Emulsions containing water-soluble acid retarding agents and methods of making and using

Abstract

Described herein is a multi-phase aqueous composition containing a surfactant; a first phase comprising water, an acid, and a water-soluble acid retarding agent; and a second phase selected from the group consisting of an immiscible organic phase, a gas, and combinations thereof. Further described are methods of making and using such compositions.

What is claimed is: 
     
         1 . A multi-phase aqueous composition comprising:
 a surfactant;   a first phase comprising water, an acid, and a water-soluble acid retarding agent; and   a second phase selected from the group consisting of an immiscible organic phase, a gas, and combinations thereof.   
     
     
         2 . The multi-phase aqueous composition of  claim 1 , wherein the acid is selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen fluoride, sulfuric acid, nitric acid, phosphoric acid, alkanesulfonic acids, arylsulfonic acids, acetic acid, formic acid, alkyl carboxylic acids, acrylic acid, lactic acid, glycolic acid, malonic acid, fumaric acid, citric acid, tartaric acid, and combinations thereof. 
     
     
         3 . The multi-phase aqueous composition of  claim 1 , wherein the water-soluble acid retarding agent is selected from the group consisting of a salt, urea or one if its derivatives, an alpha-amino acid, a beta-amino acid, a gamma-amino acid, an alcohol with one to five carbons, a surfactant having a structure in accordance with Formula I, and combinations thereof: 
       
         
           
           
               
               
           
         
         in which R 1  is a hydrocarbyl group that may be branched or straight chained, aromatic, aliphatic or olefinic and contains from about 1 to about 26 carbon atoms and may include an amine; R 2  is hydrogen or an alkyl group having from 1 to about 4 carbon atoms; R 3  is a hydrocarbyl group having from 1 to about 5 carbon atoms; and Y is an electron withdrawing group. 
       
     
     
         4 . The multi-phase aqueous composition of  claim 3 , wherein the salt comprises:
 i) a cation selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, tin, ammonium, alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium, and   ii) an anion selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, bisulfate, sulfite, bisulfite nitrate, alkanesulfonates, arylsulfonates, acetate, formate, and combinations thereof.   
     
     
         5 . The multi-phase aqueous composition of  claim 1  wherein the surfactant is a foaming agent and the second phase comprises the gas. 
     
     
         6 . The multi-phase aqueous composition of  claim 5  wherein the multi-phase aqueous composition is in the form of a foam. 
     
     
         7 . The multi-phase aqueous composition of  claim 1 , wherein the gas is selected from the group consisting of nitrogen, carbon dioxide, oxygen, helium, argon, hydrogen, methane, ethane, propane or butane, or a combination thereof. 
     
     
         8 . The multi-phase aqueous composition of  claim 1  wherein the second phase comprises the immiscible organic phase. 
     
     
         9 . The multi-phase aqueous composition of  claim 8 , wherein the multi-phase aqueous composition is in the form of an emulsion where the first phase is a continuous phase and the second phase is a discontinuous phase and is stabilized by the surfactant. 
     
     
         10 . The multi-phase aqueous composition of  claim 9  wherein the surfactant is an ethoxylated nonionic surfactant of the structure RO(CH 2 CH 2 O) n H, where R is an alkyl group of 6 to 18 carbons, and 1≤n≤10. 
     
     
         11 . The multi-phase aqueous composition of  claim 8 , wherein the multi-phase aqueous composition is in the form of an emulsion where the second phase is a continuous phase and the first phase is a discontinuous phase and is stabilized by the surfactant. 
     
     
         12 . The multi-phase aqueous composition of  claim 12  wherein the surfactant is a cationic surfactant of the structure [RNXYZ] +  A − , where R is an alkyl chain of 10 to 18 carbons. X, Y and Z are selected from methyl, ethyl, hydroxyethyl or benzyl, wherein X, Y and Z can be the same or different; and A is an anion selected from the group consisting of fluoride, chloride, bromide, iodide, acetate, sulfate, alkylsulfonate, or arylsulfonate. 
     
     
         13 . A method comprising:
 providing a multi-phase aqueous composition comprising:
 a surfactant; 
 a first phase comprising water, an acid, and a water-soluble acid retarding agent; 
 a second phase selected from the group consisting of an immiscible organic phase, a gas, and combinations thereof; and 
   treating a subterranean formation fluidly coupled to a wellbore with an oilfield treatment fluid comprising the multi-phase aqueous composition.   
     
     
         14 . The method of  claim 13 , wherein the acid is selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen fluoride, sulfuric acid, nitric acid, phosphoric acid, alkanesulfonic acids, arylsulfonic acids, acetic acid, formic acid, alkyl carboxylic acids, acrylic acid, lactic acid, glycolic acid, malonic acid, fumaric acid, citric acid, tartaric acid, and combinations thereof. 
     
     
         15 . The method of  claim 13 , wherein the water-soluble acid retarding agent is selected from the group consisting of a salt, urea or one if its derivatives, an alpha-amino acid, a beta-amino acid, a gamma-amino acid, an alcohol with one to five carbons, a surfactant having a structure in accordance with Formula I, and combinations thereof: 
       
         
           
           
               
               
           
         
         in which R 1  is a hydrocarbyl group that may be branched or straight chained, aromatic, aliphatic or olefinic and contains from about 1 to about 26 carbon atoms and may include an amine; R 2  is hydrogen or an alkyl group having from 1 to about 4 carbon atoms; R 3  is a hydrocarbyl group having from 1 to about 5 carbon atoms; and Y is an electron withdrawing group. 
       
     
     
         16 . The method of  claim 15 , wherein the salt comprises:
 i) a cation selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, tin, ammonium, alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium, and   ii) an anion selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, bisulfate, sulfite, bisulfite nitrate, alkanesulfonates, arylsulfonates, acetate, formate, and combinations thereof.   
     
     
         17 . The method of  claim 13  wherein the surfactant is a foaming agent and the second phase comprises the gas, wherein the gas is selected from the group consisting of nitrogen, carbon dioxide, oxygen, helium, argon, hydrogen, methane or ethane, or a combination thereof. 
     
     
         18 . The method of  claim 17  wherein the multi-phase aqueous composition is in the form of a foam. 
     
     
         19 . The method of  claim 13  wherein the second phase comprises the immiscible organic phase, and wherein the multi-phase aqueous composition is in the form of an emulsion where the first phase is a continuous phase and the second phase is a discontinuous phase and is stabilized by the surfactant. 
     
     
         20 . The method of  claim 13 , wherein the second phase comprises the immiscible organic phase, wherein the multi-phase aqueous composition is in the form of an emulsion where the second phase is a continuous phase and the first phase is a discontinuous phase and is stabilized by the surfactant. 
     
     
         21 . A method comprising:
 treating a subterranean formation fluidly coupled to a wellbore with an oilfield treatment fluid comprising a multi-phase aqueous composition comprising:   a surfactant comprising a foaming agent;   a first phase comprising water, an acid, and a water-soluble acid retarding agent; and   a second phase comprising a gas selected from the group consisting of nitrogen, carbon dioxide, oxygen, helium, argon, hydrogen, methane or ethane, or a combination thereof; wherein the multi-phase aqueous composition is in the form of a foam.   
     
     
         22 . The method of  claim 21 , wherein the acid is selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen fluoride, sulfuric acid, nitric acid, phosphoric acid, alkanesulfonic acids, arylsulfonic acids, acetic acid, formic acid, alkyl carboxylic acids, acrylic acid, lactic acid, glycolic acid, malonic acid, fumaric acid, citric acid, tartaric acid, and combinations thereof. 
     
     
         23 . The method of  claim 21 , wherein the water-soluble acid retarding agent is selected from the group consisting of a salt, urea or one if its derivatives, an alpha-amino acid, a beta-amino acid, a gamma-amino acid, an alcohol with one to five carbons, a surfactant having a structure in accordance with Formula I, and combinations thereof: 
       
         
           
           
               
               
           
         
         in which R 1  is a hydrocarbyl group that may be branched or straight chained, aromatic, aliphatic or olefinic and contains from about 1 to about 26 carbon atoms and may include an amine; R 2  is hydrogen or an alkyl group having from 1 to about 4 carbon atoms; R 3  is a hydrocarbyl group having from 1 to about 5 carbon atoms; and Y is an electron withdrawing group. 
       
     
     
         24 . The method of  claim 23 , wherein the salt comprises:
 i) a cation selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, tin, ammonium, alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium, and   ii) an anion selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, bisulfate, sulfite, bisulfite nitrate, alkanesulfonates, arylsulfonates, acetate, formate, and combinations thereof.   
     
     
         25 . The method of  claim 21 , wherein the multi-phase aqueous composition is formed by:
 i) introducing the surfactant and the first phase into the subterranean formation, and   ii) separately introducing the gas into the subterranean formation for contact with the surfactant and the first phase with sufficient energy to form the multi-phase aqueous composition in the form of a foam.