# US 2014/0196898 A1 · Proppant

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- Number: US 2014/0196898 A1
- Document ID: US20140196898A1
- Status: Published application
- Kind: A1
- Application number: 14/115,391
- Filed: 2012-04-25
- Published: 2014-07-17
- Earliest claimed: 2011-05-05
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Christopher Tanguay; Rajesh Kumar; Fikri Emrah Alemdaroglu
- Web page: https://patentgrep.com/patent/US20140196898A1

## CPC

- C09K 8/805: {Coated proppants}
- C09K 8/70: characterised by their form or by the form of their components, e.g. foams
- 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

A proppant includes a particle and a hybrid coating disposed about the particle. The particle is present in an amount of from about 90 to about 99.5 percent by weight based on the total weight of the proppant and the hybrid coating is present in an amount of from about 0.5 to about 10 percent by weight based on the total weight of the proppant. The hybrid coating comprises the reaction product of an isocyanate component and an alkali metal silicate solution including water and an alkali metal silicate. A method of forming the proppant includes the steps of providing the particle, the isocyanate composition, and the alkali metal silicate solution. The method also includes the steps of combining the isocyanate composition and the alkali metal silicate solution to react and form the hybrid coating and coating the particle with the hybrid coating to form the proppant.

## Claims

### Claim 1

A proppant for hydraulically fracturing a subterranean formation, said proppant comprising:
A. a particle present in an amount of from about 90 to about 99.5 percent by weight based on the total weight of said proppant; and
B. a hybrid coating disposed about said particle and present in an amount of from about 0.5 to about 10 percent by weight based on the total weight of said proppant, said hybrid coating comprising the reaction product of:
(i) an isocyanate component; and
(ii) an alkali metal silicate solution comprising water and an alkali metal silicate.

### Claim 2 (depends on 1)

A proppant as set forth in claim 1 wherein said isocyanate component comprises a polymeric isocyanate having an NCO content of about 31.5 weight percent.

### Claim 3 (depends on 1)

A proppant as set forth in claim 1 wherein said isocyanate component comprises an isocyanate prepolymer which comprises the reaction product of an isocyanate and a polyol.

### Claim 4 (depends on 1)

A proppant as set forth in claim 1 wherein said isocyanate component comprises a polycarbodiimide prepolymer having isocyanate functionality and an NCO content of from about 15 to about 50 weight percent.

### Claim 5 (depends on 4)

A proppant as set forth in claim 4 wherein said polycarbodiimide prepolymer comprises the reaction product of an isocyanate reacted in the presence of a catalyst and wherein said isocyanate is further defined as a first isocyanate comprising polymeric diphenylmethane diisocyanate and having an NCO content of about 31.5 weight percent and a second isocyanate comprising 4,4′-diphenylmethane diisocyanate and having an NCO content of about 33.5 weight percent and said polycarbodiimide prepolymer comprises the reaction product of said first and second isocyanates.

### Claim 6 (depends on 4)

A proppant as set forth in claim 4 wherein said polycarbodiimide prepolymer comprises the reaction product of a carbodiimide modified 4,4′-diphenylmethane diisocyanate heated to a reaction temperature of greater than about 150° C.

### Claim 7 (depends on 1)

A proppant as set forth in claim 1 wherein said alkali metal silicate is sodium silicate and wherein said sodium silicate is present in an amount of from about 15 to about 40 percent by weight based on the total weight of said alkali metal silicate solution.

### Claim 8 (depends on 1)

A proppant as set forth in claim 1 wherein said hybrid coating further comprises the reaction product of a polyol and/or an amine in addition to said isocyanate component and said alkali metal silicate solution.

### Claim 9 (depends on 1)

A proppant as set forth in claim 1 wherein said particle is selected from the group of minerals, ceramics, sands, nut shells, gravels, mine tailings, coal ashes, rocks, smelter slag, diatomaceous earth, crushed charcoals, micas, sawdust, wood chips, resinous particles, polymeric particles, and combinations thereof.

### Claim 10 (depends on 1)

A proppant as set forth in claim 1 wherein said particle is present in an amount of from about 94 to about 99 percent by weight based on the total weight of said proppant and said hybrid coating is present in an amount of from about 1 to about 6 percent by weight based on said total weight of said proppant.

### Claim 11 (depends on 1)

A proppant as set forth in claim 1 that is thermally stable at temperatures greater than 200° C.

### Claim 12 (depends on 1)

A proppant as set forth in claim 1 having a crush strength of 5% or less maximum fines less than sieve size 70 as measured by compressing a 23.78 g sample of said proppant in a test cylinder having a diameter of 1.5 inches for 1 hour at 10,000 psi and 121° C.

### Claim 13

A method of forming a proppant for hydraulically fracturing a subterranean formation, wherein the proppant comprises a particle and a hybrid coating disposed about the particle, said method comprising the steps of:
A. providing the particle;
B. providing an isocyanate component;
C. providing an alkali metal silicate solution comprising water and an alkali metal silicate;
D. combining the isocyanate component and the alkali metal silicate solution to react and form the hybrid coating; and
E. coating the particle with the hybrid coating to form the proppant;
wherein the particle is present in an amount of from about 90 to about 99.5 percent by weight based on the total weight of the proppant and the hybrid coating is present in an amount of from about 0.5 to about 10 percent by weight based on the total weight of the proppant.

### Claim 14 (depends on 13)

A method as set forth in claim 13 wherein the step of combining the isocyanate component and the alkali metal silicate solution to react and form the hybrid coating is conducted simultaneous with the step of coating the particle with the hybrid coating to form the proppant.

### Claim 15

A method of hydraulically fracturing a subterranean formation which defines a subsurface reservoir with a mixture comprising a carrier fluid and a proppant comprising:
A. a particle present in an amount of from about 90 to about 99.5 percent by weight based on the total weight of the proppant; and
B. a hybrid coating disposed about the particle and present in an amount of from about 0.5 to about 10 percent by weight based on the total weight of the proppant, the hybrid coating comprising the reaction product of:
(i) an isocyanate component; and
(ii) an alkali metal silicate solution comprising water and sodium silicate;
said method comprising the step of pumping the mixture into the subsurface reservoir to fracture the subterranean formation.

### Claim 16 (depends on 15)

A method as set forth in claim 15 further comprising the step of preparing the mixture comprising the carrier fluid and the proppant.

### Claim 17 (depends on 15)

A method as set forth in claim 15 wherein the isocyanate component comprises a polymeric isocyanate having an NCO content of about 31.5 weight percent.

### Claim 18 (depends on 15)

A method as set forth in claims 15 wherein the isocyanate component comprises an isocyanate prepolymer which comprises the reaction product of an isocyanate and a polyol.

### Claim 19 (depends on 15)

A method as set forth in claim 15 wherein the isocyanate component comprises a polycarbodiimide prepolymer.

### Claim 20 (depends on 15)

A method as set forth in claim 15 wherein the alkali metal silicate is sodium silicate.

### Claim 21 (depends on 15)

A method as set forth in claim 15 wherein the particle is selected from the group of minerals, ceramics, sands, nut shells, gravels, mine tailings, coal ashes, rocks, smelter slag, diatomaceous earth, crushed charcoals, micas, sawdust, wood chips, resinous particles, polymeric particles, and combinations thereof.

### Claim 22 (depends on 13)

A method as set forth in claim 13 wherein the steps of combining the isocyanate component and the alkali metal silicate solution to react and form the hybrid coating and coating the particle with the hybrid coating to form the proppant are conducted at a temperature of from about −10 to about 50° C.

### Claim 23 (depends on 13)

A method as set forth in claim 13 wherein the steps of combining the isocyanate component and the alkali metal silicate solution to react and form the hybrid coating and coating the particle with the hybrid coating to form the proppant are collectively conducted in 10 minutes or less.