Compositions and method for improving the productivity of hydrocarbon producing wells

Abstract

Compositions comprise nonionic fluorinated polymeric surfactants and solvent. The solvent comprises: at least one of a polyol or polyol ether, wherein the polyol and polyol ether have from 2 to 10 carbon atoms; and at least one monohydroxy alcohol, ether, or ketone having from 1 to 4 carbon atoms, or a mixture thereof, wherein the solvent is capable of at least one of solubilizing or displacing brine or condensate in the hydrocarbon-bearing clastic formation. Embodiments of the compositions are useful in recovery of hydrocarbons from hydrocarbon-bearing clastic formations that contain brine and/or condensate.

1 . A composition comprising:
 a nonionic fluorinated polymeric surfactant, wherein the nonionic fluorinated polymeric surfactant comprises:   (a) at least one divalent unit represented by the formula:   
       
         
           
           
               
               
           
         
         (b) at least one divalent unit represented by a formula: 
       
       
         
           
           
               
               
           
         
         wherein
 R f  represents a perfluoroalkyl group having from 1 to 8 carbon atoms; 
 R, R 1 , and R 2  are each independently hydrogen or alkyl of 1 to 4 carbon atoms; 
 n is an integer from 2 to 10; 
 EO represents —CH 2 CH 2 O—; 
 each PO independently represents —CH(CH 3 )CH 2 O— or —CH 2 CH(CH 3 )O—; 
 each p is independently an integer of from 1 to about 128; and 
 each q is independently an integer of from 0 to about 55; and 
 
         solvent comprising:
 at least one of a polyol or polyol ether, wherein the polyol and polyol ether have from 2 to 10 carbon atoms; and 
 at least one monohydroxy alcohol, ether, or ketone having from 1 to 4 carbon atoms, or a mixture thereof. 
 
       
     
     
         2 . The composition of  claim 1 , wherein the solvent is capable of at least one of solubilizing or displacing brine or condensate in a hydrocarbon-bearing clastic formation. 
     
     
         3 . The composition of  claim 1 , wherein said at least one polyol or polyol ether comprises at least one of ethylene glycol, propylene glycol, 1,3-propanediol, 1,8-octanediol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, or dipropylene glycol monomethyl ether. 
     
     
         4 . The composition of  claim 1 , wherein the solvent comprises at least one monohydroxy alcohol having from 1 to 4 carbon atoms. 
     
     
         5 . The composition of  claim 1 , wherein said at least one monohydroxy alcohol, ether, or ketone having from 1 to 4 carbon atoms comprises at least one of methanol, ethanol, isopropanol, tetrahydrofuran, or acetone. 
     
     
         6 . The composition of  claim 1 , wherein the composition is essentially free of water. 
     
     
         7 . The composition of  claim 1 , wherein the composition is homogenous at a temperature of at least 100° F. 
     
     
         8 . The composition of  claim 1 , wherein the polyol and polyol ether have a normal boiling point of less than 450° F. 
     
     
         9 . The composition of  claim 1 , wherein R f  is perfluorobutyl. 
     
     
         10 . The composition of  claim 1 , wherein the nonionic fluorinated polymeric surfactant has a number average molecular weight in the range of from 1,000 to 30,000 grams/mole. 
     
     
         11 . A method of treating a hydrocarbon-bearing clastic formation, the method comprising injecting a composition into the hydrocarbon-bearing clastic formation, wherein the composition comprises:
 a nonionic fluorinated polymeric surfactant, wherein the nonionic fluorinated polymeric surfactant comprises:   (a) at least one divalent unit represented by the formula:   
       
         
           
           
               
               
           
         
         (b) at least one divalent unit represented by a formula: 
       
       
         
           
           
               
               
           
         
         wherein
 R f  represents a perfluoroalkyl group having from 1 to 8 carbon atoms; 
 R, R 1 , and R 2  are each independently hydrogen or alkyl of 1 to 4 carbon atoms; 
 n is an integer from 2 to 10; 
 EO represents —CH 2 CH 2 O—; 
 each PO independently represents —CH(CH 3 )CH 2 O— or —CH 2 CH(CH 3 )O—; 
 each p is independently an integer of from 1 to about 128; and 
 each q is independently an integer of from 0 to about 55; and 
 
         solvent comprising:
 at least one of a polyol or polyol ether, wherein the polyol and polyol ether have from 2 to 10 carbon atoms; and 
 at least one monohydroxy alcohol, ether, or ketone having from 1 to 4 carbon atoms, or a mixture thereof, 
 wherein the solvent is capable of at least one of solubilizing or displacing brine or condensate in the hydrocarbon-bearing clastic formation. 
 
       
     
     
         12 . The method of  claim 11 , wherein the solvent is capable of at least one of solubilizing or displacing brine in the hydrocarbon-bearing clastic formation. 
     
     
         13 . The method of  claim 11 , wherein the brine comprises connate water. 
     
     
         14 . The method of  claim 11 , wherein said at least one polyol or polyol ether comprises at least one of ethylene glycol, propylene glycol, 1,3-propanediol, 1,8-octanediol, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, or dipropylene glycol monomethyl ether. 
     
     
         15 . The method of  claim 11 , wherein the solvent comprises at least one monohydroxy alcohol having from 1 to 4 carbon atoms. 
     
     
         16 . The method of  claim 11 , wherein said at least one monohydroxy alcohol, ether, or ketone having from 1 to 4 carbon atoms comprises at least one of methanol, ethanol, isopropanol, tetrahydrofuran, or acetone. 
     
     
         17 . The method of  claim 11 , wherein the composition is essentially free of water. 
     
     
         18 . The method of  claim 11 , wherein the hydrocarbon-bearing clastic formation has at least one temperature, and wherein the composition is homogenous at the temperature. 
     
     
         19 . The method of  claim 11 , wherein the polyol and polyol ether have a normal boiling point of less than 450° F. 
     
     
         20 . The method of  claim 11 , wherein R f  is perfluorobutyl. 
     
     
         21 . The method of  claim 11 , wherein the nonionic fluorinated polymeric surfactant has a number average molecular weight in the range from 1,000 to 30,000 grams/mole. 
     
     
         22 . The method of  claim 11 , wherein the hydrocarbon-bearing clastic formation is downhole. 
     
     
         23 . The method of  claim 11 , wherein downhole conditions comprise a pressure in a range from about 1 bar to 1000 bars and a temperature in a range of from about 100° F. to 400° F. 
     
     
         24 . The method of  claim 11 , wherein the composition is injected into the hydrocarbon-bearing clastic formation during fracturing, after fracturing, or during and after fracturing, the hydrocarbon-bearing clastic formation. 
     
     
         25 . The method of  claim 11 , wherein the hydrocarbon-bearing clastic formation has a wellbore therein, the method further comprising obtaining hydrocarbons from the wellbore after injecting the composition into the hydrocarbon-bearing clastic formation.