Use of multiple charged cationic compounds derived from polyamines for clay stabilization in oil and gas operations
Methods of using specific multiple charged cationic compounds, which are derived from polyamines through an aza-Michael addition with an α, β-unsaturated carbonyl compound, in a clay treatment composition to reduces clay swelling, clay migration, and sludge formation in a subterranean formation in oil and gas operations are provided. The disclosed methods or compositions are found to be more effective than those methods or compositions including commonly used for reducing clay swelling, clay migration, and sludge formation.
1. A method of stabilizing swellable clays and/or reducing formation of sludge in a subterranean formation comprising:
providing a clay treatment composition into a subterranean formation,
wherein the clay treatment composition comprises a compound or its salt derived from an aza-Michael Addition Reaction between a polyamine and an α, β-unsaturated carbonyl compound according to the following formula
and
one or more clay treatment composition agents,
wherein:
X is NH or O;
R 2 is H, CH 3 , or an unsubstituted, linear or branched C 2 -C 10 alkyl, alkenyl, or alkynyl group;
R 3 is absent or an unsubstituted, linear C 1 -C 30 alkylene group;
Y is —NR 4 R 5 R 6(+) or a salt thereof,
wherein (A) R 4 , R 5 , and R 6 are independently CH 3 ; (B) R 4 and R 5 are independently CH 3 , and R 6 is a C 2 -C 12 aromatic alkyl; or (C) R 4 and R 5 are independently CH 3 , and R 6 is —CH 2 —C 6 H 6 ,
wherein the compound is a multiple charged cationic compound having 2 or more positive charges; and
wherein the clay treatment composition stabilizes swellable clays and/or reduces formation of sludge.
2. The method according to claim 1 , wherein the polyamine is a linear, branched, or dendrimer polyamine with a general formula of NH 2 —[R 10′ ] n —NH 2 , (RNH) n —RNH 2 , H 2 N—(RNH) n —RNH 2 , or H 2 N—(RN(R′)) n —RNH 2 , wherein R 10′ is a linear or branched, unsubstituted or substituted C 2 -C 10 alkylene group, or combination thereof; R is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10 alkylene group, or combination thereof; R′ is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10 alkyl group, RNH 2 , RNHRNH 2 , or RN(RNH 2 ) 2 ; and n can be from 2 to 1,000,000.
3. The method according to claim 1 , wherein the polyamine (A) is an ethoxylated polyamine, propylated polyamine, polyamine with polyquat, polyamine with polyglycerol, or combination thereof, (B) is a linear, branched, or dendrimer polyethyleneimine, (C) comprises only primary and secondary amine groups, (D) comprises only primary, secondary, and tertiary amine groups, and/or (E) comprises only primary and tertiary amine groups.
4. The method according to claim 1 , wherein the polyamine (A) has a general formula of NH 2 —[R 10′ ] n —NH 2 , wherein R 10′ is a linear or branched, unsubstituted or substituted C 2 -C 10 alkylene group, or combination thereof; (B) has a general formula of (RNH) n —RNH 2 or H 2 N—(RNH) n —RNH 2 , wherein R is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10 alkylene group, or combination thereof; (C) has a general formula of H 2 N—(RN(R′)) n —RNH 2 , wherein R is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10 alkylene group, or combination thereof and R′ is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH(CH 3 )CH 2 —, a linear or branched, unsubstituted or substituted C 4 -C 10 alkyl group, RNH 2 , RNHRNH 2 , or RN(RNH 2 ) 2 .
5. The method according to claim 1 , wherein the polyamine (A) is diamine or triamine having an average molecular weight (M w ) of from about 60 to about 1,300; or (B) has an average molecular weight of from about 60 to about 2,000,000 Da.
6. The method according to claim 1 , wherein X is NH or O and/or R 2 is H or CH 3 .
7. The method according to claim 1 , wherein R 4 , R 5 , and R 6 are independently CH 3 .
8. The method according to claim 1 , wherein the counter ion for Y is chloride, bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate, hydrogen carbonate, hydrogen oxalate, hydrogen sulfate, hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.
9. The method according to claim 1 , wherein R 3 is CH 2 , —CH 2 CH 2 —, —CH 2 CH 2 CH 2 — or —C(CH 3 ) 2 —, an unsubstituted, linear, and saturated C 1 -C 20 alkylene group, an unsubstituted, linear, and unsaturated C 1 -C 20 alkylene group, a linear C 8 -C 18 alkyl, alkenyl, or alkynyl group, or a branched C 8 -C 20 alkyl, alkenyl, or alkynyl group.
10. The method according to claim 1 , wherein the α, β-unsaturated carbonyl compound is (3-Acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary salt (DMAEA-BCQ), or 2-(methacryloyloxy)-N,N,N-trimethylethan-1-aminium methyl sulfate (DMAEA-MSQ).
11. The method according to claim 1 , wherein the polyamine has an average molecular weight (M w ) of from about 60 to about 2,000,000 Da.
12. The method according to claim 1 , wherein the compound has an average molecular weight of from about 100 to about 2,000,000 Da and is (A) a single molecule, (B) a mixture of at least two multiple charged cationic compounds, or (C) a mixture of at least two multiple charged cationic compounds derived from the same polyamine and the α, β-unsaturated carbonyl compound, and wherein the product is (AA) a mixture of at least two multiple charged cationic compounds derived from different polyamines and the same α, β-unsaturated carbonyl compound, or (BB) a mixture of at least two multiple charged cationic compounds derived from different polyamines and different α, β-unsaturated carbonyl compounds.
13. The method according to claim 1 , wherein the compound has at least 4, 5, 6, 7, 8, 10, 15, 20, or 30 positive charges.
14. The method according to claim 1 , wherein the compound is one or more of
wherein n=0-1000,
15. The method according to claim 1 , wherein the compound is soluble in water.
16. The method according to claim 1 , wherein the clay treatment composition further comprises a carrier that is water, an alcohol, an alkylene glycol, an alkyleneglycol alkyl ether, or a combination thereof.
17. The method according to claim 1 , wherein the clay treatment composition further comprises one or more of additional functional ingredients that is a flowback aid, friction reducing agent, crosslinker, additional clay stabilizer, viscosifier, reverse emulsion breaker, coagulant/flocculant agent, biocide, corrosion inhibitor, antioxidant, polymer degradation prevention agent, permeability modifier, foaming agent, antifoaming agent, emulsifying agent, fracturing proppant, glass particulate, sand, fracture proppant/sand control agent, scavenger for H 2 S, CO 2 , and/or O 2 , gelling agent, lubricant, salt thereof, or a mixture thereof.
18. The method according to claim 17 , wherein the clay treatment composition contacts the subterranean formation independently, simultaneously, or sequentially with the additional functional ingredient, or wherein the additional functional ingredient contacts the subterranean formation with the multiple charged compound in the treatment composition or through an additional composition.
19. The method according to claim 1 , wherein the clay treatment composition further comprises: an acid, wherein the acid is hydrochloric acid, hydrofluoric acid, citric acid, formic acid, acetic acid, or mixture thereof; an alkyl phenol, fatty acid, or mixture thereof; a surfactant, wherein the surfactant is a nonionic, semi-nonionic, cationic, anionic, amphoteric, zwitterionic, Gemini, di-cationic, di-anionic surfactant, or mixtures thereof; a polymer, polymeric polyquat, or another cationic clay stabilizer; and/or a bis-quaternary ammonium compound or salt thereof.
20. The method according to claim 1 , wherein the treatment composition further comprises water that is fresh water, recycled water, salt water, surface water, produced water, or a mixture thereof.
21. The method according to claim 1 , wherein the clay treatment composition is a fracturing fluid, acidizing fluid, drilling fluid, drill-in fluid, stimulation fluid, gravel pack fluid, completion fluid, cementing fluid, or other oil and gas operation fluid.
22. The method according to claim 1 , wherein the clay treatment composition has a pH of from about 2 to about 11, and is a liquid, gel, or a mixture comprising liquid/gel and solid.
23. The method according to claim 1 , wherein the swellable clays comprises montmorillonite, smectite, saponite, nontronite, hectorite, and sauconite, kaolin, kaolinite, nacrite, dickite, hydrousmica, hydrobiotite, glauconite, illite and brammallite, chlorite, chamosite, vermiculite, attapulgite, palygoskite, sepiolite or mixtures thereof.
24. The method according to claim 1 , wherein the clay treatment composition comprises from about 40 wt-% to about 60 wt-% of the multiple charged cationic compound or its salt.