# US 10,308,857 B1 · Super-amphiphobic composite material and use of the same as inhibitor, lubricant, reservoir protectant, and accelerator in water-based drilling fluids

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- Number: US 10,308,857 B1
- Document ID: US10308857B1
- Status: Granted
- Kind: B1
- Application number: 16/257,870
- Filed: 2019-01-25
- Granted: 2019-06-04
- Earliest claimed: 2018-02-28
- Assignees: China University of Petroleum-Beijing
- Applicants: China University of Petroleum (Beijing)
- Inventors: Guancheng Jiang; Xiaoxiao Ni; Lili Yang; Guangchang Ma; Chunyao Peng; Deli Gao; Xi Wang; Jinsheng Sun; Xiaolin Pu; Kai Wang; Zhengqiang Deng; Yang Bai; Yinbo He; Xinliang Li
- Web page: https://patentgrep.com/patent/US10308857B1

## CPC

- C09K 8/032: {Inorganic additives}
- C07F 7/081: {comprising at least one atom selected from the elements N, O, halogen, S, Se or Te}
- C09K 8/5045: {containing inorganic compounds}
- C09K 8/506: containing organic compounds
- C09K 2208/10: Nanoparticle-containing well treatment fluids
- C09K 2208/12: Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
- C09K 2208/34: Lubricant additives
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

A super-amphiphobic composite material and use of the same as an inhibitor, lubricant, reservoir protectant, and accelerator in water-based drilling fluids. A method for preparing the amphiphobic composite material includes: performing a first mixing of nano-titanium dioxide and nano-silicon dioxide in an alcohol-water mixed solvent under an alkaline condition, to obtain a dispersion of nano-titanium dioxide and nano-silicon dioxide; then introducing a fluorosilicone-containing coupler into the dispersion of nano-titanium dioxide and nano-silicon dioxide and performing a second mixing. The amphiphobic composite material may be applied in water-based drilling fluids. It has an effect of strongly inhibiting hydrated swelling and disintegration, low toxicity and high compatibility; can solve problems such as well wall instability, blockage of drilling tools, and reservoir damage, etc.; and has long-term practical value in complicated wells such as extra-deep wells, horizontal wells and extended reach wells, and in mud-bearing shale formations.

## Claims

### Claim 1

A method for preparing an amphiphobic composite material, comprising:
performing a first mixing of a nano-titanium dioxide and a nano-silicon dioxide in an alcohol-water mixed solvent under alkaline conditions, to obtain a dispersion of nano-titanium dioxide and nano-silicon dioxide;
introducing a fluorosilicone-containing coupler into the dispersion of nano-titanium dioxide and nano-silicon dioxide and performing a second mixing; and performing a solid-liquid separation of the product of the second mixing to obtain the amphiphobic composite material;
wherein, a molar ratio of the titanium dioxide to the silicon dioxide to the fluorosilicone-containing coupler is 1:0.5-5:0.01-0.5, a particle size of the nano-titanium dioxide is 50-500 nm, and a particle size of the nano-silicon dioxide is 50-500 nm.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the molar ratio of the titanium dioxide to the silicon dioxide to the fluorosilicone-containing coupler is 1: 1-3:0.05-0.2.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the particle size of the nano-titanium dioxide is 50-200 nm, and the particle size of the nano-silicon dioxide is 50-200 nm.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the fluorosilicone-containing coupler is one or more of heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, tridecafluorooctyl trimethoxysilane, tridecafluorooctyl triethoxysilane, dodecafluoroheptyl trimethoxysilane, dodecafluoroheptyl triethoxysilane, nonafluorohexyl trimethoxysilane, nonafluorohexyl triethoxysilane, pentafluorophenyl trimethoxysilane, and pentafluorophenyl triethoxysilane.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the step of performing a first mixing is performed at a pH of 8-10.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the step of performing a first mixing is performed at a pH of 8-9.

### Claim 7 (depends on 1)

The method according to claim 1, where in the step of performing a first mixing, there is 500-1,500 mL of the alcohol-water mixed solvent per 100 g of the total weight of the nano-titanium dioxide and the nano-silicon dioxide.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the alcohol-water mixed solvent has volume ratio of alcohol solvent to water of 1:2-10.

### Claim 9 (depends on 7)

The method according to claim 7, wherein the alcohol-water mixed solvent includes an alcohol solvent, and the alcohol solvent is one or more of ethanol, methanol, n-propanol, and iso-propanol.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the step of performing a first mixing includes mixing by ultrasonic dispersion, and conditions in the step of performing a first mixing include: a temperature of 10-40° C., an ultrasonic dispersion time of 10-30 min; and
wherein the step of performing a second mixing includes mixing by stirring, and conditions in the step of performing a second mixing include: a temperature of 55-95° C., a stirring rate of 200-500 rpm, a time of 8-20 h.

### Claim 11 (depends on 2)

The method according to claim 2, wherein the particle size of the nano-titanium dioxide is 50-200 nm, and the particle size of the nano-silicon dioxide is 50-200 nm.

### Claim 12 (depends on 11)

The method according to claim 11, wherein the fluorosilicone-containing coupler is one or more of heptadecafluorodecyl trimethoxysilane, heptadecafluorodecyl triethoxysilane, tridecafluorooctyl trimethoxysilane, tridecafluorooctyl triethoxysilane, dodecafluoroheptyl trimethoxysilane, dodecafluoroheptyl triethoxysilane, nonafluorohexyl trimethoxysilane, nonafluorohexyl triethoxysilane, pentafluorophenyl trimethoxysilane, and pentafluorophenyl triethoxysilane.

### Claim 13 (depends on 1)

An amphiphobic composite material prepared by the method of claim 1.

### Claim 14 (depends on 13)

The amphiphobic composite material according to claim 13, wherein the molar ratio of the titanium dioxide to the silicon dioxide to the fluorosilicone-containing coupler is 1: 1-3:0.05-0.2.

### Claim 15 (depends on 13)

A water-based drilling fluid containing the amphiphobic composite material according to claim 13.

### Claim 16 (depends on 15)

The water-based drilling fluid according to claim 15, wherein the water-based drilling fluid includes a content of the amphiphobic composite material of 0.1-0.5 wt % based on total weight of the water-based drilling fluid excluding a weighting agent.

### Claim 17 (depends on 16)

The water-based drilling fluid according to claim 16, wherein the water-based drilling fluid includes a content of the amphiphobic composite material of 0.2-0.5 wt % based on total weight of the water-based drilling fluid excluding a weighting agent.

### Claim 18 (depends on 16)

A method of drilling an oil or gas well comprising;
drilling a well, and
adding the water-based drilling fluid of claim 16 to the well.