Methods of using ionic liquids as paraffin inhibitors, pour point depressants and cold flow improvers

Patent metadata

Field	Value
Publication number	US-12180428-B2
Application number	US-201916509418-A
Country	US
Kind code	B2
Filing date	Jul 11, 2019
Priority date	Jul 11, 2018
Publication date	Dec 31, 2024
Grant date	Dec 31, 2024

Abstract

The disclosure relates to the use of ionic liquids as paraffin inhibitors, pour point depressant or cold flow improvers in the production, treatment and refining of hydrocarbon fluids.

First claim

What is claimed is:

1. A method of modifying the pour point or cold flow of crude oil or gas, or reducing the deposition of paraffin from crude oil or gas, during production of the crude oil or gas from a subterranean reservoir, the method comprising:
(a) adding to the produced crude oil or gas in the subterranean reservoir an ionic liquid of the formula:
A + X −   (I)

wherein:
A is or contains nitrogen; and
X is an anion selected from the group consisting of anionic copolymers of alpha olefins and maleic anhydride, esters, amides, imides or derivatives thereof; anionic acrylamido-methyl propane sulfonate/acrylic acid copolymers; anionic homopolymers, copolymers and terpolymers of one or more acrylates, methacrylates and acrylamides, optionally copolymerized with one or more ethylenically unsaturated monomers; anionic phosphated maleic copolymers; an anionic homo or copolymer of an oxirane or methyloxirane; anionic copolymers of ethylene and vinyl acetate; and mixtures thereof or a methyl oxirane; and
(b) retarding, delaying, minimizing, reducing, inhibiting or preventing phase separation of paraffin wax formed in the crude oil or gas by dispersing the paraffin wax in the crude oil or gas containing the ionic liquid in the subterranean reservoir; or enhancing fluidity of the crude oil or gas while flowing the crude oil or gas containing the ionic liquid from the subterranean reservoir through a conduit; or depressing the pour point of the crude oil or gas in the subterranean reservoir when the crude oil or gas contains paraffin wax and further contains the ionic liquid.

2. The method of claim 1 , wherein anion X is selected from the group consisting of anionic acrylamido-methyl propane sulfonate/acrylic acid copolymers; anionic homopolymers, copolymers and terpolymers of one or more acrylates, methacylates and acrylamides, optionally copolymerized with one or more ethylenically unsaturated monomers; anionic ethylene vinyl acetate copolymers; anionic phosphated maleic copolymers and mixture thereof or a zwitterion.

3. A method of modifying the pour point or cold flow of crude oil or reducing the deposition of paraffin from the crude oil during production of the crude oil from an underground reservoir, the method comprising:
(a) adding to the crude oil in the underground reservoir an ionic liquid of the formula:
R 1 R 2 R 3 A + R 8 A + R 5 R 6 R 7 X −   (III)

wherein:
each A in formula (III) is or contains nitrogen; and
X is an anion selected from the group consisting of halides; hydroxyl; carbonates; alkyl carbonates; bicarbonates; carboxylates; hydroxycarboxylates; sulfonates; sulfates; bisulfites; thiocyanates; dithiocarbonates; trithiocarbonates; carbamates; dithiocarbamates; xanthates; sulfides; polysulfides; alkoxides; anionic urea; anionic alkyl substituted phosphines; anionic amino fatty acids; anionic alkoxylated fatty acids; anionic acrylamido-methyl propane sulfonate/acrylic acid copolymers; anionic phosphated maleic copolymers; anionic metal complexes; sulfur or silicon containing anions; anionic phosphate esters; anionic thiophosphate esters; anionic phosphonate esters; anionic thiophosphonate esters; anionic thiols; anionic natural products; anionic phenols; anionic phenol resins; anionic copolymers of alpha olefins and maleic anhydride, esters, amides, imides or derivatives thereof; anionic alkyl substituted phosphines; and anionic homopolymers, copolymers and terpolymers of one or more acrylates, methacrylates acrylamides and acids, optionally copolymerized with one or more ethylenically unsaturated monomers; anionic homo and copolymers of oxirane and/or methyloxirane; anionic copolymers of olefins and vinyl acetate; and mixtures thereof; and further wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen; benzyl; alkylbenzyl, or oxyalkyl; a straight or branched alkyl group, an alkylbenzyl group, an arylalkyl group, a straight or branched chain alkenyl group, a hydroxyalkyl group or a hydroxyalkylbenzyl group; and a polyoxyalkylene group; and R 8 is a straight or branched alkylene group, an alkylene oxyalkylene, or an alkylene polyoxyalkylene or a zwitterion; and further wherein R groups may be joined to form a heterocyclic nitrogen, sulfur or phosphorus containing ring; and
(b) retarding, delaying, minimizing, reducing, inhibiting or preventing phase separation of paraffin wax formed in the crude oil by dispersing the paraffin wax in the crude oil containing the ionic liquid in the subterranean reservoir; or enhancing fluidity of the crude oil while flowing the crude oil containing the ionic liquid from the subterranean reservoir through a conduit; or depressing the pour point of the crude oil in the subterranean reservoir when the crude oil contains paraffin wax and further contains the ionic liquid.

4. The method of claim 3 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen; benzyl; oxyalkyl; a straight or branched C 1-30 alkyl group; a C 7-30 alkylbenzyl group; a C 7-30 arylalkyl group; a straight or branched C 3-30 alkenyl group; a C 1-30 hydroxyalkyl group; a C 7-30 hydroxyalkylbenzyl group; and a polyoxyalkylene group and further wherein R groups may be joined to form a heterocyclic nitrogen or phosphorus containing ring; and R 8 is a straight or branched C 1-30 alkylene, an alkylene oxyalkylene, or an alkylene polyoxyalkylene.

5. The method of claim 4 , wherein X is an anionic oxirane or methyloxirane homo or copolymer containing (CH 2 CH 2 O) x CH 2 CH(CH 3 )O) 4 where x and y are independently selected from 1 to 1500 and mixtures thereof; an anionic ethylene vinyl copolymer; or an anionic olefin and maleic acid or anhydride optionally esterified with an alcohol.

6. The method of claim 4 , wherein X of (I), (II) or (III) is a hydroxide, halide, anionic bicarbonate, anionic carbonate, anionic alkyl carbonate, anionic alkoxide or anionic carboxylate or a combination thereof.

7. The method of claim 3 , wherein X is selected from the group consisting of anionic condensation polymers of alkylene oxides and glycols, anionic ethylene oxide/propylene oxide copolymers, arylsulfonates, anionic ureas, anionic thioureas, anionic polyether polyols, anionic polyethers, anionic polyol esters, anionic polyesters, anionic polyglycol esters, anionic polyurethanes, anionic oxyalkylated polymers condensation polymers of di-propylene glycol as well as trimethylol propane; anionic phenolic polymers, anionic alkyl substituted phenol formaldehyde resins, anionic oxyalkylated phenol formaldehyde resins, anionic alkoxylated epoxy resins, anionic diepoxides, anionic melamine acid colloids, alkylaryl sulfonates, alkylarylsulfonate, anionic amine salts, anionic aminomethylated polyacrylamide; anionic condensates of o-toluidine and formaldehyde; anionic polyalkylene glycols; sulfonated glycerides; sulfonated oils; anionic acetylated castor oils; anionic oxyalkylated ether sulfate salts, anionic copolymers of olefins and vinyl acetate; and anionic oxirane or methyloxirane polymers and mixtures thereof.

8. The method of claim 3 , wherein X is selected from the group consisting of anionic ethylene vinyl acetate copolymers, anionic maleic olefin alkyl esters, anionic acrylate esters, anionic methacrylic esters, copolymers of maleic anhydride and α,β-unsaturated compounds, optionally reacted with primary monoalkylamines and/or aliphatic alcohols, anionic products of the reaction of alkenylspirobislactones with amines; anionic products of the reaction of α,β-unsaturated dicarboxylic anhydrides, α,β-unsaturated compounds and polyoxyalkylene ethers; anionic phenol formaldehyde resins or a mixture thereof.

Assignees

• Baker Hughes Llc
• Baker Hughes Holdings Llc

Inventors

• Weers Jerry

Classifications

• C10G2400/02

  Gasoline · CPC title

• C10G2300/4075

  Limiting deterioration of equipment · CPC title

• C10G2300/206

  Asphaltenes · CPC title

• C10G2300/205

  Metal content · CPC title

• C10G2300/202

  Heteroatoms content, i.e. S, N, O, P · CPC title