Phosphonated polysaccharides and gels and process for making same

Patent metadata

Field	Value
Publication number	US-10844140-B2
Application number	US-201916294021-A
Country	US
Kind code	B2
Filing date	Mar 6, 2019
Priority date	Jun 10, 2015
Publication date	Nov 24, 2020
Grant date	Nov 24, 2020

Abstract

Products and processes that are related to phosphonated polysaccharide compositions, including phosphonated polysaccharide gels, having a substituent degree of substitution with a lower limit of 0.02 and an upper limit of 3, and having a weight average molecular weight with an upper limit of 5,000,000 g/mole, as well as to oil field application or fracturing fluid compositions comprising such phosphonated polysaccharide compositions.

First claim

What is claimed is:

1. A process to produce a phosphonated polysaccharide gel composition comprising at least one phosphonated guar, at least one phosphonated guar derivative, or mixtures thereof, the process comprising:
contacting an effective amount of haloalkylphosphonic acid to an aqueous or semi-aqueous polysaccharide mixture, the polysaccharide mixture comprising at least one polysaccharide selected from at least one guar, at least one guar derivative, or mixtures thereof, to phosphonate the polysaccharide, wherein the resulting phosphonated polysaccharide has a substituent degree of substitution with a lower limit of 0.05 and an upper limit of 3, and a weight average molecular weight with an upper limit of 5,000,000 g/mole; and
crosslinking the phosphonated polysaccharide with a metal cation to form a phosphonated polysaccharide gel, wherein the metal cation is selected from compounds of iron and wherein the binding energy is at least 40 kJ/mol.

2. The process of claim 1 wherein the lower limit of the substituent degree of substitution is 0.055.

3. The process of claim 1 wherein the lower limit of the substituent degree of substitution is 0.7.

4. The process of claim 1 wherein the lower limit of the substituent degree of substitution is 1.

5. The process of claim 1 wherein the phosphonated polysaccharide is selected from phosphonated guar; phosphonated carboxymethyl guar (CMG);
phosphonated hydroxyethyl guar (HEG); phosphonated hydroxypropyl guar (HPG);
phosphonated carboxymethylhydroxypropyl guar (CMHPG); phosphonated hydrophobically modified guar (HM guar); phosphonated hydrophobically modified carboxymethyl guar (HMCM guar); phosphonated hydrophobically modified hydroxyethyl guar (HMHE guar); phosphonated hydrophobically modified hydroxypropyl guar (HMHP guar; phosphonated hydrophobically modified carboxymethylhydroxypropyl guar (HMCMHP guar); or any combination thereof.

6. The process of claim 1 wherein the at least one phosphonated polysaccharide is selected from phosphonated cationic carboxymethyl guar (CMG), phosphonated cationic hydroxyethyl guar (HEG), phosphonated cationic hydroxypropyl guar (HPG), phosphonated cationic carboxymethylhydroxypropyl guar (CMHPG), phosphonated cationic hydrophobically modified hydroxypropyl guar (cationic HMHP guar), phosphonated hydrophobically modified cationic guar (HM cationic guar) or any combination thereof.

7. The process of claim 1 wherein contacting the polysaccharide mixture with an effective amount of the haloalkylphosphonic acid to phosphonated the polysaccharide is carried out at a temperature of between 60° C. and 90° C.

8. The process of claim 1 wherein contacting the polysaccharide mixture with an effective amount of the haloalkylphosphonic acid to phosphonate the polysaccharide is carried out under agitation for a period of 10 hours or more.

9. The process of claim 1 wherein the haloalkylphosphonic acid is chloroalkylphosphonic acid.

10. The process of claim 1 further comprising the step of adding a base to the mixture.

11. The process of claim 2 wherein no initiator is added during the reaction.

12. A method of treating a subterranean formation, comprising:
introducing an oilfield application fluid into a wellbore penetrating the subterranean formation, the oilfield application fluid comprising a polysaccharide composition comprising at least one phosphonated guar, at least one phosphonated guar derivative, or mixtures thereof, the polysaccharide composition having a substituent degree of substitution with a lower limit of 0.05 and an upper limit of 3, and having a weight average molecular weight with an upper limit of 5,000,000 g/mole; and
crosslinking the polysaccharide composition with a metal cation to form a phosphonated polysaccharide gel, wherein the metal cation is selected from compounds of iron and wherein the binding energy is at least 40 kJ/mol.

13. The method of claim 12 wherein the step of introducing the oilfield application fluid into the wellbore penetrating the subterranean formation comprises introducing the oilfield application fluid at a pressure sufficient to create, expand or sustain a fracture in the subterranean formation.

14. The method of claim 12 wherein the oilfield application fluid further comprises one or more surfactants, one or more scale inhibitors, one or more stabilizers or any combination of the foregoing.

15. The process of claim 1 wherein the contacting the polysaccharide mixture with an effective amount of the haloalkylphosphonic acid to phosphonated the polysaccharide is carried out at a temperature of between 60° C. and 80° C.

16. The process of claim 1 wherein the contacting the polysaccharide mixture with an effective amount of the haloalkylphosphonic acid to phosphonated the polysaccharide is carried out at a temperature of between 65° C. and 75° C.

17. The process of claim 1 wherein contacting the polysaccharide mixture with an effective amount of the haloalkylphosphonic acid to phosphonate the polysaccharide is carried out under agitation for a period of 12 hours or more.

18. The process of claim 1 wherein contacting the polysaccharide mixture with an effective amount of the haloalkylphosphonic acid to phosphonate the polysaccharide is carried out under agitation for a period of 20 hours or more.

19. The process of claim 1 wherein contacting the polysaccharide mixture with an effective amount of the haloalkylphosphonic acid to phosphonate the polysaccharide is carried out under agitation for a period of 22 hours or more.

20. The process of claim 1 further comprising adding NaOH to the mixture.

Assignees

• Rhodia Operations

Inventors

• Timbart Laurianne
• Lizarraga Gilda
• Woodward Gary
• Kesavan Subramanian
• Wilson David James

Classifications

• C09K8/035 Primary

  Organic additives · CPC title

• E21B43/26

  by forming crevices or fractures · CPC title

• C08L5/00

  Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00 · CPC title

• C09K2208/20

  Hydrogen sulfide elimination · CPC title

• C09K8/40

  Spacer compositions, e.g. compositions used to separate well-drilling from cementing masses · CPC title