Method of treating proppants and fractures in-situ with fluorinated silane

Abstract

Method of treating proppant particles present in a fractured subterranean geological formation comprising hydrocarbons in-situ with fluorinated silane.

1 . (canceled) 
     
     
         2 . A method of treating proppant particles present in a fractured subterranean geological formation comprising hydrocarbons, the method comprising injecting fluorinated silane into the fracture to treat the proppant particles in-situ, wherein the fluorinated silane is selected from the group consisting of:
   Rf{-Q-[SiY 3-x (R) x ] y } z ;   a polymeric fluorinated composition comprising:
 at least one divalent unit represented by the formula: 
   
       
         
           
           
               
               
           
         
          and
 at least one of
 at least one divalent unit represented by the formula: 
 
 
       
       
         
           
           
               
               
           
         
         
            or
 a chain-terminating group represented by the formula:
   —S—W—SiY 3-x (R) x ; and 
 
 
         
         a fluorinated urethane oligomer of at least two repeat units comprising:
 at least one end group represented by the formula —O—Z—Rf 2 , and 
 at least one end group represented by the formula —X 1 —W—SiY 3-x (R) x ; 
 
       
       wherein
 Rf is a monovalent or multivalent perfluoropolyether group having two or more in-chain oxygen atoms; 
 Rf 2  is a monovalent perfluoroalkyl group optionally interrupted by at least one —O—; 
 each R is independently selected from the group consisting of alkyl having one to six carbon atoms and aryl; 
 Q is a divalent or trivalent organic linking group; 
 each Y is independently selected from the group consisting of hydroxyl, alkoxy, acyloxy, and halogen; 
 each R 1  is independently selected from the group consisting of hydrogen and alkyl having one to four carbon atoms; 
 each W is independently selected from the group consisting of alkylene, arylalkylene, and arylene, wherein alkylene is optionally interrupted by or substituted by at least one heteroatom; 
 each X is independently selected from the group consisting of —NH—, —O—, and —S—; 
 X 1  is selected from the group consisting of —N(H)—, —N(CH 3 —, —N(C 6 H 5 )—, —S—, —O—, —O—C(O)—NH—, and 
 
       —O-alkylene-O—C(O)—NH—;
 Z is a divalent organic linking group; 
 x is 0, 1, or 2; 
 y is 1 or 2; and 
 z is 1, 2, 3, or 4. 
 
     
     
         3 . The method according to  claim 2 , wherein the fluorinated silane comprises at least one fluorinated urethane oligomer of at least two repeat units comprising:
 at least one end group represented by the formula —O—(CH 2 ) n N(R 4 )S(O) 2 —Rf 3 , and   at least one end group represented by the formula —NH—(CH 2 ) n —SiY 3 ;   
       wherein
 R 4  is alkyl having one to four carbon atoms; 
 Rf 3  is a perfluoroalkyl group having from one to eight carbon atoms; 
 each Y is independently selected from the group consisting of hydroxyl, alkoxy, acyloxy, and halogen; and 
 each n is independently an integer from 1 to 4. 
 
     
     
         4 . The method according to  claim 2 , wherein at least a portion of the proppant particles are ceramic particles. 
     
     
         5 . The method according to  claim 2 , wherein at least a portion of the proppant particles are engineered particles. 
     
     
         6 . The method according to  claim 2 , wherein at least a portion of the proppant particles are at least 500 micrometers in size. 
     
     
         7 . The method according to  claim 2 , wherein at least a portion of the treated proppant particles have a plurality of pores, and wherein at least a portion of the treated proppant particles have at least one of water or oil imbibition up to 95% as compared to comparable, untreated proppant particles. 
     
     
         8 . A method of fracturing a subterranean geological formation comprising hydrocarbons, the method comprising:
 injecting a hydraulic fluid into a subterranean geological formation comprising hydrocarbons at a rate and pressure sufficient to open a fracture therein;   injecting into the fracture a fracture fluid comprising a plurality of proppant particles; and   subsequent to the injection of the hydraulic and fracture fluids, injecting fluorinated silane into the fracture to treat the proppant particles in-situ, wherein the fluorinated silane is selected from the group consisting of:
   Rf{-Q-[SiY 3-x (R) x ] y } z ; 
   a polymeric fluorinated composition comprising:
 at least one divalent unit represented by the formula: 
   
       
         
           
           
               
               
           
         
          and
 at least one of
 at least one divalent unit represented by the formula: 
 
 
       
       
         
           
           
               
               
           
         
         
            or
 a chain-terminating group represented by the formula:
   —S—W—SiY 3-x (R) x ; and 
 
 
         
         a fluorinated urethane oligomer of at least two repeat units comprising:
 at least one end group represented by the formula —O—Z—Rf 2 , and 
 at least one end group represented by the formula —X 1 —W—SiY 3-x (R) x ; 
 
       
       wherein
 Rf is a monovalent or multivalent perfluoropolyether group having two or more in-chain oxygen atoms; 
 Rf 2  is a monovalent perfluoroalkyl group optionally interrupted by at least one —O—; 
 each R is independently selected from the group consisting of alkyl having one to six carbon atoms and aryl; 
 Q is a divalent or trivalent organic linking group; 
 each Y is independently selected from the group consisting of hydroxyl, alkoxy, acyloxy, and halogen; 
 each R 1  is independently selected from the group consisting of hydrogen and alkyl having one to four carbon atoms; 
 each W is independently selected from the group consisting of alkylene, arylalkylene, and arylene, wherein alkylene is optionally interrupted by or substituted by at least one heteroatom; 
 each X is independently selected from the group consisting of —NH—, —O—, and —S—; 
 X 1  is selected from the group consisting of —N(H)—, —N(CH 3 )—, —N(C 6 H 5 )—, —S—, —O—, —O—C(O)—NH—, and —O-alkylene-O—C(O)—NH—; 
 Z is a divalent organic linking group; 
 x is 0, 1, or 2; 
 y is 1 or 2; and 
 z is 1, 2, 3, or 4. 
 
     
     
         9 . (canceled) 
     
     
         10 . The method according to  claim 8 , wherein the fluorinated silane comprises at least one fluorinated urethane oligomer of at least two repeat units comprising:
 at least one end group represented by the formula —O—(CH 2 ) n N(R 4 )S(O) 2 —Rf 3 , and   at least one end group represented by the formula —NH—(CH 2 ) n —SiY 3 ;   
       wherein
 R 4  is alkyl having one to four carbon atoms; 
 Rf 3  is a perfluoroalkyl group having from one to eight carbon atoms; 
 each Y is independently selected from the group consisting of hydroxyl, alkoxy, acyloxy, and halogen; and 
 each n is independently an integer from 1 to 4. 
 
     
     
         11 . The method according to  claim 8 , wherein at least a portion of the proppant particles are ceramic particles. 
     
     
         12 . The method according to  claim 8 , wherein at least a portion of the proppant particles are engineered particles. 
     
     
         13 . The method according to  claim 8 , wherein at least a portion of the proppant particles are at least 500 micrometers in size. 
     
     
         14 . The method according to  claim 8 , wherein at least a portion of the treated proppant particles have a plurality of pores, and wherein at least a portion of the treated proppant particles have at least one of water or oil imbibition up to 95% as compared to comparable, untreated proppant particles. 
     
     
         15 . A method of fracturing a subterranean geological formation comprising hydrocarbons, the method comprising:
 injecting a hydraulic fluid into a subterranean geological formation comprising hydrocarbons at a rate and pressure sufficient to open a fracture therein;   injecting fluorinated silane into the fracture to treat the fracture in-situ, wherein the fluorinated silane is selected from the group consisting of:
   Rf{-Q-[SiY 3-x (R) x ] y } z ; 
   a polymeric fluorinated composition comprising:
 at least one divalent unit represented by the formula: 
   
       
         
           
           
               
               
           
         
          and
 at least one of
 at least one divalent unit represented by the formula: 
 
 
       
       
         
           
           
               
               
           
         
         
            or
 a chain-terminating group represented by the formula:
   —S—W—SiY 3-x (R) x ; and 
 
 
         
         a fluorinated urethane oligomer of at least two repeat units comprising:
 at least one end group represented by the formula —O—Z—Rf 2 , and 
 at least one end group represented by the formula —X 1 —W—SiY 3-x (R) x ; 
 
       
       wherein
 Rf is a monovalent or multivalent perfluoroalkyl group optionally interrupted by at least one —O—; 
 Rf 2  is a monovalent perfluoroalkyl group optionally interrupted by at least one —O—; 
 each R is independently selected from the group consisting of alkyl having one to six carbon atoms and aryl; 
 Q is a divalent or trivalent organic linking group; 
 each Y is independently selected from the group consisting of hydroxyl, alkoxy, acyloxy, and halogen; 
 each R 1  is independently selected from the group consisting of hydrogen and alkyl having one to four carbon atoms; 
 each W is independently selected from the group consisting of alkylene, arylalkylene, and arylene, wherein alkylene is optionally interrupted by or substituted by at least one heteroatom; 
 each X is independently selected from the group consisting of —NH—, —O—, and —S—; 
 X 1  is selected from the group consisting of —N(H)—, —N(CH 3 —, —N(C 6 H 5 )—, —S—, —O—, —O—C(O)—NH—, and —O-alkylene-O—C(O)—NH—; 
 Z is a divalent organic linking group; 
 x is 0, 1, or 2; 
 y is 1 or 2; and 
 z is 1, 2, 3, or 4, and 
 after injecting the fluorinated silane into the fracture, injecting a fracture fluid comprising a plurality of proppant particles into the fracture. 
 
     
     
         16 . The method according to  claim 15 , wherein prior to injecting the fluorinated silane into the fracture, the method further comprises injecting a fracture fluid comprising a plurality of proppant particles into the fracture. 
     
     
         17 . (canceled) 
     
     
         18 . The method according to  claim 15 , wherein at least some of the proppants injected into the fracture are treated with the fluorinated silane prior to their injection. 
     
     
         19 . The method according to  claim 15 , wherein the fluorinated silane comprises at least one fluorinated urethane oligomer of at least two repeat units comprising:
 at least one end group represented by the formula —O—(CH 2 ) n N(R 4 )S(O) 2 —Rf 3 , and   at least one end group represented by the formula —NH—(CH 2 ) n —SiY 3 ;   
       wherein
 R 4  is alkyl having one to four carbon atoms; 
 Rf 3  is a perfluoroalkyl group having from one to eight carbon atoms; 
 each Y is independently selected from the group consisting of hydroxyl, alkoxy, acyloxy, and halogen; and 
 each n is independently an integer from 1 to 4. 
 
     
     
         20 . The method according to  claim 15 , wherein the fracture has a conductivity improved by the presence of fluorinated siloxane which is a condensation product of the fluorinated silane.