IP Library Granted Patent US 9,297,244
Granted Patent B2
US 9,297,244 · App. 13/838,806 · Granted Mar 29, 2016

Self-suspending proppants for hydraulic fracturing comprising a coating of hydrogel-forming polymer

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Quick Facts
Patent No.
US 9,297,244
App. No.
13/838,806
Granted
Mar 29, 2016
Kind
B2
Abstract

The invention provides for modified proppants, comprising a proppant particle and a hydrogel coating, wherein the hydrogel coating localizes on the surface of the proppant particle to produce the modified proppant, methods of manufacturing such proppants and methods of use.

Claims (31)

1. A modified proppant, comprising a proppant particle substrate and a coating of a hydrogel-forming polymer, wherein the coating localizes on the surface of the proppant particle substrate to produce the modified proppant;

wherein the proppant particle substrate comprises sand;

wherein the coating comprises a hydrogel-forming polymer having a weight average molecular weight of ≧about 1 million g/mol, wherein the hydrogel-forming polymer comprises polyacrylamide; and

wherein the modified proppant is made by an invert emulsion coating technique in which the proppant particle substrate is combined with an invert emulsion in which the oil phase forms the continuous phase of the emulsion and a solution or dispersion of the hydrogel-forming polymer in water forms the discontinuous, emulsified phase;

wherein the hydrogel-forming polymer forms a substantially continuous film on the surface of the proppant particle which is crosslinked.

2. The modified proppant of claim 1 , wherein the shearing ratio of the proppant as determined by a Shear Analytical Test is ≧0.6.

3. The modified proppant of claim 1 , wherein the modified proppant undergoes a volumetric expansion of at least 100% upon hydration in an excess of water.

4. The modified proppant of claim 1 , wherein the modified proppant undergoes a volumetric expansion of at least 500% upon hydration in an excess of water.

5. The modified proppant of claim 1 , wherein the amount of coating is less than about 5 wt % of the total dry weight.

6. The modified proppant of claim 1 , further comprising an alcohol selected from the group consisting of ethylene glycol, propylene glycol, glycerol, propanol, and ethanol.

7. The modified proppant of claim 1 , wherein the weight average molecular weight of the hydrogel-forming polymer is ≧about 5 million g/mol.

8. The modified proppant of claim 7 , wherein a crosslinking agent is applied to the substantially continuous film on the surface of the proppant particle.

9. The modified proppant of claim 8 , wherein the crosslinking agent is covalent.

10. The modified proppant of claim 1 , wherein the proppant is free-flowing when dry or after being subjected to a relative humidity of between about 80%-90% for one hour at 25-35° C.

11. The modified proppant of claim 10 , wherein a crosslinking agent is applied to the substantially continuous film on the surface of the proppant particle.

12. The modified proppant of claim 11 , wherein the crosslinking agent is a covalent crosslinking agent.

13. The modified proppant of claim 1 , wherein the proppant is dry.

14. The modified proppant of claim 13 , wherein a crosslinking agent is applied to the substantially continuous film on the surface of the proppant particle.

15. The modified proppant of claim 14 , wherein the crosslinking agent is a covalent crosslinking agent.

16. The modified proppant of claim 1 , wherein a crosslinking agent is applied to the substantially continuous film on the surface of the proppant particle.

17. The modified proppant of claim 16 , wherein the crosslinking agent is a covalent crosslinking agent.

18. The modified proppant of claim 17 , wherein the substantially continuous film is crosslinked in an amount sufficient to prevent premature hydration of the hydrogel-forming polymer.

19. The modified proppant of claim 16 , wherein the modified proppant is free flowing in 80-90% relative humidity at 25-50° C.

20. A hydraulic fracturing formulation, comprising the modified proppant of claim 1 and an aqueous carrier liquid.

21. A method of fracturing a well, comprising:

introducing the hydraulic fracturing formulation of claim 20 into the well in an effective volume and at an effective pressure for hydraulic fracturing,

thereby fracturing the well.

22. In a process for fracturing a geological formation penetrated by a well in which a fracing fluid containing a proppant is charged into the geological formation with pulsed pressure,

a method for reducing the amount of thickening agent that is added to the fracing fluid comprising selecting as the proppant the modified proppant of claim 1 .

23. The method of claim 22 , wherein the modified proppant hydrates essentially completely within 2 hours of first being combined with the fracing fluid.

24. The method of claim 23 , wherein the modified proppant hydrates essentially completely within 10 minutes of first being combined with the fracing fluid.

Assignments (19)
SECURITY INTEREST Recorded Mar 31, 2025
From: COVIA SOLUTIONS LLC; COVIA HOLDINGS LLC
To: JPMORGAN CHASE BANK, N.A., AS COLLATERAL AGENT
Reel/Frame 070681/0759 →
RELEASE OF SECURITY INTEREST Recorded Feb 26, 2025
From: PNC BANK, NATIONAL ASSOCIATION
To: COVIA SOLUTIONS INC.; COVIA HOLDINGS LLC
Reel/Frame 070343/0973 →
MERGER Recorded Jan 31, 2025
From: SELF-SUSPENDING PROPPANT LLC
To: COVIA SOLUTIONS INC.
Reel/Frame 070077/0097 →
CORPORATE CONVERSION Recorded Jan 31, 2025
From: COVIA SOLUTIONS INC.
To: COVIA SOLUTIONS LLC
Reel/Frame 070077/0560 →
SECURITY INTEREST Recorded Dec 27, 2021
From: COVIA SOLUTIONS INC.; COVIA HOLDINGS LLC
To: PNC BANK, NATIONAL ASSOCIATION
Reel/Frame 058581/0517 →
SECURITY INTEREST Recorded Jan 29, 2021
From: COVIA HOLDINGS LLC (FORMERLY COVIA HOLDINGS CORPORATION)
To: WILMINGTON SAVINGS FUND SOCIETY, FSB
Reel/Frame 055173/0660 →
RELEASE OF SECURITY INTEREST Recorded Jan 1, 2021
From: WILMINGTON SAVINGS FUND SOCIETY, FSB
To: COVIA HOLDINGS LLC (FORMERLY COVIA HOLDINGS CORPORATION)
Reel/Frame 054886/0318 →
SECURITY INTEREST Recorded Oct 19, 2020
From: BARCLAYS BANK PLC
To: WILMINGTON SAVINGS FUND SOCIETY, FSB
Reel/Frame 054113/0352 →
SECURITY INTEREST Recorded Aug 27, 2018
From: COVIA HOLDINGS CORPORATION; FAIMOUNT SANTROL INC.; TECHNISAND, INC.; SELF-SUSPENDING PROPPANT LLC
To: BARCLAYS BANK PLC, AS COLLATERAL AGENT
Reel/Frame 047320/0483 →
RELEASE OF SECURITY INTEREST Recorded Jun 9, 2018
From: BARCLAYS BANK PLC
To: SELF-SUSPENDING PROPPANT LLC
Reel/Frame 046036/0627 →
RELEASE OF SECURITY INTEREST Recorded Jun 9, 2018
From: PNC BANK, NATIONAL ASSOCIATION
To: SELF-SUSPENDING PROPPANT LLC
Reel/Frame 046036/0705 →
SECURITY INTEREST Recorded Nov 6, 2017
From: FAIRMOUNT SANTROL INC.; SELF-SUSPENDING PROPPANT LLC; TECHNISAND, INC.
To: PNC BANK, NATIONAL ASSOCIATION
Reel/Frame 044040/0380 →
SECURITY INTEREST Recorded Nov 2, 2017
From: SELF-SUSPENDING PROPPANT LLC
To: BARCLAYS BANK PLC
Reel/Frame 044014/0878 →
RELEASE OF SECURITY INTEREST IN PATENTS FILED AT R/F 038322/0170 Recorded Nov 1, 2017
From: BARCLAYS BANK PLC
To: SELF-SUSPENDING PROPPANT LLC
Reel/Frame 044654/0001 →
SECURITY INTEREST Recorded Apr 19, 2016
From: SELF-SUSPENDING PROPPANT LLC
To: BARCLAYS BANK PLC, AS COLLATERAL AGENT
Reel/Frame 038322/0170 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 17, 2013
From: SOANE ENERGY LLC
To: SELF-SUSPENDING PROPPANT LLC
Reel/Frame 031222/0032 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 1, 2013
From: SOANE ENERGY LLC
To: SELF-SUSPENDING PROPPANT LLC
Reel/Frame 030324/0898 →
LICENSE Recorded May 1, 2013
From: SELF-SUSPENDING PROPPANT LLC
To: SOANE LABS LLC
Reel/Frame 030325/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 18, 2013
From: MAHONEY, ROBERT P.; SOANE, DAVID S.; HERRING, MARIE K.; KINCAID, KEVIN P.; CASADO PORTILLA, ROSA; WUTHRICH, PHILIP
To: SOANE ENERGY, LLC
Reel/Frame 030239/0558 →