Method for controlling the rheology of an aqueous fluid and gelling agent therefor

Abstract

A method for controlling the rheology of aqueous systems, particularly for those intended for underground use, includes injecting an aqueous fluid containing a surfactant gelling agent into the system. The surfactant gelling agents are, for example, fatty aliphatic amidoamine oxides, salts of an alkoxylated monoamine with an aromatic dicarboxylic acid, and salts of an alkyldiamine with an aromatic dicarboxylic acid. The surfactant gelling agents can be absorbed onto particulate supports to facilitate delivery of the gelling agent. The additives may be incorporated in the viscoelastic fluid to tailor its use in hydraulic fluids, drilling muds, fracture fluids, and in applications such as permeability modification, gravel packing, cementing, and the like.

1. A method for controlling the rheology of  treating an underground formation with a viscoelastic fluid in  generated from an aqueous system, said method comprising:
 adding at least one gelling agent to said aqueous system in an amount effective to form said viscoelastic fluid, wherein said gelling agent comprises: 
 a) providing one or more gelling agents selected from the group consisting of i) an  one or more amidoamine oxide  oxides of the general formula 
                 
   
 
       wherein R 1  is a saturated or unsaturated, straight or branched chain aliphatic group of from about 7 to about 30 carbon atoms, R 2  is a divalent alkaline  alkylene group of from 2 to about 6 carbon atoms, R 3  and R 4  are the same or different and are alkyl or hydroxy alkyl of from 1 to about 4 carbon atoms, or R 3  and R 4  together with the nitrogen atom to which they are bonded form a heterocyclic ring of up to 6 members, and ; 
   ii) a quaternary  one or more ammonium salt  salts obtained from the reaction of a monoamine or diamine possessing at least one secondary or tertiary amine group with the amine nitrogen directly bonded to a saturated or unsaturated, straight or branched chain aliphatic group of from about 12 to about 30 carbon atoms and an aromatic dicarboxylic acid; or    iii) mixtures of i) and ii)    
 b) adding said gelling agent to an aqueous fluid in an amount sufficient to form a viscoelastic fluid ; and  
 c)  injecting said viscoelastic fluid into ansaid underground formation in order to treat said underground formation.  
 
     
     
       2. The method of  claim 1  wherein the gelling agent is the  an amidoamine oxide. 
     
     
       3. The method of  claim 2  wherein R 1  is an aliphatic group of from about 17 to about 21 carbon atoms, and R 2  is an alkylene group of from about 2 to about 4 carbon atoms. 
     
     
       4. The method of  claim 2  wherein R 1  is an aliphatic group derived from tallow having an iodine value of from about 40 to about 65, and R 2  is an alkylene group having 3 carbon atoms. 
     
     
       5. The method of  claim 2  wherein R 1  is selected from the group consisting of tallow alkyl, hardened tallow alkyl, rapeseed alkyl, hardened rapeseed alkyl, coco alkyl, oleyl and soya alkyl, R 2  is an alkylene group having three carbon atoms, and R 3  and R 4  are each methyl. 
     
     
       6. The method of  claim 2  wherein R 3  and R 4  together with the amine nitrogen to which they are bonded form a heterocyclic group having a 5-member ring derived from pyrrolidine. 
     
     
       7. The method of  claim 2  wherein R 3  and R 4  together with the amine nitrogen to which they are bonded form a heterocyclic group having a 6-member ring derived from piperidine. 
     
     
       8. The method of  claim 2  wherein R 3  and R 4  together with the amine nitrogen to which they are bonded form a heterocyclic group having a 6-member ring derived from morpholine. 
     
     
       9. The method of  claim 1  wherein the gelling agent is a salt of an alkoxylated monoamine with an aromatic dicarboxylic acid having the following general formula 
                 
 
       wherein R 5  is a saturated or unsaturated, straight or branched chain aliphatic group of from about 12 to about 30 carbon atoms, R 6  and R 7  are the same or different and are hydrogen, methyl or ethyl, Ar is an aromatic group, x is 1 or 2, y is 0 or 1, and the sum of x and y is 2. 
     
     
       10. The method of  claim 9  wherein R 5  is an aliphatic group of from about 18 to about 22 carbon atoms. 
     
     
       11. The method of  claim 9  wherein R 5  is selected from the group consisting of tallow alkyl, coco alkyl, stearyl, oleyl, and soya alkyl, R 6  and R 7  are each methyl, and the dicarboxylic acid is phthalic acid. 
     
     
       12. The method of  claim 9  wherein the aromatic group Ar includes at least one ring substituent selected from the group consisting of F, Cl, Br, I, NO 2 , alkyl and OH. 
     
     
       13. The method of  claim 1  wherein the gelling agent is the  an ammonium salt of  derived from an alkyl diamine with  and an aromatic dicarboxylic acid, said gelling agent having the formula 
                 
 
       wherein R 8  is a saturated or unsaturated, straight or branched chain aliphatic group of from about 12 to about 30 carbon atoms, R 9  is a divalent alkylene group of from about 2 to about 6 carbon atoms, and Ar is an aromatic group, and R 10 , R 11  and R 12  are the same or different and are individually selected from the group consisting of hydrogen, C 1 -C 4 -alkyl, 2-hydroxyethyl and 2-hydroxypropyl. 
     
     
       14. The method of  claim 13  wherein R 8  is an aliphatic group of from about 18 to about 22 carbon atoms, and R 9  is an alkylene group of from about 2 to about 4 carbon atoms. 
     
     
       15. The method of  claim 13  wherein R 8  is selected from the group consisting of tallow alkyl, hardened tallow alkyl, hardened rapeseed alkyl, oleyl and cocoalkyl, R 9  is an alkylene group of 3 carbon atoms, and the aromatic dicarboxylic acid is isophthalic acid. 
     
     
       16. The method of  claim 13  wherein the aromatic group Ar includes at least one ring substituent selected from the group consisting of F, Cl, Br, I, NO 2 , alkyl and OH. 
     
     
       17. The method of  claim 1  wherein the gelling agent is present in the aqueous  viscoelastic fluid at a concentration of from about 0.5% to about 10% by weight. 
     
     
       18. The method of  claim 1  wherein the gelling agent is present in the aqueous  viscoelastic fluid at a concentration of from about 2% to about 8% by weight. 
     
     
       19. The method of  claim 1  wherein the gelling agent is present in the aqueous  viscoelastic fluid at a concentration of from about 4% to about 6% by weight. 
     
     
       20. The method of  claim 1  further including the step of absorbing the gelling agent on a dispersible particulate support prior to adding the gelling agent to the aqueous fluid  system. 
     
     
       21. The method of  claim 20  wherein said particulate support is chosen from the group consisting of silica, silicates, alumina, aluminates, silicoaluminates, sodium sulfate, potassium sulfate, magnesium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, carbon black, borax, cellulose, hydroxycellulose, and hydroxyethyl cellulose. 
     
     
       22. The method of  claim 20  wherein the gelling agent is the amidoamine oxide, and the particulate support is chosen from the group consisting of silica, silicates, alumina, aluminates, silicoaluminates, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, carbon black, borax, cellulose, hydroxycellulose, hydroxyethyl cellulose, sodium carbonate, potassium carbonate, and calcium carbonate. 
     
     
       23. The method of  claim 1  further including the step of adding to said aqueous fluid  system in addition to said gelling agent, at least one additive selected from the group consisting of lubricants, corrosion inhibitors, colorants, dyes, deodorants, bacteriacides, chelating agents, antifreeze agents, anti-wear agents, extreme pressure additives, hydrotopes, and viscosity modifiers. 
     
     
       24. The method of  claim 1  further including the step of adding to said aqueous fluid  system in addition to said gelling agent at least one compound selected from the group consisting of alcohol, and hydrocarbon. 
     
     
       25. The method of  claim 24  wherein said component is an alcohol selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, isoamyl, alcohol, n-butanol, sec. butanol, and tert. butanol. 
     
     
       26. The method of  claim 25  wherein said alcohol is isopropanol. 
     
     
       27. The method of  claim 1  further including the step of adding a polymeric material to said aqueous  viscoelastic fluid. 
     
     
       28. A method for controlling the rheology of fluid in an aqueous system comprising:
 a) providing one or more gelling agents selected from the group consisting of amidoamine oxides of the general formula 
                 
   
       wherein R 1  is a saturated or unsaturated, straight or branched chain aliphatic group of from about 7 to about 30 carbon atoms, R 2  is a divalent alkylene group of from 2 to about 6 carbon atoms, together with the nitrogen atom to which they are bonded, R 3  and R 4  form a heterocyclic ring of up to 6 members;
 b) adding said gelling agent to an aqueous fluid in an amount sufficient to form a viscoelastic fluid; and  
 c) injecting said viscoelastic fluid into the aqueous system.  
 
     
     
       29. The method of  claim 28  wherein R 3  and R 4  together with the amine nitrogen to which they are bonded form a heterocyclic group having a  5 -member ring derived from pyrrolidine. 
     
     
       30. The method of  claim 28  wherein R 3  and R 4  together with the amine nitrogen to which they are bonded form a heterocyclic group having a  6 -member ring derived from piperidine. 
     
     
       31. The method of  claim 28  wherein R 3  and R 4  together with the amine nitrogen to which they are bonded form a heterocyclic group having a  6 -member ring derived from morpholine. 
     
     
       32. A method of preparing a gelling agent comprising:
 a) reacting a compound of the general formula RNHR′NH  2  wherein R is a saturated or unsaturated, straight or branched chain aliphatic group having about 18 carbon atoms and R′ is a divalent alkylene group of from about 2 to about 6 carbon atoms, with phthalic  isophthalic acid at a temperature of at least about 40° C. in an aqueous solution;  
 b) removing water from the aqueous solution to recover a powder containing an aromatic dicarboxylic acid salt.  
 
     
     
       33. A composition of matter comprising:
 an aromatic dicarboxylic acid salt of the formula 
                 
 
 
       wherein R is a saturated or unsaturated straight or branched chain aliphatic group having about 18 carbon atoms and R′ is a divalent alkylene group of from about 2 to about 6 carbon atoms and Ar is an aromatic group. 
     
     
       34. A composition as in  claim 33  in the form of a powder. 
     
     
       35. A composition as in  claim 33  wherein the aromatic dicarboxylic acid salt is prepared by reacting a compound of the formula RNHR′NH 2  wherein R is a saturated or unsaturated straight or branched chain aliphatic group having about 18 carbon atoms and R′ is a divalent alkylene group of from about 2 to about 6 carbon atoms with phthalic  isophthalic acid. 
     
     
       36. The method of  claim 1 , wherein said underground application is a fracturing application, wherein in said fracturing application said viscoelastic fluid is injected into said underground formation at a pressure sufficient to fracture the formation.  
     
     
       37. The method of  claim 36  which additionally comprises facilitating a decrease in viscosity of said viscoelastic fluid in the subterranean formation subsequent to fracturing same.  
     
     
       38. The method of  claim 36  wherein said viscoelastic fluid additionally comprises brine.  
     
     
       39. A method for modifying the permeability of an underground formation which comprises generating a viscoelastic fluid in accordance with  claim 1  wherein said injecting is performed through a wellbore and into said formation in an amount effective to modify the permeability of said formation.  
     
     
       40. The method of  claim 39  wherein said viscoelastic fluid additionally comprises a dispersible particulate support.  
     
     
       41. The method of  claim 40  wherein said particulate support is at least one selected from the group consisting of silica, silicates, alumina, aluminates, silicoaluminates, sodium sulfate, potassium sulfate, magnesium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, carbon black, borax, cellulose, hydroxycellulose and hydroxyethyl cellulose.  
     
     
       42. The method of  claim 1  wherein said underground application is selected from the group consisting of underground drilling, hydraulic fracturing, permeability modification of underground formations, gravel packing and cementing.