Hydrate inhibitor carrying hydrogel

Patent metadata

Field	Value
Publication number	US-10696801-B2
Application number	US-201615575704-A
Country	US
Kind code	B2
Filing date	May 27, 2016
Priority date	May 27, 2015
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

A gas hydrate hydrogel inhibitor comprising at least one polymer hydrogel particle having from 50 to 100% hydrogel content, the at least one polymer hydrogel particle including an inhibitor selected from the group consisting of: at least one thermodynamic hydrate inhibitor, at least one kinetic hydrate inhibitor, or a combination thereof.

First claim

The invention claimed is:

1. A gas hydrate hydrogel inhibitor comprising at least one polymer hydrogel particle having from 50 to 100% hydrogel content, the at least one polymer hydrogel particle including an inhibitor comprising at least one thermodynamic hydrate inhibitor, at least one kinetic hydrate inhibitor, or a combination thereof.

2. The gas hydrate hydrogel inhibitor according to claim 1 , wherein each polymer hydrogel particle comprises from 70 to 100% hydrogel content.

3. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the hydrogel particle can typically swell and retain from 50 wt % up to 99 wt % water within the structure of the hydrogel particle.

4. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the polymer hydrogel particles contain between 5 and 50 wt % of the thermodynamic inhibitor.

5. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the polymer hydrogel particles contain kinetic hydrate inhibitor in aqueous inhibitor solution is from 0.01 to 10 wt.

6. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the inhibitor is at least one of: absorbed into or formed with the hydrogel particle.

7. The gas hydrate hydrogel inhibitor according to claim 6 , wherein the hydrogel comprises a cross-linked polymer where a polymer network is the inhibitor.

8. The gas hydrate hydrogel inhibitor according to claim 7 , wherein a cross-linked polymer structure of the hydrogel comprises between 0.01% and 50% cross-linker, with the remaining content comprising a KHI polymer hydrogel.

9. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the thermodynamic hydrate inhibitor comprises methanol, mono-ethylene glycol (MEG), diethylene glycol (DEG) or a combination thereof.

10. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the kinetic hydrate inhibitor comprises homo- and co-polymers of at least one of N-vinyl pyrrolidone, N-vinyl caprolactam, vinylcaprolactam, vinylpyrrolidone, vinylpiperidone acryloylpyrrolidine, acryloylmorpholine, aspartamide, Oligomeric amine oxide, N-methyl-N-vinyl acetamide, N-isopropylacrylamide, ethylacrylaminde, diethylacrylamide, isobutylacrylamide, isopropylmethacrylamide, butylacrylate or a combination thereof.

11. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the kinetic hydrate inhibitor comprises poly(vinylpyrrolidone), polyvinylcaprolactam, polyethyloxazoline, poly-L-proline, polyacryloylpyrrolidine, polyethylmaleimide, ring-opened polyethyloxazoline, ring-closed polyethyloxazoline, polyetherdiamine, polyallyl isopentanamide, polypyrrolidinyl aspartate (polyAS), polyglyoxylpyrrolidine (polyGP), dodecyl-2-(2-caprolactamyl) ethanamide, modified AMPS polymers where R 1 is an alkyl tail of 1 to 6 carbon atoms and R 2 is H or Me, and wherein n is from 1 to 1000:

Amidated maleic anhydride copolymers comprising:

wherein M + is H + , a metal ion or a quarternary ammonium ion, and wherein n is from 1 to 1000,
or a combination thereof.

12. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the polymer hydrogel particles comprise aqueous content of between 70 and 99 wt %.

13. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the polymer hydrogel particles comprise a polymer content of less than or equal to 15 wt %.

14. The gas hydrate hydrogel inhibitor according to claim 1 , wherein the polymer hydrogel particles comprise a cross-linked polymer used as hydrogel comprising a plurality of homogenous polymers comprising: polyacrylic acid, hydrolysed polyacrylamide or polyacrylamide-co-acrylic acid, polyacrylamide-co-acrylic acid partial sodium salt, poly(acrylic acid-co-maleic acid), poly(N-isopropylacrylamide), polyvinylcaprolactam, or polyvinyl N-vinyl caprolactam.

15. A method of forming a gas hydrate hydrogel inhibitor comprising:
providing a plurality of hydrogel particles having from 50 to 100% hydrogel content; and
swelling the hydrogel particles with an aqueous inhibitor solution including an inhibitor comprising: at least one thermodynamic hydrate inhibitor, at least one kinetic hydrate inhibitor or a combination thereof.

16. The method according to claim 15 , wherein the inhibitor comprises the at least one thermodynamic hydrate inhibitor and the concentration of the at least one thermodynamic inhibitor in an aqueous inhibitor solution is from 5 to 50 wt %.

17. A method of forming a gas hydrate inhibitor comprising at least one polymer hydrogel particle having from 50 to 100% hydrogel content, the method comprising:
forming a hydrogel with, around, or with and around at least one inhibitor,
wherein the inhibitor comprising: at least one thermodynamic hydrate inhibitor, at least one kinetic hydrate inhibitor or a combination thereof.

18. The method according to claim 17 , wherein the inhibitor comprises the at least one kinetic hydrate inhibitor and the concentration of the kinetic hydrate inhibitor is from 0.01 to 10 wt %.

19. The method according to claim 15 , wherein the hydrogel particles are formed by:
(i) providing a first solution comprising:
(a) a polymer having a repeating monomer unit comprising at least two different pendant functional groups, wherein at least one of the at least two pendant functional groups is a carboxyl or activated carboxylate group; and
(b) a cross-linking agent having at least two pendant functional groups capable of forming a covalent bond with the carboxyl or activated carboxylate group;
and
(ii) reacting the cross-linking agent with the polymer so that a cross-linked polymer is formed,
wherein a desired hydrogel particle size is formed by either:
suspending the first solution within a second solution, wherein the first solution is immiscible with the second solution, then subsequently reacting the cross-linking agent with the polymer; or
freeze drying the cross-linked polymer; and then comminuting the freeze dried cross-linked polymer to form dried hydrogel particles of a desired size.

20. The method according to claim 17 , wherein the hydrogel particles are formed by:
(i) providing a first solution comprising:
(a) a polymer having a repeating monomer unit comprising at least two different pendant functional groups, wherein at least one of the at least two pendant functional groups is a carboxyl or activated carboxylate group; and
(b) a cross-linking agent having at least two pendant functional groups capable of forming a covalent bond with the carboxyl or activated carboxylate group;

and
(ii) reacting the cross-linking agent with the polymer so that a cross-linked polymer is formed,
wherein a desired hydrogel particle size is formed by either:
suspending the first solution within a second solution, wherein the first solution is immiscible with the second solution, then subsequently reacting the cross-linking agent with the polymer; or
freeze drying the cross-linked polymer; and then comminuting the freeze dried cross-linked polymer to form dried hydrogel particles of a desired size.

Assignees

• Commw Scient Ind Res Org

Inventors

• Wood Colin David
• Seo Yutaek
• Tian Wendy Wenjun

Classifications

• C09K8/52 Primary

  Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning · CPC title

• C08J3/075 Primary

  Macromolecular gels · CPC title

• C08F226/06

  by a heterocyclic ring containing nitrogen · CPC title

• C10L2250/06

  Particle, bubble or droplet size · CPC title

• C10L3/107

  Limiting or prohibiting hydrate formation · CPC title