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1. WO2021007441 - CONTAMINANT REMEDIATION WITH FUNCTIONALIZED (METH)ACRYLIC POLYMER OR COPOLYMER MACROPARTICULATES AND SYSTEMS RELATED THERETO

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[ EN ]

CLAIMS

What is claimed is the following:

1. A method comprising:

exposing a substance in need of contaminant remediation to a plurality of macroparticulates;

wherein the macroparticulates comprise a reaction product of an epoxide-containing (meth)acrylic polymer or copolymer and a compound bearing a nitrogen nucleophile;

forming contaminant-laden macroparticulates by adsorbing or bonding a contaminant from the substance in need of contaminant remediation onto a surface of the macroparticulates; and

separating the contaminant-laden macroparticulates from the substance in need of contaminant remediation.

2. The method of claim 1, wherein the epoxide-containing (meth)acrylic

polymer or copolymer is formed into a predetermined shape prior to conversion into the reaction product, and the reaction product has a larger volume than does the predetermined shape from which the reaction product was produced.

3. The method of claim 1 or claim 2, wherein the reaction product contains an internal cavity after reacting the epoxide-containing (meth)acrylic polymer or copolymer with the compound bearing the nitrogen nucleophile.

4. The method of any one of claims 1-3, wherein the epoxide-containing

(meth)acrylic polymer or copolymer comprises a monomer selected from the group consisting of


and any combination thereof, wherein R is H or a methyl group.

5. The method of any one of claims 1-4, wherein the compound bearing the nitrogen nucleophile comprises iminodiacetic acid, ethylenediamine, N,N'- bis(aminoethyl)ethylenediamine, or tris(aminoethyl)amine.

6. The method of any one of claims 1-5, wherein the compound bearing the nitrogen nucleophile is further functionalized after being reacted with the (meth)acrylic polymer or copolymer.

7. The method of any one of claims 1-6, wherein the reaction product is

substantially spherical in shape.

8. The method of any one of claims 1-6, wherein the reaction product has a random shape.

9. The method of any one of claims 1-8, wherein the substance in need of contaminant remediation comprises contaminated water.

10. The method of claim 9, wherein the contaminated water comprises produced water or flowback water obtained from a wellbore.

11. The method of claim 9 or claim 10, further comprising:

separating reclaimed water from the contaminant-laden macroparticulates, the reclaimed water having a decreased concentration of the contaminant compared to the contaminated water;

forming a treatment fluid with the reclaimed water; and introducing the treatment fluid into a wellbore penetrating a subterranean formation.

12. The method of any one of claims 1-11, wherein the contaminant comprises at least one contaminant selected from the group consisting of a divalent metal, a monovalent metal, a monovalent anion, a divalent or trivalent transition metal, a polyatomic anion, a hydrophobic substance, and any combination thereof.

13. The method of any one of claims 1-11, wherein the contaminant comprises at least one contaminant selected from the group consisting of a divalent metal ion, a barium cation, an iron (II) cation, an iron (III) cation, a sulfate anion, and any combination thereof.

14. The method of any one of claims 1-11, wherein the contaminant comprises an alkali metal ion, an alkaline earth metal ion, a halide ion, a phosphate, a nitrate, a borate, an arsenate, a silicate, a selenite, a titanium ion, a chromium ion, a manganese ion, an iron ion, a ruthenium ion, an osmium ion, a cobalt ion, a rhodium ion, an iridium ion, a nickel ion, a palladium ion, a platinum ion, a copper ion, a silver ion, a gold ion, a zinc ion, a cadmium ion, a mercury ion, an aluminum ion, a boron ion, and any combination thereof.

15. The method of any one of claims 1-14, further comprising :

visually or spectroscopically interrogating the plurality of macroparticulates to determine whether the plurality of macroparticulates has become saturated with the contaminant.

16. The method of any one of claims 1-15, further comprising :

recovering the contaminant from the contaminant-laden macroparticulates.

17. The method of any one of claims 1-16, wherein the substance in need of contaminant remediation is provided as a continuous flow to the plurality of macroparticulates.

18. The method of claim 17, further comprising:

determining a pre-purification contaminant profile of the substance in need of contaminant remediation in the continuous flow; and

determining a post-purification contaminant profile of the substance in need of contaminant remediation in the continuous flow after exposing the substance to the plurality of macroparticulates.

19. The method of claim 18, further comprising:

recirculating the substance in need of contaminant remediation to the plurality of macroparticulates if the post-purification contaminant profile exceeds a specified contaminant threshold.

20. The method of any one of claims 17-19, further comprising:

visually or spectroscopically interrogating the plurality of macroparticulates or the substance in need of contaminant remediation while the plurality of macroparticulates is exposed to the continuous flow; and

determining whether the plurality of macroparticulates has become saturated with the contaminant.

21. The method of any one of claims 17-20, further comprising:

replacing the plurality of macroparticulates without disrupting the continuous flow.

22. The method of any one of claims 17-21, wherein the plurality of

macroparticulates is housed in a removable cartridge.

23. The method of any one of claims 1-22, wherein the reaction product is

formed from the epoxide-containing (meth)acrylic polymer or copolymer and a polyamine, a first amine of the polyamine forming a covalent bond to the (meth)acrylic polymer or copolymer through opening of an epoxide group or aminolysis of an ester and one or more second amine groups of the polyamine being further modified with one or more functionalities capable of binding or adsorbing at least one contaminant from the substance in need of contaminant remediation after the first amine group has reacted.

24. The method of claim 23, wherein the polyamine comprises a C2-C8

alkylenediamine, N,N'-bis(aminoethyl)ethylenediamine, or a branched polyamine.

25. A system comprising :

a continuous flow line configured to receive a substance in need of contaminant remediation;

a plurality of macroparticulates located within the continuous flow line; wherein the macroparticulates comprise a reaction product of an epoxide-containing (meth)acrylic polymer or copolymer and a compound bearing a nitrogen nucleophile; and

at least one detector configured to interrogate the substance in need of contaminant remediation or the plurality of macroparticulates within the continuous flow line.

26. The system of claim 25, wherein the epoxide-containing (meth)acrylic

polymer or copolymer is formed into a predetermined shape prior to conversion into the reaction product, and the reaction product has a larger volume than does the predetermined shape from which the reaction product was produced.

27. The system of claim 25 or claim 26, wherein one or more removable

cartridges are disposed within the continuous flow line, the one or more removable cartridges containing the plurality of macroparticulates.

28. The system of claim 27, further comprising :

a first contaminant interrogation zone upstream of the one or more removable cartridges; and

a second contaminant interrogation zone downstream of the one or more removable cartridges.

29. The system of claim 27 or claim 28, wherein the one or more removable cartridges comprise a plurality of removable cartridges.

30. The system of any one of claims 27-29, wherein the one or more removable cartridges at least comprise one or more first cartridges configured to sequester a first contaminant and one or more second cartridges configured to sequester a second contaminant different than the first contaminant.

31. The system of claim 30, wherein the one or more first cartridges comprise two or more first cartridges and the one or more second cartridges comprise two or more second cartridges.

32. The system of any one of claims 27-31, wherein the one or more removable cartridges comprise two or more cartridges, at least one of the two or more cartridges being disposed in the continuous flow line and at least one of the two or more cartridges being in latent fluid communication with the continuous flow line.

33. The system of claim 32, wherein the two or more cartridges are arranged in a swing bed configuration within the continuous flow line.

34. The system of claim 32, wherein the two or more cartridges are arranged upon a movable assembly in fluid communication with the continuous flow line.

35. The system of any one of claims 27-34, wherein the one or more removable cartridges are configured for visual or spectroscopic interrogation of the plurality of macroparticulates.

36. The system of any one of claims 27-35, further comprising:

a recirculation line configured to recirculate at least a portion of the substance in need of contaminant remediation in the continuous flow line to a location upstream of the one or more removable cartridges.

37. The system of any one of claims 25-36, further comprising:

a processor configured to select a plurality of macroparticulates having a selected functionalization based upon a pre-purification contaminant profile of the substance in need of contaminant remediation.

38. The system of any one of claims 25-37, wherein the reaction product

contains an internal cavity after reacting the epoxide-containing

(meth)acrylic polymer or copolymer with the compound bearing the nitrogen nucleophile.

39. The system of any one of claims 25-38, wherein the epoxide-containing

(meth)acrylic polymer or copolymer comprises a monomer selected from the group consisting of


and any combination thereof, wherein R is H or a methyl group.

40. The system of any one of claims 25-39, wherein the compound bearing the nitrogen nucleophile comprises iminodiacetic acid, ethylenediamine, N,N'- bis(aminoethyl)ethylenediamine, or tris(aminoethyl)amine.

41. The system of any one of claims 25-40, wherein the compound bearing the nitrogen nucleophile is further functionalized after being reacted with the (meth)acrylic polymer or copolymer.

42. The system of any one of claims 25-41, wherein the reaction product is

substantially spherical in shape.

43. The system of any one of claims 25-41, wherein the reaction product has a random shape.

44. The system of any one of claims 25-43, wherein the reaction product is formed from the epoxide-containing (meth)acrylic polymer or copolymer and a polyamine, a first amine group of the polyamine forming a covalent bond to the (meth)acrylic polymer or copolymer through opening of an epoxide group or aminolysis of an ester and one or more second amine groups of the polyamine being further modified with one or more functionalities capable of binding or adsorbing at least one contaminant from the substance in need of contaminant remediation after the first amine group has reacted.

45. The system of claim 44, wherein the polyamine comprises a C2-C8

alkylenediamine, N,N'-bis(aminoethyl)ethylenediamine, or a branched polyamine.