Self-suspending proppants for hydraulic fracturing
The present invention provides modified proppants, and methods for their manufacture. In embodiments, the modified proppant comprises a proppant particle and a hydrogel coating, wherein the hydrogel coating is applied to a surface of the proppant particle and localizes on the surface to produce the modified proppant. In embodiments, formulations are disclosed comprising the modified particles, and methods are disclosed for using the formulations.
1. A method of fracturing a subterranean geological formation comprising introducing into said formation a treatment fluid wherein the fluid comprises an aqueous fracturing fluid and a modified proppant having hydrophilic properties while suspended during transport, the modified proppant being self-suspending in the aqueous fracturing fluid, wherein the suspended modified proppant comprises a proppant particle and a swollen hydrogel coating,
wherein the hydrogel coating is applied to a surface of the proppant particle and localizes on the surface,
wherein the hydrogel coating has a thickness between about 10% to about 1000% of the average diameter of the proppant particle when suspended and a thickness between about 0.01% to about 20% of the average diameter of the proppant particle when dry, wherein the dry hydrogel coating contains less than 1% by weight of residual liquid, and
wherein the hydrogel coating is crosslinked.
2. The method of claim 1 , wherein the hydrogel coating is selected from the group consisting of polyacrylamide, copolymers of acrylamide with anionic and cationic comonomers, copolymers of acrylamide with hydrophobic comonomers, poly(acrylic acid), poly(acrylic acid) salts, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, alginate, carrageenan, locust bean gum, carboxymethyl guar, carboxymethyl hydroxypropyl guar gum, hydrophobically associating swellable emulsion (HASE) polymers, latex polymers, and starches.
3. The method of claim 2 , wherein the hydrogel coating comprises a starch.
4. The method of claim 1 , wherein the hydrogel coating is applied to the surface as a liquid.
5. The method of claim 1 , wherein the hydrogel coating comprises a hydrophobic comonomer selected from the group consisting of alkyl acrylate esters, N-alkyl acrylamides, N-isopropylacrylamide, propylene oxide, styrene, and vinylcaprolactam.
6. The method of claim 1 , wherein the hydrogel coating comprises a polymer selected from the group consisting of polyacrylamide, poly(acrylic acid), copolymers of acrylamide with acrylic acid salts, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, carboxymethyl guar, carboxymethyl hydroxypropyl guar gum, hydrophobically associating swellable emulsion polymers, and latex polymers.
7. The method of claim 1 , wherein the hydrogel coating further comprises chemical additives selected from the group consisting of scale inhibitors, biocides, breakers, wax control agents, asphaltene control agents, and tracers.
8. The method of claim 1 , further comprising a cationic/anionic polymer pair comprising a cationic polymer and an anionic polymer.
9. The method of claim 8 , wherein the cationic polymer is selected from polydiallyldimethylammonium chloride (poly-(DADMAC)), linear polyethylenimine (LPEI), branched polyethylenimine (BPEI), chitosan, and cationic polyacrylamide.
10. The method of claim 1 , wherein the crosslinking is with a covalent crosslinker.
11. The method of claim 10 , wherein the covalent crosslinker comprises a functional group selected from the group consisting of an epoxide, an anhydride, an aldehyde, a diisocyanate, and a carbodiamide.
12. The method of claim 11 , wherein the covalent crosslinker is selected from the group consisting of polyethylene glycol, diglycidyl ether, epichlorohydrin, maleic anhydride, formaldehyde, glyoxal, glutaraldehyde, toluene diisocyanate, and methylene diphenyl diisocyanate, 1-ethyl-3-(3-dimethylaminopropyl) carbodiamide.
13. The method of claim 1 , further comprising adding a delayed hydration additive to the fluid.
14. The method of claim 13 , wherein the delayed hydration additive is selected from the group consisting of a low hydrophilic-lipophilic balance surfactant, an exclusion agent capable of excluding a finishing surfactant, a light ionic crosslinking agent, a light covalent crosslinking agent and a monovalent salt charge shielder.
15. The method of claim 1 , further comprising adding an alcohol selected from the group consisting of ethylene glycol, propylene glycol, glycerol, propanol, and ethanol to the hydrogel coating.
16. The method of claim 1 , further comprising adding an anticaking agent to the hydrogel coating.
17. The method of claim 1 , wherein the hydrogel coating comprises a water-swellable polymer and wherein the hydrogel coating is crosslinked by an amount which is sufficient to prevent the water-swellable polymer from completely desorbing into solution yet not so much as to prevent the water-swellable polymer from swelling when contacted with an aqueous fracturing fluid, thereby reducing the rate at which the modified proppant settles as it is transported towards the far end of the fracture.
18. The method of claim 17 , wherein the modified proppant exhibits an expanded settled bed height which is substantially retained after having been subjected to shear at a shear rate of about 550 s −1 for 10 minutes.
19. The method of claim 18 , wherein after having been subjected to shear at a shear rate of about 550 s −1 for 10 minutes the expanded bed height of the modified proppant is at least about75% of the settled bed height of the proppant before shearing begins.
20. The method of claim 1 , wherein the modified proppant is made by applying the hydrogel coating to a surface of the proppant particle and then drying so that the hydrogel coating contains less than 1% by weight of residual liquid.
21. The method of claim 20 , further comprising preparing the treatment fluid by combining the dried modified proppant with the aqueous fracturing fluid.
22. The method of claim 21 , wherein the hydrogel coating comprises a water-swellable polymer and further wherein the hydrogel coating is crosslinked by an amount which is sufficient to prevent the water-swellable polymer from completely desorbing into solution yet not so much as to prevent the water-swellable polymer from swelling when contacted with an aqueous fracturing fluid, thereby reducing the rate at which the modified proppant settles as it is transported towards the far end of the fracture.
23. The method of claim 22 , wherein the modified proppant exhibits an expanded settled bed height which is substantially retained after having been subjected to shear at a shear rate of about 550 s −1 for 10 minutes.
24. The method of claim 23 , wherein the proppant particle is sand, resincoated sand, ceramics or bauxite.
25. The method of claim 23 , wherein the hydrogel coating is made from a polymer which is selected so that when 1 to 3 grams of the dried modified proppant is added to 100 ml of tap water in a 100 ml graduated cylinder and then inverted 8 times, the modified proppant exhibits a settling time which is about 2 to about 7 times the settling time of the proppant particle.
26. The method of claim 1 , wherein the hydrogel coating is made from a polymer which is selected so that when 1 to 3 grams of the dried modified proppant is added to 100 ml of tap water in a 100 ml graduated cylinder and then inverted 8 times, the modified proppant exhibits a settling time which is about 2 to about 7 times the settling time of the proppant particle.
27. The method of claim 26 , wherein the modified proppant exhibits an expanded settled bed height which is substantially retained after having been subjected to shear at a shear rate of about 550 s −1 for 10 minutes.
28. The method of claim 1 , wherein the proppant particle is sand, resin-coated sand, ceramics or bauxite.