IP Library Granted Patent US 9,303,236
Granted Patent B2
US 9,303,236 · App. 14/321,461 · Granted Apr 5, 2016

Oilfield cleaner and corrosion inhibitor comprising a polyamine sulfonic acid salt

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Quick Facts
Patent No.
US 9,303,236
App. No.
14/321,461
Granted
Apr 5, 2016
Kind
B2
Abstract

Disclosed herein are cleaner/corrosion inhibiting compositions useful in applications relating to the production, transportation, storage, and separation of crude oil and natural gas. Also disclosed herein are methods of using the compositions as cleaners/corrosion inhibitors, particularly in applications relating to the production, transportation, storage, and separation of crude oil and natural gas.

Claims (61)

1. A composition for inhibiting corrosion and/or removing hydrocarbonaceous deposits in oil and gas applications, the composition comprising a polyamine sulfonic acid salt component and a synergist selected from the group consisting of thioglycolic acid, 3,3′-dithiodipropionic acid, thiosulfate, thiourea, 2-mercaptoethanol, L-cysteine, tert-butyl mercaptan, and combinations thereof.

2. The composition of claim 1 wherein the polyamine sulfonic acid salt component is formed by reaction of a polyamine component with a sulfonic acid component.

3. The composition of claim 2 , wherein the polyamine component comprises a polyalkylene polyamine, wherein the polyalkylene polyamine comprises a polyethylene polyamine, a polypropylene polyamine, a polybutylene polyamine, or a combination thereof.

4. The composition of claim 3 , wherein the polyamine component comprises a mixture of tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and hexaethyleneheptamine (HEHA).

5. The composition of claim 2 , wherein the sulfonic acid component is selected from the group consisting of an aryl sulfonic acid, an alkyl sulfonic acid, an arylalkyl sulfonic acid, and a combination thereof.

6. The composition of claim 1 , wherein the polyamine sulfonic acid salt component comprises a salt selected from the group consisting of:

a tetraethylenepentamine dodecylbenzenesulfonic acid salt;

a pentaethylenehexamine dodecylbenzenesulfonic acid salt;

a hexaethyleneheptamine dodecylbenzenesulfonic acid salt;

and a combination thereof.

7. The composition of claim 1 , further comprising a corrosion inhibitor component.

8. The composition of claim 7 , wherein the corrosion inhibitor component comprises an imidazoline of Formula (I) or an imidazolinium salt of Formula (II):

wherein

R 10 is a C 1 -C 20 alkyl or a C 1 -C 20 alkoxyalkyl group;

R 12 and R 13 are independently a C 1 -C 6 alkyl group or hydrogen,

R 11 and R 14 are independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, or C 1 -C 6 arylalkyl;

and

X − is halide, chloride, bromide, iodide, carbonate, sulfonate, phosphate, or an anion of an organic carboxylic acid;

or a tautomer thereof.

9. The composition of claim 8 , wherein R 10 is an alkyl mixture typical in tall oil fatty acid (TOFA), R 11 is benzyl, R 12 and R 13 are each hydrogen, R 14 is hydroxyethyl, and

X − is chloride.

10. The composition of claim 7 , wherein the corrosion inhibitor component comprises a compound of Formula (III):

wherein

R 9 is an alkyl group, an aryl group, or an arylalkyl group, wherein said alkyl groups have from 1 to about 18 carbon atom; and

X − is chloride, bromide, or iodide.

11. The composition of claim 10 , wherein R 9 is benzyl, and X − is chloride.

12. The composition of claim 7 , wherein the corrosion inhibitor component comprises an ethoxylated amine.

13. The composition of claim 12 , wherein the ethoxylated amine is ethoxylated tallow amine.

14. A method of inhibiting corrosion at a surface and/or removing hydrocarbonaceous deposits from a surface, the method comprising adding a composition to a fluid which contacts a surface of a wellbore or equipment used in production, processing, transportation, storage or separation of the fluid to inhibit corrosion and/or remove hydrocarbonaceous deposits from the surface, the composition comprising a polyamine sulfonic acid salt component, and the fluid comprising natural gas or a liquid hydrocarbon.

15. The method of claim 14 , wherein an effective amount of the composition is provided at the surface when the composition provides greater than or equal to 40% schmoo removal in a Dynamic Schmoo Removal Loop (“DSRL”) test conducted at a dosage of 500 or 1,000 ppm of the composition in brine at 122° F.

16. The composition of claim 1 wherein the

polyamine sulfonic acid salt component comprises at least one salt selected from a tetraethylenepentamine dodecylbenzenesulfonic acid salt, a pentaethylenehexamine dodecylbenzenesulfonic acid salt, and a hexaethyleneheptamine dodecylbenzenesulfonic acid salt;

the synergist comprises 2-mercaptoethanol; and

the composition further comprises methanol; and

optionally comprises a corrosion inhibitor component comprising an imidazolinium salt, a pyridinium salt, and an ethoxylated alkyl amine.

17. The composition of claim 16 , wherein the polyamine sulfonic acid salt component comprises a mixture of a tetraethylenepentamine dodecylbenzenesulfonic acid salt, a pentaethylenehexamine dodecylbenzenesulfonic acid salt, and a hexaethyleneheptamine dodecylbenzenesulfonic acid salt.

18. The composition of claim 16 , wherein the polyamine sulfonic acid salt component is present in an amount of 10-70 wt. %, the corrosion inhibitor component is present in an amount of 5-50 wt. %, 2-mercaptoethanol is present in an amount of 1-20 wt. %, and methanol is present in an amount of 10-80 wt. %, based on the total weight of the composition.

19. The method of claim 14 , wherein an effective amount of the composition is provided at the surface when the composition provides at least 95% protection after 12 hours for a 1018 carbon steel working electrode in a bubble test, wherein the bubble test is characterized by:

(a) a testing temperature of about 60° C.;

(b) a carbon dioxide saturated liquid medium of 10% field crude oil and 90% synthetic brine; and

(c) an inhibitor dosage of 20 ppm of the composition based on total fluids.

20. The method of claim 14 wherein the equipment comprises a pipeline, a storage vessel, downhole injection tubing, a flow line, or an injection line.

21. The method of claim 14 wherein the liquid hydrocarbon comprises crude oil, heavy oil, processed residual oil, bituminous oil, coker oil, gas oil, fluid catalytic cracker feed or slurry, naphtha, diesel fuel, fuel oil, jet fuel, gasoline, or kerosene.

22. The method of claim 14 wherein the polyamine sulfonic acid salt component comprises a salt selected from the group consisting of:

a tetraethylenepentamine dodecylbenzenesulfonic acid salt;

a pentaethylenehexamine dodecylbenzenesulfonic acid salt;

a hexaethyleneheptamine dodecylbenzenesulfonic acid salt;

and a combination thereof; and/or

the composition further comprises a corrosion inhibitor comprising:

(A) an imidazoline of Formula (I) or an imidazolinium salt of Formula (II):

wherein

R 10 is a C 1 -C 20 alkyl or a C 1 -C 20 alkoxyalkyl group;

R 12 and R 13 are independently a C 1 -C 6 alkyl group or hydrogen,

R 11 and R 14 are independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 hydroxyalkyl, or C 1 -C 6 arylalkyl; and

X − is halide, chloride, bromide, iodide, carbonate, sulfonate, phosphate, or an anion of an organic carboxylic acid;

or a tautomer thereof;

(B) a compound of Formula (III):

wherein

R 9 is an alkyl group, an aryl group, or an arylalkyl group, wherein said alkyl groups have from 1 to about 18 carbon atom; and

X − is chloride, bromide, or iodide; or

(C) an ethoxylated amine.

Assignments (6)
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jul 17, 2025
From: JPMORGAN CHASE BANK, N.A.
To: CHAMPIONX LLC; APERGY ESP SYSTEMS, LLC; APERGY BMCS ACQUISITION CORP; HARBISON-FISCHER, INC.; NORRIS RODS, INC.,; NORRIS RODS, INC.,; NORRISEAL-WELLMARK, INC.; PCS FERGUSON, INC.; QUARTZDYNE, INC.; US SYNTHETIC CORPORATION
Reel/Frame 072004/0019 →
RELEASE OF SECURITY INTEREST Recorded Jun 7, 2022
From: BANK OF AMERICA, N.A.
To: CHAMPIONX USA INC.
Reel/Frame 060304/0267 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 22, 2020
From: ECOLAB USA INC.
To: CHAMPIONX USA INC.
Reel/Frame 053849/0537 →
SECURITY INTEREST Recorded Jun 5, 2020
From: CHAMPIONX USA INC.
To: BANK OF AMERICA, N.A.
Reel/Frame 052848/0368 →
SECURITY INTEREST Recorded Jun 5, 2020
From: CHAMPIONX USA INC.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 053250/0001 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 5, 2015
From: BENNETT, BRIAN MICHAEL; MANCUSO, SEBASTIAN DENNIS
To: ECOLAB USA INC.
Reel/Frame 034900/0017 →