Proppants derived from crosslinking mixed aromatic resins

Patent metadata

Field	Value
Publication number	US-12466992-B2
Application number	US-202318174264-A
Country	US
Kind code	B2
Filing date	Feb 24, 2023
Priority date	Mar 4, 2022
Publication date	Nov 11, 2025
Grant date	Nov 11, 2025

Abstract

A variety of methods are disclosed, including, in one embodiment, a method of making crosslinked aromatic resin beads comprising: contacting a linker agent and a catalyst with an aromatic feedstock at a first temperature effective to react the linker agent with molecules in the aromatic feedstock to form a pre-polymer mixture; combining the pre-polymer mixture with an antisolvent; agitating the pre-polymer mixture and the antisolvent; and heating the pre-polymer mixture and antisolvent to a second temperature to react the pre-polymer mixture to form crosslinked aromatic resin beads, wherein the pre-polymer mixture is dispersed as droplets in the antisolvent.

First claim

The invention claimed is:

1 . A method of making crosslinked aromatic resin beads comprising:
contacting a linker agent and a catalyst with an aromatic feedstock at a first temperature effective to react the linker agent with molecules in the aromatic feedstock to form a pre-polymer mixture in the absence of any solvent; combining the pre-polymer mixture with an antisolvent; agitating the pre-polymer mixture and the antisolvent; and heating the pre-polymer mixture and antisolvent to a second temperature to react the pre-polymer mixture to form crosslinked aromatic resin beads, wherein the pre-polymer mixture is dispersed as droplets in the antisolvent.

2 . The method of claim 1 wherein the linker agent has a structure of Formula 1

where circle represents an aromatic hydrocarbon or aromatic heterocyclic moiety, each FG (functional group) is independently selected from aldehyde, vinyl, halogen, hydroxyl, acyl halide, tosylate, mesylate, or carboxylic acid, each X is independently selected from the group consisting of alkylene, cycloalkylene, arylene, and combinations thereof, where each R is independently H or alkyl, n is an integer from 0 to 5, and m is 5-n.

3 . The method of claim 1 wherein the linker agent has a structure of Formula 2

where each FG (functional group) is independently selected from the group consisting of aldehyde, vinyl, halogen, hydroxyl, acyl halide, tosylate, mesylate, carboxylic acid, and combinations thereof, each X is independently selected from the group consisting of alkylene, cycloalkylene, arylene, and combinations thereof, where each R is independently H or alkyl, n is an integer from 0 to 5, and m is 5-n.

4 . The method of claim 1 wherein the linker agent has a structure of Formula 3

where each FG (functional group) is independently selected from the group consisting of aldehyde, vinyl, halogen, hydroxyl, acyl halide, tosylate, mesylate, carboxylic acid, and combinations thereof, each X is independently selected from the group consisting of alkylene, cycloalkylene, arylene, and combinations thereof, each R is independently selected from H or alkyl, y1+y2 is an integer between 2 and 8 and ml+m2=8−(y1+y2).

5 . The method of claim 1 wherein the linker agent has a structure of Formula 4

where each FG (functional group) is independently selected from the group consisting of aldehyde, vinyl, halogen, hydroxyl, acyl halide, tosylate, mesylate, carboxylic acid, and combinations thereof, each X independently selected from the group consisting of alkylene, cycloalkylene, arylene, and combinations thereof, each R is, independently selected from H or alkyl, y1+y2 is an integer between 2 and 10, and m1+m2=10−(y1+y2).

6 . The method of claim 1 wherein the linker agent comprises at least structure selected from the group consisting of:

isomers thereof, and combinations thereof.

7 . The method of claim 1 wherein the linker agent is present in an amount of about 1% to about 200% by weight of the aromatic feedstock.

8 . The method of claim 1 wherein the catalyst comprises an inorganic acid, an organic acid, a Lewis acid, or combinations thereof.

9 . The method of claim 1 wherein the catalyst is selected from the group consisting of trimethylaluminum, aluminum chloride, zinc chloride, ferric chloride, methanesulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, p-toluenesulfonic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, tungstic acid, phosphotungstic acid, polyoxometalates, naphthalenesulfonic acid, benzenesulfonic acid, hydrochloric acid, hydrobromic acid, biphenylsulfonic acid, benzenetrisulfonic acid, alkyl benzyl sulfonic acid, and combinations thereof.

10 . The method of claim 1 wherein the catalyst is present in an amount of about 0.1% to about 10% by weight of the total weight of the linker agent and the aromatic feedstock.

11 . The method of claim 1 wherein the aromatic feedstock comprises at least one aromatic feedstock selected from the group consisting of steam cracker tar, main column bottoms, vacuum residue, C5 rock, C3-C5 rock, slurry oil, asphaltenes, bitumen, K-pot bottoms, lube extracts, p-xylene, m-xylene, o-xylene, mixed xylenes, aromatic solvent, heavy aromatic solvent, aromatic 200, aromatic 150, aromatic 100, reformate, mixed alkylated naphthalenes, pyrolysis gasoline, BTEX (benzene, toluene, ethylbenzene, and xylene), and combinations thereof.

12 . The method of claim 1 wherein the pre-polymer mixture further comprises coke in an amount of about 1% to about 95% by weight of the pre-polymer mixture, wherein the coke is added as a filler.

13 . The method of claim 1 wherein the antisolvent comprises at least one antisolvent selected from the group consisting of saturated hydrocarbons with carbon numbers from C20 to C40, polydimethyl siloxanes (PDMS), and copolymers of dimethyl and diphenyl siloxanes.

14 . The method of claim 1 wherein the crosslinked aromatic resin beads have a particle size in a range of about 150 to about 400 microns.

Assignees

• Exxonmobil Technology & Engineering Company

Inventors

• Gordon Peter A
• Zhou Huaxing
• Bair Joseph S
• Deflorio Victor
• Nittoli Mikel A

Classifications

• C09K8/70

  characterised by their form or by the form of their components, e.g. foams · CPC title

• C09K8/80 Primary

  Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open · CPC title

• C09K8/887 Primary

  containing cross-linking agents · CPC title