Methods for making and using novel foamer compositions

Abstract

Methods for using new general purpose foaming agents having application as drilling fluid foaming agents or as any foaming agent needed an a wide variety of applications is disclosed including at least one anionic surfactant, at least one cationic surfactant, and mixtures thereof and one or more zwitterionic compounds. The foaming agents can also include additive to augment the properties of the foaming agent for a given application.

We claim: 
     
         1 . A method for foaming a downhole fluid comprising the steps of:
 adding to the fluid a gas and an effective amount of a foaming composition comprising a first anionic surfactant including anionic surfactants having between 2 and about 10 carbon atoms and a second anionic surfactant including anionic surfactants having between about 10 to about 24 carbon atoms in a single addition, in multiple additions or continual additions to form a foamed downhole fluid,   where the foaming composition is biodegradable, is heat stable at a temperature of 280° F., has a near zero Zeta potential, and produces no residuals at temperatures up to 280° F.   
     
     
         2 . The method of  claim 1 , wherein the first and second anionic surfactants are selected from the group consisting of anionic sulfate surfactants, alkyl ether sulfonates, alkylaryl sulfonates, and mixtures or combinations. 
     
     
         3 . The method of  claim 2 , wherein:
 the anionic sulfate surfactants comprise sodium or ammonium alcohol ether sulfate surfactants or mixtures thereof;   the alkyl ether sulfonates comprises compounds of the general formula R 2 [—(O—(R 3 O) m —(R 4 O) n —(R 5 )] y SO 3 X, where: R 2 =alkyl, alkenyl, amine, alkylamine, dialkylamine, trialkylamine, aromatic, polyaromatic, cycloalkane, cycloalkene, R 3  and R 4 ′C 2 H 4  or C 3 H 6  or C 4 H 8,  m is greater or equal to 1, n is greater or equal to 0, n+m=1 to 30, y is greater or equal to 1, X=alkali metal or alkaline earth metal or ammonium or amine or mixtures thereof; and   the alkylaryl sulfonates selected from the group consisting of alkylbenzene sulfonic acids and their salts, dialkylbenzene disulfonic acids and their salts, dialkylbenzene sulfonic acids and their salts, alkyltoluene/alkyl xylene sulfonic acids and their salts, alkylnaphthalene sulfonic acids/condensed alkyl naphthalene sulfonic acids and their salts, alkylphenol sulfonic acids/condensed alkylphenol sulfonic acids and their salts, or mixtures thereof.   
     
     
         4 . The method of  claim 3 , wherein ammonium alcohol ether sulfate surfactants comprise compounds of the general formula R 1 O—(CH 2 CH 2 O) n SO 3 NH 4 , where R 1  is a carbon-containing group including an alkyl group, an aryl group, an alkaryl group, an aralkyl group or mixture thereof. 
     
     
         5 . The method of  claim 1 , wherein:
 the first anionic surfactant comprises a sodium or ammonium alcohol ether sulfate surfactant or mixtures thereof, where the sodium or ammonium alcohol ether sulfate surfactants having between about 4 and about 10 carbon atoms, and   the second anionic surfactant comprises a sodium or ammonium alcohol ether sulfate surfactant or mixtures thereof, where the sodium or ammonium alcohol ether sulfate surfactants having between about 12 and about 18 carbon atoms.   
     
     
         6 . The method of  claim 1 , wherein the foaming composition further includes:
 a zwitterionic compound selected from the group consisting of betaine(s), sulfo-betaine(s), amino acid(s), phospholipid(s), and mixtures or combinations thereof;   a cationic surfactant including a bis quaternary ammonium halide or mixtures thereof; or   an additive selected from the group consisting of a winterizing agent, a foam booster, a anti-freeze agents, a solvent, a sodium salt of alpha olefin sulfonate (AOS), an acid salt, a nonionic surfactant, a fatty acid, a foam enhancer and mixtures or combinations thereof.   
     
     
         7 . The method of  claim 6 , wherein the betaines are selected from compounds of:
 (1) the general structure R 6 ,R 7 ,R 8 N + —R 9 —CO 2   − , where R 6 , R 7 , and R 8  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, and R 9  is an alkenyl group, alkenyloxide group or mixtures thereof;   (2) the general structure R 10 (R 7 ,R 8 N + —R 9 —CO 2   − ) n , where R 7  and R 8  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, R 9  is an alkenyl group, alkenyloxide group or mixtures thereof, and R 10  is a multivalent substituent having a valency n between 2 and about 6;   (3) the general structure R 12 —C(O)—N(R 11 )—R 13 —N + (R 7 ,R 8 )—R 9 —CO 2   − , where R 7 , R 8 , R 11  and R 12  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, and R 9  and R 13  are the same or different alkenyl group, alkenyloxide group or mixtures thereof;   (4) the general structure R 14 —[R 15 —C(O)—N(R 11 )—R 13 —N + (R 7 ,R 8 )—R 9 —CO 2   − ] m , where R 7 , R 8  and R 11  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, R 9 , R 13  and R 15  are the same or different alkenyl group, alkenyloxide group or mixtures thereof and R 14  is a multivalent substituent having a valency m between 2 and about 6; and   (5) mixtures or combinations thereof.   
     
     
         8 . The method of  claim 7 , wherein the betaines are selected from group consisting of cocamidopropyl betaine, 5-(1-piperidiniomethyl)-1H-tetrazolide, and mixtures or combinations thereof. 
     
     
         9 . The method of  claim 6 , wherein:
 the sulfo-betaines are selected from group consisting of N-decyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; dimethylbenzyl-(3-sulfopropyl)ammonium; dimethylethyl-(3-sulfopropyl)ammonium; dimethyl-(2-hydroxyethyl)-(3-sulfopropyl)ammonium; 4-n-hexylbenzoylamido-propyl-dimethylammoniosulfobetaine; N-methyl-N-(3-sulfopropyl)morpholinium; 4-n-octylbenzoylamido-propyl-dimethylammoniosulfobetaine; 1-(3-sulfopropyl)pyridium; N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, and mixtures or combination thereof; and   the phospholipids are selected from the group consisting of phosphatidylcholine, phosphatidylserine, phosphalidylethanolamine, sphingomyelin and other ceramides, and mixtures or combinations thereof,   the winterizing agent is selected from the group consisting of lithium formate, sodium formate, potassium formate, cesuim formate, triethyanolamine formate, and mixtures or combinations;   the foam booster comprises a cellosolve of the general formula R 9 OCH 2 CH 2 OH where R 9  is an alkyl group having between about 2 and about 8 carbon atoms and mixtures or combinations;   the anti-freeze agents selected from the group consisting of alcohols, glycols or other freezing point depressing agents and mixtures or combinations;   the solvent selected from the group consisting of water, alcohols, ethers, esters and mixtures or combinations thereof;   the sodium salt of alpha olefin sulfonate (AOSs) selected from the group consisting of short chain alpha olefin sulfonates having between about 2 and about 10 carbon atoms, longer chain alpha olefin sulfonates having between about 10 and about 24 carbon atoms and mixtures or combinations thereof;   the acid salts selected from the group consisting of cyclamic acid salts such as sodium (cyclamate), potassium, salts of sulfonated methyl esters having between about 12 and about 22 carbon atoms, where the salt is sodium, potassium, ammonium, alkylammonium, salts of 2-aminoethane sulfonic acids, where the salt is an alkali metal, ammonium, or alkylammonium, and mixtures or combinations thereof;   the nonionic surfactant is selected from the group consisting of polyalkylene oxide, amine oxides such as lauramine oxide and mixtures or combinations;   the fatty acid is selected from the group consisting of lauric acid, oleic acid, stearic acid and mixtures or combinations; and   the foam enhancer selected from the group consisting of a linear dodecyl benzene sulfonic acid salt, a sarcosinate salt, and mixtures or combinations thereof.   
     
     
         10 . A method for supply a foaming composition to a downhole fluid comprising the steps of:
 inserting at least one capillary coiled tubing into a well borehole to a desired depth below a fluid depth in the borehole, and   feeding a gas and an effective amount of a foaming composition comprising a first anionic surfactant including anionic surfactants having between 2 and about 10 carbon atoms and a second anionic surfactant including anionic surfactants having between about 10 to about 24 carbon atoms in single, multiple and/or continuation additions depending on the requirements to form a foamed downhole fluid,   where the amount is sufficient to achieve desired foamed fluid characteristics by decreasing fluid weight allowing gas to flow out of the well.   
     
     
         11 . The method of  claim 10 , wherein the first and second anionic surfactants are selected from the group consisting of anionic sulfate surfactants, alkyl ether sulfonates, alkylaryl sulfonates, and mixtures or combinations. 
     
     
         12 . The method of  claim 11 , wherein:
 the anionic sulfate surfactants comprise sodium or ammonium alcohol ether sulfate surfactants or mixtures thereof;   the alkyl ether sulfonates comprises compounds of the general formula R 2 [—(O—(R 3 O) m —(R 4 O) n —(R 5 )] y SO 3 X, where: R 2 =alkyl, alkenyl, amine, alkylamine, dialkylamine, trialkylamine, aromatic, polyaromatic, cycloalkane, cycloalkene, R 3  and R 4 ═C 2 H 4  or C 3 H 6  or C 4 H 8,  m is greater or equal to 1, n is greater or equal to 0, n+m=1 to 30, y is greater or equal to 1, X=alkali metal or alkaline earth metal or ammonium or amine or mixtures thereof; and   the alkylaryl sulfonates selected from the group consisting of alkylbenzene sulfonic acids and their salts, dialkylbenzene disulfonic acids and their salts, dialkylbenzene sulfonic acids and their salts, alkyltoluene/alkyl xylene sulfonic acids and their salts, alkylnaphthalene sulfonic acids/condensed alkyl naphthalene sulfonic acids and their salts, alkylphenol sulfonic acids/condensed alkylphenol sulfonic acids and their salts, or mixtures thereof.   
     
     
         13 . The method of  claim 12 , wherein ammonium alcohol ether sulfate surfactants comprise compounds of the general formula R 1 O—(CH 2 CH 2 O) n SO 3 NH 4 , where R 1  is a carbon-containing group including an alkyl group, an aryl group, an alkaryl group, an aralkyl group or mixture thereof. 
     
     
         14 . The method of  claim 10 , wherein:
 the first anionic surfactant comprises a sodium or ammonium alcohol ether sulfate surfactant or mixtures thereof, where the sodium or ammonium alcohol ether sulfate surfactants having between about 4 and about 10 carbon atoms, and   the second anionic surfactant comprises a sodium or ammonium alcohol ether sulfate surfactant or mixtures thereof, where the sodium or ammonium alcohol ether sulfate surfactants having between about 12 and about 18 carbon atoms.   
     
     
         15 . The method of  claim 10 , wherein the foaming composition further includes:
 a zwitterionic compound selected from the group consisting of betaine(s), sulfo-betaine(s), amino acid(s), phospholipid(s), and mixtures or combinations thereof;   a cationic surfactant including a bis quaternary ammonium halide or mixtures thereof; or   an additive selected from the group consisting of a winterizing agent, a foam booster, a anti-freeze agents, a solvent, a sodium salt of alpha olefin sulfonate (AOS), an acid salt, a nonionic surfactant, a fatty acid, a foam enhancer and mixtures or combinations thereof.   
     
     
         16 . The method of  claim 15 , wherein the betaines are selected from compounds of:
 (1) the general structure R 6 ,R 7 ,R 8 N + —R 9 —CO 2   − , where R 6 , R 7 , and R 8  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, and R 9  is an alkenyl group, alkenyloxide group or mixtures thereof;   (2) the general structure R 10 (R 7 ,R 8 N + —R 9 —CO 2   − ) n , where R 7  and R 8  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, R 9  is an alkenyl group, alkenyloxide group or mixtures thereof, and R 10  is a multivalent substituent having a valency n between 2 and about 6;   (3) the general structure R 12 —C(O)—N(R 11 )—R 13 —N + (R 7 ,R 8 )—R 9 —CO 2   − , where R 7 , R 8 , R 11  and R 12  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, and R 9  and R 13  are the same or different alkenyl group, alkenyloxide group or mixtures thereof;   (4) the general structure R 14 —[R 15 —C(O)—N(R 11 )—R 13 —N + (R 7 ,R 8 )—R 9 —CO 2   − ] m , where R 7 , R 8  and R 11  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, R 9 , R 13  and R 15  are the same or different alkenyl group, alkenyloxide group or mixtures thereof and R 14  is a multivalent substituent having a valency m between 2 and about 6; and   (5) mixtures or combinations thereof.   
     
     
         17 . The method of  claim 16 , wherein the betaines are selected from group consisting of cocamidopropyl betaine, 5-(1-piperidiniomethyl)-1H-tetrazolide, and mixtures or combinations thereof. 
     
     
         18 . The method of  claim 15 , wherein:
 the sulfo-betaines are selected from group consisting of N-decyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; dimethylbenzyl-(3-sulfopropyl)ammonium; dimethylethyl-(3-sulfopropyl)ammonium; dimethyl-(2-hydroxyethyl)-(3-sulfopropyl)ammonium; 4-n-hexylbenzoylamido-propyl-dimethylammoniosulfobetaine; N-methyl-N-(3-sulfopropyl)morpholinium; 4-n-octylbenzoylamido-propyl-dimethylammoniosulfobetaine; 1-(3-sulfopropyl)pyridium; N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, and mixtures or combination thereof; and   the phospholipids are selected from the group consisting of phosphatidylcholine, phosphatidylserine, phosphalidylethanolamine, sphingomyelin and other ceramides, and mixtures or combinations thereof,   the winterizing agent is selected from the group consisting of lithium formate, sodium formate, potassium formate, cesuim formate, triethyanolamine formate, and mixtures or combinations;   the foam booster comprises a cellosolve of the general formula R 9 OCH 2 CH 2 OH where R 9  is an alkyl group having between about 2 and about 8 carbon atoms and mixtures or combinations;   the anti-freeze agents selected from the group consisting of alcohols, glycols or other freezing point depressing agents and mixtures or combinations;   the solvent selected from the group consisting of water, alcohols, ethers, esters and mixtures or combinations thereof;   the sodium salt of alpha olefin sulfonate (AOSs) selected from the group consisting of short chain alpha olefin sulfonates having between about 2 and about 10 carbon atoms, longer chain alpha olefin sulfonates having between about 10 and about 24 carbon atoms and mixtures or combinations thereof;   the acid salts selected from the group consisting of cyclamic acid salts such as sodium (cyclamate), potassium, salts of sulfonated methyl esters having between about 12 and about 22 carbon atoms, where the salt is sodium, potassium, ammonium, alkylammonium, salts of 2-aminoethane sulfonic acids, where the salt is an alkali metal, ammonium, or alkylammonium, and mixtures or combinations thereof;   the nonionic surfactant is selected from the group consisting of polyalkylene oxide, amine oxides such as lauramine oxide and mixtures or combinations;   the fatty acid is selected from the group consisting of lauric acid, oleic acid, stearic acid and mixtures or combinations; and   the foam enhancer selected from the group consisting of a linear dodecyl benzene sulfonic acid salt, a sarcosinate salt, and mixtures or combinations thereof.   
     
     
         19 . A method comprising the steps of:
 injecting, into a downhole fluid, a gas and an effective amount of a foaming composition comprising a first anionic surfactant including anionic surfactants having between 2 and about 10 carbon atoms and a second anionic surfactant including anionic surfactants having between about 10 to about 24 carbon atoms to form a foamed downhole fluid,   adding a supplemental amount of the foaming composition and the gas to reform a foam, and   repeating the last three steps.   
     
     
         20 . The method of  claim 19 , further comprising the steps of:
 prior to the adding step, adding a defoaming agent to the foam as the foam exits the well to break the foam,   separating production fluids from the fluid, and   repeating the adding steps, the adding the defoaming step, and the separating step.   
     
     
         21 . The method of  claim 19 , wherein the first and second anionic surfactants are selected from the group consisting of anionic sulfate surfactants, alkyl ether sulfonates, alkylaryl sulfonates, and mixtures or combinations. 
     
     
         22 . The method of  claim 21 , wherein:
 the anionic sulfate surfactants comprise sodium or ammonium alcohol ether sulfate surfactants or mixtures thereof;   the alkyl ether sulfonates comprises compounds of the general formula R 2 [—(O—(R 3 O) m —(R 4 O) n —(R 5 )] y SO 3 X, where: R 2 =alkyl, alkenyl, amine, alkylamine, dialkylamine, trialkylamine, aromatic, polyaromatic, cycloalkane, cycloalkene, R 3  and R 4 ═C  2 H 4  or C 3 H 6  or C 4 H 8  m is greater or equal to 1, n is greater or equal to 0, n+m=1 to 30, y is greater or equal to 1, X=alkali metal or alkaline earth metal or ammonium or amine or mixtures thereof; and   the alkylaryl sulfonates selected from the group consisting of alkylbenzene sulfonic acids and their salts, dialkylbenzene disulfonic acids and their salts, dialkylbenzene sulfonic acids and their salts, alkyltoluene/alkyl xylene sulfonic acids and their salts, alkylnaphthalene sulfonic acids/condensed alkyl naphthalene sulfonic acids and their salts, alkylphenol sulfonic acids/condensed alkylphenol sulfonic acids and their salts, or mixtures thereof.   
     
     
         23 . The method of  claim 22 , wherein ammonium alcohol ether sulfate surfactants comprise compounds of the general formula R 1 O—(CH 2 CH 2 O) n SO 3 NH 4 , where R 1  is a carbon-containing group including an alkyl group, an aryl group, an alkaryl group, an aralkyl group or mixture thereof. 
     
     
         24 . The method of  claim 19 , wherein:
 the first anionic surfactant comprises a sodium or ammonium alcohol ether sulfate surfactant or mixtures thereof, where the sodium or ammonium alcohol ether sulfate surfactants having between about 4 and about 10 carbon atoms, and   the second anionic surfactant comprises a sodium or ammonium alcohol ether sulfate surfactant or mixtures thereof, where the sodium or ammonium alcohol ether sulfate surfactants having between about 12 and about 18 carbon atoms.   
     
     
         25 . The method of  claim 19 , wherein the foaming composition further includes:
 a zwitterionic compound selected from the group consisting of betaine(s), sulfo-betaine(s), amino acid(s), phospholipid(s), and mixtures or combinations thereof;   a cationic surfactant including a bis quaternary ammonium halide or mixtures thereof; or   an additive selected from the group consisting of a winterizing agent, a foam booster, a anti-freeze agents, a solvent, a sodium salt of alpha olefin sulfonate (AOS), an acid salt, a nonionic surfactant, a fatty acid, a foam enhancer and mixtures or combinations thereof.   
     
     
         26 . The method of  claim 25 , wherein the betaines are selected from compounds of:
 (1) the general structure R 6 ,R 7 ,R 8 N + —R 9 —CO 2   − , where R 6 , R 7 , and R 8  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, and R 9  is an alkenyl group, alkenyloxide group or mixtures thereof;   (2) the general structure R 10 (R 7 ,R 8 N + —R 9 —CO 2   − ) n , where R 7  and R 8  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, R 9  is an alkenyl group, alkenyloxide group or mixtures thereof, and R 10  is a multivalent substituent having a valency n between 2 and about 6;   (3) the general structure R 12 —C(O)—N(R 11 )—R 13 —N + (R 7 ,R 8 )—R 9 —CO 2   − , where R 7 , R 8 , R 11  and R 12  are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, and R 9  and R 13  are the same or different alkenyl group, alkenyloxide group or mixtures thereof;   (4) the general structure R 14 —[R 15 —C(O)—N(R 11 )—R 13 —N + (R 7 ,R 8 )—R 9 —CO 2   − ] m , where R 7 , R 8  and R 11 are the same or different carbon-containing group, amido carbon-containing group, ether carbon-containing group, or mixtures thereof, R 9 , R 13  and R 15  are the same or different alkenyl group, alkenyloxide group or mixtures thereof and R 14  is a multivalent substituent having a valency m between 2 and about 6; and   (5) mixtures or combinations thereof.   
     
     
         27 . The method of  claim 26 , wherein the betaines are selected from group consisting of cocamidopropyl betaine, 5-(1-piperidiniomethyl)-1H-tetrazolide, and mixtures or combinations thereof. 
     
     
         28 . The method of  claim 25 , wherein:
 the sulfo-betaines are selected from group consisting ofN-decyl-N,N-dimethyl-3-ammonio-1-propanesulfonate; dimethylbenzyl-(3-sulfopropyl)ammonium; dimethylethyl-(3-sulfopropyl)ammonium; dimethyl-(2-hydroxyethyl)-(3-sulfopropyl)ammonium; 4-n-hexylbenzoylamido-propyl-dimethylammoniosulfobetaine; N-methyl-N-(3-sulfopropyl)morpholinium; 4-n-octylbenzoylamido-propyl-dimethylammoniosulfobetaine; 1-(3-sulfopropyl)pyridium; N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, and mixtures or combination thereof; and   the phospholipids are selected from the group consisting of phosphatidylcholine, phosphatidylserine, phosphalidylethanolamine, sphingomyelin and other ceramides, and mixtures or combinations thereof,   the winterizing agent is selected from the group consisting of lithium formate, sodium formate, potassium formate, cesuim formate, triethyanolamine formate, and mixtures or combinations;   the foam booster comprises a cellosolve of the general formula R 9 OCH 2 CH 2 OH where R 9  is an alkyl group having between about 2 and about 8 carbon atoms and mixtures or combinations;   the anti-freeze agents selected from the group consisting of alcohols, glycols or other freezing point depressing agents and mixtures or combinations;   the solvent selected from the group consisting of water, alcohols, ethers, esters and mixtures or combinations thereof;   the sodium salt of alpha olefin sulfonate (AOSs) selected from the group consisting of short chain alpha olefin sulfonates having between about 2 and about 10 carbon atoms, longer chain alpha olefin sulfonates having between about 10 and about 24 carbon atoms and mixtures or combinations thereof;   the acid salts selected from the group consisting of cyclamic acid salts such as sodium (cyclamate), potassium, salts of sulfonated methyl esters having between about 12 and about 22 carbon atoms, where the salt is sodium, potassium, ammonium, alkylammonium, salts of 2-aminoethane sulfonic acids, where the salt is an alkali metal, ammonium, or alkylammonium, and mixtures or combinations thereof;   the nonionic surfactant is selected from the group consisting of polyalkylene oxide, amine oxides such as lauramine oxide and mixtures or combinations;   the fatty acid is selected from the group consisting of lauric acid, oleic acid, stearic acid and mixtures or combinations; and   the foam enhancer selected from the group consisting of a linear dodecyl benzene sulfonic acid salt, a sarcosinate salt, and mixtures or combinations thereof.