Methods For Recovering Hydrocarbon Materials From Subterranean Formations

Abstract

A method for recovering hydrocarbon material from a subterranean formation includes introducing a treatment fluid into the subterranean formation. One treatment fluid includes at least one organometallic material having a metal or metalloid from Group III of the Periodic Table or a transition metal. An optional second fluid having an organophosphorous material can also be introduced. Another treatment fluid includes the reaction product of a transition metal compound and a silicon-containing material.

The invention claimed is: 
     
         1 . A method for recovering hydrocarbon material from a subterranean formation, comprising:
 introducing at least one treatment fluid into the subterranean formation, wherein the at least one treatment fluid comprises at least one organometallic material, and   wherein the at least one treatment fluid is introduced before or after a fracking fluid.   
     
     
         2 . The method of  claim 1 , comprising the steps of:
 introducing a first treatment fluid into the subterranean formation, the first treatment fluid comprising an organometallic material; and   introducing a second treatment fluid into the subterranean formation, the second treatment fluid comprising an organophosphorous material.   
     
     
         3 . The method of  claim 2 , wherein the organometallic material comprises a metal or metalloid selected from Group III of the Periodic Table. 
     
     
         4 . The method of  claim 2 , wherein the organometallic material comprises a transition metal. 
     
     
         5 . The method of  claim 4 , wherein the transition metal is selected from Group IIIB, IVB, VB and VIB of the Periodic Table. 
     
     
         6 . The method of  claim 2 , wherein the organometallic material comprises a metal selected from the group consisting of aluminum, titanium, zirconium, lanthanum, hafnium, tungsten, niobium, and tantalum. 
     
     
         7 . The method of  claim 2 , wherein the organometallic material comprises a C1 to C18 alkoxide group. 
     
     
         8 . The method of  claim 2 , wherein the organometallic material is dissolved or dispersed in a non-aqueous diluent. 
     
     
         9 . The method of  claim 2 , wherein the organophosphorous material comprises an acid selected from the group consisting of organophosphoric acid, organophosphonic acid, organophosphinic acid, and derivatives thereof. 
     
     
         10 . The method of  claim 9 , wherein the organophosphorous material comprises organophosphonic acid. 
     
     
         11 . The method of  claim 2 , wherein the organophosphorous material comprises at least one group selected from an aliphatic group, an olefinic group, and an aryl-substitute group. 
     
     
         12 . The method of  claim 2 , further comprising introducing a stabilization fluid comprising an aqueous solution including divalent metal cations into the subterranean formation prior to introducing the first treatment fluid. 
     
     
         13 . The method of  claim 2 , wherein the organophosphorous material comprises a fluorinated material. 
     
     
         14 . A method for recovering hydrocarbon material from a subterranean formation, comprising:
 introducing at least one treatment fluid into the subterranean formation, wherein the at least one treatment fluid comprises a material comprising the reaction product of:
 (a) a transition metal compound; and 
 (b) a silicon-containing material, 
   wherein the at least one treatment fluid is introduced before or after a fracking fluid.   
     
     
         15 . The method of  claim 14 , wherein the transition metal compound includes a transition metal selected from the group consisting of niobium, lanthanum, and transition metals having electrons in the f orbital. 
     
     
         16 . The method of  claim 14 , wherein the transition metal compound includes a transition metal selected from Period 6 of the Periodic Table of Elements. 
     
     
         17 . The method of  claim 14 , wherein the transition metal compound includes a transition metal selected from the group consisting of La, Hf, Ta, W and Nb. 
     
     
         18 . The method of  claim 14 , wherein the transition metal compound includes ligands selected from alkoxide, halide, keto acid, amine, and acylate. 
     
     
         19 . The method of  claim 18 , wherein the ligand of the transition metal compound is a chloride. 
     
     
         20 . The method of  claim 14 , wherein the silicon-containing material has a formula selected from:
   R 1   4-x SiA x or(R 1   3 Si) y B   or an organo(poly)siloxane and an organo(poly)silazane containing units of the formula:   
       
         
           
           
               
               
           
         
         where: R 1  are identical or different and are a hydrocarbon or substituted hydrocarbon radical containing from 1 to 100 carbon atoms, 
       
       
         
           
           
               
               
           
         
         A is hydrogen, halogen, OH, OR 2  or
 B is NR 3   3-y , 
 
         R 2  is a hydrocarbon or substituted hydrocarbon radical containing from 1 to 12 carbon atoms,
 R 3  is hydrogen or is the same as R 1    
 x is 1,2 or 3, and 
 y is 1 or 2. 
 
       
     
     
         21 . The method of  claim 20 , wherein the silicon-containing material has the following formula:
   R 1   4-x SiA x      where R 1  is a fluoro-substituted hydrocarbon and A is OR 2 .   
     
     
         22 . The method of  claim 21 , wherein R 1  is of the structure: 
       
         
           
           
               
               
           
         
         where Y is F or C n F 2n+1 ; m is 4 to 20; n is 1 to 6; R 2  is alkyl containing from 1 to 4 carbon atoms; and p is 0 to 18. 
       
     
     
         23 . The method of  claim 21 , wherein the fluoro-substituted hydrocarbon is of the structure: 
       
         
           
           
               
               
           
         
         where A is an oxygen radical or a chemical bond; n is 1 to 6; Y is F or C n F2 n+1 ; b is at least 1; m is 0 to 6 and p is 0 to 18. 
       
     
     
         24 . The method of  claim 14 , wherein the silicon-containing material is an organo(poly)siloxane or an organo(poly)silazane. 
     
     
         25 . The method of  claim 24 , wherein the organo(poly)siloxane and organo(poly)silazane include units of the formula: 
       
         
           
           
               
               
           
         
         where R 1  are identical or different and are a hydrocarbon or substituted hydrocarbon radicals containing from 1 to 12 carbon atoms and R 3  is hydrogen or is the same as R 1 . 
       
     
     
         26 . The method of  claim 25 , wherein the organo(poly)siloxane contains additional units of the formula:
   R 5   2 SiO 2      where R 5  contains a halogen.   
     
     
         27 . The method of  claim 26 , wherein the halogen is F or Cl. 
     
     
         28 . The method of  claim 25 , wherein the organo(poly)siloxane and organo(poly)silazane have a number average molecular weight of at least 400. 
     
     
         29 . The method of  claim 28 , wherein the organo(poly)siloxane has a number average molecular weight of 1,000 to 5,000,000. 
     
     
         30 . The method of  claim 14 , further comprising introducing a stabilization fluid comprising an aqueous solution including divalent metal cations into the subterranean formation prior to introducing the treatment fluid. 
     
     
         31 . A method for recovering hydrocarbon material from a subterranean formation, comprising:
 introducing a first treatment fluid comprising divalent metal cations into the subterranean formation; and   introducing a second treatment fluid into the subterranean formation, wherein the second treatment fluid comprises a material comprising the reaction product of:
 (a) a transition metal compound; and 
 (b) a silicon-containing material, 
   wherein the first treatment fluid and/or the second treatment fluid are introduced before or after a fracking fluid.