# US 11,306,241 B2 · Geochemically-driven wettability modification for subterranean surfaces

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- Number: US 11,306,241 B2
- Document ID: US11306241B2
- Status: Granted
- Kind: B2
- Application number: 16/617,777
- Filed: 2017-06-30
- Published: 2020-06-18
- Granted: 2022-04-19
- Earliest claimed: 2017-06-30
- Assignees: Halliburton Energy Services, Inc.
- Applicants: Halliburton Energy Services, Inc.
- Inventors: Enrique Antonio Reyes; Denise Nicole Benoit; Ronald Glen Dusterhoft
- Web page: https://patentgrep.com/patent/US11306241B2

## CPC

- C09K 8/68: containing organic compounds
- C09K 8/602: {containing surfactants}
- C09K 8/64: Oil-based compositions
- C09K 8/703: {Foams}
- C09K 8/82: Oil-based compositions (C09K8/64 takes precedence)
- C09K 8/86: containing organic compounds
- C09K 8/94: Foams
- E21B 43/255: {including the injection of a gaseous medium as treatment fluid into the formation}
- E21B 43/26: by forming crevices or fractures
- E21B 43/2605: {using gas or liquefied gas}
- E21B 43/267: reinforcing fractures by propping
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS

## Abstract

Systems, methods, and compositions that provide an energized natural gas (ENG) fracturing fluid including a complexing agent. A fracturing fluid may include: methane; water; a complexing agent; a surfactant; and wherein the fracturing fluid is an emulsion, the water is in a continuous phase of the emulsion, and methane is in a discrete phase of the emulsion.

## Claims

### Claim 1

A method comprising:
preparing a liquid additive comprising:
a base fluid;
a complexing agent selected from the group consisting of methylglycindiacetic acid (MGDA), glutamic acid diacetic acid (GLDA), (Hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), hydroxyiminodisuccinic acid (HIDS), polyether multicarboxylic acids, diethylenetriamine pentaacetate (DTPA), oxalic acid, citric acid, glycolic acid, lactic acid, and maleic acid, N-(Phosphonomethyl)iminodiacetic acid (PMIDA), phosphonotricarboxylic acid, and combinations thereof; and
a water wetting surfactant;
increasing a pressure of the liquid additive to above a fracture gradient of a subterranean formation;
increasing a pressure of a natural gas stream, wherein the natural gas stream comprises liquefied natural gas or a compressed natural gas, to above the fracture gradient of the subterranean formation;
mixing the liquid additive and natural gas stream to form a fracturing fluid;
injecting the fracturing fluid into the subterranean formation;
fracturing the subterranean formation to form or extend at least one fracture;
allowing the complexing agent to react with the subterranean formation to form a surfactant bonding site; and
adhering the water wetting surfactant to the surfactant bonding site.

### Claim 2 (depends on 1)

The method of claim 1 wherein the base fluid is selected from the group consisting of water, a liquid hydrocarbon, and combinations thereof.

### Claim 3 (depends on 1)

The method of claim 1 wherein the liquid additive further comprises a proppant.

### Claim 4 (depends on 1)

The method of claim 1 wherein the complexing agent is present in the liquid additive in an amount of about 0.01% to about 5% by weight.

### Claim 5 (depends on 1)

The method of claim 1 wherein the surfactant is selected from the group consisting of branched or linear C10-C18 alcohols, ethoxylated C8-C18 alkanolamides, ethoxylated tall oils, ethoxylated C8-C18 alkylmines, C8-C16 alkylpolyglucosides, dodecylbenzene sulfonate salts, alkyl diphenylether sulfonate salts, alpha olefin sulfonate salts, C8-C16 alkyl sulfate salts, C8-C18 amine oxides, benzyldimethylalkanolammonium chlorides, betaine compounds, or sultain compounds, and combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1 wherein the surfactant is present in the liquid additive in an amount of about 0.01% to about 5% by weight.

### Claim 7 (depends on 1)

The method of claim 1 wherein the liquid additive further comprises a foaming agent.

### Claim 8 (depends on 1)

The method of claim 1 wherein the natural gas stream is increased in pressure by a pump when the natural gas stream is the liquefied natural gas or a compressor when the natural gas stream is the compressed natural gas.

### Claim 9 (depends on 1)

The method of claim 1, wherein the liquid additive further comprises a friction reducing polymer present in an amount of about 0.01% to about 0.15% by weight of the water.

### Claim 10 (depends on 1)

The method of claim 1, wherein the natural gas stream is pressurized to at least about 35 MPa up to about 100 MPa.

### Claim 11

A method comprising:
preparing a liquid additive comprising:
a base fluid;
a complexing agent selected from the group consisting of methylglycindiacetic acid (MGDA), glutamic acid diacetic acid (GLDA), (Hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), hydroxyiminodisuccinic acid (HIDS), polyether multicarboxylic acids, diethylenetriamine pentaacetate (DTPA), oxalic acid, citric acid, glycolic acid, lactic acid, and maleic acid, N-(Phosphonomethyl)iminodiacetic acid (PMIDA), phosphonotricarboxylic acid, and combinations thereof;
a water wetting surfactant; and
a proppant;
increasing a pressure of the liquid additive to above a fracture gradient of a subterranean formation;
increasing a pressure of a liquefied natural gas to above the fracture gradient of the subterranean formation;
heating the liquefied natural gas to produce a gaseous natural gas;
mixing the liquid additive and gaseous natural gas to form a fracturing fluid;
injecting the fracturing fluid into the subterranean formation;
fracturing the subterranean formation to form or extend at least one fracture;
allowing the complexing agent to react with the subterranean formation to form a surfactant bonding site; and
adhering the water wetting surfactant to the surfactant bonding site.

### Claim 12 (depends on 11)

The method of claim 11 wherein the base fluid is selected from the group consisting of water, a liquid hydrocarbon, and combinations thereof.

### Claim 13 (depends on 11)

The method of claim 11 wherein the complexing agent is present in the liquid additive in an amount of about 0.01% to about 5% by weight.

### Claim 14 (depends on 11)

The method of claim 11 wherein the surfactant is selected from the group consisting of branched or linear C10-C18 alcohols, ethoxylated C8-C18 alkanolamides, ethoxylated tall oils, ethoxylated C8-C18 alkylmines, C8-C16 alkylpolyglucosides, dodecylbenzene sulfonate salts, alkyl diphenylether sulfonate salts, alpha olefin sulfonate salts, C8-C16 alkyl sulfate salts, C8-C18 amine oxides, benzyldimethylalkanolammonium chlorides, betaine compounds, or sultain compounds, and combinations thereof.

### Claim 15 (depends on 11)

The method of claim 11 wherein the surfactant is present in the liquid additive in an amount of about 0.01% to about 5% by weight.

### Claim 16 (depends on 11)

The method of claim 11 wherein the liquid additive further comprises a foaming agent.

### Claim 17 (depends on 11)

The method of claim 11 wherein the pressure of the liquefied natural gas is increased in pressure by a pump.

### Claim 18 (depends on 11)

The method of claim 11, wherein the proppant is present in an amount of about 0.1 ppg to about 10 ppg.

### Claim 19 (depends on 11)

The method of claim 11, wherein the liquid additive further comprises a friction reducing polymer present in an amount of about 0.01% to about 0.15% by weight of the water.

### Claim 20 (depends on 11)

The method of claim 11, wherein the natural gas stream is pressurized to at least about 35 MPa up to about 100 MPa.