# US 2021/0277314 A1 · Demulsifying agents for crude oil based on random alkylacrylic-aminoalkylacrylic-carboxyalkylacrylic terpolymers of controlled molecular mass

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- Number: US 2021/0277314 A1
- Document ID: US20210277314A1
- Status: Published application
- Kind: A1
- Application number: 16/914,776
- Filed: 2020-06-29
- Published: 2021-09-09
- Earliest claimed: 2020-02-27
- Assignees: Instituto Mexicano Del Petroleo
- Applicants: Instituto Mexicano Del Petroleo
- Inventors: Cesar Andres FLORES SANDOVAL; Flavio Salvador VAZQUEZ MORENO; Fernando ALVAREZ RAMIREZ; Gerardo ZAVALA OLIVARES; Jessica Valeria FUENTES SANTIAGO; Edgar Benedicto ZAMORA GUERRERO; Citlally Janinne VARGAS MARTINEZ
- Web page: https://patentgrep.com/patent/US20210277314A1

## CPC

- C10G 33/04: with chemical means
- C08F 2/22: Emulsion polymerisation
- C08F 220/18: with acrylic or methacrylic acids
- C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate}
- C08F 220/34: Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate}
- C08L 33/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A problem the oil industry faces is the presence of great water and salt amounts in crude oil streams, which cannot be easily removed by conventional dehydrating polymers. Moreover, the acid stimulation of wells evokes the chemical degradation of the polyethers and phenolic resins used as demulsifiers, drastically reducing their water and salt removal efficiency. Disclosed herein are new terpolymers which are combinations of three derivative monomers from alkyl acrylate, aminoalkyl acrylate, and carboxyalkyl acrylate, synthesized via emulsion polymerization by semi-continuous process under starving feed conditions, in order to ensure both the homogeneity of the polymer chains and the randomness of the monomers. The dissolutions of the random terpolymers have displayed a comparable, and even superior, water removal efficiency when dosed in light or heavy crude oils. The random alkylacrylic-aminoalkylacrylic-carboxyalkylacrylic terpolymers present an outstanding performance as emulsion breakers, water droplets coalescers, and aqueous phase clarifiers.

## Claims

### Claim 1

A synthesis of a random alkylacrylic-aminoacrylic-carboxyacrylic terpolymer, wherein the random alkylacrylic-aminoacrylic-carboxyacrylic terpolymer is employed as demulsifying agent of crude oil, with API densities from 3 to 40° API, and comprises structural formula (1) and molecular masses within 1,200 and 664,200 g·mol−1:
where:
R1, R2, R3, R4, R5 and R6 are independent radicals, represented by the groups mentioned below:
R1=an aliphatic chain selected from the group consisting of CH3 (methyl), C2H5 (ethyl), C4H9 (n-butyl), C4H9 (iso-butyl), C4H9 (tert-butyl), C5H11 (pentyl), C6H13 (n-hexyl), C6H11 (di(ethyleneglycol)ethylether), C8H17 (2-ethylhexyl), C9H19 (3,5,5-trimethylhexyl), C8H17 (n-octyl), C8H17 (iso-octyl), C8H9 (ethyleneglycol phenylether), C10H21 (n-decyl), C10H21 (isodecyl), C10H19 (10-undecenyl), C10H19 (tert-butylciclohexyl), C12H25 (n-dodecyl), C18H37 (n-octadecyl), C8H9O (2-phenoxyethyl), C3H7O (2-methoxyethyl), C5H11O2 (2-(2-methoxyethoxy)ethyl), C5H9O (tetrahydrofurfuryl), C5H9O (2-tetrahydropyranyl), C13H27 (tridecyl), and C22H45 (behenyl), wherein the aliphatic chain can contain heteroatoms as ether groups, as well as aromatic fragments like benzene rings;
R2═CH4N (methylamine), C3H6N (2-ethylamine), C3H8N (3-propylamine), C4H10N (2-(dimethylamino)ethyl), C6H14N (2-(diethylamino)ethyl), C5H12N (3-(dimethylamino)propyl), and C6H12NO (N-morpholinyl ethyl);
R3═C3H5O2 (2-carboxyethyl), C4H7O2 (3-carboxypropyl), and C5H9O2 (carboxybutyl);
R4, R5 and R6═H (hydrogen), CH3 (methyl);
and where:
x, y, and z are natural numbers within the following ranges:
x=from 4 to 900;
y=from 4 to 900; and
z=from 4 to 900; and
wherein “x”, “y”, and “z” could appear as random sequences.

### Claim 2 (depends on 1)

The synthesis of random alkylacrylic-aminoacrylic-carboxyacrylic terpolymers, as demulsifying agents of crude oils, according to claim 1, where the alkylacrylic monomer is selected from a group consisting of: methyl acrylate, ethyl acrylate, butyl acrylate, pentyl acrylate, iso-bornyl acrylate, iso-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 3,5,5-trimethylhexyl acrylate, 2-methoxyethyl acrylate, 2-phenoxyethyl acrylate, 4-tert-butylcyclohexyl acrylate, octyl acrylate, iso-decyl acrylate, decyl acrylate, lauryl acrylate, tridecyl acrylate, octadecyl acrylate, and behenyl acrylate.

### Claim 3 (depends on 1)

The synthesis of random alkylacrylic-aminoalkylacrylic-carboxyalkylacrylic terpolymers, as demulsifying agents of crude oils, according to claim 1, where the aminoalkylacrylic monomer is selected from a group consisting of: 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-(dimethylamino)ethyl acrylate, 2-(dimethylamino)ethyl methacrylate, 3-aminopropyl acrylate, 3-(dimethylamino)propyl acrylate, 3-(dimethylamino)propyl methacrylate, 2-(diethylamino)ethyl acrylate, 2-(diethylamino)ethyl methacrylate, 2-N-ethylmorpholine methacrylate.

### Claim 4 (depends on 1)

The synthesis of random alkylacrylic-aminoalkylacrylic-carboxyalkylacrylic terpolymers, as demulsifying agents of crude oils, according to claim 1, where the carboxyalkyl acrylate monomer is selected from a group consisting of: 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 4-carboxybutyl acrylate, 2-carboxyethyl methacrylate, 3-carboxypropyl methacrylate, and 4-carboxybutyl methacrylate.

### Claim 5 (depends on 2)

The synthesis through emulsion polymerization of random alkylacrylic-aminoacrylic-carboxyacrylic terpolymers, in accordance with claim 2, where the monomers are fed from an addition tank, to form a pre-emulsion with the following monomer rates: the alkylacrylic monomer between about 50.0 and about 99.0 wt %, the aminoalkylacrylic between about 0.5 and about 49.5 wt %, and the carboxyalkylacrylic monomers between about 0.5 and about 49.5 wt %.

### Claim 6 (depends on 1)

The use of random alkylacrylic-aminoalkylacrylic-carboxyalkylacrylic terpolymers as demulsifying agents of crude oils, according to claim 1, wherein the terpolymer is formulated as a solution employing organic solvents.

### Claim 7 (depends on 6)

The use of random alkylacrylic-aminoalkylacrylic-carboxyalkylacrylic terpolymers employed as demulsifying agents of crude oils, in accordance with claim 6, where the organic solvents employed for the formulation possess boiling points between about 35 and about 200° C.

### Claim 8 (depends on 6)

The use of random alkylacrylic-aminoalkylacrylic-carboxyalkylacrylic terpolymers employed as demulsifying agents of crude oils, in accordance with claim 6, where the organic solvents employed in the formulation are selected from a group consisting of: dichloromethane, methanol, ethanol, isopropanol, chloroform, benzene, benezene derivatives, toluene, xylene, turbosine, and naphtha; individually or as a mixture of the aforementioned.

### Claim 9 (depends on 6)

The use of random alkylacrylic-aminoalkylacrylic-carboxyalkykacrylic terpolymers employed as demulsifying agents of crude oils, in accordance with claim 6, where the concentration of the formulation of the random acrylic terpolymers is within about 10.0 and about 50.0 wt %.

### Claim 10 (depends on 6)

The use of random alkylacrylic-aminoalkylacrylic-carboxyalkykacrylic terpolymers employed as demulsifying agents of crude oils, in accordance with claim 6, where the formulations are dosed between about 10 and about 2,000 ppm.

### Claim 11

A random alkylacrylic-aminoacrylic-carboxyacrylic terpolymer employed as demulsifying agent of crude oil, with API densities from 3 to 40° API, comprising structural formula (1) and molecular masses within 1,200 and 664,200 g·mol−1:
where:
R1, R2, R3, R4, R5 and R6 are independent radicals, represented by the groups mentioned below:
R1=an aliphatic chain selected from the group consisting of CH3 (methyl), C2H5 (ethyl), C4H9 (n-butyl), C4H9 (iso-butyl), C4H9 (tert-butyl), C5H11 (pentyl), C6H13 (n-hexyl), C6H11 (di(ethyleneglycol)ethylether), C8H17 (2-ethylhexyl), C9H19 (3,5,5-trimethylhexyl), C8H17 (n-octyl), C8H17 (iso-octyl), C8H9 (ethyleneglycol phenylether), C10H21 (n-decyl), C10H21 (isodecyl), C10H19 (10-undecenyl), C10H19 (tert-butylciclohexyl), C12H25 (n-dodecyl), C18H37 (n-octadecyl), C8H9O (2-phenoxyethyl), C3H7O (2-methoxyethyl), C5H11O2 (2-(2-methoxyethoxy)ethyl), C5H9O (tetrahydrofurfuryl), C5H9O (2-tetrahydropyranyl), C13H27 (tridecyl), and C22H45 (behenyl), wherein the aliphatic chain can contain heteroatoms as ether groups, as well as aromatic fragments like benzene rings;
R2═CH4N (methylamine), C3H6N (2-ethylamine), C3H8N (3-propylamine), C4H10N (2-(dimethylamino)ethyl), C6H14N (2-(diethylamino)ethyl), C5H12N (3-(dimethylamino)propyl), and C6H12NO (N-morpholinyl ethyl);
R3═C3H5O2 (2-carboxyethyl), C4H7O2 (3-carboxypropyl), and C5H9O2 (carboxybutyl);
R4, R5 and R6═H (hydrogen), CH3 (methyl);
and where:
x, y, and z are natural numbers within the following ranges:
x=from 4 to 900;
y=from 4 to 900; and
z=from 4 to 900; and
wherein “x”, “y”, and “z” could appear as random sequences.