# US 8,772,204 B2 · Fluorosurfactants and treatment fluids for reduction of water blocks, oil blocks, and/or gas condensates and associated methods

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- Number: US 8,772,204 B2
- Document ID: US8772204B2
- Status: Granted
- Kind: B2
- Application number: 13/417,020
- Filed: 2012-03-09
- Published: 2012-07-05
- Granted: 2014-07-08
- Earliest claimed: 2009-09-03
- Assignees: Halliburton Energy Services, Inc.
- Applicants: Lewis R. Norman; Rajesh K. Saini
- Inventors: Lewis R. Norman; Rajesh K. Saini
- Web page: https://patentgrep.com/patent/US8772204B2

## CPC

- C09K 8/52: Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K 8/035: Organic additives
- C09K 8/602: {containing surfactants}
- C09K 8/604: {Polymeric surfactants}
- C09K 8/68: containing organic compounds
- C09K 8/78: for preventing sealing
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

The present invention relates to fluids useful for subterranean operations, and more particularly, to fluorosurfactants useful for the reduction of water blocks, gas blocks, and/or gas condensates and their associated treatment fluids and methods. Provided is a method of treating a subterranean formation. The Method may comprise contacting the subterranean formation with a fluorosurfactant. The fluorosurfactant may comprise an amine group, wherein the amine group comprises at least one substituent selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group, and combinations thereof, wherein the at least one substituent comprises about 3 carbons to about 22 carbons. Also provided are polymeric surfactants and treatment fluids that comprise fluorosurfactants.

## Claims

### Claim 1

A treatment fluid comprising:
a carrier fluid; and
a cationic fluorosurfactant comprising an amine group, wherein the amine group comprises at least one substituent comprising about 3 carbons to about 22 carbons and selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group, and combinations thereof.

### Claim 2 (depends on 1)

The treatment fluid of claim 1 wherein the fluorosurfactant comprises a polymeric surfactant comprising repeating nitrogens that comprise the at least one substituent.

### Claim 3 (depends on 1)

The treatment fluid of claim 1 wherein the amine group is positively charged.

### Claim 4 (depends on 1)

The treatment fluid of claim 1 wherein the amine group is a quaternary amine.

### Claim 5 (depends on 1)

The treatment fluid of claim 1 wherein the fluorosurfactant comprises a surfactanthaving the following general structure:
Wherein:
R1 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group;
R2 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to about 8 carbon atoms;
R3 is a fluoroalkyl group or a fluoroalkenyl group, branched or unbranched, comprising about 3 to about 22 carbon atoms;
R4 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R5 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R6 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising about 1 to about 8 carbon atoms, or —(CR4R5)m—N+R1R2R3.X−;
m is about 3 to about 8;
Z is either alkyl, O, NH or S;
n is about 1 to about 6; and
X− is an anion.

### Claim 6 (depends on 1)

The treatment fluid of claim 1 wherein the fluorosurfactant comprises a surfactant having the following general structure:
Wherein:
R3 is an fluoroalkyl group that is either saturated or unsaturated comprising about 3 to about 12 carbon atoms; and
X− is an anion.

### Claim 7 (depends on 1)

The treatment fluid of claim 1 wherein the fluorosurfactant comprises a surfactant having the following general structure:
Wherein:
R1 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising about 1 to about 8 carbon atoms, end-capped ethylene oxide, or end-capped propylene oxide;
R2 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, end capped ethylene oxide, or end-capped propylene oxide;
R3 is a fluoroalkyl group or a fluoroalkenyl group, branched or unbranched, comprising about 3 to about 22 carbon atoms;
R4 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R5 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R6 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising 3 to 22 carbon atoms, or —(CR4R5)m—N+R1R2R3.X−;
m is about 1 to about 6;
n is about 1 to about 6;
a and b are individually from about 1 to about 200, wherein the ratio of a to b is from about 1:4 to about 4:1; and
X− is an anion.

### Claim 8 (depends on 1)

The treatment fluid of claim 1 wherein the fluorosurfactant is present in the treatment fluid in an amount of about 0.01% to about 10% by weight of the treatment fluid.

### Claim 9 (depends on 1)

The treatment fluid of claim 1 wherein the fluorosurfactant comprises a reaction product of a reaction comprising polyethylene imine and perfluoroalkyl halide.

### Claim 10 (depends on 1)

The treatment fluid of claim 1 wherein the substituent comprises the fluoroalkyl group and wherein the fluoroalkyl group comprises a perfluoroalkyl group.

### Claim 11 (depends on 1)

The treatment fluid of claim 1 wherein the treatment fluid further comprises at least one additive selected from the group consisting of a proppant particulate, a gravel particulate, a gelling agent, a crosslinking agent, a salt, an additional surfactant, a fluid loss control additive, an acid, gas, a surface modifying agent, a tackifying agent, a foamer, a corrosion inhibitor, a scale inhibitor, a catalyst, a clay control agent, a biocide, a friction reducer, an antifoam agent, a bridging agent, a dispersant, a flocculant, H2S scavenger, CO2 scavenger, an oxygen scavenger, a lubricant, a viscosifier, a breaker, a weighting agent, a relative permeability modifier, a resin, a wetting agent, and a coating enhancement agent.

### Claim 12 (depends on 1)

The treatment fluid of claim 1 wherein the treatment fluid further comprises a non-fluoro surfactant in ratio of the non-fluoro surfactant to the fluorosurfactant of from about 1:99 to about 99:1.

### Claim 13 (depends on 1)

The treatment fluid of claim 1 wherein the treatment fluid further comprises a non-fluoro quaternary surfactant.

### Claim 14

A treatment fluid comprising:
a carrier fluid; and
a fluorosurfactant in an amount of about 0.01% to about 10% by weight of the treatment fluid, wherein the fluorosurfactant has the following general structure:
Wherein:
R1 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising about 1 to about 8 carbon atoms, end-capped ethylene oxide, or end-capped propylene oxide;
R2 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, end capped ethylene oxide, or end-capped propylene oxide;
R3 is a fluoroalkyl group or a fluoroalkenyl group, branched or unbranched, comprising about 3 to about 22 carbon atoms;
R4 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R5 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R6 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising 3 to 22 carbon atoms, or —(CR4R5)m—N+R1R2R3.X−;
m is about 1 to about 6;
n is about 1 to about 6;
a and b are individually from about 1 to about 200, wherein the ratio of a to b is from about 1:4 to about 4:1; and
X− is an anion.

### Claim 15 (depends on 14)

The treatment fluid of claim 14 wherein the treatment fluid further comprises at least one additive selected from the group consisting of a proppant particulate, a gravel particulate, a gelling agent, a crosslinking agent, a salt, an additional surfactant, a fluid loss control additive, an acid, gas, a surface modifying agent, a tackifying agent, a foamer, a corrosion inhibitor, a scale inhibitor, a catalyst, a clay control agent, a biocide, a friction reducer, an antifoam agent, a bridging agent, a dispersant, a flocculant, H2S scavenger, CO2 scavenger, an oxygen scavenger, a lubricant, a viscosifier, a breaker, a weighting agent, a relative permeability modifier, a resin, a wetting agent, and a coating enhancement agent.

### Claim 16 (depends on 14)

The treatment fluid of claim 14 wherein the treatment fluid further comprises a non-fluoro quaternary surfactant.

### Claim 17

A treatment fluid comprising:
a carrier fluid;
a cationic fluorosurfactant comprising a positively charged amine group, wherein the amine group comprises at least one substituent comprising about 3 carbons to about 22 carbons and selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group, and combinations thereof; and
a non-fluoro quaternary surfactant

### Claim 18 (depends on 17)

The treatment fluid of claim 17 wherein the fluorosurfactant has the following general structure:
Wherein:
R1 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group;
R2 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to about 8 carbon atoms;
R3 is a fluoroalkyl group or a fluoroalkenyl group, branched or unbranched, comprising about 3 to about 22 carbon atoms;
R4 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R5 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R6 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising about 1 to about 8 carbon atoms, or —(CR4R5)m—N+R1R2R3.X−;
m is about 3 to about 8;
Z is either alkyl, O, NH or S;
n is about 1 to about 6; and
X− is an anion.

### Claim 19 (depends on 17)

The treatment fluid of claim 17 wherein the fluorosurfactant has the following general structure:
Wherein:
R3 is an fluoroalkyl group that is either saturated or unsaturated comprising about 3 to about 12 carbon atoms; and
X− is an anion.

### Claim 20 (depends on 17)

The treatment fluid of claim 17 wherein the fluorosurfactant has the following general structure:
Wherein:
R1 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising about 1 to about 8 carbon atoms, end-capped ethylene oxide, or end-capped propylene oxide;
R2 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, end capped ethylene oxide, or end-capped propylene oxide;
R3 is a fluoroalkyl group or a fluoroalkenyl group, branched or unbranched, comprising about 3 to about 22 carbon atoms;
R4 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R5 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, or a fluoroalkyl group comprising about 1 to 8 carbon atoms;
R6 is a hydrogen atom, an alkyl group comprising about 1 to about 8 carbon atoms, a fluoroalkyl group comprising 3 to 22 carbon atoms, or —(CR4R5)m—N+R1R2R3.X−;
m is about 1 to about 6;
n is about 1 to about 6;
a and b are individually from about 1 to about 200, wherein the ratio of a to b is from about 1:4 to about 4:1; and
X− is an anion.