Silane-Functionalized Polyalkyleneimine Clay Stabilizer for Treatment of Subterranean Formations

Abstract

Various embodiments disclosed relate to a silane-functionalized polyalkyleneimine (PAI) clay stabilizer for treatment of subterranean formations. In various embodiments, the present invention provides a method of treating a subterranean formation. The method can include placing in the subterranean formation a silane-functionalized PAI clay stabilizer.

What is claimed is: 
     
         1 . A composition comprising a silane-functionalized polyalkyleneimine (PAI) clay stabilizer, wherein the composition is active to stabilize a clay of a subterranean clay formation against clay swelling, clay migration, and fines generation in the subterranean formation via covalent silyl bond formation and electrostatic interaction between the clay and the silane-functionalized PAI clay stabilizer. 
     
     
         2 . The composition of  claim 1 , wherein the silane-functionalized PAI clay stabilizer is a polymer comprising a repeating unit having the following structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence of R 1  and D in the same repeating unit,
 R 1  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —(X) m — CH 2 —CHE-N(R 2 ) 2 , and D is H, or 
 R 1  and D together in the same repeating unit form a (C 1 -C 10 )heterocycle with the N to which R 1  is bound, 
 
 at each occurrence, X is independently selected from the group consisting of —(CH 2 ) 2 —O—, —(CH 2 ) 3 —O—, —(CH 2 ) 2 —S—, —(CH 2 ) 3 —S—, and a —(C 1-10 )alkylene-, 
 at each occurrence, m is about 0 to about 10, 
 at each occurrence, L 1  is a substituted or unsubstituted (C 1 -C 20 )hydrocarbylene interrupted by 0, 1, 2, or 3 groups independently selected from —O—, —S—, and substituted or unsubstituted —NH—, 
 at each occurrence, R A  is independently selected from —O—R B , —H, and —R B , wherein at least one R A  of each —Si—(R A ) 3  is —O—R B , 
 at each occurrence, R B  is independently substituted or unsubstituted (C 1 -C 20 )hydrocarbyl, 
 at each occurrence of R 2  and E in the same R 1  or in the same R 3 ,
 R 2  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —(X) m —CH 2 —CHF—N(R 3 ) 2 , and E is H, or 
 R 2  and E together in the same R 1  or in the same R 3  form a (C 1 -C 10 )heterocycle with the N to which R 2  is bound, 
 
 at each occurrence of R 3  and F in the same R 2 ,
 R 3  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —(X) m —CH 2 —CHE-N(R 2 ) 2 , and F is H, or 
 R 3  and F together in the same R 2  form a (C 1 -C 10 )heterocycle with the N to which R 3  is bound, 
 
 at one or more occurrences, at least one group selected from R 1 , R 2 , and R 3  in the silane-functionalized PAI clay stabilizer molecule is a silicon-containing group, and 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         3 . The composition of  claim 2 , wherein the silane-functionalized PAI clay stabilizer has the structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence of R 4  in an end group not including G, R 4  is independently selected from the group consisting of —H and -L 1 -Si—(R A ) 3 , 
 at each occurrence of R 4  and G in the same end group,
 R 4  is independently selected from the group consisting of —H and -L 1 -Si—(R A ) 3  and G is H, or 
 R 4  and G together in the same end group form a (C 1 -C 10 )heterocycle with the N to which R 4  is bound, 
 
 n is about 2 to about 1,000,000, and 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         4 . The composition of  claim 2 , wherein the silane-functionalized PAI clay stabilizer has the structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence, R 4  is independently selected from the group consisting of —H and -L 1 -Si—(R A ) 3 , 
 n is about 2 to about 1,000,000, and 
 
       
       each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
     
     
         5 . The composition of  claim 1 , wherein the silane-functionalized PAI clay stabilizer is a polymer comprising a repeating unit having the following structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence, R 1  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —CH 2 —CH 2 —N(R 2 ) 2 , 
 at each occurrence, L 1  is a substituted or unsubstituted (C 1 -C 20 )hydrocarbylene interrupted by 0, 1, 2, or 3 groups independently selected from —O—, —S—, and substituted or unsubstituted —NH—, 
 at each occurrence, R A  is independently selected from —O—R B , —H, and —R B , wherein at least one R A  of each —Si—(R A ) 3  is —O—R B , 
 at each occurrence, R B  is independently substituted or unsubstituted (C 1 -C 20 )hydrocarbyl, 
 at each occurrence, R 2  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —CH 2 —CH 2 —N(R 3 ) 2 , 
 at each occurrence, R 3  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —CH 2 —CH 2 —N(R 2 ) 2 , 
 at one or more occurrences, at least one group selected from R 1 , R 2 , and R 3  in the silane-functionalized clay stabilizer PAI molecule is a silicon-containing group, and 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         6 . The composition of  claim 1 , wherein the silane-functionalized PAI clay stabilizer has the structure 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence, R 1  is independently selected from the group consisting of —H, —CH 2 —CH(OH)—(C 1 -C 5 )alkylene-O—(C 1 -C 10 )alkylene-Si(O—(C 1 -C 10 )alkyl) 3 , and —CH 2 —CH 2 —N(R 2 ) 2 , wherein at each occurrence, each (C 1 -C 10 )alkylene, (C 1 -C 8 )alkylene, and (C 1 -C 10 )alkyl is independently selected, 
 at each occurrence, R 2  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —CH 2 —CH 2 —N(R 3 ) 2 , 
 at each occurrence, R 3  is independently selected from the group consisting of —H, -L 1 -Si—(R A ) 3 , and —CH 2 —CH 2 —N(R 2 ) 2 , 
 at each occurrence, R 4  is independently selected from the group consisting of —H and -L 1 -Si—(R A ) 3 , 
 at one or more occurrences, at least one group selected from R 1 , R 2 , R 3 , and R 4  in the silane-functionalized clay stabilizer PAI molecule is a silicon-containing group, 
 n is about 2 to about 1,000,000, and 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         7 . The composition of  claim 1 , wherein the silane-functionalized PAI clay stabilizer is prepared by:
 forming a mixture comprising a silane-functionalized epoxide and a PAI; and   allowing the mixture to react to form the silane-functionalized PAI clay stabilizer.   
     
     
         8 . The composition of  claim 7 , wherein the PAI is a polymer comprising a repeating unit having the structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence of R 1  and D in the same repeating unit, 
 R 1  is independently selected from the group consisting of —H and —(X) m —CH 2 —CHE-N(R 2 ) 2 , and D is H, or 
 R 1  and D together in the same repeating unit form a (C 1 -C 10 )heterocycle with the N to which R 1  is bound, 
 at each occurrence, X is independently selected from the group consisting of —(CH 2 ) 2 —O—, —(CH 2 ) 3 —O—, —(CH 2 ) 2 —S—, —(CH 2 ) 3 —S—, and a —(C 1-10 )alkylene-, 
 at each occurrence, m is about 0 to about 10, 
 at each occurrence of R 2  and E in the same R 1  or in the same R 3 ,
 R 2  is independently selected from the group consisting of —H and —(X) m —CH 2 —CHF—N(R 3 ) 2 , and E is H, or 
 R 2  and E together in the same R 1  or in the same R 3  form a (C 1 -C 10 )heterocycle with the N to which R 2  is bound, 
 
 at each occurrence of R 3  and F in the same R 2 ,
 R 3  is independently selected from the group consisting of —H and —(X) m —CH 2 —CHE-N(R 2 ) 2 , and F is H, or 
 R 3  and F together in the same R 2  form a (C 1 -C 10 )heterocycle with the N to which R 3  is bound, and 
 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         9 . The composition of  claim 8 , wherein the PAI is PEI, wherein m is 0, D, E, and F are H, wherein the PEI is a polymer comprising a repeating unit having the structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence, R 1  is independently selected from the group consisting of —H and —CH 2 —CH 2 —N(R 2 ) 2 , 
 at each occurrence, R 2  is independently selected from the group consisting of —H, and —CH 2 —CH 2 —N(R 3 ) 2 , 
 at each occurrence, R 3  is independently selected from the group consisting of —H, and —CH 2 —CH 2 —N(R 2 ) 2 , and 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         10 . The composition of  claim 9 , wherein the PEI has the structure: 
       
         
           
           
               
               
           
         
         wherein
 n is about 2 to about 1,000,000, and 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         11 . The composition of  claim 1 , wherein the silane-functionalized PAI clay stabilizer has the structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence, R 1  is independently selected from the group consisting of —H, —CH 2 —CH(OH)—CH 2 —O—(CH 2 ) 3 —Si(OCH 3 ) 3 , and —CH 2 —CH 2 —N(R 2 ) 2 , 
 at each occurrence, R 2  is independently selected from the group consisting of —H, —CH 2 —CH(OH)—CH 2 —O—(CH 2 ) 3 —Si(OCH 3 ) 3 , and —CH 2 —CH 2 —N(R 2 ) 2 , 
 at each occurrence, R 3  is independently selected from the group consisting of —H, —CH 2 —CH(OH)—CH 2 —O—(CH 2 ) 3 —Si(OCH 3 ) 3 , and —CH 2 —CH 2 —N(R 2 ) 2 , 
 at each occurrence, R 4  is independently selected from the group consisting of —H and —CH 2 —CH(OH)—CH 2 —O—(CH 2 ) 3 —Si(OCH 3 ) 3 , 
 at one or more occurrences, at least one group selected from R 1 , R 2 , R 3 , and R 4  in the silane-functionalized PAI clay stabilizer molecule is a silicon-containing group, 
 n is about 2 to about 1,000,000, and 
 each amine group is independently in the form of a neutral amine or a protonated cationic amine. 
 
       
     
     
         12 . The composition of  claim 1 , wherein the composition further comprises a proppant, a resin-coated proppant, or a combination thereof. 
     
     
         13 . The composition of  claim 1 , wherein the clay stabilizer composition is dispersed or dissolved in a carrier fluid. 
     
     
         14 . The composition of  claim 1 , wherein the composition further comprises a secondary clay stabilizer. 
     
     
         15 . The composition of  claim 14 , wherein the secondary clay stabilizer comprises potassium chloride, a non-polymeric ionic liquid, an inorganic phosphate, a polyalkoxy diamine or a salt thereof, choline or a choline derivative, an oligomethylene diamine or a salt thereof, an addition product of carboxymethyl cellulose and an organic amine, 1,2-cyclohexanediamine or a salt thereof, a salt of a phosphoric acid ester of an oxyalkylated polyol, a combination of a partially hydrolyzed acrylic copolymer potassium chloride and polyanionic cellulose, a quaternary ammonium compound, a polymer based on dialkyl aminoalkyl methacrylate, an aqueous solution containing a polymer with hydrophilic and hydrophobic groups, a reaction product of a polyhydroxyalkane and an alkylene oxide, or a combination thereof. 
     
     
         16 . A composition comprising a silane-functionalized epoxide and a PAI, wherein
 the silane-functionalized epoxide and the PAI are reactable to form a silane-functionalized PAI clay stabilizer; and   the composition is active to stabilize a clay of a subterranean clay formation against clay swelling, clay migration, and fines generation in the subterranean formation via covalent silyl bond formation and electrostatic interaction between the clay and the silane-functionalized PAI clay stabilizer.   
     
     
         17 . The composition of  claim 16 , wherein the composition comprises a pH of about 8 to about 10. 
     
     
         18 . The composition of  claim 16 , wherein the silane-functionalized epoxide has the structure: 
       
         
           
           
               
               
           
         
         wherein
 at each occurrence, L 1A  is a substituted or unsubstituted (C 1 -C 20 )alkylene interrupted by —O—, 
 at each occurrence, R A  is independently selected from —O—R B , —H, and —R B , wherein at least one R A  of each —Si—(R A ) 3  is —O—R B , and 
 at each occurrence, R B  is independently substituted or unsubstituted (C 1 -C 20 )hydrocarbyl. 
 
       
     
     
         19 . The composition of  claim 16 , wherein the silane-functionalized epoxide has the structure: 
       
         
           
           
               
               
           
         
       
     
     
         20 . A system comprising:
 a tubular disposed in a subterranean formation; and   a pump configured to pump a clay stabilizer composition comprising a silane-functionalized polyalkyleneimine (PAI) clay stabilizer in the subterranean formation through the tubular, wherein the clay stabilizer composition is active to stabilize a clay of a subterranean clay formation against clay swelling, clay migration, and fines generation in the subterranean formation via covalent silyl bond formation and electrostatic interaction between the clay and the silane-functionalized PAI clay stabilizer.