Foam resin sealant for zonal isolation and methods for making and using same

Abstract

Foamable epoxy-based zonal isolation sealing compositions include epoxy resin and a blowing agent and methods for isolating zones in borehole of oil and gas wells using the compositions, where the foam nature of the cured seals provide sufficient compressibility and resiliency to be used with expandable tubing without substantial loss in sealant integrity and in squeeze operations.

We claim: 
     
         1 . A foamable epoxy-based composition comprising:
 an adjustable resin amount of an epoxy resin system including one epoxy resin or a plurality of epoxy resins,   an adjustable curing amount of a cure system including one curing agent or a plurality of curing agents, where the curing agents comprise a first type of curing agents including polyamine curing agents, alkoxylated polyamine curing agents, or mixtures and combinations thereof, and a second type of curing agents including heterocyclic amine curing agents, and one blowing agent or a plurality of blowing agents,   where the adjustable resin amount, the adjustable curing amount, and a type of curing agents are adjusted to form: 1) a low temperature foamable epoxy-based composition curing at a low temperature range between about 50° F. of to about 90° F.; 2) a mid temperature foamable epoxy-based composition curing at a mid temperature range between about 90° F. to about 150° F.; or 3) a high temperature foamable epoxy-based composition curing at a high curing temperature range between about 150° F. to about 300° F., and   where the compositions cure to form a compressible cured foam zonal isolation structure that continues to expand after setting allowing the structure to intrude into surface cavities and crevices of a borehole penetrating a formation or a formation zone, while adhering to an outer surface of a tubing string disposed in the borehole resulting in improved sealing and improved sealing integrity of the structure and when a section of the tubing string is expanded to form a compressed structure, where the compressed structure has substantially no loss in seal integrity or zonal isolation.   
     
     
         2 . The method of  claim 1 , wherein the zonal isolation structure cures to form a cured foam epoxy composition having sufficient compressibility and resilience properties to permit compression of the composition without substantial loss in seal integrity or zonal isolation. 
     
     
         3 . The composition of  claim 1 , further comprising:
 a solvent system including aromatic solvents, heterocyclic aromatic solvents, or mixtures and combinations thereof.   
     
     
         4 . The composition of  claim 1 , wherein the epoxy resins comprise: (a) glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions; (b) epoxy resins prepared by the reaction of epichlorohydrin with mononuclear di- and tri-hydroxy phenolic compounds; (c) epoxidized derivatives of natural oils with mixed long-chain saturated and unsaturated acids having between about 14 and 20 carbon atoms; (d) polyepoxides derived from esters of polycarboxylic acids with unsaturated alcohols; (e) polyepoxides derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids; (f) epoxidized butadiene based polymers; (g) epoxidized derivatives of dimers of dienes, and (h) mixtures or combinations thereof. 
     
     
         5 . The composition of  claim 4 , wherein the epoxy resins have a molecular weight between about 50 and about 10,000. 
     
     
         6 . The composition of  claim 1 , wherein:
 the high temperature foamable epoxy-based composition includes the first type of curing agents,   the mid temperature foamable epoxy-based composition includes the second type of curing agents, and   the low temperature foamable epoxy-based composition includes the second type of curing agents.   
     
     
         7 . The composition of  claim 1 , wherein the alkoxylated polyamine curing agents comprise alkoxylated aliphatic polyamines, alkoxylated cycloaliphatic polyamines, alkoxylated aromatic polyamines, alkoxylated heterocyclic polyamines or mixtures and combinations thereof. 
     
     
         8 . The method of  claim 1 , wherein the first type of curing agents comprise alkoxylated N-alkyl- and N-alkylenyl-substituted 1,3-diaminopropanes or mixtures and combinations thereof. 
     
     
         9 . The composition of  claim 1 , wherein the second type of curing agents comprise pyrrolidine, alkyl pyrrolidines, oxazoline, alkyl oxazolines, triazoles, alkyl triazoles, pyrazolidine, alkyl pyrazolidine, piperidine, alkyl piperidines, piperazine, alkyl piperazines, imidazoline, imidazolidine, alkyl imidazolidines, azepane, alkyl azepane, azepine, alkyl azepines, morpholine, alkyl morpho lines, diazapines, alkyl diazapines, or mixtures and combinations thereof. 
     
     
         10 . The composition of  claim 1 , wherein the solvent system comprise alkyl pyridines and the first type of curing agents comprise an ethoxylated N-tallow-1,3-diaminopropane, where the degree of ethoxylation is approximately 10 moles ethoxylate per mole of tallow diamine. 
     
     
         11 . The composition of  claim 1 , wherein:
 the high temperature foamable epoxy-based composition comprises:
 from about 60 wt. % to about 85 wt. % of the epoxy resin system, 
 from about 1 wt. % to about 15 wt. % of the first type of curing agents, 
 from 0 wt. % to about 39 wt. % of the solvent system, and 
 from about 5 wt. % to about 15 wt. % the blowing agents based on the weight of the other components; 
   the mid temperature foamable epoxy-based composition comprises:
 from about 70 wt. % to about 50 wt. % the epoxy resin system, 
 from about 30 wt. % to about 50 wt. % of the second type of curing agents, 
 from about 5 wt. % to about 15 wt. % the blowing agent or the mixture of blowing agents based on the weight of the other components, and 
 from 0 wt. % to about 20 wt. % of a or solvent system, and 
   the low-temperature foamable epoxy-based composition comprises:
 from about 75 wt. % to about 99 wt. % of the epoxy resin system, 
 from about 25 wt. % to about 1 wt. % of the second type of curing agents, 
 from about 5 wt. % to about 20 wt. % the blowing agents or the mixture of blowing agents based on the weight of the other components, and 
 from 0 wt. % to about 20 wt. % of a solvent system, 
   where the solvent system reduces the viscosity of the compositions for ease of pumping.   
     
     
         12 . The composition of  claim 11 , wherein:
 the epoxy resin system comprises glycidyl ethers epoxy resins,   for the high temperature foamable epoxy-based composition, the first type of curing agents comprise alkoxylated polyamines,   for the mid temperature and low temperature foamable epoxy-based compositions, the second type of curing agents comprise heterocyclic amines,   the solvent system comprises an aromatic heterocyclic solvent or a mixture of aromatic heterocyclic solvents, and   the blowing agents comprise aryl hydrazides.   
     
     
         13 . The composition of  claim 12 , wherein:
 the epoxy resin system comprises a glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions,   the first type of curing agents comprise an ethoxylated N-tallow-1,3-diaminopropane, where the degree of ethoxylation is approximately 10 moles ethoxylate per mole of tallow diamine,   the second type of curing agents comprise heterocyclic amines,   the solvent system comprises a mixture of alkyl pyridines, and   the blowing agent comprises p-toluenesulfohydrazide, 4-methylbenzene p-toluenesulfohydrazide or mixtures thereof.   
     
     
         14 . A foamable epoxy-based composition comprising:
 from about 60 wt. % to about 85 wt. % of an epoxy resin system,   from about 1 wt. % to about 15 wt. % of a cure system,   from about 0 wt. % to about 39 wt. % of a solvent system including aromatic solvents, heterocyclic aromatic solvents, or mixtures and combinations thereof, and   from about 5 wt. % to about 15 wt. % a blowing agent or a mixture of blowing agents based on the weight of the other components,   where the composition cures at a temperature between about 150° F. to about 300° F. and where the compositions cure to form a compressible zonal isolation structure that continues to expand after setting allowing the structure to intrude into surface cavities and crevices of a borehole penetrating a formation or a formation zone, while adhering to an outer surface of a tubing string disposed in the borehole resulting in improved sealing and improved sealing integrity of the structure.   
     
     
         15 . The composition of  claim 14 , wherein:
 the epoxy resin system comprises: (a) glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions; (b) epoxy resins prepared by the reaction of epichlorohydrin with mononuclear di- and tri-hydroxy phenolic compounds; (c) epoxidized derivatives of natural oils with mixed long-chain saturated and unsaturated acids having between about 14 and 20 carbon atoms; (d) polyepoxides derived from esters of polycarboxylic acids with unsaturated alcohols; (e) polyepoxides derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids; (f) epoxidized butadiene based polymers; (g) epoxidized derivatives of dimers of dienes, and (h) mixtures or combinations thereof, and   the cure system comprises polyamine curing agents, alkoxylated polyamine curing agents, or mixtures and combinations thereof, where the alkoxylated polyamine curing agents comprise alkoxylated aliphatic polyamines, alkoxylated cycloaliphatic polyamines, alkoxylated aromatic polyamines, alkoxylated heterocyclic polyamines or mixtures and combinations thereof.   
     
     
         16 . The composition of  claim 15 , wherein the epoxy resins have a molecular weight between about 50 and about 10,000. 
     
     
         17 . The composition of  claim 15 , wherein:
 the epoxy resin system comprises glycidyl ethers epoxy resins,   the curing system comprises alkoxylated polyamines,   the solvent system comprises an aromatic heterocyclic solvent or a mixture of aromatic heterocyclic solvents, and   the blowing agent or the mixture blowing agents comprise aryl hydrazides.   
     
     
         18 . The composition of  claim 15 , wherein:
 the epoxy resin system comprises a glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions,   the curing system comprises an ethoxylated N-tallow-1,3-diaminopropane, where the degree of ethoxylation is approximately 10 moles ethoxylate per mole of tallow diamine,   the solvent system comprises a mixture of alkyl pyridines, and   the blowing agent or the mixture blowing agents comprise p-toluenesulfohydrazide, 4-methylbenzene p-toluenesulfohydrazide or mixtures thereof.   
     
     
         19 . A foamable epoxy-based composition comprising:
 from about 70 wt. % to about 50 wt. % the epoxy resin system,   from about 30 wt. % to about 50 wt. % of the cure system,   from 0 wt. % to about 20 wt. % of a solvent system including aromatic solvents, heterocyclic aromatic solvents, or mixtures and combinations thereof, and   from about 5 wt. % to about 15 wt. % a blowing agent or a mixture of blowing agents based on the weight of the other components, and   where the composition cures at a temperature between about 90° F. to about 150° F. and where the compositions cure to form a compressible zonal isolation structure that continues to expand after setting allowing the structure to intrude into surface cavities and crevices of a borehole penetrating a formation or a formation zone, while adhering to an outer surface of a tubing string disposed in the borehole resulting in improved sealing and improved sealing integrity of the structure.   
     
     
         20 . The composition of  claim 19 , wherein:
 the epoxy resin system comprises: (a) glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions; (b) epoxy resins prepared by the reaction of epichlorohydrin with mononuclear di- and tri-hydroxy phenolic compounds; (c) epoxidized derivatives of natural oils with mixed long-chain saturated and unsaturated acids having between about 14 and 20 carbon atoms; (d) polyepoxides derived from esters of polycarboxylic acids with unsaturated alcohols; (e) polyepoxides derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids; (f) epoxidized butadiene based polymers; (g) epoxidized derivatives of dimers of dienes, and (h) mixtures or combinations thereof, and   the cure system comprises pyrrolidine, alkyl pyrrolidines, oxazoline, alkyl oxazolines, triazoles, alkyl triazoles, pyrazolidine, alkyl pyrazolidine, piperidine, alkyl piperidines, piperazine, alkyl piperazines, imidazoline, imidazolidine, alkyl imidazolidines, azepane, alkyl azepane, azepine, alkyl azepines, morpholine, alkyl morpho lines, diazapines, alkyl diazapines, or mixtures and combinations thereof.   
     
     
         21 . The composition of  claim 19 , wherein:
 the epoxy resin system comprises glycidyl ethers epoxy resins,   the curing system comprises heterocyclic amines,   the solvent system comprises an aromatic heterocyclic solvent or a mixture of aromatic heterocyclic solvents, and   the blowing agents comprise aryl hydrazides.   
     
     
         22 . The composition of  claim 19 , wherein:
 the epoxy resin system comprises a glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions,   the curing system comprises heterocyclic amines,   the solvent system comprises a mixture of alkyl pyridines, and   the blowing agent comprises p-toluenesulfohydrazide, 4-methylbenzene p-toluenesulfohydrazide or mixtures thereof.   
     
     
         23 . A foamable epoxy-based composition comprising:
 from about 75 wt. % to about 99 wt. % of an epoxy resin system,   from about 1 wt. % to about 25 wt. % of a cure system,   from 0 wt. % to about 20 wt. % of a solvent system including aromatic solvents, heterocyclic aromatic solvents, or mixtures and combinations thereof, and   from about 5 wt. % to about 20 wt. % the blowing agents based on the weight of the other components,   where the composition cures at a temperature between about 50° F. of to about 90° F. band where the compositions cure to form a compressible zonal isolation structure that continues to expand after setting allowing the structure to intrude into surface cavities and crevices of a borehole penetrating a formation or a formation zone, while adhering to an outer surface of a tubing string disposed in the borehole resulting in improved sealing and improved sealing integrity of the structure.   
     
     
         24 . The composition of  claim 23 , wherein:
 the epoxy resin system comprises: (a) glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions; (b) epoxy resins prepared by the reaction of epichlorohydrin with mononuclear di- and tri-hydroxy phenolic compounds; (c) epoxidized derivatives of natural oils with mixed long-chain saturated and unsaturated acids having between about 14 and 20 carbon atoms; (d) polyepoxides derived from esters of polycarboxylic acids with unsaturated alcohols; (e) polyepoxides derived from esters prepared from unsaturated alcohols and unsaturated carboxylic acids; (f) epoxidized butadiene based polymers; (g) epoxidized derivatives of dimers of dienes, and (h) mixtures or combinations thereof, and   the cure system comprises pyrrolidine, alkyl pyrrolidines, oxazoline, alkyl oxazolines, triazoles, alkyl triazoles, pyrazolidine, alkyl pyrazolidine, piperidine, alkyl piperidines, piperazine, alkyl piperazines, imidazoline, imidazolidine, alkyl imidazolidines, azepane, alkyl azepane, azepine, alkyl azepines, morpholine, alkyl morpho lines, diazapines, alkyl diazapines, or mixtures and combinations thereof.   
     
     
         25 . The composition of  claim 23 , wherein:
 the epoxy resin system comprises glycidyl ethers epoxy resins,   the cure system comprises heterocyclic amines,   the solvent system comprises an aromatic heterocyclic solvent or a mixture of aromatic heterocyclic solvents, and   the blowing agent or the mixture of blowing agents comprise aryl hydrazides.   
     
     
         26 . The composition of  claim 23 , wherein:
 the epoxy resin system comprises a glycidyl ethers epoxy resin prepared by the reaction of epichlorohydrin with a compound containing a hydroxyl group carried out under alkaline reaction conditions,   the cure system comprises heterocyclic amines,   the solvent system comprises a mixture of alkyl pyridines, and   the blowing agent or the mixture of blowing agents comprises p-toluenesulfohydrazide, 4-methylbenzene p-toluenesulfohydrazide or mixtures thereof.