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Title:
COMPOUNDS AND COMPOSITIONS USEFUL AS DEMULSIFIERS
Document Type and Number:
WIPO Patent Application WO/2020/040633
Kind Code:
A1
Abstract:
The present invention generally relates to compounds of Formula (I) disclosed herein, methods for their synthesis and uses thereof. The disclosed compounds may be useful in preventing and/or mitigating microemulsion formation in enhanced oil recovery methods.

Inventors:
BORHAN NOORAZLENAWATI (MY)
Application Number:
PCT/MY2019/050046
Publication Date:
February 27, 2020
Filing Date:
August 23, 2019
Export Citation:
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Assignee:
PETROLIAM NASIONAL BERHAD PETRONAS (MY)
International Classes:
C07C243/30; C07C241/02; C09K8/58
Domestic Patent References:
WO2016188683A12016-12-01
Foreign References:
US4238349A1980-12-09
Other References:
FEUER, H. ET AL.: "Maleic Hydrazide. I. Reactions with Selected Electrophilic Reagents", J. AM. CHEM. SOC., vol. 80, no. 21, 1958, pages 5873 - 5877, XP055687859
DATABASE Chemical Abstract 4 August 2006 (2006-08-04), retrieved from STN Database accession no. 898607-76-6
DATABASE Chemical Abstract 24 August 2002 (2002-08-24), retrieved from STN Database accession no. 444767-91-3
DATABASE Chemical Abstract 28 November 2000 (2000-11-28), retrieved from STN Database accession no. 304648-74-6
Attorney, Agent or Firm:
SPRUSON & FERGUSON (M) SDN BHD (MY)
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Claims:
Claims

1. A compound of formula (I):

Formula (I) wherein:

Ri is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R2 and R3 are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R4 and R5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof.

2. The compound of claim 1 , wherein R^ is optionally substituted branched or

unbranched C6-C24 alkyl.

3. The compound of claim 1 or 2, wherein R^ is C6-C24 alkyl.

4. The compound of any one of claims 1 to 3, wherein each of R2, R3, R4 and R5 is hydrogen.

5. The compound of any one of claims 1 to 4, wherein R6 is CrC5 alkyl.

6. The compound of any one of claims 1 to 5, wherein is Ci4-Ci8 alkyl, each of R2,

R3, R4 and R5 is hydrogen, and R6 is CrC5 alkyl.

7. The compound of any one of claims 1 to 6, wherein the compound of formula (I) is:

or stereoisomers, mixture of stereoisomers or salts thereof.

8. The compound of any one of claims 1 to 6, wherein the compound of formula (I) is:

or stereoisomers, mixture of stereoisomers or salts thereof.

9. A demulsifier composition comprising:

(i) the compound of formula (I)

Formula (I)

wherein:

R! is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl; R2 and R3 are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R4 and R5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof,

(ii) quaternized fatty acid trialkanolamine ester;

(iii) polysorbate polyester

(iv) aromatic solvent

10. The demulsifier composition of claim 9, comprising 20 to 40 vol% of a compound of formula (I).

11. The demulsifier composition of claim 9 or 10, comprising:

(i) 20 to 40 vol% of a compound of formula (I);

(ii) 10 to 20 vol% of quarternized fatty acid trialkanolamine ester;

(iii) 10 to 20 vol% polysorbate polyester; and

(iv) 40 to 60 vol% aromatic solvent

wherein components (i) to (iv) make up 100vol%.

12. The demulsifier composition of any one of claims 9 to 11 , comprising:

(i) 20 vol% of a compound of formula (I);

(ii) 20 vol% of quarternized fatty acid trialkanolamine ester;

(iii) 20 vol% polysorbate polyester; and

(iv) 40 vol% aromatic solvent .

13. The demulsifier composition of any one of claims 9 to 11 , comprising:

(i) 40 vol% of a compound of formula (I); (ii) 10 vol% of quarternized fatty acid trialkanolamine ester;

(iii) 10 vol% polysorbate polyester; and

(iv) 40 vol% aromatic solvent .

14. The demulsifier composition of any one of claims 9 to 13, wherein the compound of formula (I) is of any one of claims 1 to 8.

15. A method for inhibiting or preventing the formation of an emulsion using a

demulsifier composition comprising the compound of formula (I):

Formula (I) wherein:

Ri is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R2 and R3, are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R4 and R5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof.

16. The method of claim 15, wherein the emulsion is a microemulsion.

17. The method of claim 15 or 16, wherein the emulsion or microemulsion comprises a naphthenic acid, salt thereof or a mixture thereof.

18. The method of any one of claims 15 to 17, wherein the compound of formula (I) is at a concentration of about 5 ppm to about 100 ppm.

19. The method of any one of 15 to 18, wherein the process temperature is from about 25°C to about 80°C.

20. The method of any one of claims 15 to 19, wherein the process pH is from pH 4 to pH 12.

21. The method of any one of claims 15 to 20, wherein the demulsifier composition further comprises at least a second demulsifier.

22. A method of preparing a compound of formula (I):

Formula (I) wherein:

R, is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R2 and R3 are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R4 and R5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl; R6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof

comprising reacting a compound of formula (II):

with compounds of formula (III) and (IV):

R6 OH (IV) in the presence of a catalyst.

23. The method of claim 22, wherein the catalyst is selected from the group consisting of /V,/V-dimethylformaamide, acetonitrile, acetone, and dimethyl sulfoxide.

24. The method of claim 22 or 23, wherein the reaction is performed at a temperature of 80°C to 90°C.

Description:
Description

Title of Invention : Compounds and Compositions Useful as

Demulsifiers

Technical Field

The present invention generally relates to compounds and compositions useful in preventing and/or mitigating the formation of microemulsions during enhanced oil recovery methods. The present invention also relates to methods of synthesis and uses thereof.

Background Art

Crude oil is a vital source of energy for the world and makes a major contribution to the world economy.

Conventional oil production strategies have followed primary depletion, secondary recovery and tertiary recovery processes. During the primary depletion stage, reservoir drive uses a number of natural mechanisms to displace oil from porous rocks. Recovery factor during the primary recovery stage may average 5- 20%. At some point, there will be insufficient underground pressure to force oil to the surface. Secondary recovery methods are then applied wherein the oil is subjected to immiscible displacement with injected fluids such as water or gas. Typical recovery factor after primary and secondary oil recovery operations may be between 30-50%. Much of the remaining oil is trapped in porous media. Tertiary, or enhanced oil recovery (EOR) methods may then be used to recover additional oil.

Crude oil is a complex mixture composed of many compounds, and contains naphthenic acids. Although the term“naphthenic acids” was originally used to describe acids that contain naphthenic rings, today this term is used in a more general sense and refers to all cyclic, acyclic, and aromatic acids in crude oil. The first class crudes type have a very high percentage of low molecular weight from 250 to 650 Dalton (saturated, acyclic) C18 to C34 monocarboxylic acids or monoprotic acids with double bond equivalent (DBE) = 1. There is no evidence for the presence of higher molecular weight polycylic tetracarboxylic (ARN) acids, or C30 monoprotic acids of 443 Dalton. The second class crudes type have a molecular weight from 250 to 950 Dalton monoprotic acids with DBE > 1 around C30 which typically contains 4 to 6 DBE. Taking into account the carboxylate group, this would imply 4 to 5 saturated rings if these species are purely aliphatic. This may be explained by a polycyclic structure or, perhaps more plausibly, by the presence of an aromatic ring. A single phenyl ring would add 4 DBE to the structure, for a total of 5 DBE. Structures with 6 DBE can be accounted for by the presence of a single additional saturated ring. It is worth noting that these structures have a molecular weight of 444 Dalton, and therefore a 4-6 DBE around C30 MPA is likely to be responsible for the intense peak at 443 Dalton.

The formation waters from the oil fields are of low salinity, with low calcium levels from 70mg/l to 300 mg/I and high bicarbonate concentration from 1 ,000 - 5,000 mg/I. The formation water pH arise when sodium carbonate was introduce in the system of pH 9.2-9.7.

During enhanced oil recovery, the mixing of naphthenic acids in crude oil with alkaline surfactant polymers (ASP) results in a complex mixture of microemulsions, which are undesirable. The adsorption of carboxylic acids and sodium ions also contributes to microemulsion stabilization during enhanced oil recovery methods. When the water phase is at high pH, carboxylate acid components in crude oil will ionize and exhibit a hydrophilic nature that causes naphthenic acid molecules to congregate at the oil-water interface. This dramatically lowers the interfacial tension (I FT), and increases dilatational elasticity at stabilized interfaces which enhance microemulsion stability. Practically this mechanism has been exploited by many to devise enhanced oil recovery processes, using either simply added alkali or a combination of surfactant- assisted and/or polymer-assisted alkaline flooding. The chemical structure and molecular weight of acids capable of lowering I FT and stabilizing emulsions appear to vary quite broadly and may include simple alkyl carboxylic acids, alkylbenzene carboxylic acids, fused aromatic ring acids which are collectively called naphthenic acids in crude oils. This may be evidence that naphthenic acids form the strongest microemulsion interfaces through the formation of layered lamellar liquid crystalline films. The microemulsion stabilization may be through the formation of a cohesive film that in turn can be strongly anchored to the interface by binding of cations, such as sodium and calcium. Some studies have revealed that some acids can interact with asphaltenes to stabilize both oil-in-water (O/W) and (W/O) microemulsions, depending upon the pH and concentrations. A number of these acidic species are found to be associated with the asphaltene fraction when the crude oil is precipitated with an alkane. In the presence of a large amount of acids, the stabilization of W/O microemulsion might be greatly influenced by acids instead of asphaltenes. Microemulsion stabilization by lamellar liquid crystalline films is very closely related to the crude oil acid mechanism at the oil-water interface. It is well-known that acids and their soaps form these interfacial phases at sufficiently high concentrations and that adsorption at the oil-water interface serves as a means to concentrate these species. Many reports in the last several years have documented this mechanism, and it appears to occur with a very broad range of different types of acids and their soaps.

The presence of these microemulsions is disadvantageous and creates problems such as productions delays, inferior sales products and choked oil flow in pipelines. The removal of these microemulsions is often difficult, expensive and potentially hazardous to human health and the environment.

Hence, there remains a need for compounds and compositions which prevent or mitigate the formation of such microemulsions.

Summary of Invention

The present disclosure relates to compounds and compositions useful in mitigating and/or preventing microemulsion formation during enhanced oil recovery processes.

According to a first aspect, there is provided a compound of formula (I):

Formula (I) wherein:

Ri is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R 2 and R 3 , are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R 6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof.

Advantageously, the use of the disclosed compounds may be non-hazardous and not harmful to the environment.

Further advantageously, the disclosed compounds may be formed from readily available and cheap starting materials.

Further advantageously, the compounds of formula (I) may mitigate or prevent microemulsion formation during enhanced oil recovery operations, and thus increase the amount and/or quality of crude oil extracted from carbonate reservoirs.

In another aspect, there is provided a demulsifier composition comprising:

(i) the compound of formula (I)

Formula (I)

wherein:

Ri is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R 2 and R 3 , are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R 6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof,

(i) quaternized fatty acid trialkanolamine ester;

(ii) Polysorbate ester; and

(iii) aromatic solvent.

Advantageously, the disclosed demulsifier compositions may be able to prevent or mitigate the formation of emulsions or microemulsions in low doses and hence provide cost savings.

Further advantageously, the disclosed demulsifier compositions may be useful in keeping the basic sediment and water (BS&W) value in the extracted crude oil low, prferably <0.5%.

In a further aspect, there is provided a method for inhibiting or preventing the formation of an emulsion using a demulsifier composition comprising the compound of formula (I):

Formula (I) wherein:

R, is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl; R 2 and R 3 , are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R 6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof.

When used in enhanced oil recovery methods, good quality separation of oil and water and minimal microemulsions may be advantageously obtained in the extracted crude oil.

In another aspect, there is provided a method of preparing a compound of formula (I):

Formula (I) wherein:

R, is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R 2 and R 3 , are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R 6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof

comprising reacting a compound of formula (II):

with compounds of formula (III) and (IV):

Rs OH (IV)

in the presence of a catalyst.

Definitions

The following words and terms used herein shall have the meaning indicated.

As used herein, unless otherwise specified, the following terms have the following meanings, and unless otherwise specified, the definitions of each term (i.e. moiety or substituent) apply when that term is used individually or as a component of another term (e.g., the definition of aryl is the same for aryl and for the aryl portion of arylalkyl, alkylaryl, arylalkynyl, and the like).

As used herein, the term“water cut” refers to the percentage or fraction of water compared to the oil produced during production.

As used herein, the term "alkyl" includes within its meaning monovalent (“alkyl”) and divalent (“alkylene”) straight chain or branched chain saturated aliphatic groups having from 1 to 20 carbon atoms, eg, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. For example, the term alkyl includes, but is not limited to, methyl, ethyl, 1 -propyl, isopropyl, 1 -butyl, 2-butyl, isobutyl, tert-butyl, amyl, 1 ,2- dimethylpropyl, 1 ,1-dimethylpropyl, pentyl, isopentyl, hexyl, 4-methylpentyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1 ,2- dimethylbutyl, 1 ,3-dimethylbutyl, 1 ,2,2-trimethylpropyl, 1 ,1 ,2-trimethylpropyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicodecyl and the like. Alkyl groups may be optionally substituted.

As used herein, the term "alkenyl" refers to divalent straight chain or branched chain unsaturated aliphatic groups containing at least one carbon-carbon double bond and having from 2 to 20 carbon atoms, eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. For example, the term alkenyl includes, but is not limited to, ethenyl, propenyl, butenyl, 1-butenyl, 2-butenyl, 2-methylpropenyl, 1- pentenyl, 2-pentenyl, 2-methylbut-1-enyl, 3-methylbut-1-enyl, 2-methylbut-2-enyl, 1- hexenyl, 2-hexenyl, 3-hexenyl, 2,2-dimethyl-2-butenyl, 2-methyl-2-hexenyl, 3-methyl-1- pentenyl, 1 ,5-hexadienyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicodecenyl and the like. Alkenyl groups may be optionally substituted. As used herein, the term“olefin” refers to alkenyl with one carbon-carbon double bond. An “alpha-olefin” refers to an olefin having a double bond at the primary or alpha position.

As used herein, the term "alkynyl" refers to divalent straight chain or branched chain unsaturated aliphatic groups containing at least one carbon-carbon triple bond and having from 2 to 20 carbon atoms, eg, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. For example, the term alkynyl includes, but is not limited to, ethynyl, propynyl, butynyl, 1-butynyl, 2-butynyl, 2-methylpropynyl, 1-pentynyl, 2-pentynyl, 2-methylbut-1-ynyl, 3-methylbut-1-ynyl, 2-methylbut-2-ynyl, 1-hexynyl, 2- hexynyl, 3-hexynyl, 2,2-dimethyl-2-butynyl, 2-methyl-2-hexynyl, 3-methyl-1-pentynyl, 1 ,5-hexadiynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicodecynyl and the like. Alkynyl groups may be optionally substituted.

The term“carbocycle”, or variants such as“carbocyclic ring” as used herein, includes within its meaning any stable 3, 4, 5, 6, or 7-membered monocyclic or bicyciic or 7, 8, 9, 10, 11 , 12, or 13-membered bicyciic or tricyclic, any of which may be saturated, partially unsaturated, or aromatic. The term“carbocycle” includes within its meaning cycloalkyl, cycloalkenyl and aryl groups. Examples of such carbocycles include, but are not limited to, cydopropyl, cyclobutyi, cydopentyl, cydobexyl, cycloheptyl, adamantyl, cydoocty!, [3.3.0]bicydooctane, [4.3.0]bicydononane, [4.4 0]bicydodecane (decalin), [2.2.2]bicydooctane, fluorenyl, phenyl, naphthyl, indanyl, adamantyl, or tetrahydronaphthyl (tetralin). Preferred carbocydes, unless otherwise specified, are cydopropyl, cyclobutyi, cydopentyl, cyclohexyl, phenyl, naphthyl, and Indanyl. Carbocydes may be optionally substituted.

The term "cycloalkyl" as used herein refers to a non-aromatic mono- or multicyclic ring system comprising about 3 to about 10 carbon atoms. The cycloalkyl can be optionally substituted with one or more "ring system substituents" which may be the same or different, and are as defined herein. Non-limiting examples of suitable monocyclic cycloalkyls include cydopropyl, cydopentyl, cyclohexyl, cycloheptyl and the like. Non-limiting examples of suitable multicyclic cycloalkyls include 1 -decalinyl, norbornyl, adamantyl and the like. Further non-limiting examples of cycloalkyl include the following:

The term "cycloalkenyl" as used herein refers to a non-aromatic mono or multicyclic ring system comprising about 3 to about 10 carbon atoms which contains at least one carbon-carbon double bond. Non-limiting examples of suitable monocyclic cycloalkenyls include cyclopentenyl, cyclohexenyl, cyclohepta-1 ,3-dienyl, and the like. Non-limiting example of a suitable multicyclic cycloalkenyl is norbornylenyl, as well as unsaturated moieties of the examples shown above for cycloalkyl. Cycloalkenyl groups may be optionally substituted.

The term“aryl”, or variants such as“aromatic group” or“arylene” as used herein refers to monovalent (“aryl”) and divalent (“arylene”) single, polynuclear, conjugated or fused residues of aromatic hydrocarbons having from 6 to 10 carbon atoms. Such groups include, for example, phenyl, biphenyl, naphthyl, phenanthrenyl, and the like. Aryl groups may be optionally substituted.

The term “halogen”, or variants such as “halide” or “halo” as used herein, includes within its meaning fluorine, chlorine, bromine and iodine.

The term "heteroaryl" as used herein refers to an aromatic monocyclic or multicyclic ring system comprising about 5 to about 14 ring atoms, preferably about 5 to about 10 ring atoms, in which one or more of the ring atoms is an element other than carbon, for example nitrogen, oxygen or sulfur, alone or in combination. "Heteroary!" may also include a heteroary! as defined above fused to an ary! as defined above. Non- limiting examples of suitable heteroaryls include pyridyl, pyraziny!, furany!, thienyl, pyrimidinyl, pyridone (including N-substituted pyridones), isoxazolyl, isothiazolyl, oxazolyi, thiazo!y!, pyrazolyl, furazanyi, pyrrolyl, pyrazo!yl, triazolyi, 1 ,2,4-thiadiazolyi, pyrazinyl, pyridazinyi, quinoxaiinyl, phthalaziny!, oxindolyl, imidazo[1 ,2-ajpyridinyi, imidazo[2,1 -bjthiazoiyl, benzofurazanyl, indoiyi, azaindoiyl, benzimidazoly!, benzothienyl, quinolinyi, imidazolyl, thienopyridyl, quinazolinyl, thienopyrimidyi, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindolyl, 1 ,2,4-friazinyi, benzothiazolyi and the like. The term "heteroary!" also refers to partially saturated heteroary! moieties such as, for example, tetrahydroisoquinolyl, tetrahydroqulnoly! and the like. Heteroaryl groups may be optionally substituted.

The term "heterocycle" as used herein refers to a group comprising a covalently closed ring herein at least one atom forming the ring is a carbon atom and at least one atom forming the ring is a heteroatom. Heterocyclic rings may be formed by three, four, five, six, seven, eight, nine, or more than nine atoms, any of which may be saturated, partially unsaturated, or aromatic. Any number of those atoms may be heteroatoms (i.e. , a heterocyclic ring may comprise one, two, three, four, five, six, seven, eight, nine, or more than nine heteroatoms). Herein, whenever the number of carbon atoms in a heterocycle is indicated (e.g., C1-C6 heterocycle), at least one other atom (the heteroatom) must be present in the ring. Designations such as "C1-C6 heterocycle" refer only to the number of carbon atoms in the ring and do not refer to the total number of atoms in the ring. It is understood that the heterocylic ring will have additional heteroatoms in the ring. In heterocycles comprising two or more heteroatoms, those two or more heteroatoms may be the same or different from one another. Heterocycles may be optionally substituted. Binding to a heterocycle can be at a heteroatom or via a carbon atom. Examples of heterocycles include heterocycloalkyls (where the ring contains fully saturated bonds) and heterocycloalkenyls (where the ring contains one or more unsaturated bonds) such as, but are not limited to the following:

wherein D, E, F, and G independently represent a heteroatom. Each of D, E, F, and G may be the same or different from one another.

The term“optionally substituted” as used herein means the group to which this term refers may be unsubstituted, or may be substituted with one, two, three or more groups other than hydrogen provided that the indicated atom’s normal valency is not exceeded, and that the substitution results in a stable compound. Such groups may be, for example, halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, baloalkyl, haloalkoxy, aryl alkoxy, a!ky!tbio, hydroxya!ky!, alkoxya!ky!, cycloalkyl, cydoalkyla!koxy, alkanoyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy, a!ky!suifony!alkyl, arylsulfonyl, aryisuifonyloxy, aryisu!fonylalkyl, aikyisu!fonamido, a!ky!a ido, aikyisu!fonamidoa!ky!, alkylamldoalkyl, arylsulfonamido, arylcarboxamido, arylsulfonamidoalkyl, ary!carboxamidoalkyl, aroyl, aroyWalkyl, arylalkanoyl, acyl, aryl, ary!alkyl, aikyiaminoaikyi, a group R x R y N~, ROCO(CH 2 ) m , R x CON(R y )(CH 2 ) ni , R x R y NCO(CH 2 ) ni , R x R y N8Q 2 (CH 2 ) m or R x S0 2 NR y (CH 2 ) m (where each of R x and R y is independently selected from hydrogen or alkyl , or where appropriate R x R y forms part of carbocy!ic or heterocyclic ring and m is 0, 1 , 2, 3 or 4), a group R x R y N(CH 2 ) P - or R x R y N(CH 2 ) P 0- (wherein p is 1 , 2, 3 or 4); wherein when the substituent is R x R y N(CH 2 ) p - or R x R y N(CH 2 ) p 0 R x with at least one CH 2 of the (CH 2 ) P portion of the group may also form a carbocyclyi or heterocycly! group and R y may be hydrogen, alkyl.

The word“substantially” does not exclude“completely” e.g. a composition which is “substantially free” from Y may be completely free from Y. Where necessary, the word “substantially” may be omitted from the definition of the invention.

Unless specified otherwise, the terms "comprising" and "comprise", and grammatical variants thereof, are intended to represent "open" or "inclusive" language such that they include recited elements but also permit inclusion of additional, unrecited elements.

As used herein, the term "about", in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1 % of the stated value, and even more typically +/- 0.5% of the stated value.

Throughout this disclosure, certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub- ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1 , 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

Certain embodiments may also be described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the disclosure. This includes the generic description of the embodiments with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.

Detailed Disclosure of Embodiments

The present disclosure relates to compounds of formula (I), compositions and uses thereof, and methods for their preparation.

The present disclosure provides a compound of formula (I):

Formula (I) wherein:

Ri is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R 2 , and R 3 , are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R 6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof.

Ri may be optionally substituted branched or unbranched C 6 -C 2 4 alkyl (i.e. 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24 carbon atoms), C 8 - C22 alkyl, C1 0 -C2 0 alkyl, C12-C1 8 alkyl, C14-C1 8 alkyl, o C 6 , C 7 , Cs, Cg, C1 0 , Cn , C12, C1 3 , C14, C15, C1 6 , C17, C1 8 , C1 9 , C2 0 , C21 , C22, C2 3 , or C24 alkyl. Ri may be optionally substituted branched or unbranched C 6 -C 2 4 alkenyl (i.e. 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24 carbon atoms), C 8 -C 2 2 alkenyl, Ci 0 -C 2 o alkenyl, C12-C1 8 alkenyl, C14-C1 8 alkenyl, or C 6 , C 7 , Cs, Cg, C1 0 , Cn , C12, C1 3 , C14, C15, C1 6 , Ci 7 , C1 8 , C1 9 , C2 0 , C21 , C22, C2 3 , or C24 alkenyl. R1 may be optionally substituted branched or unbranched C 6 -C 2 4 alkynyl (i.e. 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24 carbon atoms), C 8 -C 2 2 alkynyl, C1 0 -C2 0 alkynyl, C12-C1 8 alkynyl, C14-C1 8 alkynyl, or C 6 , C 7 , Cs, Cg, C1 0 , Cn , C12, C1 3 , C14, C15, C1 6 , Ci 7 , Cis, C1 9 , C 2 o, C21 , C 22 , C2 3 , or C 2 4 alkynyl. R1 may be substituted or unsubstituted. R may be branched or unbranched. R may be a straight-chained C alkyl. R may be a straight-chained Ci 8 alkyl.

R 2 may be H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl. R 2 may be H, optionally substituted branched or unbranched C to C 6 alkyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C 2 to C 6 alkneyl (i.e. 2, 3, 4, 5, 6 carbon atoms), or optionally substituted branched or unbranched C 2 to C 6 alkynyl (i.e. 2, 3, 4, 5, 6 carbon atoms). R 2 may be H.

R 3 may be H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl. R 3 may be H, optionally substituted branched or unbranched C to C 6 alkyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C to C 6 alkneyl (i.e. 2, 3, 4, 5, 6 carbon atoms), or optionally substituted branched or unbranched C 2 to C 6 alkynyl (i.e. 2, 3, 4, 5, 6 carbon atoms). R 3 may be H.

R 4 may be H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl , optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl. R 4 may be H, cyano, F, Cl, Br, I, hydroxyl, optionally substituted branched or unbranched C to C 6 alkyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C 2 to C 6 alkenyl (i.e. 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C 2 to C 6 alkynyl (i.e. 2, 3, 4, 5, 6 carbon atoms), optionally substituted C to C 6 alkoxy (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted amino of formula -N(R) 2 , optionally substituted to C 6 acyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted C 3 - C12 cycloalkyl (i.e. 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12 carbon atoms), optionally substituted substituted C4-C12 cycloalkenyl (i.e. 4, 5, 6, 7, 8, 9, 10, 11 , 12 carbon atoms), optionally substituted C4-C12 heterocycloalkyl (i.e. 4, 5, 6, 7, 8, 9, 10, 1 1 , 12 carbon atoms), optionally substituted C 6 -Ci 2 aryl (i.e. 6, 7, 8, 9, 10, 1 1 , 12 carbon atoms), or optionally substituted C 6 -Ci 2 heteroaryl (i.e. 6, 7, 8, 9, 10, 11 , 12 carbon atoms), wherein R may be H, optionally substituted CrC 6 alkyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted C 2 -C 6 alkenyl (i.e. 2, 3, 4, 5, 6 carbon atoms), or optionally substituted C 2 - C 6 alkynyl (i.e. 2, 3, 4, 5, 6 carbon atoms). R 4 may be H.

R 5 may be H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl. R 5 may be H, cyano, F, Cl, Br, I, hydroxyl, optionally substituted branched or unbranched Ci to C 6 alkyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C 2 to C 6 alkenyl (i.e. 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C 2 to C 6 alkynyl (i.e. 2, 3, 4, 5, 6 carbon atoms), optionally substituted Ci to C 6 alkoxy (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted amino of formula -N(R) 2 , optionally substituted Ci to C 6 acyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted C 3 - C 12 cycloalkyl (i.e. 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12 carbon atoms), optionally substituted substituted C 4 -Ci 2 cycloalkenyl (i.e. 4, 5, 6, 7, 8, 9, 10, 11 , 12 carbon atoms), optionally substituted C 4 -Ci 2 heterocycloalkyl (i.e. 4, 5, 6, 7, 8, 9, 10, 1 1 , 12 carbon atoms), optionally substituted C 6 -Ci 2 aryl (i.e. 6, 7, 8, 9, 10, 1 1 , 12 carbon atoms), or optionally substituted C 6 -C 12 heteroaryl (i.e. 6, 7, 8, 9, 10, 11 , 12 carbon atoms), wherein R may be H, optionally substituted CrC 6 alkyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted C 2 -C 6 alkenyl (i.e. 2, 3, 4, 5, 6 carbon atoms), or optionally substituted C 2 - C 6 alkynyl (i.e. 2, 3, 4, 5, 6 carbon atoms). R 5 may be H.

R 6 may be H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl. R 6 may be H, F, Cl, Br, I, optionally substituted branched or unbranched Ci to C 6 alkyl (i.e. 1 , 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C 2 to C 6 alkenyl (i.e. 2, 3, 4, 5, 6 carbon atoms), optionally substituted branched or unbranched C 2 to C 6 alkynyl (i.e. 2, 3, 4, 5, 6 carbon atoms). R 6 may be methyl. The present disclosure also provides compounds of formula (I) or stereoisomers, mixture of stereoisomers or salts thereof wherein each of R 2 , R 3 , R 4 and R 5 is hydrogen.

The present disclosure further provides compounds of formula (I) or stereoisomers, mixture of stereoisomers or salts thereof wherein R 6 is C r C 5 alkyl.

The present disclosure also provides compounds of formula (I) or stereoisomers, mixture of stereoisomers or salts thereof wherein ^ is Ci 4 -Ci 8 alkyl, each of R 2 , R 3 , R 4 and R 5 is hydrogen, and R 6 is C r C 5 alkyl.

The present disclosure further provides compounds of formula (I) or stereoisomers, mixture of stereoisomers or salts thereof wherein is Ci 6 alkyl, each of R 2 , R 3 , R 4 and R 5 is hydrogen, and R 6 is methyl.

The present disclosure also provides compounds of formula (I) or stereoisomers, mixture of stereoisomers or salts thereof wherein ^ is Ci 8 alkyl, each of R 2 , R 3 , R 4 and R 5 is hydrogen, and R 6 is methyl. The present disclosure also provides compounds of formula (I) or stereoisomers, mixture of stereoisomers or salts thereof wherein the compound of formula (I) is Compound A (or also referred to as Demulsifier A):

Methyl (2Z)-4-(2-heptadecanyoylhydrazinyl)-4-oxobut-2-enoate

Compound A.

The present disclosure also provides compounds of formula (I), or stereoisomers, mixture of stereoisomers or salts thereof wherein the compound of formula (I) is Compound B (or also referred to as Demulsifier B):

Methyl (2Z)-4-(2-nonadecanyoylhydrazinyl)-4-oxobut-2-enoate

Compound B.

The compounds of Formula (I) may comprise a primary ester head and two secondary amide heads. The compounds of Formula (I) may be useful in mitigating and/or preventing microemulsion formation by neutralization of cations in the naphthenic acids by the functional binding of the two secondary amide heads and the primary ester head in the compounds of formula (I). The binding of the primary ester head with naphthenic acid cations may form a protection barrier which advantageously prevents and/or mitigates the formation of microemulsions between alkaline surfactant polymers and naphthenate acid which eliminates the amphoteric nature of naphthenic acids. The use of compounds of formula (I) may also result in a competing reaction in the reaction between alkaline surfactant polymer and naphthenate acid, hence preventing and/or mitigating microemulsion formation between alkaline surfactant polymer and naphthenate acid.

The present disclosure also provides a demulsifier composition comprising:

(i) the compound of formula (I):

Formula (I) wherein:

Ri is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl; R 2 , and R 3 , are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R 6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof,

(ii) quaternized fatty acid trialkanolamine ester,

(iii) polysorbate polyester,

(iv) aromatic solvent.

Ri, R 2 , R 3 , R 4 , R 5 , and R 6 may be defined as disclosed above.

The disclosed demulsifier composition may comprise about 20 vol% to about 40 vol% of a compound of formula (I), or about 25 vol% to about 40 vol%, or about 30 vol% to about 40 vol%, or about 35 vol% to about 40 vol%, or about 20 vol% to about 35 vol%, or about 20 vol% to about 30 vol%, or about 20 vol% to about 25 vol%, or about 20 vol%, or about 22 vol%, or about 24 vol%, or about 26 vol%, or about 28 vol%, or about 30 vol%, or about 32 vol%, or about 34 vol%, or about 36 vol%, or about 38 vol%, or about 40 vol%.

The quaternized fatty acid trialkanolamine ester may be of the following Formula (V):

Formula (V)

wherein R 7 at each occurrence is independently selected from optionally substituted Ci 2 to C 20 alkyl;

n at each occurrence is independently selected from 1 , 2, 3, 4, or 5;

R s and R g are each independently selected from H, optionally substituted alkyl, optionally substituted alkoxy, hydroxyl, -C(0)OR 7 ; and

X is a counterion.

R 7 may be optionally substituted branched or unbranched Ci 2 -C 20 alkyl (i.e. 12, 13, 14, 15, 16, 17, 18, 19, 20 carbon atoms), Ci 4 -C 20 alkyl, Ci 6 -C 20 alkyl, Ci 8 -C 20 alkyl, or Ci 2 , Ci 3 , Ci 4 , Ci 5 , Ci 6 , Ci 7 , Ci 8 , Ci 9 , C 20 alkyl. R 7 may be substituted or unsubstituted. R 7 may be branched or unbranched. R 7 may be a straight-chained Ci 2-2g alkyl. R 7 may be a straight-chained and unsubstituted Ci 2-20 alkyl. n may be 1 , 2, 3, 4 or 5.

R s may be H, optionally substituted alkyl, optionally substituted alkoxy, or hydroxyl. R 8 may be optionally substituted Ci, C 2 , C 3 , C 4 , C 5 or C 6 alkyl or alkyoxy.

R g may be H, optionally substituted alkyl, optionally substituted alkoxy, or hydroxyl. R 8 may be optionally substituted Ci, C 2 , C 3 , C 4 , C 5 or C 6 alkyl or alkyoxy.

X is a counterion. The counterion may be a monoanion or a polyanion. For example, the counterion may be a monoanion, such as hydroxide anion, alkoxide anion, sulfonate anion. The counterion may be CH 3 S0 4 .

The quaternized fatty acid trialkanolamine ester may be a quaternized fatty acid trimethanolamine, a quaternized fatty acid triethanolamine, a quaternized fatty acid tripropanolamine, a quaternized fatty acid tributanolamine, or a quaternized fatty acid tripentanolamine. The quaternized fatty acid trialkanolamine ester may be a decosoft esterquat softener palm oil derivative, an oleic acid-based triethanolamine esterquat.

The quaternized fatty acid trialkanolamine ester may be selected from the group consisting of Formulas (V-l) or (V-ll):

Formula (V -II)

Formula (V -III)

The disclosed demulsifier composition may comprise about 20 vol% to about 40 vol% quaternized fatty acid trialkanolamine ester, or about 25 vol% to about 40 vol%, or about 30 vol% to about 40 vol%, or about 35 vol% to about 40 vol%, or about 20 vol% to about 35 vol%, or about 20 vol% to about 30 vol%, or about 20 vol% to about 25 vol%, or about 20 vol%, or about 22 vol%, or about 24 vol%, or about 26 vol%, or about 28 vol%, or about 30 vol%, or about 32 vol%, or about 34 vol%, or about 36 vol%, or about 38 vol%, or about 40 vol%.

The polysorbate polyester may be of following formula (VI):

Formula (VI) wherein:

R 10 is an optionally substituted Cm to C 2 o alkyl; and the sum of w, x, y and z is in the range of 15 to 30.

R 10 may be optionally substituted branched or unbranched Ci 0 -C 2 o alkyl (i.e. 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20 carbon atoms), C12-C2 0 alkyl, Ci 4 -C 20 alkyl,

Ci 6 -C 2 o alkyl, Cis-C 2 o alkyl, or C1 0 , Cn , Ci 2 , C1 3 , C14, C15, C1 6 , C17, C1 8 , C1 9 , C 2o alkyl. R 10 may be substituted or unsubstituted. R 10 may be branched or unbranched. R 10 may be a straight-chained Cio -20 alkyl. R 10 may be a straight- chained and unsubstituted C 10-20 alkyl.

The sum of w, x, y and z may be 15 to 30, 20 to 30, 25 to 30, 15 to 25, 15 to

20, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, or 30.

The polysorbate polyester may be a polysorbate polyester containing 20, 40, 60 or 80 polysorbate acids. The polysorbate polyester may be Kemelix 3515X, 3551X, 3697X, 3702X, 3725X, 3736X, 3738X, 3743X, 3744X, and D510, ethoxylated surfactants, obtained from Croda Oil and Gas. The Kemelix 3702X may have a relative solubility number of 17.

The disclosed demulsifier composition may comprise about 10 vol% to about 20 vol% polysorbate polyester, or about 12 vol% to about 20 vol%, about 14 vol% to about 20 vol%, about 16 vol% to about 20 vol%, about 18 vol% to about 20 vol%, about 10 vol% to about 18 vol%, about 10 vol% to about 16 vol%, about 10 vol% to about 14 vol%, about 10 vol% to about 12 vol%, or about 10 vol%, about 11 vol%, about 12 vol%, about 13 vol%, about 14 vol%, about 15 vol%, about 16 vol%, about 17 vol%, about 18 vol%, about 19 vol%, or about 20 vol%.

The aromatic solvent may be an aromatic hydrocarbon solvent. The aromatic solvent may be selected from the group consisting of toluene, xylene, hexane, cyclohexane, benzene, or mixtures thereof. The aromatic solvent may be Solvesso 150 (CAS Registry No. 64742-95-6; distillation range of 180 to 215°C; Flash Point (closed cup) 62°C; min 98 wt% aromatics) and/or Solvesso 200 obtained from ExxonMobil Corporation. The aromatic solvent may display the following properties:

The disclosed demulsifier composition may comprise about 40 vol% to about 60 vol% aromatic solvent, or about 45 vol% to about 60 vol%, or about 50 vol% to about 60 vol%, or about 55 vol% to about 60 vol%, about 40 vol% to about 55 vol%, about 40 vol% to about 40 vol%, about 40 vol% to about 45 vol%, or about 40 vol%, about 42 vol%, about 44 vol%, about 46 vol%, about 48 vol%, about 50 vol%, about 52 vol%, about 54 vol%, about 56 vol%, about 58 vol%, or about 60 vol%. The disclosed demulsifier composition may comprise:

(i) 20 to 40 vol% of a compound of formula (I), such as compound A or compound B;

(ii) 10 to 20 vol% of quarternized fatty acid trialkanolamine ester;

(iii) 10 to 20 vol% polysorbate polyester; and

(iv) 40 to 60 vol% aromatic solvent .

wherein components (i) to (iv) make up 100vol%.

The disclosed demulsifier composition may comprise:

(i) 20 vol% of a compound of formula (I) such as compound A or compound B;

(ii) 20 vol% of quarternized fatty acid trialkanolamine ester; (iii) 20 vol% polysorbate polyester; and

(iv) 40 vol% aromatic solvent.

The disclosed demulsifier composition may comprise:

(i) 40 vol% of a compound of formula (I) such as compound A or compound B;

(ii) 10 vol% of quarternized fatty acid trialkanolamine ester;

(iii) 10 vol% polysorbate polyester; and

(iv) 40 vol% aromatic solvent.

The present disclosure also relates to a method for inhibiting or preventing the formation of an emulsion using a demulsifier composition comprising the compound of formula (I):

Formula (I) wherein:

R, is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R 2 and R 3 , are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl; R 6 is H, halogen, substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof.

Ri, R 2 , R 3 , R 4 , R 5 , and R 6 may be defined as disclosed above.

The emulsion may be a microemulsion. The emulsion or microemulsion may comprise naphthenic acid, salt thereof or a mixture thereof.

The compound of formula (I) may be at a concentration of about 5 ppm to about 100 ppm, about 5 ppm to about 95 ppm, about 5 ppm to about 90 ppm, about 5 ppm to about 85 ppm, about 5 ppm to about 80 ppm, about 5 ppm to about 75 ppm, about 5 ppm to about 70 ppm, about 5 ppm to about 65 ppm, about 5 ppm to about 60 ppm, about 5 ppm to about 55 ppm, about 5 ppm to about 50 ppm, about 5 ppm to about 45 ppm, about 5 ppm to about 40 ppm, about 5 ppm to about 35 ppm, about 5 ppm to about 30 ppm, about 5 ppm to about 25 ppm, about 5 ppm to about 20 ppm, about 5 ppm to about 15 ppm, about 5 ppm to about 10 ppm, about 10 ppm to about 100 ppm, about 15 ppm to about 100 ppm, about 20 ppm to about 100 ppm, about 25 ppm to about 100 ppm, about 30 ppm to about 100 ppm, about 35 ppm to about 100 ppm, about 40 ppm to about 100 ppm, about 45 ppm to about 100 ppm, about 50 ppm to about 100 ppm, about 55 ppm to about 100 ppm, about 60 ppm to about 100 ppm, about 65 ppm to about 100 ppm, about 70 ppm to about 100 ppm, about 75 ppm to about 100 ppm, about 80 ppm to about 100 ppm, about 85 ppm to about 100 ppm, about 90 ppm to about 100 ppm, about 95 ppm to about 100 ppm, about 10 ppm to about 50 ppm, about 10 ppm to about 50 ppm, about 10 ppm to about 50 ppm, about 10 ppm to about 50 ppm, about 10 ppm to about 50 ppm, or about 5 ppm, about 10 ppm, about 15 ppm, about 20 ppm, about 25 ppm, about 30 ppm, about 35 ppm, about 40 ppm, about 45 ppm, about 50 ppm, about 55 ppm, about 60 ppm, about 65 ppm, about 70 ppm, about 75 ppm, about 80 ppm, about 85 ppm, about 90 ppm, about 95 ppm, about 100 ppm.

The process temperature of the disclosed method may be from about 25 °C to about 80 °C, or about 25 °C to about 75 °C, about 25 °C to about 70 °C, about 25 °C to about 65 °C, about 25 °C to about 60 °C, about 25 °C to about 55 °C, about 25 °C to about 50 °C, about 25 °C to about 45 °C, about 25 °C to about 40 °C, about 25 °C to about 35 °C, about 25 °C to about 30 °C, about 30 °C to about 80 °C, about 35 °C to about 80 °C, about 40 °C to about 80 °C, about 45 °C to about 80 °C, about 50 °C to about 80 °C, about 55 °C to about 80 °C, about 60 °C to about 80 °C, about 65 °C to about 80 °C, about 70 °C to about 80 °C, about 75 °C to about 80 °C, about 30 °C to about 60 °C, or about 25 °C, about 30 °C, about 35 °C, about 40 °C, about 45 °C, about 50 °C, about 55 °C, about 30 °C, about 60 °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C.

The process pH of the disclosed method may be from about pH 4 to about pH 12, or about pH 5 to about pH 12, about pH 5 to about pH 12, about pH 6 to about pH 12, about pH 7 to about pH 12, about pH 8 to about pH 12, about pH 9 to about pH 12, about pH 10 to about pH 12, about pH 11 to about pH 12, about pH 4 to about pH 11 , about pH 4 to about pH 10, about pH 4 to about pH 9, about pH 4 to about pH 8, about pH 4 to about pH 7, about pH 4 to about pH 6, about pH 4 to about pH 5, about pH 7 to about pH 9, or about pH 4, about pH 5, about pH 6, about pH 7, about pH 8, about pH 9, about pH 10, about pH 11 , about pH 12.

The demulsifier composition may further comprise at least a second demulsifier. The second demulsifier may be a polysorbate polyester, nanomaterial silicone-bio demulsifier such as poly ester cellulose-silicone base biochemical or poly ester -amine cellulose silicone based biochemical, or mixtures thereof.

The present disclosure further provides a method of preparing a compound of formula (I):

Formula (I) wherein:

R, is an optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, or optionally substituted branched or unbranched alkynyl;

R 2 and R 3 are independently selected from H, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

R 4 and R 5 are independently selected from H, cyano, halogen, hydroxyl, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl, optionally substituted alkoxy, optionally substituted amino, optionally substituted acyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted heterocycloalkyl, optionally substituted aryl or optionally substituted heteroaryl;

R 6 is H, halogen, optionally substituted branched or unbranched alkyl, optionally substituted branched or unbranched alkenyl, optionally substituted branched or unbranched alkynyl;

or stereoisomers, mixture of stereoisomers or salts thereof,

comprising reacting a compound of formula (II):

with compounds of formula (III) and (IV):

in the presence of a catalyst.

Ri, R 2 , R 3 , R 4 , R 5 , and R 6 may be defined as disclosed above.

The catalyst of the disclosed method may be elected from the group consisting of /V,/V-dimethylformaamide (DMF), acetonitrile, acetone, and dimethyl sulfoxide (DMSO).

The reaction temperature of the disclosed method may be in the range of about 80°C to about 90°C, or about 82°C to about 90°C, about 84°C to about 90°C, about 86°C to about 90°C, about 88°C to about 90°C, about 80°C to about 88°C, about 80°C to about 86°C, about 80°C to about 84°C, about 80°C to about 82°C, or about 80°C, about 81 °C, about 82°C, about 83°C, about 84°C, about 85°C, about 86°C, about 87°C, about 88°C, about 89°C, about 90°C.

Brief Description of Drawings

The accompanying drawings illustrate a disclosed embodiment and serves to explain the principles of the disclosed embodiment. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.

Fig.lA

[Fig. 1A] is a gas chromatography mass spectra of compound A in dichloromethane (DCM).

Fig.l B

[Fig. 1 B] is a gas chromatography mass spectra of compound A in chloroform.

Fig.2A

[Fig. 2A] shows a differential scanning calorimetry (DSC) plot measuring the melting point of compound A.

Fig.2B

[Fig. 2B] shows a differential scanning calorimetry (DSC) plot measuring the wax appearance temperature (WAT) (or cloud point) of compound A.

Fig.3

[Fig. 3] is a graph showing the percentage of microemulsion formed at various water cuts using Alkaline Surfactant Polymer (ASP) cocktails at various concentrations.

Fig.4A

[Fig. 4A] is a graph showing the percentage of microemulsion formed with respect to retention time at 30°C and 40% water cut (WC) using Formulation A of the present invention at different concentrations of demulsifer.

Fig. 4B

[Fig. 4B] is a graph showing the percentage of microemulsion formed with respect to retention time at 30°C and 40% water cut (WC) using Formulation B of the present invention at different concentrations of demulsifer. Fig.4C

[Fig. 4C] is a graph showing the percentage of microemulsion formed with respect to retention time at 30°C and 60% water cut using Formulation A of the present invention at different concentrations of demulsifer.

Fig.4D

[Fig. 5D] is a graph showing the percentage of microemulsion formed with respect to retention time at 30°C and 60% water cut using Formulation B of the present invention at different concentrations of demulsifer.

Fig.4E

[Fig. 4E] is a graph showing the percentage of microemulsion formed with respect to retention time at 30°C and 80% water cut using Formulation A of the present invention at different concentrations of demulsifer.

Fig.4F

[Fig. 4F] is a graph showing the percentage of microemulsion formed with respect to retention time at 30°C and 80% water cut using Formulation B of the present invention at different concentrations of demulsifer.

Fig.5A

[Fig. 5A] is a graph showing the percentage of microemulsion formed with respect to retention time at 60°C and 40% water cut using Formulation A of the present invention at different concentrations of demulsifer.

Fig.5B

[Fig. 5A] is a graph showing the percentage of microemulsion formed with respect to retention time at 60°C and 40% water cut using Formulation B of the present invention at different concentrations of demulsifer.

Fig.5C

[Fig. 5C] is a graph showing the percentage of microemulsion formed with respect to retention time at 60°C and 60% water cut using Formulation A of the present invention at different concentrations of demulsifer. Fig. 5D

[Fig. 5D] is a graph showing the percentage of microemulsion formed with respect to retention time at 60°C and 60% water cut using Formulation B of the present invention at different concentrations of demulsifer.

Fig.5E

[Fig. 5E] is a graph showing the percentage of microemulsion formed with respect to retention time at 60°C and 80% water cut using Formulation A of the present invention at different concentrations of demulsifer.

Fig.5F

[Fig. 5F] is a graph showing the percentage of microemulsion formed with respect to retention time at 60°C and 80% water cut using Demulsifier of Formulation B of the present invention at different concentrations of demulsifer.

Fig.6A

[Fig. 6A] is a graph showing the percentage of microemulsion formed with respect to retention time at 80°C and 40% water cut using Formulation A of the present invention at different concentrations of demulsifer.

Fig.6B

[Fig. 6B] is a graph showing the percentage of microemulsion formed with respect to retention time at 80°C and 40% water cut using Formulation B of the present invention at different concentrations of demulsifer.

Fig.6C

[Fig. 6C] is a graph showing the percentage of microemulsion formed with respect to retention time at 80°C and 60% water cut using Formulation A of the present invention at different concentrations of demulsifer.

Fig.6D

[Fig. 6D] is a graph showing the percentage of microemulsion formed with respect to retention time at 80°C and 60% water cut using Formulation B of the present invention at different concentrations of demulsifer. Fig.6E

[Fig. 6E] is a graph showing the percentage of microemulsion formed with respect to retention time at 80°C and 80% water cut using Formulation A of the present invention at different concentrations of demulsifer.

Fig.6F

[Fig. 6F] is a graph showing the percentage of microemulsion formed with respect to retention time at 80°C and 80% water cut using Formulation B of the present invention at different concentrations of demulsifer.

Fig.7A

[Fig. 7A] is a graph showing the percentage of basic sediment and water (BS&W) with respect to demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 30°C and 40% water cut.

Fig.7B

[Fig. 7B] is a graph showing the percentage of basic sediment and water (BS&W) with respect to demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 30°C and 60% water cut.

Fig.7C

[Fig. 7C] is a graph showing the percentage of basic sediment and water (BS&W) with respect to demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 30°C and 80% water cut.

Fig.8A

[Fig. 8A] is a graph showing the percentage of basic sediment and water (BS&W) with respect to each demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 60°C and 40% water cut.

Fig.8B

[Fig. 8B] is a graph showing the percentage of basic sediment and water (BS&W) with respect to each demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 60°C and 60% water cut. Fig.8C

[Fig. 8C] is a graph showing the percentage of basic sediment and water (BS&W) with respect to each demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 60°C and 80% water cut.

Fig.9A

[Fig. 9A] is a graph showing the percentage of basic sediment and water (BS&W) with respect to each demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 80°C and 40% water cut.

Fig.9B

[Fig. 9B] is a graph showing the percentage of basic sediment and water (BS&W) with respect to each demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 80°C and 60% water cut.

Fig.9C

[Fig. 9C] is a graph showing the percentage of basic sediment and water (BS&W) with respect to each demulsifier concentration of (i) Formulation A; and (ii) Formulation B at 80°C and 80% water cut.

Fig.10

[Fig. 10] is a general schematic showing the testing procedure of dynamic flow loop tests.

Fig.11

[Fig. 11] is a differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using a blank.

Fig.12

[Fig. 12] is a differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 10 ppm of demulsifer in Formulation A.

Fig.13

[Fig. 13] is a differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 10 ppm of demulsifer in Formulation B. Fig.14

[Fig. 14] is a differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 25 ppm of demulsifer in Formulation A.

[Fig.15]

[Fig. 15] is a differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 25 ppm of demulsifer in Formulation B.

[Fig.16]

[Fig. 16 is a differential pressure plot at 0.45 MPa (4.5 bar), 30 °C and 20% water cut using 50 ppm of a comparative demulsifier composition.

[Fig.17]

[Fig. 17] is a differential pressure plot at 0.45 MPa (4.5 bar), 30 °C and 20% water cut using 200 ppm of a comparative demulsifier composition.

[Fig.18]

[Fig. 18] is a differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 20% water cut using 100 ppm of a comparative demulsifier composition.

[Fig.19]

[Fig. 19] is a graph showing the percentage of basic sediment and water (BS&W) in crude oil after being treated with a comparative demulsifer composition at varying concentrations and temperatures.

Examples

Non-limiting examples of the invention and a comparative example will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention. Example 1 - Microemulsions

Production fluids recovered from reservoirs contain a mixture of both hydrocarbons (gas and oil) and water. It is necessary to separate this mixture into parts. During enhanced oil recovery, the addition of surfactants and polymers to the production fluids complicates the separation process, as they produce tight micellar microemulsions. An embodiment of the disclosure is a method for breaking the microemulsions of produced liquids recovered after an Alkaline Surfactant Polymer (ASP) flood by adding a compound of the present invention.

Various Alkaline Surfactant Polymer (ASP) cocktails were made by mixing various amounts of Produce Water (PW) with 0.5 to 1 wt% sulfonate surfactant, and 000 to 2000 ppm polyacrylamide polymer.

Various microemulsions were made by mixing a crude oil with equal amount of ASP cocktail. The amount of these chemicals simulates the expected breakthrough (production) fluids from a surfactant-polymer flood. Fig. 3 and Table 1 shows the percentage of microemulsion formed at various water cuts using ASP cocktails at varying ratios of ASP:PW. As shown in Fig. 3, increasing ASP concentration increased the formation of microemulsion. All ratios of ASP:PW had severe microemulsion formation. Fig. 3 shows that microemulsion formation was highest for 40% water cut. At 60% and 80% water cut, the percentage of emulsion increased with increasing concentration of ASP.

[Table 1]

Example 2 - General Synthesis

Compound A

Fatty hydrazides (R-C=0-NH-NH 2 ) were reacted with maleic anhydrides under reflux for 6 hours at about 80 °C to about 90 °C in methanol (R-OH) with N,N-dimethylformaamide as catalyst, as shown in Scheme 1.

Scheme 1

Example if fatty Rl= 16 and Rb=Cl {alcohol, glycol or any compound has -OH group) fi, fi -d j meth yiform aam ide { D M F }

Example 2a - Analysis of Compound A

R = C16

methyl (2Z)-4-(2-heptadecanoylhydrazinyl)-4-oxobut-2-enoate

Molecular Formula: C22H40N2O4

Formula Weight: 396.564

Composition: C(66.63%) H(10.17%) N(7.06%) 0(16.14%)

Molar Refractivity: 1 13.05 ± 0.3 cm 3

Molar Volume: 400.6 ± 3.0 cm 3

Parachor: 985.4 ± 4.0 cm 3

Index of Refraction: 1.476 ± 0.02

Surface Tension: 36.5 ± 3.0 dyne/cm

Density: 0.989 ± 0.06 g/cm 3

Dielectric Constant: Not available

Polarizability: 44.81 ± 0.5 10 24 cm 3

RDBE: 4

Monoisotopic Mass: 396.298808 Da

Nominal Mass: 396 Da

Average Mass: 396.564 Da

M+: 396.298259 Da

M-: 396.299356 Da

[M+H]+: 397.306084 Da

[M+H]-: 397.307181 Da [M-H]+: 395.290434 Da

[M-H]-: 395.291531 Da

Example 2b - Analysis of Compound B

R = C18 methyl (2Z)-4-(2-nonadecanoylhydrazinyl)-4-oxobut-2-enoate

Molecular Formula: C24H44N2O4

Formula Weight: 424.61716

Composition: C(67.89%) H(10.44%) N(6.60%) 0(15.07%)

Molar Refractivity: 122.31 ± 0.3 cm 3

Molar Volume: 433.6 ± 3.0 cm 3

Parachor: 1064.9 ± 4.0 cm 3

Index of Refraction: 1 .476 ± 0.02

Surface Tension: 36.3 ± 3.0 dyne/cm

Density: 0.979 ± 0.06 g/cm 3

Dielectric Constant: Not available

Polarizability: 48.49 ± 0.5 10 24 cm 3

RDBE: 4

Monoisotopic Mass: 424.330108 Da

Nominal Mass: 424 Da

Average Mass: 424.6172 Da

M+: 424.329559 Da

M-: 424.330656 Da

[M+H]+: 425.337384 Da

[M+H]-: 425.338482 Da

[M-H]+: 423.321734 Da

[M-H]-: 423.322831 Da

Figs. A, and 1 B are GSMS spectra of Compound A in Fig. A: dichloromethane (retention time R t 4.16); Fig. B: chloroform (retention time R t . Compound A may be made according to a method of Example 1.

Referring to Fig. 2A, the melting point of 68.45 °C of compound A shows the characteristic fatty acid carbon number used contains either palmitic C16 (63.1 °C) or stearic C18 (68.8 °C).

Referring to Fig. 2B, the wax appearance temperature (WAT) or cloud point measured is 26.34 °C which is when compound A is waxy at room temperature. Example 3 - Water Composition

The water composition from an exemplary reservoir is shown in Table 2. This water was used in the experiments of the examples below.

Example 3 - Demulsifier Compositions

Table 3 shows exemplary demulsifying formulations comprising demulsifier compounds of the present invention.

[Table 3]

Example 4 - Effect of Demulsifier Formulations on Percentage of Microemulsion

Laboratory tests were conducted using Formulation A and Formulation B. The following testing results demonstrate that percentage of microemulsion decreased using demulsifier formulations of the present invention.

The testing procedure is summarized as follows:

1. An ASP cocktail was prepared which contained 0.5 to 1 wt% of surfactants and 1000 to 2000 ppm polymer, in a ratio of ASP: PW of 20:80 at 40% water cut at a temperature of 30 °C, simulating the produced fluid from ASP flooding.

2. The above fluid was mixed at a shearing rate that simulates production flowrate and produced a microemulsion.

3. Steps 1 and 2 were repeated twice to produce a total of three bottles.

4. Formulation A or Formulation B was added into each bottle with the following concentrations of demulsifier: 10 ppm, 25 ppm and 50 ppm.

5. The bottles were shaken and placed into a constant temperature water bath at 30 °C.

6. The percentage of microemulsion was measured over a time period of 2 hours.

7. The above test was repeated at temperatures of 60 °C and 80 °C using Formulations A and B with varying concentrations of demulsifier (10 ppm, 25 ppm and 50 ppm) at different water cuts (40% WC, 60% WC and 80% WC). The test matrixes are shown below in Table 4 and the results for these tests are shown in Figs. 4A to 4F.

[Table 4]

As shown in Figs. 4A to 4F, 5A to 5F and 6A to 6F, increasing concentration of demulsifier (from 10 ppm, 25 ppm, to 50 ppm) and increasing temperature (from 30 °C to 80 °C) improves the demulsification in both 40% water cut and 60% water cut. At a lower temperature of 30 °C, increasing water cut percentage level by water dilution or crude washing strategy would optimise the use of determining the concentration of demulsifier. Increasing the temperature and concentration of demulsifier would also shorten the retention time for breaking up the emulsion and hasten separation of the oil and water phase.

Example 5 - Effect of Demulsifier Formulations on percentage of Basic Sediment and Water (BS&W)

Laboratory tests were conducted using Formulations A and B. The following testing results demonstrate that percentage of BS&W decreased using demulsifiers of the present invention.

The testing procedure is summarized as follows:

1. Centrifuge tubes were cleaned and any sediment was dislodged at the tip of the tube by using a suitable brush. The tube was rinsed with crude oil if necessary.

2. The sampling point was flushed out for 30 seconds by slowly opening the valves. The valves were adjusted to maintain steady flow. The sample was added directly into the 100ml centrifuge tubes. Two centrifuge tubes were filled to the 100ml mark.

3. Four to six drops of Formulation A or Formulation B were added using a plastic dropper to the centrifuge tubes. The Formulation A or B and crude oil sample were mixed thoroughly by shaking the tubes vigorously. The tubes were immersed into a water bath to the 100ml mark and maintained at a pre-determined temperature for ten minutes or the tubes were placed into a heating block for 10 minutes.

4. The centrifuge tubes were placed into a centrifuge machine. It was ensured that the centrifuge was properly balanced.

5. The samples were centrifuged at about 1500 RPM for 5 to 10 minutes.

6. The centrifuge machine was completely stopped before opening the lid.

7. The levels of the crude oil, emulsion and water interface were recorded and reported in percentage (%). The sample with Formulation A or B showed total water only. If the emulsion was not totally resolved, step 3 to 6 were repeated until only free water was obtained.

8. Readings that were lower than 0.025% were recorded as trace. The emulsion, free water and sediment were recorded as separate readings.

9. The above test was performed at temperatures of 40 °C, 60 °C and 80 °C using varying concentrations of demulsifiers (10 ppm, 25 ppm and 50 ppm) at different water cuts (40% WC, 60% WC and 80% WC). The readings are shown below in Table 5 and the results for these tests are shown in Figs. 7 A to 7C, 8A to 8C, and 9A to 9C. [Table 5]

As shown in Table 5 and Figs. 7A to 7C, 8A to 8C, and 9A to 9C, increasing the concentration of demulsifier (from 10 ppm, 25 ppm, to 50 ppm) and increasing the temperature (from 30 °C to 80 °C) improve the demulsification.

Example 6a - General Testing Procedure of Dynamic Flow Loop Tests

Referring to Fig. 10, dynamic flow loop tests were carried out at 30°C and 60 °C and 0.45 MPa (4.5 bar) with a 20%, 40% and 60% water cut off match field separator conditions. Crude oil (10) and brine (12) were injected into a mixing cell equipped with a sealed homogeniser (14) operating at 13,500 rpm. The combined fluids then flowed from the mixing cell through two in-line filters. The first was a coarse filter (22)/baffle and the second was a 7 pm fine filter. The differential pressure (dP) across the fine filter (24) was measured and plotted (16), allowing assessment of the viscosity of the fluids and any blockages arising from solids formation. The fluids then entered a glass separator where the oil/brine interface and any emulsion formed were observed and photographed. The entire apparatus was housed inside an oven and pressurised to replicate the conditions in a low- pressure separator in the field. The oil was drawn from the oil outlet (18) for BS&W measurement at the end of the test. The brine was drawn from the brine outlet (20).

The differential pressure plots for various tests are shown in Figs. 11 to 15.

Example 6b - Effect of Demulsifier Compositions on Differential Pressure and pH

Fig. 11 shows the differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using a blank. Fig. 12 shows the differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 10 ppm of Demulsifier A in Formulation A, Fig. 13 shows the differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 10 ppm of Demulsifier B in Formulation B, Fig. 14 shows the differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 25 ppm of Demulsifier A in Formulation A, and Fig. 15 shows the differential pressure plot at 0.45 MPa (4.5 bar), 60 °C and 40% water cut using 25 ppm of Demulsifier B in Formulation B.

Figs. 11 to 15 show that Formulations comprising Demulsifiers A and B have the ability to lower the differential pressure (dP) compared to a blank without demulsifier treatment. This showed the ability of Formulations comprising Demulsifiers A and B in reducing viscous microemulsions formed by ASPs, by being useful in naphthenate inhibition and separating oil and water phases.

Comparative Example

A comparative demulsifier composition (Breaxit EC2032A, Nalco Champion) at concentrations of 50 ppm, 100 ppm and 200 ppm were tested.

Fig. 16 shows the differential pressure plot using 50 ppm of comparative demulsifier composition at 0.45 MPa (4.5 bar), 30 °C and 20% water cut, Fig. 17 shows the differential pressure plot using 200 ppm of comparative demulsifier composition at 0.45 MPa (4.5 bar), 30 °C and 20% water cut, and Fig. 18 shows the differential pressure plot using 100 ppm of comparative demulsifier composition at 0.45 MPa (4.5 bar), 60 °C and 20% water cut.

As shown in Figs. 16 to 18, the differential pressure (dp) did not reduce after time which indicated that the comparative demulsifer composition was unable to treat viscous microemulsions generated by ASP, even at high concentrations. The crude sampled from this test showed that the BS&W was unable to meet performance targets (Table 7, Fig. 19). [Table 7]

Industrial Applicability

The compounds of formula (I) and demulsifier compositions comprising them may be useful in preventing and/or mitigating emulsions or microemulsions during enhanced oil recovery. Advantageously, the use of the disclosed compounds may be non-hazardous and not harmful to the environment. Further advantageously, the disclosed compounds may be formed from readily available and cheap starting materials. Also advantageously, the compounds of formula (I) may mitigate or prevent microemulsion formation during enhanced oil recovery operations, and thus increase the amount and/or quality of crude oil extracted from carbonate reservoirs. It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.