Copolymers for use as paraffin behavior modifiers

• US 9,163,194 B2
• Filed: 12/11/2012
• Issued: 10/20/2015
• Est. Priority Date: 12/13/2011
• Status: Active Grant

• Current Assignee: Baker Hughes Holdings LLC (Baker Hughes Company)
• Original Assignee: Baker Hughes Incorporated (Baker Hughes Company)
• Inventors: Sonne, Jennifer Louise, Hilfiger, Matthew
• Primary Examiner(s): WEISS, PAMELA HL
• Application Number:
  US13/710,921
• Publication Number:
  US 20130150272A1
• Time in Patent Office: 1,043 Days
• Field of Search: 443/13, 443/51, 443/53, 166/308.6, 436/29, 436/139, 585/10, 585/11, 585/12, 585/14, 585/17, 208/15, 208/20, 208/21, 208/24
• US Class Current: 1/1
• CPC Class Codes: C09K 8/524 organic depositions, e.g. paraffins or asphaltenes
• CPC Class Codes: C10L 1/238 obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds C10L1/221 takes precedence
• CPC Class Codes: C10L 10/14 for improving low temperature properties
• CPC Class Codes: C10M 129/66 Epoxidised acids or esters
• CPC Class Codes: C10M 129/68 Esters epoxidised C10M129/66
• CPC Class Codes: C10M 133/06 having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 145/26 Polyoxyalkylenes
• CPC Class Codes: C10M 159/005 Macromolecular compounds, e.g. macromolecular compounds composed of alternatively specified monomers not covered by the same main group
• CPC Class Codes: C10M 159/12 Reaction products
• CPC Class Codes: C10M 2205/022 Ethene
• CPC Class Codes: C10M 2209/043 used as base material
• CPC Class Codes: C10M 2209/062 Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
• CPC Class Codes: C10M 2209/10 Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2209/101 Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
• CPC Class Codes: C10M 2209/102 Polyesters
• CPC Class Codes: C10M 2209/103 Polyethers, i.e. containing di- or higher polyoxyalkylene groups
• CPC Class Codes: C10M 2209/104 of alkylene oxides containing two carbon atoms only
• CPC Class Codes: C10M 2209/105 of alkylene oxides containing three carbon atoms only
• CPC Class Codes: C10M 2209/108 etherified
• CPC Class Codes: C10M 2209/109 esterified
• CPC Class Codes: C10M 2209/12 : Polysaccharides, e.g. cellulose, biopolymers
• CPC Class Codes: C10M 2217/02 : Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2217/042 : between the nitrogen-containing monomer and an aldehyde or ketone
• CPC Class Codes: C10M 2217/044 : Polyamides
• CPC Class Codes: C10N 2020/04 : Molecular weight; Molecular weight distribution
• CPC Class Codes: C10N 2030/02 : Pour-point; Viscosity index
• CPC Class Codes: C10N 2030/04 : Detergent property or dispersant property
• CPC Class Codes: C10N 2030/08 : Resistance to extreme temperature
• CPC Class Codes: C10N 2030/68 : Shear stability
• CPC Class Codes: C10N 2040/25 : Internal-combustion engines
• CPC Class Codes: C10N 2060/00 : Chemical after-treatment of the constituents of the lubricating composition
• CPC Class Codes: C10N 2060/06 : by epoxydes or oxyalkylation reactions

Abstract

Lactone/alkylene oxide polymers are useful as additives to inhibit or prevent the deposition of paraffin in hydrocarbon fluids, particularly crude oil produced from a subterranean formation. These polymers are random or block polymers made from addition reactions of a hydroxyl- and/or amine-containing base compound with at least one lactone monomer and at least one alkylene oxide monomer. In one non-limiting embodiment the lactone monomer is optional.

Claims

1. A method of modifying the behavior of paraffin in a hydrocarbon fluid, the method comprising:

adding to the hydrocarbon fluid comprising paraffin an effective amount of a polymer to modify the behavior of paraffin therein, where the hydrocarbon fluid is selected from the group consisting of crude oil, condensate, and home heating oil, where the polymer comprises one selected from the group consisting of;

a random or block polymer made from addition reactions of a base compound selected from the group consisting of hydroxyl-containing base compounds, amine-containing base compounds and combinations thereof, with at least one lactone monomer and at least one alkylene oxide monomer,

a random or block polymer made from addition reactions of a base compound selected from the group consisting of hydroxyl-containing base compounds, amine-containing base compounds and combinations thereof, with at least one alkylene oxide monomer, and

combinations thereof;

measuring paraffin deposition for the hydrocarbon fluid both with and without the polymer by a method comprising;

setting a cold finger probe to a temperature below the crude oil Wax Appearance Temperature (WAT) of the hydrocarbon fluid,

setting the crude oil temperature to be at or above the WAT,

stirring the crude oil,

inserting the cold finger probe into the stirred crude oil for about 16 hours, and

comparing by weight a deposition on the cold finger probe for the hydrocarbon fluid with the polymer to a deposition on the cold finger probe for the hydrocarbon fluid without the polymer, and

determining if there is a difference between the density of the depositions that indicates paraffin behavior modification;

where the modification of paraffin behavior is selected from the group consisting of inhibiting or preventing the deposition of paraffin, modifying the crystal structure of the paraffin, lowering the pour point of the hydrocarbon fluid and dispersing the paraffin in the hydrocarbon fluid, as compared to the paraffin behavior in the absence of the polymer.

2. The method of claim 1 where:

the at least one lactone monomer is selected from the group of lactones of formula (I) having 3 to 7 carbon atoms in the central ring, where formula (I) has the chemical structure;

3. The method of claim 2 where the hydroxyl- or amine-containing base compound is a hydroxylamine that is selected from the group consisting of ethanolamine;

diethanolamine;

triethanolamine, and mixtures thereof.

4. The method of claim 1 where:

the weight ratio of at least one lactone monomer to the hydroxyl- or amine-containing base compound ranges from about 0.1;

1 to about 99.9;

1; and

the weight ratio of at least one alkylene oxide monomer to the hydroxyl- or amine-containing base compound ranges from about 99.9;

1 to about 0.1;

1.

5. The method of claim 1 where the weight average molecular weight of the polymer ranges from about 2000 to about 1,500,000 g/mol.

6. The method of claim 1 where the effective amount of the polymer ranges from about 5 to about 10,000 ppm, based on the hydrocarbon fluid.

7. The method of claim 1 where the polymer is capped by reaction with a monofunctional monomer selected from the group consisting of monoepoxides, monofunctional carboxylic acids, and combinations thereof.

8. The method of claim 7 where the monofunctional monomer is selected from the group consisting of styrene oxide, glycidal ether, benzylglycidal ether, C1-C24 glycidal ether, acid anhydrides, C2-C24 carbocyclic acids, and combinations thereof.

9. The method of claim 1 where the polymer is blended with at least one additional polymer selected from the group consisting of ethylene-vinyl acetate (EVA), alkylphenol formaldehyde resins, and combinations thereof.

10. A method of modifying the behavior of paraffin in a hydrocarbon fluid, the method comprising:

adding to the hydrocarbon fluid comprising paraffin from about 5 to about 10,000 ppm, based on the hydrocarbon fluid, of a polymer to modify the behavior of paraffin therein, where the hydrocarbon fluid is selected from the group consisting of crude oil, condensate, and home heating oil, where the polymer comprises one selected from the group consisting of;

a random or block polymer made from addition reactions of a base compound selected from the group consisting of hydroxyl-containing base compounds, amine-containing base compounds and combinations thereof, with at least one lactone monomer and at least one alkylene oxide monomer,

a random or block polymer made from addition reactions of a base compound selected from the group consisting of hydroxyl-containing base compounds, amine-containing base compounds and combinations thereof, with at least one alkylene oxide monomer, and

combinations thereof;

where the polymer has a weight average molecular weight of the polymer ranges from about 2000 to about 1,500,000 g/mol, and

measuring paraffin deposition for the hydrocarbon fluid both with and without the polymer by a method comprising;

setting a cold finger probe to a temperature below the crude oil Wax Appearance Temperature (WAT) of the hydrocarbon fluid,

setting the crude oil temperature to be at or above the WAT,

stirring the crude oil,

inserting the cold finger probe into the stirred crude oil for about 16 hours, and

comparing by weight a deposition on the cold finger probe for the hydrocarbon fluid with the polymer to a deposition on the cold finger probe for the hydrocarbon fluid without the polymer, and

determining if there is a difference between the density of the depositions that indicates paraffin behavior modification;

where the modification of paraffin behavior is selected from the group consisting of inhibiting or preventing the deposition of paraffin, modifying the crystal structure of the paraffin, lowering the pour point of the hydrocarbon fluid and dispersing the paraffin in the hydrocarbon fluid, as compared to the paraffin behavior in the absence of the polymer.

11. The method of claim 10 where:

the at least one lactone monomer is selected from the group of lactones of formula (I) having 3 to 7 carbon atoms in the central ring, where formula (I) has the chemical structure;

12. The method of claim 11 where the hydroxyl- or amine-containing base compound is a hydroxylamine that is selected from the group consisting of ethanolamine;

diethanolamine;

triethanolamine, and mixtures thereof.

13. The method of claim 10 where:

the weight ratio of at least one lactone monomer to the hydroxyl- or amine-containing base compound ranges from about 0.1;

1 to about 99.9;

1; and

the weight ratio of at least one alkylene oxide monomer to the hydroxyl- or amine-containing base compound ranges from about 99.9;

1 to about 0.1;

1.

14. The method of claim 10 where the polymer is capped by reaction with a monofunctional monomer selected from the group consisting of monoepoxides, monofunctional carboxylic acids, and combinations thereof.

15. The method of claim 14 where the monofunctional monomer is selected from the group consisting of styrene oxide, glycidal ether, benzylglycidal ether, C1-C24 glycidal ether, acid anhydrides, C2-C24 carbocyclic acids;

and combinations thereof.

16. A method of modifying the behavior of paraffin in a hydrocarbon fluid, the method comprising:

adding to the hydrocarbon fluid comprising paraffin from about 5 to about 1000 ppm, based on the hydrocarbon, to modify the behavior of paraffin therein, where the hydrocarbon fluid is selected from the group consisting of crude oil, condensate, and home heating oil, where the polymer comprises one selected from the group consisting of;

a random or block polymer made from addition reactions of a base compound selected from the group consisting of hydroxyl-containing base compounds, amine-containing base compounds and combinations thereof, with at least one lactone monomer and at least one alkylene oxide monomer,

a random or block polymer made from addition reactions of a base compound selected from the group consisting of hydroxyl-containing base compounds, amine-containing base compounds and combinations thereof, with at least one alkylene oxide monomer, and

combinations thereof where;

the at least one lactone monomer is selected from the group of lactones of formula (I) having 3 to 7 carbon atoms in the central ring, where formula (I) has the chemical structure;

17. The method of claim 16 where the hydroxyl- or amine-containing base compound is a hydroxylamine that is selected from the group consisting of ethanolamine;

diethanolamine;

triethanolamine, and mixtures thereof.

18. The method of claim 16 where:

the weight ratio of at least one lactone monomer to the hydroxyl- or amine-containing base compound ranges from about 0.1;

1 to about 99.9;

1; and

the weight ratio of at least one alkylene oxide monomer to the hydroxyl- or amine-containing base compound ranges from about 99.9;

1 to about 0.1;

1.

19. The method of claim 16 where the weight average molecular weight of the polymer ranges from about 2000 to about 1,500,000 g/mol.