Treating a subterranean formation with a composition having multiple curing stages
The present invention relates to compositions for treatment of subterranean formations including a curable resin that is amine-curable and a curing agent having a structure including at least one primary amine and at least one secondary amine, and methods of using the same. In various embodiments, the present invention provides a method of treating a subterranean formation. The method can include obtaining or providing a composition including a curable resin that is amine-curable and a curing agent having a structure including at least one primary amine and at least one secondary amine. The method can include placing the composition in a subterranean formation downhole.
1. A method of treating a subterranean formation, comprising:
placing in the subterranean formation a composition comprising:
a curable resin, wherein the resin is amine-curable; and
a curing agent having a structure comprising at least one primary amine and at least one secondary amine
wherein the composition has at least a first and a second curing stage and a consolidation strength of the first stage being less than a consolidation strength of the second stage, wherein the first curing stage comprises curing of the curable resin with the primary amine group of the curing agent, and wherein the second curing stage comprises curing of the curable resin with the secondary amine of the curing agent.
2. The method of claim 1 , wherein the composition further comprises at least one of proppant and gravel.
3. The method of claim 1 , comprising fracturing the subterranean formation to form at least one fracture in the subterranean formation.
4. The method of claim 1 , further comprising at least partially curing the composition.
5. The method of claim 4 , further comprising removing partially cured resin from the subterranean formation before the curing is complete.
6. The method of claim 1 , wherein the curable resin comprises at least one of an epoxy resin and an isocyanate resin.
7. The method of claim 1 , wherein the composition further comprises at least one tackifier.
8. The method of claim 1 , wherein the curing agent is at least one of an unsymmetrical diamine and a polyamine.
9. The method of claim 1 , wherein the curing agent has the structure:
(NH 2 ) n -A-(NHR 1 ) m ,
wherein:
A is selected from the group consisting of a substituted or unsubstituted (C 1 -C 30 )hydrocarbylene interrupted or terminated by 0, 1, 2, or 3 O or S atoms, and a substituted or unsubstituted (C 2 -C 5 )hydrocarbylenepoly(oxy(C 2 -C 5 )hydrocarbylene);
R 1 at each occurrence is independently selected from the group consisting of substituted or unsubstituted (C 1 -C 30 )hydrocarbyl interrupted or terminated by 0, 1, 2, or 3 O or S atoms, substituted or unsubstituted (C 2 -C 5 )hydrocarbylenepoly(oxy(C 2 -C 5 )hydrocarbylene), substituted or unsubstituted (C 1 -C 30 )heteroaryl, and —OH; and
n and m are each independently 1 to about 1,000.
10. The method of claim 9 , wherein the curing agent has the structure:
H 2 N-A-NHR 1 .
11. The method of claim 9 , wherein the curing agent has the structure:
wherein:
R 2 is selected from the group consisting of substituted or unsubstituted (C 1 -C 30 )hydrocarbyl interrupted or terminated by 0, 1, 2, or 3 O or S atoms, substituted or unsubstituted (C 2 -C 5 )hydrocarbylenepoly(oxy(C 2 -C 5 )hydrocarbylene), substituted or unsubstituted (C 1 -C 30 )heteroaryl, —H, halo, nitro, trihalomethyl, cyano, and —OH; and
p is 1 to about 30.
12. The method of claim 9 , wherein the curing agent has the structure:
wherein:
R 2 is selected from the group consisting of substituted or unsubstituted (C 1 -C 30 )hydrocarbyl interrupted or terminated by 0, 1, 2, or 3 O or S atoms, substituted or unsubstituted (C 2 -C 5 )hydrocarbylenepoly(oxy(C 2 -C 5 )hydrocarbylene), substituted or unsubstituted (C 1 -C 30 )heteroaryl, —H, halo, nitro, trihalomethyl, cyano, and —OH; and
p is 0 to about 30.
13. The method of claim 1 , wherein the curing agent has the structure:
wherein:
R 1 is selected from the group consisting of (C 1 -C 8 )alkyl, (C 5 -C 15 )aryl, (C 5 -C 15 )heteroaryl, and —OH,
R 2 is selected from the group consisting of (C 1 -C 8 )alkyl, (C 5 -C 15 )aryl, (C 5 -C 15 )heteroaryl, —H, halo, nitro, trihalomethyl, cyano, and —OH, and
p is 1 to about 6.
14. The method of claim 1 , wherein the composition further comprises a second curing agent comprising at least one of an amine, an aromatic amine, an aliphatic amine, a cyclo-aliphatic amine, piperidine, triethylamine, benzyldimethylamine, N,N-dimethylaminopyridine, 2-(N,N-dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, n-beta-(aminoethyl)-gamma-aminopropyl trimethoxysilane, or any combination thereof.
15. The method of claim 1 , wherein the composition further comprises at least one of a carrier fluid, a silane coupling agent, a surfactant, a hydrolyzable ester, or any combination thereof.
16. A system for performing the method of claim 1 , the system comprising:
a tubular disposed in the subterranean formation; and
a pump configured to pump the composition through the tubular in the subterranean formation.
17. A method of treating a subterranean formation, comprising:
placing a composition in the subterranean formation, the subterranean formation comprising a fracture, the composition comprising:
a proppant or gravel coated with a mixture comprising:
a curable resin, wherein the resin is amine-curable;
a curing agent having a structure comprising at least one primary amine and at least one secondary amine;
a surfactant; and
a carrier fluid,
wherein the mixture has at least a first and a second curing stage and a consolidation strength of the first stage being less than a consolidation strength of the second stage, wherein the first curing stage comprises curing of the curable resin with the primary amine group of the curing agent, and wherein the second curing stage comprises curing of the curable resin with the secondary amine of the curing agent; and
curing the composition.
18. A composition for treatment of a subterranean formation, comprising:
a curable resin, wherein the resin is amine-curable;
a curing agent having a structure comprising at least one primary amine and at least one secondary amine; and
a proppant or gravel,
wherein the composition has at least a first and a second curing stage and a consolidation strength of the first stage being less than a consolidation strength of the second stage, wherein the first curing stage comprises curing of the curable resin with the primary amine group of the curing agent, and wherein the second curing stage comprises curing of the curable resin with the secondary amine of the curing agent.