IP Library Granted Patent US 9,784,414
Granted Patent B2
US 9,784,414 · App. 13/209,119 · Granted Oct 10, 2017

Drag reduction of asphaltenic crude oils

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Quick Facts
Patent No.
US 9,784,414
App. No.
13/209,119
Granted
Oct 10, 2017
Kind
B2
Abstract

A process for preparing a drag reducing polymer which is to be added to a liquid hydrocarbon. The liquid hydrocarbon has an asphaltene content of at least about 3 weight percent and an API gravity of less than about 26°. The drag reducing polymer can comprise the residues of a monomer having at least one heteroatom. Treatment of the liquid hydrocarbon with the drag reducing polymer allows a reduction in pressure drop associated with turbulent flow of the liquid hydrocarbon through a conduit.

Claims (45)

1. A process comprising:

a) obtaining a first batch of a first monomer comprising 2-ethylhexyl methacrylate;

b) obtaining a second batch of a second monomer;

c) preparing a mixture comprising the first monomer and the second monomer; and

d) polymerizing the mixture via emulsion polymerization to produce a latex drag reducing polymer comprising a copolymer that includes at least 25,000 repeating units, and e) adding the latex drag reducing polymer to a heavy crude oil; wherein the latex drag reducing polymer has a weight average molecular weight of at least 5 million g/mol, the latex drag reducing polymer providing at least a 20 percent drag reduction in heavy crude oil as it flows through a pipeline during use, the heavy crude oil comprising an asphaltene content of at least 3 weight percent and an API gravity of less than about 26°.

2. The process of claim 1 , wherein the second monomer is n-butyl acrylate.

3. The process of claim 1 , wherein the mixture is an 80/20 weight percent blend of 2-ethylhexyl methacrylate monomer (80 percent) and n-butyl acrylate monomer (20 percent).

4. The process of claim 1 , wherein the mixture comprises between 68 and 92 weight percent of 2-ethylhexyl methacrylate monomer.

5. The process of claim 1 , wherein second monomer has the following chemical structure:

wherein R 1 is selected from the group consisting of (a) H and (b) a C1-C10 alkyl radical; and

wherein R 2 is selected from the group consisting of (a) H, (b) a C1-C30 alkyl radical, (c) a C5-C30 substituted or unsubstituted cycloalkyl radical, (d) a C6-C20 substituted or unsubstituted aryl radical, (e) an aryl-substituted C1-C10 alkyl radical, and (f) a —(CH2CH2O) x —R A or —(CH2CH(CH3)O) x —R A radical, wherein x is in the range of from 1 to 50 and R A is selected from the group consisting of (i) H, (ii) a C1-C30 alkyl radical, and (iii) a C6-C30 alkylaryl radical.

6. The process of claim 1 , wherein the latex drag reducing polymer provides at least 36.7 percent drag reduction in the heavy crude oil as it flows through a pipeline during use.

7. The process of claim 1 , wherein the latex drag reducing polymer provides at least 42.5 percent drag reduction in the heavy crude oil as it flows through a pipeline during use.

8. The process of claim 1 , wherein the copolymer comprises at least 50,000 repeating units.

9. The process of claim 1 , wherein the second monomer comprises a heteroatom.

10. The process of claim 1 , wherein the latex drag reducing polymer has little or no crosslinking.

11. The process of claim 1 , the drag reducing polymer being added to the heavy crude oil in an amount between about 0.1 ppmw and about 500 ppmw without causing a decrease in viscosity of the heavy crude oil, and wherein the drag reducing polymer reduces friction loss associated with the turbulent flow of the heavy crude oil through the pipeline.

12. The process of claim 11 , wherein the heavy crude oil has an asphaltene content of at least about 5 weight percent and the API gravity of the heavy crude oil is in the range of from 5° to 23°.

13. The process of claim 11 , wherein the asphaltene content of the heavy crude oil is in the range of from 4 to about 35 weight percent and the API gravity of the heavy crude oil is in the range of from 5° to 23°.

14. The process of claim 1 , wherein the latex drag reducing polymer has a solubility parameter within about 10 percent of a solubility parameter of the heavy crude oil.

15. A process comprising:

a) obtaining a first batch of a first monomer comprising 2-ethylhexyl methacrylate;

b) obtaining a second batch of a second monomer;

c) preparing a mixture comprising the first monomer and the second monomer;

d) polymerizing the mixture via emulsion polymerization to produce a latex drag reducing polymer comprising a copolymer that includes at least 25,000 repeating units; and

e) testing the latex drag reducing polymer by adding it to a heavy crude oil to assess the heavy crude oil's affinity for the latex drag reducing polymer;

wherein the latex drag reducing polymer has a weight average molecular weight of at least 5 million g/mol, the latex drag reducing polymer providing at least a 20 percent drag reduction in heavy crude oil as it flows through a pipeline during use, the heavy crude oil comprising an asphaltene content of at least 3 weight percent and an API gravity of less than about 26°.

16. A process comprising:

a) obtaining a first batch of a monomer comprising 2-ethylhexyl methacrylate;

b) preparing a reaction mixture comprising the monomer, at least one surfactant, and an initiation system; and

d) polymerizing the mixture via emulsion polymerization to produce a latex drag reducing polymer that includes at least 25,000 repeating units, wherein the latex drag reducing polymer has a weight average molecular weight of at least 5 million g/mol;

e) adding the latex drag reducing polymer to a heavy crude oil having an asphaltene content of at least 3 weight percent and an API gravity of less than about 26° in a pipeline, the drag reducing polymer being added to the heavy crude oil in an amount between about 0.1 ppmw and about 500 ppmw without causing a decrease in viscosity of the heavy crude oil, and wherein the drag reducing polymer reduces friction loss associated with the turbulent flow of the heavy crude oil through the pipeline to provide at least 20 percent drag reduction.

17. A process comprising:

(a) obtaining a drag reducing polymer formed from 2-ethylhexyl methacrylate, the drag reducing polymer having been formed via emulsion polymerization of a reaction mixture comprising 2-ethylhexyl methacrylate monomer, at least one surfactant, and an initiation system, wherein the drag reducing polymer comprises at least 25,000 repeating units and has a weight average molecular weight of at least 5 million g/mol;

(b) adding the drag reducing polymer into a pipeline containing a liquid hydrocarbon having an asphaltene content of at least 3 weight percent and an API gravity of less than about 26°, the drag reducing polymer being added in an amount between about 0.1 ppmw and about 500 ppmw without causing a decrease in viscosity of the liquid hydrocarbon, and wherein the drag reducing polymer provides at least 20 percent drag reduction in the liquid hydrocarbon as it flows through the pipeline.

18. The process of claim 17 , wherein the liquid hydrocarbon has an asphaltene content of at least 5 weight percent and an API gravity in the range of from 5° to 23°.

19. The process of claim 17 , wherein the drag reducing polymer is a homopolymer of 2-ethylhexyl methacrylate that comprises at least 50,000 repeating units.

20. The process of claim 17 , wherein the drag reducing polymer has a solubility parameter within 2.5 MPa 1/2 of a solubility parameter of the liquid hydrocarbon.

21. The process of claim 17 , wherein the drag reducing polymer provides at least 36.7 percent drag reduction in the liquid hydrocarbon as it flows through the pipeline.

22. The process of claim 17 , wherein the drag reducing polymer provides at least 42.5 percent drag reduction in the liquid hydrocarbon as it flows through the pipeline.

23. A process comprising:

(a) obtaining a drag reducing polymer formed from one or more monomers having the following chemical structure:

wherein R 1 is selected from the group consisting of (a) H and (b) a C1-C10 alkyl radical; and

wherein R 2 is a C1-C30 alkyl radical, the drag reducing polymer having been formed via emulsion polymerization of a reaction mixture comprising the one or more monomers, at least one surfactant, and an initiation system, wherein the drag reducing polymer comprises at least 25,000 repeating units and has a weight average molecular weight of at least 5 million g/mol;

(b) adding the drag reducing polymer into a pipeline containing a liquid hydrocarbon having an asphaltene content of at least 5 weight percent and API gravity in the range of from 5° to 23°, the drag reducing polymer being added in an amount between about 0.1 ppmw and about 500 ppmw without causing a decrease in viscosity of the liquid hydrocarbon, and wherein the drag reducing polymer provides at least 20 percent drag reduction in the liquid hydrocarbon as it flows through the pipeline.

Assignments (5)
CHANGE OF NAME Recorded Jan 10, 2017
From: LUBRIZOL SPECIALTY PRODUCTS, INC.
To: LIQUIDPOWER SPECIALTY PRODUCTS, INC.
Reel/Frame 041315/0038 →
CHANGE OF NAME Recorded Apr 8, 2014
From: PHILLIPS SPECIALTY PRODUCTS INC.
To: LUBRIZOL SPECIALTY PRODUCTS, INC.
Reel/Frame 032623/0161 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 24, 2014
From: PHILLIPS 66 COMPANY
To: PHILLIPS SPECIALTY PRODUCTS INC.
Reel/Frame 032277/0019 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 15, 2012
From: CONOCOPHILLIPS COMPANY
To: PHILLIPS 66 COMPANY
Reel/Frame 028213/0824 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 20, 2011
From: BAO, ZHIYI; MILLIGAN, STUART N.; OLECHNOWICZ, MICHAEL
To: CONOCOPHILLIPS COMPANY
Reel/Frame 026936/0503 →