosulfate at a concentration greater than about 2 pounds per thousand gallons of fluid. 
     
     
         31 . The process of  claim 1 , wherein the process includes a step of mixing an additives package with one or more other fluids in the well head. 
     
     
         32 . The process of  claim 1 , wherein the process includes a step of mixing an additives package with one or more fluids prior to injecting into a subterranean formation. 
     
     
         33 . The process of  claim 1 , wherein the fluid composition includes an encapsulated bromate and potassium chloride; and wherein the amine compound includes an alkanolamine. 
     
     
         34 . The process of  claim 1 , wherein the fluid composition includes potassium chloride, a guar gum; a boron salt; an alkanolamine; sodium hydroxide; a gluconate salt; and a metal bromate. 
     
     
         35 . The process of  claim 1 , wherein the fluid composition includes:
 a metallic base at a concentration from about 0.5 to about 50 pounds per thousand gallons of Fluid.   
     
     
         36 . The process of  claim 1 , wherein the process includes a step of continuously mixing an additives package with water. 
     
     
         37 . A petroleum based product made using the hydrocarbon recovered by the process of  claim 1 . 
     
     
         38 . The process of  claim 1 , wherein the fluid composition includes:
 i) at least 50 wt. % of a carrier liquid including water, based on the total weigh of the fluid composition;   ii) 0.599 kg to 18.0 kg of a refined guar gum per m 3  of the fluid composition;   iii) a cross-linking agent including 1 m 3  to 50 m 3  of a boron salt per 1000 m 3  of the fluid composition;   iv) from 0.05 m 3  to 100 m 3  of high temperature stabilizers per 1000 m 3  of the fluid composition, wherein the high temperature stabilizer includes an amine compound and a thiosulfate, wherein the concentration of the amine compound is from 0.05 m 3  to 20  3  per 1000 m 3  of the fluid composition, and wherein the amine compound includes an alkanolamine;   v.) a sufficient amount of sodium hydroxide so that the fluid composition has a pH from about 10 to about 13.5 at a temperature of about 25° C.;   vi) from 0.119 kg to 9.59 kg of a gluconate salt per m 3  of the fluid composition; and   vii) from 0.024 kg to 7.91 kg of a metal bromate per m 3  of the fluid composition;   wherein the concentration of any titanium and zirconium cross-linking agents is less than 20 weight percent based on the total weight of the cross-linking agents in the fluid composition; the weight ratio of the thiosulfate to the metal halide salt is from 1:20 to 2:1; and   the fluid composition is characterized as having good shear stability such that the viscosity of the fluid composition increases by at least 10% when the shear rate is decreased from about 100 s −1  to about 30 s −1  after being at an elevated temperature of about 149° C. for about 20 minutes.   
     
     
         39 . A kit for fracturing a subterranean formation comprising
 i) one or more gelling agents; and   ii) a high temperature stabilizer including a thiosulfate and an amine; and   iii) a cross-linking agent.