IP Library Granted Patent US 8,932,996
Granted Patent B2
US 8,932,996 · App. 13/348,279 · Granted Jan 13, 2015

Gas hydrate inhibitors and methods for making and using same

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Quick Facts
Patent No.
US 8,932,996
App. No.
13/348,279
Granted
Jan 13, 2015
Kind
B2
Abstract

Methods relate to using phosphate and/or nitrate brines to reduce hydrate formation in flowlines under conditions conducive for hydrate formation in the absence of the phosphate and/or nitrate brine. The phosphate and/or nitrate brines may include compatible anti-corrosion additives.

Claims (72)

1. A method for inhibiting gas hydrate formation in downhole fluids comprising:

using a downhole fluid including:

a base fluid comprising a nitrate brine, and

an inhibiting amount of a corrosion system including:

at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,

where the downhole fluid is selected from the group consisting of a drilling fluid, a completion fluid, and a production fluid,

where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the downhole fluid, and

where the additives reduce or prevent corrosion by the base fluid.

2. The method of claim 1 , wherein the downhole fluid further include:

an effective amount of a foaming system and a gas to form a foamed downhole fluid having desired foam properties.

3. The method of claim 1 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.

4. The method of claim 3 , wherein:

the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,

the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and

the transition metal nitrate brines are zinc nitrate brines.

5. The method of claim 4 , wherein:

the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof, and

the sulfonic acids include, without limitation, alkyl sulfonic acids, alkenyl sulfonic acids, aryl sulfonic acids, where the alkyl groups include 1 to about 20 carbon atoms, the alkenyl groups include 2 to about 20 carbon atoms and the aryl groups include 5 to about 30 carbon atoms.

6. A method for inhibiting gas hydrate formation in drilling fluids comprising:

using a drilling fluid including:

a base fluid comprising a nitrate brine, and

an inhibiting amount of a corrosion system including:

at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,

where the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof,

where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the base fluid, and

where the additives reduce or prevent corrosion by the base fluid.

7. The method of claim 6 , wherein the drilling fluid further include:

an effective amount of a foaming system and a gas to form a foamed drilling fluid having desired foam properties.

8. The method of claim 6 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.

9. The method of claim 8 , wherein:

the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,

the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and

the transition metal nitrate brines are zinc nitrate brines.

10. The method of claim 9 , wherein:

the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof, and

the sulfonic acids include, without limitation, alkyl sulfonic acids, alkenyl sulfonic acids, aryl sulfonic acids, where the alkyl groups include 1 to about 20 carbon atoms, the alkenyl groups include 2 to about 20 carbon atoms and the aryl groups include 5 to about 30 carbon atoms.

11. A method for inhibiting gas hydrate formation in completion fluids comprising:

using a drilling fluid including:

a base fluid comprising a nitrate brine, and

an inhibiting amount of a corrosion system including:

at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,

where the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof,

where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the completion fluid, and

where the additives reduce or prevent corrosion by the base fluid.

12. The method of claim 11 , wherein the completion fluid further include:

an effective amount of a foaming system and a gas to form a foamed completion fluid having desired foam properties.

13. The method of claim 11 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.

14. The method of claim 13 , wherein:

the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,

the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and

the transition metal nitrate brines are zinc nitrate brines.

15. The method of claim 14 , wherein:

the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof, and

the sulfonic acids include, without limitation, alkyl sulfonic acids, alkenyl sulfonic acids, aryl sulfonic acids, where the alkyl groups include 1 to about 20 carbon atoms, the alkenyl groups include 2 to about 20 carbon atoms and the aryl groups include 5 to about 30 carbon atoms.

16. A method for inhibiting gas hydrate formation in production fluids comprising:

using a production fluid including:

a base fluid comprising a nitrate brine, and

an inhibiting amount of a corrosion system including:

at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,

where the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof,

where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the production fluid, and

where the additives reduce or prevent corrosion by the base fluid.

17. The method of claim 16 , wherein the production fluid further include:

an effective amount of a foaming system and a gas to form a foamed production fluid having desired foam properties.

18. The method of claim 16 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.

19. The method of claim 18 , wherein:

the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,

the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and

the transition metal nitrate brines are zinc nitrate brines.

20. The method of claim 19 , wherein:

the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof, and

the sulfonic acids include, without limitation, alkyl sulfonic acids, alkenyl sulfonic acids, aryl sulfonic acids, where the alkyl groups include 1 to about 20 carbon atoms, the alkenyl groups include 2 to about 20 carbon atoms and the aryl groups include 5 to about 30 carbon atoms.

Assignments (11)
PATENT SECURITY INTEREST ASSIGNMENT AGREEMENT Recorded Apr 26, 2023
From: DEUTSCHE BANK TRUST COMPANY AMERICAS
To: WELLS FARGO BANK, NATIONAL ASSOCIATION
Reel/Frame 063470/0629 →
RELEASE OF SECURITY INTEREST Recorded Oct 1, 2021
From: WILMINGTON TRUST, NATIONAL ASSOCIATION
To: WEATHERFORD TECHNOLOGY HOLDINGS, LLC; WEATHERFORD NETHERLANDS B.V.; WEATHERFORD NORGE AS; HIGH PRESSURE INTEGRITY, INC.; PRECISION ENERGY SERVICES, INC.; WEATHERFORD CANADA LTD; WEATHERFORD SWITZERLAND TRADING AND DEVELOPMENT GMBH; PRECISION ENERGY SERVICES ULC; WEATHERFORD U.K. LIMITED
Reel/Frame 057683/0423 →
SECURITY INTEREST Recorded Oct 1, 2021
From: WEATHERFORD TECHNOLOGY HOLDINGS, LLC; WEATHERFORD NETHERLANDS B.V.; WEATHERFORD NORGE AS; HIGH PRESSURE INTEGRITY, INC.; PRECISION ENERGY SERVICES, INC.; WEATHERFORD CANADA LTD.; WEATHERFORD SWITZERLAND TRADING AND DEVELOPMENT GMBH; WEATHERFORD U.K. LIMITED
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 057683/0706 →
RELEASE OF SECURITY INTEREST Recorded Aug 28, 2020
From: WELLS FARGO BANK, NATIONAL ASSOCIATION
To: WEATHERFORD TECHNOLOGY HOLDINGS, LLC; WEATHERFORD NETHERLANDS B.V.; WEATHERFORD NORGE AS; HIGH PRESSURE INTEGRITY, INC.; PRECISION ENERGY SERVICES, INC.; WEATHERFORD CANADA LTD.; WEATHERFORD SWITZERLAND TRADING AND DEVELOPMENT GMBH; PRECISION ENERGY SERVICES ULC; WEATHERFORD U.K. LIMITED
Reel/Frame 053838/0323 →
SECURITY INTEREST Recorded Aug 28, 2020
From: WEATHERFORD TECHNOLOGY HOLDINGS, LLC; WEATHERFORD NETHERLANDS B.V.; WEATHERFORD NORGE AS; HIGH PRESSURE INTEGRITY, INC.; PRECISION ENERGY SERVICES, INC.; WEATHERFORD CANADA LTD.; WEATHERFORD SWITZERLAND TRADING AND DEVELOPMENT GMBH; PRECISION ENERGY SERVICES ULC; WEATHERFORD U.K. LIMITED
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 054288/0302 →
SECURITY INTEREST Recorded Dec 26, 2019
From: WEATHERFORD TECHNOLOGY HOLDINGS, LLC; WEATHERFORD NETHERLANDS B.V.; WEATHERFORD NORGE AS; HIGH PRESSURE INTEGRITY, INC.; PRECISION ENERGY SERVICES, INC.; WEATHERFORD CANADA LTD.; WEATHERFORD SWITZERLAND TRADING AND DEVELOPMENT GMBH; PRECISION ENERGY SERVICES ULC; WEATHERFORD U.K. LIMITED
To: DEUTSCHE BANK TRUST COMPANY AMERICAS, AS ADMINISTRATIVE AGENT
Reel/Frame 051419/0140 →
SECURITY INTEREST Recorded Dec 18, 2019
From: WEATHERFORD TECHNOLOGY HOLDINGS LLC; WEATHERFORD NETHERLANDS B.V.; WEATHERFORD NORGE AS; HIGH PRESSURE INTEGRITY INC.; PRECISION ENERGY SERVICES INC.; WEATHERFORD CANADA LTD.; WEATHERFORD SWITZERLAND TRADING AND DEVELOPMENT GMBH; PRECISION ENERGY SERVICES ULC; WEATHERFORD U.K. LIMITED
To: WELLS FARGO BANK NATIONAL ASSOCIATION AS AGENT
Reel/Frame 051891/0089 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 24, 2019
From: THE LUBRIZOL CORPORATION
To: WEATHERFORD TECHNOLOGY HOLDINGS, LLC
Reel/Frame 048977/0357 →
MERGER Recorded Mar 13, 2019
From: LUBRIZOL OILFIELD SOLUTIONS, INC.
To: THE LUBRIZOL CORPORATION
Reel/Frame 048581/0260 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 9, 2015
From: CLEARWATER INTERNATIONAL, L.L.C.
To: LUBRIZOL OILFIELD SOLUTIONS, INC.
Reel/Frame 036822/0379 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 21, 2012
From: FALANA, OLUSEGUN MATTHEW; MORROW, MICHAEL; ZAMORA, FRANK G.
To: CLEARWATER INTERNATIONAL, LLC
Reel/Frame 027734/0978 →