Organosilicon containing compositions for enhancing hydrocarbon production and method of using the same

Abstract

Compositions useful in the reduction of excessive water in oil and gas wells and other subterranean formations comprises an organosilicon compound and a relative permeability modifier (RPM) macromolecule. The RPM is capable of impeding the production of water. The organosilicon compound is capable of forming a water-soluble silanol by hydrolysis and is preferably either an organosilane halide or organosilane alkoxide. The composition is introduced into the subterranean formation for the purpose of selectively reducing excessive production of aqueous fluids. The composition may be employed in well treatment fluids introduced into production wells or injection wells. The compositions may also be utilized in conjunction with stimulation treatments and with introduction of other well treatment fluids. By introducing the composition into fluid passages of the formation, the water producing zones can be selectively blocked off. Thus, the ability of fluids to flow through the aqueous fluid containing fluid passages is selectively reduced resulting in the reduced production of aqueous fluids while maintaining production of hydrocarbons. Core flow test results show effectiveness at permeability as high as 7.0 Darcy under high rate flow conditions.

What is claimed is:  
     
         1 . A method for reducing or eliminating the production of water in an oil or gas well by introducing into the well an aqueous composition comprising a mixture of: 
 (a) an organosilicon compound capable of forming a water-soluble silanol by hydrolysis; and    (b) a relative permeability modifier (RPM) macromolecule capable of impeding the production of water.    
     
     
         2 . The method of  claim 1 , wherein the concentration of RPM in the aqueous composition is between from about 100 to about 80,000 ppm.  
     
     
         3 . The method of  claim 1 , wherein the concentration of organosilicon compound is between from about 500 to about 20,000 ppm.  
     
     
         4 . The method of  claim 1 , wherein the organosilicon compound is capable of binding both to the RPM as well as formation substrate minerals in the well.  
     
     
         5 . The method of  claim 4 , wherein the formation substrate minerals include quartz, clay, shale, silt, chert, zeolite, or a combination thereof.  
     
     
         6 . The method of  claim 1 , wherein the formation permeability in the oil or gas well is between from about 0.1 to about 8,000 md.  
     
     
         7 . The method of  claim 1 , wherein the organosilicon compound is an organosilane halide of the formula:  
       
         
           
           
               
               
           
         
       
       wherein X is a halogen, R 1  is an organic radical having from 1 to about 50 carbon atoms, and R 2  and R 3  are the same or different halogens or organic radicals having from 1 to about 50 carbon atoms.  
     
     
         8 . The method of  claim 7 , wherein X is a halogen selected from the group consisting of chlorine, bromine and iodine, R 1  is an alkyl, alkenyl, alkoxide or aryl group having from 1 to about 18 carbon atoms and R 2  and R 3  are the same or different halogens selected from the group consisting of chlorine, bromine and iodine or alkyl, alkenyl, alkoxide or aryl group having from 1 to about 18 carbon atoms.  
     
     
         9 . The method of  claim 8 , wherein X is chlorine.  
     
     
         10 . The method of  claim 7 , wherein the organosilane halide is selected from methyldiethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, diethyldiiodosilane, dipropyldichlorosilane, dipropyldibromosilane, butyltrichlorosilane, phenyltribromosilane, diphenyldichlorosilane, tolyltribromosilane, propyldimethoxychlorosilane and methylphenyldichlorosilane.  
     
     
         11 . The method of  claim 1 , wherein the organosilicon compound is an organosilane alkoxide of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 4 , R 5  and R 6  are independently selected from hydrogen and organic radicals having from 1 to about 50 carbon atoms, provided not all of R 4 , R 5  and R 6  are hydrogen; and R 7  is an organic radical having from 1 to about 50 carbon atoms.  
     
     
         12 . The method of  claim 11 , wherein R 4 , R 5  and R 6  are independently selected from hydrogen, amine, alkyl, alkenyl, aryl and carbohydroxyl groups having from 1 to about 18 carbon atoms, with at least one of the R 4 , R 5  and R 6  groups not being hydrogen, and R 7  is selected from amine, alkyl, alkenyl, and aryl groups having from 1 to 18 carbon atoms.  
     
     
         13 . The method of  claim 1 , wherein the RPM macromolecule has a molecular weight between from about 50,000 to about 20,000,000 g/mole.  
     
     
         14 . The method of  claim 13 , wherein the RPM macromolecule has a molecular weight between from about 100,000 to about 5,000,000 g/mole.  
     
     
         15 . The method of  claim 14 , wherein the RPM macromolecule has a molecular weight between from about 250,000 to about 2,000,000 g/mole.  
     
     
         16 . The method of  claim 1 , wherein the RPM macromolecule is derived from acrylamide.  
     
     
         17 . The method of  claim 16 , wherein the RPM macromolecule is a homopolymer or copolymer of acrylamide which has been sulfonated or quaternized.  
     
     
         18 . The method of  claim 16 , wherein the RPM macromolecule is a copolymer of acrylamide and at least one monomer selected from acrylic acid, (meth)acrylic acid, dimethyldiallylammonium chloride, acrylamidoethyltrimethylammonium chloride, methacrylamidoethyltrimethylammonium chloride, acrylamidomethylpropanesulfonic acid, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, N-vinylmethylacetamide, acrylamidoethyltrimethylammonium chloride, vinyl sulfonic acid, maleic acid, itaconic acid, styrene sulfonic acid, vinylsulfonic acid, methylenebisacrylamide and vinylphosphonic acid and sulfonate monomers thereof.  
     
     
         19 . The method of  claim 1 , wherein the RPM macromolecule is a polyvinyl alcohol or polysiloxane.  
     
     
         20 . The method of  claim 19 , wherein the polyvinylalcohol has a degree of hydrolysis between from about 50% to about 100%.  
     
     
         21 . The method of  claim 1 , wherein the RPM macromolecule is a hydrophilic polymer selected from natural gums and a chemically modified derivative thereof.  
     
     
         22 . The method of  claim 21 , wherein the RPM macromolecule is guar, carrageenan, gum Arabic, gum ghatti, karaya, tragacanth, pectin, starch, locust bean gum, scleroglucan, tamarind, xanthan gums or a hydroxyethyl, hydroxypropyl, hydroxypropylcarboxymethyl, hydroxyethylcarboxymethyl, carboxymethyl or methyl cellulose derivative.  
     
     
         23 . A method for controlling water by treating a subterranean formation in a production well, comprising introducing a water control treatment fluid into said formation through said production well, said water control treatment fluid comprising: 
 (a) an organosilicon compound comprising an organosilane halide or an organosilane alkoxide; and    (b) a relative permeability modifier (RPM) macromolecule capable of impeding the production of water wherein said water control treatment fluid is introduced at a flow rate less than that necessary to fracture said formation.    
     
     
         24 . The method of  claim 23 , wherein the organosilicon compound is capable of binding both to the RPM macromolecule as well as to formation substrate minerals.  
     
     
         25 . The method of  claim 24 , wherein the formation substrate minerals include quartz, clay, shale, silt, chert, zeolite, or a combination thereof.  
     
     
         26 . The method of  claim 23 , wherein the formation permeability in the subterranean formation is from about 0.1 to about 8,000 md.  
     
     
         27 . A method for treating a subterranean formation, comprising: 
 (a) introducing a water control treatment fluid into said formation, said water control treatment fluid comprising: 
 (i.) an organosilicon compound comprising an organosilane halide or an organosilane alkoxide; and  
 (ii.) a relative permeability modifier (RPM) macromolecule capable of impeding the production of water  
 wherein said water control treatment fluid is introduced into said subterranean formation prior to, together with, or following a hydraulic fracturing or stimulation fluid into said subterranean formation.  
   
     
     
         28 . The method of  claim 27 , wherein the organosilicon compound is capable of binding both to the RPM as well as to formation substrate minerals.  
     
     
         29 . The method of  claim 28 , wherein the formation substrate minerals include quartz, clay, shale, silt, zeolite or a combination thereof.  
     
     
         30 . The method of  claim 27 , wherein the formation permeability ranges from about 0.1 to about 8,000 md.  
     
     
         31 . A method of treating a subterranean water injection well by introducing a treatment fluid into said formation through said water injection well, said treatment fluid comprising: 
 (a) an organosilicon compound capable of forming a water-soluble silanol by hydrolysis; and    (b) a relative permeability modifier (RPM) macromolecule capable of reducing the permeability of the primary water pathway within the formation wherein said treatment fluid is introduced at a flow rate below that necessary to fracture said formation.    
     
     
         32 . The method of  claim 31 , wherein the organosilicon compound is capable of binding both to the RPM macromolecule as well as to formation substrate minerals.  
     
     
         33 . The method of  claim 32 , wherein the formation substrate minerals include quartz, clay, shale, silt, chert, zeolite, or a combination thereof.  
     
     
         34 . The method of  claim 31 , wherein the formation permeability of the subterranean water injection well is from about 0.1 to about 8,000 md.  
     
     
         35 . The method of  claim 1 , wherein the organosilicon compound and RPM macromolecule is present in the aqueous composition in an amount capable of imparting a resistance factor for water of greater than about 5 and a resistance factor for oil of less than about 2, each of said water and oil resistance factors being measured at a laminar stable flow rate at constant pressure.  
     
     
         36 . The method of  claim 27 , wherein the water control treatment is introduced into the formation at flow rates below a flow rate that would cause pressures to exceed those necessary to fracture the formation.  
     
     
         37 . The method of  claim 1 , wherein the aqueous composition is a stimulation fluid.  
     
     
         38 . The method of  claim 23 , wherein the aqueous composition is introduced into the subterranean formation prior to, together with, or following a stimulation fluid.  
     
     
         39 . The method of  claim 23 , wherein the water control treatment fluid further comprises a mutual solvent.  
     
     
         40 . The method of  claim 35 , wherein the resistance factor for water is greater than 8.0.  
     
     
         41 . A water treatment fluid for use in an oil or gas well comprising a mixture of: 
 (a) an organosilicon compound capable of forming a water soluble silanol by hydrolysis; and    (b) a relative permeability modifier (RPM) macromolecule capable of impeding the production of water in the oil or gas well.    
     
     
         42 . The water treatment fluid of  claim 41 , wherein the concentration of RPM in the water treatment fluid is between from about 100 to about 80,000 ppm.  
     
     
         43 . The water treatment fluid of  claim 41 , wherein the concentration of organosilicon compound is between from about 500 to about 20,000 ppm.  
     
     
         44 . The water treatment fluid of  claim 41 , wherein the organosilicon compound is capable of binding both to the RPM as well as formation substrate minerals in the well.  
     
     
         45 . The water treatment fluid of  claim 41 , wherein the organosilicon compound is an organosilane halide of the formula:  
       
         
           
           
               
               
           
         
       
       wherein X is a halogen, R 1  is an organic radical having from 1 to 50 carbon atoms, and R 2  and R 3  are the same or different halogens or organic radicals having from 1 to 50 carbon atoms.  
     
     
         46 . The water treatment fluid of  claim 45 , wherein X is a halogen selected from the group consisting of chlorine, bromine and iodine, R 1  is an alkyl, alkenyl or aryl group having from 1 to about 18 carbon atoms and R 2  and R 3  are the same or different halogens or alkyl, alkenyl or aryl group having from 1 to about 18 carbon atoms.  
     
     
         47 . The water treatment fluid of  claim 46 , wherein X is chlorine.  
     
     
         48 . The water treatment fluid of  claim 41 , wherein the organosilicon compound is an organosilane halide selected from methyldiethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethyldibromosilane, diethyldiiodosilane, dipropyldichlorosilane, dipropyldibromosilane, butyltrichlorosilane, phenyltribromosilane, diphenyldichlorosilane, tolyltribromosilane, propyldimethoxychlorosilane and methylphenyldichlorosilane.  
     
     
         49 . The method of  claim 41 , wherein the organosilicon compound is an organosilane alkoxide of the formula:  
       
         
           
           
               
               
           
         
       
       wherein R 4 , R 5  and R 6  are independently selected from hydrogen and organic radicals having from 1 to about 50 carbon atoms, provided not all of R 4 , R 5  and R 6  are hydrogen and R 7  is an organic radical having from 1 to about 50 carbon atoms.  
     
     
         50 . The water treatment fluid of  claim 49 , wherein R 4 , R 5  and R 6  are independently selected from hydrogen, amine, alkyl, alkenyl, aryl and carbohydroxyl groups having from 1 to about 18 carbon atoms, with at least one of the R 4 , R 5  and R 6  groups not being hydrogen and R 7  is selected from amine, alkyl, alkenyl, and aryl groups having from 1 to about 18 carbon atoms.  
     
     
         51 . The water treatment fluid of  claim 41 , wherein the RPM macromolecule has a molecular weight between from about 50,000 to about 20,000,000 g/mole.  
     
     
         52 . The water treatment fluid of  claim 51 , wherein the RPM macromolecule has a molecular weight between from about 100,000 to about 5,000,000 g/mole.  
     
     
         53 . The water treatment fluid of  claim 52 , wherein the RPM macromolecule has a molecular weight between from about 250,000 to about 2,000,000 g/mole.  
     
     
         54 . The water treatment fluid of  claim 41 , wherein the RPM macromolecule is derived from acrylamide.  
     
     
         55 . The water treatment fluid of  claim 54 , wherein the RPM macromolecule is a homopolymer or copolymer of acrylamide which has been sulfonated or quaternized.  
     
     
         56 . The water treatment fluid of  claim 41 , wherein the RPM macromolecule is a copolymer of acrylamide and at least one monomer selected from acrylic acid, (meth)acrylic acid, dimethyldiallylammonium chloride, acrylamidoethyltrimethylammonium chloride, methacrylamidoethyltrimethylammonium chloride, acrylamidomethylpropanesulfonic acid, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, N-vinylmethylacetamide, acrylamidoethyltrimethylammonium chloride, vinyl sulfonic acid, maleic acid, itaconic acid, styrene sulfonic acid, methylenebisacrylamide, vinylsulfonic acid and vinylphosphonic acid and sulfonate monomers thereof.  
     
     
         57 . The water treatment fluid of  claim 41 , wherein the RPM macromolecule is a polyvinylalcohol or polysiloxane.  
     
     
         58 . The water treatment fluid of  claim 57 , wherein the polyvinylalcohol has a degree of hydrolysis between from about 50% to about 100%.  
     
     
         59 . The water treatment fluid of  claim 41 , wherein the RPM macromolecule is a hydrophilic polymer selected from natural gums and a chemically modified derivative thereof.  
     
     
         60 . The water treatment fluid of  claim 59 , wherein the RPM macromolecule is guar, carrageenan, gum Arabic, gum ghatti, karaya, tragacanth, pectin, starch, locust bean gum, scleroglucan, tamarind, xanthan gums or hydroxyethyl, hydroxypropyl, hydroxypropylcarboxymethyl, hydroxyethylcarboxymethyl, carboxymethyl or methyl cellulose derivative.