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Title:
WINTERIZED MATURING AGENT, VISCOSITY REDUCER AND PRODUCTION ENHANCER
Document Type and Number:
WIPO Patent Application WO/2020/061671
Kind Code:
A1
Abstract:
The present disclosure provides a storage and freeze thaw stable liquid treatment composition comprising a solvent package and a chemical treatment agent. The liquid treatment composition may be used in various applications, such as in the production, improved recovery and processing of light, medium, heavy and extra- heavy crude oil at temperatures ranging from about -40° to about 80 °C.

Inventors:
WORSLEY KEN (CA)
GOBIN TYLER (CA)
LECHMAN DAN (CA)
FOUQUET MARINE (CA)
Application Number:
PCT/CA2018/000181
Publication Date:
April 02, 2020
Filing Date:
September 26, 2018
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
EXALTEXX INC (CA)
International Classes:
C09K3/00; C09K3/18; C09K5/20; C09K8/524; C10G75/04; E21B37/06; E21B43/22; F17D1/17
Foreign References:
CA2999615A12016-06-09
US8263114B22012-09-11
US5152886A1992-10-06
US8529687B22013-09-10
CA2424903A12003-10-23
Attorney, Agent or Firm:
SMART & BIGGAR (CA)
Download PDF:
Claims:
Claims:

1 . A liquid treatment composition comprising: (i) a solvent package comprising a mixture of two or more of: an aromatic solvent; an alcohol; a saturated hydrocarbon solvent; an ether solvent; a ketone solvent; a glycol solvent; an ester solvent; an aldehyde solvent; a nitrogen-containing solvent; a sulfur-containing solvent and a terpene solvent; (ii) a chemical treatment agent comprising a mixture of a strong acid, a fatty acid, an amine, an oxidizing agent and an aliphatic alcohol; and optionally (iii) an oil field additive wherein the liquid treatment composition is stable and flowable at a temperature within a range of about -40 °C to about 80 °C.

2. The liquid treatment composition according to claim 1 , wherein the solvent package comprises at least an aromatic solvent.

3. The liquid treatment composition according to claim 2, wherein the solvent package further comprises an alcohol.

4. The liquid treatment composition according to claim 1 , wherein the liquid treatment comprises at least about 45% by weight of the solvent package, where the % by weight is based on the total weight of the liquid treatment composition.

5. The liquid treatment composition according to claim 4, wherein the liquid treatment composition comprises less than about 95% by weight of the solvent package, where the % by weight is based on the total weight of the liquid treatment composition.

6. The liquid treatment composition according to claim 1 , wherein the liquid treatment composition is substantially free of a paraffinic hydrocarbon solvent.

7. The liquid treatment composition according to claim 1 , wherein the chemical treatment agent comprises from about 0.1 % by weight to about 10% by weight of the strong acid, from about 5% by weight to about 80% by weight of the fatty acid, from about 0.1 % by weight to about 20% by weight of the amine, from about 2% by weight to about 30% by weight of the oxidizing agent and from about 0.1 % by weight to about 30% by weight of the aliphatic alcohol, where the % by weight is based on the total weight of the chemical treatment agent.

8. The liquid treatment composition according to claim 7, wherein the liquid treatment composition comprises at least about 10% by weight of the chemical treatment agent, where the % by weight is based on the total weight of the liquid treatment composition.

9. The liquid treatment composition according to claim 8, wherein the liquid treatment composition comprises less than about 45% by weight of the chemical treatment agent, where the % by weight is based on the total weight of the liquid treatment composition.

10. The liquid treatment composition according to claim 1 , further comprising one or more of an anionic surfactant, a cationic surfactant, a pour point depressant and a paraffin inhibitor.

1 1 The liquid treatment composition according to claim 1 , wherein the liquid treatment composition has a pour point that is at least 2°C lower than a composition comprising the chemical treatment agent in the absence of the solvent package

12. A packaged product comprising: a) a container having at least an outlet; and b) a liquid treatment composition according to claim 1.

13. The packaged product according to claim 12, wherein the liquid treatment composition is freeze-thaw stable at a temperature as low as about -40 °C.

14. A method for winterizing or freeze protecting a chemical treatment agent comprising admixing the chemical agent comprising a mixture of a strong acid, a fatty acid, an amine, an oxidizing agent and an aliphatic alcohol with a solvent package comprising a mixture of two or more of: an aromatic solvent; an alcohol; a saturated hydrocarbon solvent; an ether solvent; a ketone solvent; a glycol solvent; an ester solvent; an aldehyde solvent; a nitrogen-containing solvent; a sulfur-containing solvent and a terpene solvent and optionally one or more oil field additives to form a treatment composition wherein the treatment composition remains liquid and flowable at a temperature as low as about -40 °C to about 80 °C.

15. The method according to claim 14, wherein the liquid treatment composition has a pour point that is at least 3°C lower than the pour point of the chemical treatment agent.

16. A method comprising: storing a liquid treatment composition according to claim 1 in an enclosed container at a first temperature between about -40 °C and about 60 °C; removing the liquid treatment composition from the container at a second temperature between about -40 °C and about 60 °C; and applying the liquid treatment composition to a hydrocarbon composition.

17. A method for improving the cold flow properties of a hydrocarbon composition comprising adding an effective amount of a liquid treatment composition according to claim 1 to the hydrocarbon composition.

18. The method according to claim 17, wherein the liquid treatment composition is added to the hydrocarbon composition after the hydrocarbon composition has been extracted from a well in a subterranean formation.

19. The method according to claim 18, wherein the liquid treatment is added to the hydrocarbon composition by batch treatment, continuous injection, squeezing or any combination thereof.

20. The method according to claim 17, wherein the effective amount of the liquid treatment composition that is added to the hydrocarbon composition is at least about 100 ppm.

21. The method according to claim 20, wherein the effective amount of the liquid treatment composition that is added to the hydrocarbon composition is at least about 1000 ppm.

22. The method according to claim 17, wherein the effective amount of the liquid treatment composition that is added to the hydrocarbon composition is between about 100 ppm to about 20,000 ppm.

23. The method according to claim 17, wherein the effective amount of the liquid treatment composition that is added to the hydrocarbon composition is between about 500 ppm to about 5000 ppm.

24. A method comprising adding an effective amount of a liquid treatment composition according to claim 1 to a hydrocarbon composition to form a treated hydrocarbon composition and subjecting the treated hydrocarbon composition to a temperature between about -40 °C to about 80 °C.

25. The method according to claim 24, further comprising the step of conveying the treated hydrocarbon composition through a flowline, a pipeline, a capillary string, an umbilical, an annulus, a pump, a valve, a flowmeter, a pressure gauge, a heat exchanger, a separator or any combination thereof.

26. A method for recovering crude oil from a subterranean formation having at least one well penetrating the formation and in fluid communication therewith, comprising the steps of: (a) injecting into the well and the formation an effective amount of a liquid treatment composition according to claim 1 ; (b) allowing the liquid treatment composition to disperse into the formation; and (c) recovering the crude oil.

27. A method for reducing the viscosity of a hydrocarbon composition in a significantly non-reversible manner, comprising the steps of: adding an effective amount of the liquid treatment composition according to claim 1 to the hydrocarbon composition, and dispersing the liquid treatment composition throughout a portion of the hydrocarbon composition.

28. The method according to claim 27, wherein the hydrocarbon composition comprises crude oil.

29. The method according to claim 28, wherein the viscosity of the crude oil is reduced by an amount in a range between about 1 % to about 60%, based on a viscosity of the crude oil prior to treatment with the liquid treatment composition.

30. A method for inhibiting paraffin wax and/or asphaltene precipitate blockage in a flowline transporting a hydrocarbon composition comprising paraffin and asphaltene, the method comprising the steps of adding an effective amount of a liquid treatment composition according to claim 1 to the hydrocarbon composition to produce a treated hydrocarbon composition; and transporting the treated hydrocarbon composition through the flowline under conditions conducive for formation of paraffin wax and/or asphaltene precipitate in the hydrocarbon composition whereby paraffin wax and/or asphaltene precipitate is inhibited from forming within the flowline by the addition of the liquid treatment composition.

31 . A system for preventing the formation of paraffin wax and/or asphaltene precipitate blockage in a flowline comprising: a flowline configured for connection with a well penetrating a subterranean formation and operable for transporting a hydrocarbon composition obtained from the well, and an injection conduit fluidly connected to the flowline and configured for adding a liquid treatment composition according to claim 1 to the flowline wherein the injection conduit is fluidly connected to a liquid treatment composition source comprising the liquid treatment composition.

32. The system according to claim 31 , wherein the liquid treatment composition source is a storage tank, drum or vessel.

33. A method of modifying the behavior of paraffin and/or asphaltene in a hydrocarbon composition, the method comprising the steps of: adding to the hydrocarbon composition comprising paraffin and asphaltene an effective amount of a liquid treatment composition according to claim 1 to modify the behavior of paraffin and/or asphaltene therein, wherein the modification of paraffin and/or asphaltene behavior is at least one of: inhibiting or preventing the deposition of paraffin and/or asphaltene; modifying the crystal structure of the paraffin; lowering the viscosity of the hydrocarbon composition; lowering the pour point of the hydrocarbon composition; lowering the cloud point of the hydrocarbon composition; and dispersing the paraffin and/or asphaltene in the hydrocarbon composition, as compared to the paraffin and/or asphaltene behavior in the absence of the liquid treatment composition.

Description:
WINTERIZED MATURING AGENT, VISCOSITY REDUCER AND

PRODUCTION ENHANCER

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] Not applicable.

FIELD

[0002] The present disclosure generally relates to a liquid treatment composition which remains stable and flowable at temperatures ranging from about -40 °C to about 80 °C. In particular, the liquid treatment composition generally includes a solvent package and a chemical treatment agent and is useful in various applications, including, but not limited to, the production, improved recovery and processing of light, medium, heavy and extra-heavy crude oil.

BACKGROUND

[0003] Crude oil produced from subterranean formations typically contains many kinds of hydrocarbons, including paraffins and asphaltenes. Paraffin is a common name for a group of alkane hydrocarbons having the general formula C n H2n + 2, where n is the number of carbon atoms. Paraffins are divided into three groups: gases at room temperature (the lowest carbon number alkanes, CrC 4 ), liquids at room temperature (intermediate carbon number alkanes, C 5 -Ci 7 ), and solids at room temperature (paraffin wax, the heaviest alkanes, Ci 8 and above). At low temperatures (or at temperatures below the melting point for respective alkanes), long-chained alkanes are known to crystallize and form large wax crystals having a sponge-like structure. Other constituents of the paraffin-containing crude oil can also be trapped in the crystal structures which can lead to a faster growth of the wax network. The wax crystals may agglomerate or mass together, leading to their deposition in well bores, tubing, pipelines and/or the associated production equipment through which the crude oil must pass when extracted from the well during recovery. Furthermore, the formation of a solid wax phase leads to an increased viscosity, which means that the crude oil becomes significantly more difficult to handle.

[0004] In comparison, asphaltenes are present in the oil phase of crude oil as micellar colloids, the individual micelles consisting of several different molecules. The micelles differ in size according to the temperature and composition of the oil phase. For example, it is known that lighter aromatic hydrocarbons in crude oil stabilize the asphaltene micelles. However, asphaltenes are often precipitated under production conditions which results in the formation of highly viscous, wax-like to solid residues on the oil-containing formation surrounding the well, and also on the surfaces of the production equipment resulting in a considerable reduction in the production rate.

[0005] Removal and/or inhibition of paraffin wax and asphaltene residue is typically attempted using various mechanical and/or thermal methods. These remedial methods include pigging or scraping, insulating equipment and flow lines to prevent loss of heat, or applying heat by means of a heated liquid (for e.g., hot oil or hot water). In addition, chemical methods are often used, such as the incorporation of chemical additives (so-called flow improvers), which interact with the precipitating asphaltenes and paraffin wax, resulting in the modification of their shape, size and adhesion properties, for example:

U.S. Pat. No. 9,045,676 which discloses a mixture of fatty acid esters that allows asphaltenes to remain in suspension and/or dissolve in heavy crude oil;

WO 2017/120455 which discloses the use of a solvent and an alkoxylated phenol-formaldehyde to reduce the viscosity of heavy and extra heavy crude oil;

U.S. Pat. Publ. No. 2016/0102267 which discloses a mixture of a water soluble anionic surfactant and a non-aromatic solvent and its use as a crude oil friction reducer; U.S. Pat. Publ. No. 2016/0102241 which discloses the use of phosphoglycerides and vegetable oil to reduce the viscosity of heavy and extra heavy crude oil;

U.S. Pat. Publ. No. 2016/0046855 which discloses the use of a quaternary ammonium salt to control the deposition of asphaltenes in crude oil;

U.S. Pat. No. 8,529,687 which discloses the use of an oxidizing agent to oxidize asphaltenes that have been separated from an asphaltene-containing composition;

U.S. Pat. Nos. 8,287,721 and 5,152,886 which disclose the use of HCI and oleic acid to reduce the content of asphaltenes and paraffin wax in crude oil;

U.S. Pat. No. 8,022,1 18 which discloses a high molecular weight polymer dispersed in an aqueous phase and its use in improving the flow properties of crude oil in a pipeline;

U.S. Pat. Publ. No. 2006/0035793 which discloses a non-aqueous composition containing a phosphate plasticizing agent, fatty acids and surfactants for use in liquefying and dissolving paraffin wax and asphaltenes in crude oil;

U.S. Pat. No. 6,31 1 ,367 which discloses the use of various ester and ether reaction products to disperse asphaltenes in crude oil; and

Can. Pat. App. No. 2,424,903 which discloses the use of a product formed from the reaction of an amine and a carboxylic, phosphonic or sulfonic acid to disperse asphaltenes in crude oil;

Although effective at temperatures above freezing, many of the additives used in chemical methods to modify the properties of paraffin wax and asphaltenes will solidify at lower temperatures, such as -20 °C, and are therefore not particularly useful in the field when exposed to winter conditions. SUMMARY

[0006] The present disclosure is generally directed to a liquid treatment composition that is stable and flowable at temperatures ranging from about -40 °C to about 80 °C comprising a solvent package, a chemical treatment agent and optionally one or more oil field additives.

[0007] The liquid treatment composition of the present disclosure may be used in various methods and applications, including but not limited to: reducing the viscosity of a hydrocarbon composition; reducing the pour point of a hydrocarbon composition; reducing the cloud point of a hydrocarbon composition; reducing the amount and/or size of paraffin wax and/or asphaltene precipitates in a hydrocarbon composition; extracting a hydrocarbon composition from a subterranean formation and enhancing the recovery of such hydrocarbon composition; or cleaning and washing a hydrocarbon composition-producing well, transport line or production equipment that comes in contact with a hydrocarbon composition wherein the well, transport line or process equipment comprises organic residue (for e.g. deposited paraffin wax and/or asphaltenes).

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 depicts the dynamic viscosity of treated and untreated crude oil samples obtained from a production formation;

[0009] Figure 2 depicts the sodium and calcium concentration of treated and untreated crude oil samples obtained from a production formation; and

[0010] Figure 3 depicts the dynamic viscosity of treated and untreated crude oil samples obtained from a production formation.

DETAILED DESCRIPTION

[0011] It has surprisingly been found when a particular solvent package is combined with a particular chemical treatment agent to form a liquid treatment composition according to the present disclosure, the liquid treatment composition remains stable and flowable at a range of temperatures, including temperatures significantly below freezing, thus allowing the liquid treatment composition to be used in a variety of conditions, such as, during winter conditions. In addition, it has surprisingly been found when the liquid treatment composition of the present disclosure is added to a hydrocarbon composition to form a treated hydrocarbon composition, the treated hydrocarbon composition can exhibit one or more enhanced properties, such as, but not limited to, a lower viscosity, a lower amount of asphaltene and/or paraffin wax precipitate, a lower amount of condensate salts, a lower pour point, a lower cloud point, the ability to flow at temperatures from about -40 °C to about 80 °C, and an improved maturation over time. It could not have been predicted that the addition of the solvent package to the chemical treatment agent to form a liquid treatment composition or the addition of the liquid treatment composition to a hydrocarbon composition would have such a beneficial combination of physical and performance properties. Such a combination of properties is believed to be unexpected in the art, since it is generally known that desirable improvements in one property often result in a concomitant undesirable reduction in one or more other properties. In any event, rarely do two properties that have some sort of correlation in a composition of matter both desirably get better with changes in that composition of matter, rather, the properties are usually trade-offs.

[0012] The following terms shall have the following meanings:

[0013] If appearing herein, the term "comprising" and derivatives thereof are not intended to exclude the presence of any additional component, step or procedure, whether or not the same is disclosed herein. In order to avoid any doubt, all compositions claimed herein through use of the term "comprising" may include any additional additive, adjuvant, or compound, unless stated to the contrary. In contrast, the term, "consisting essentially of" if appearing herein, excludes from the scope of any succeeding recitation any other component, step or procedure, except those that are not essential to operability and the term "consisting of", if used, excludes any component, step or procedure not specifically delineated or listed. The term "or", unless stated otherwise, refers to the listed members individually as well as in any combination.

[0014] The articles "a" and "an" are used herein to refer to one or to more than one (i.e. to at least one) of the grammatical objects of the article. The phrases "in one embodiment", "according to one embodiment" and the like generally mean the particular feature, structure, or characteristic following the phrase is included in at least one embodiment of the present disclosure, and may be included in more than one embodiment of the present disclosure. Importantly, such phrases do not necessarily refer to the same embodiment. If the specification states a component or feature "may", "can", "could", or "might" be included or have a characteristic, that particular component or feature is not required to be included or have the characteristic.

[0015] The term "about" as used herein can allow for a degree of variability in a value or range, for example, it may be within 10%, within 5%, or within 1 % of a stated value or of a stated limit of a range.

[0016] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but to also include all of the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range from 1 to 6, should be considered to have specifically disclosed sub-ranges, such as, from 1 to 3 or from 2 to 4 or 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.

[0017] In the methods and processes described herein, the steps may be carried out in any order, except when a temporal or operational sequence is explicitly recited. Furthermore, specified steps may be carried out concurrently unless explicit claim language recites that they be carried out separately. [0018] The term "hydrocarbon composition" refers to a composition comprising at least one liquid hydrocarbon compound. The hydrocarbon composition can include a composition having compounds comprising only hydrogen and carbon and compounds comprising other elements in addition to hydrogen and carbon. Thus, the term "hydrocarbon composition" is not intended to describe compositions comprising only hydrocarbons. For example, crude oil, crude oil condensate and the various streams which are produced during extraction of hydrocarbon compounds from subterranean formations as well as crude oil distillate, residual fuel or residual oil all fall within the definition of hydrocarbon composition even though these compositions can contain compounds comprising elements in addition to hydrogen and carbon.

[0019] The term "crude oil" denotes all types of mineral oils found in nature. Crude oil includes oils obtained from wells, shale, rock and/or sand among others. The proportion of hydrocarbon compounds in crude oil can vary, for instance, from about 5% by weight to almost 100% by weight, based on the total weight of the crude oil, and comprises many different molecules that can be grouped into four families of compounds: saturates aromatics, resins and asphaltenes. Saturates generally constitute the lightest fraction of the crude oil, while Ci 8+ long-chain linear paraffins represent the heavy fraction of the crude oil. Crude oil can further be classified as super light, light, medium, heavy or extra heavy which refers to the oil’s relative density based on the American Petroleum Institute (API) Gravity.

[0020] The term "crude oil distillate" refers to any distillation overhead product, be it a fuel, oil, and/or some other product, obtained from the distillation (atmospheric or subatmospheric) of crude oil or refined crude oil. Crude oil distillates also include fuels, oils, or other products that have been obtained from the distillation of crude oil or from the thermal cracking and/or catalytic cracking of crude oil. Other processes which can be practiced on the crude oil during or prior to obtaining the crude oil distillate include solvent extraction, caustic treating, acid treating, dewaxing, desulfurizing, and reforming among other crude oil refining processes.

[0021] The term "residual oil" and "residual fuel" refers to any products, be it fuel or oil, at least partially composed of residual components, or residues, from the distillation (atmospheric or subatmospheric) of crude oil and/or refined crude oil. The terms "residual oil" and "residual fuel" also includes fuels, oils, and other products that have been obtained from the distillation of thermally and/or catalytically cracked crude oil. Other processes which can be practiced on the crude oil during or prior to obtaining the residual fuel or residual oil include solvent extraction, caustic treating, acid treating, dewaxing, desulfurizing, and reforming among other crude oil refining processes.

[0022] Parameters, such as pour point and cloud point (or wax appearance temperature), are often used to measure the flowability and wax precipitate formation properties of various compositions. Pour point (ASTM D-97) is defined as the lowest temperature at which a material will flow when chilled without disturbance under specified conditions while the cloud point (ASTM D-2500) is the temperature at which precipitates first appear as a haze in a material upon cooling. A material's pour point indicates the temperature at which (if not before) the formation of solid or semi-solid precipitate particles can begin to affect the flowability and/or pumpability of these materials under low temperature conditions making their transport and pumping difficult if not near impossible. A material's cloud point indicates the temperature at which the waxy constituents having the lowest solubility (typically those having the highest molecular weight) begin to precipitate. [0023] The term“substantially free” refers to a composition or mixture in which a particular compound is present in an amount that has no material effect on the composition or mixture. In some embodiments, substantially free may be less than 2% by weight or less than 1 % by weight or less than 0.5% by weight or less than 0.1 % by weight or less than 0.05% by weight or even less than 0.01 % by weight, based on the total weight of the composition. In some embodiments, substantially free means the particular compound is not present in any amount in the respective composition (i.e. 0.0 % by weight, based on the total weight of the respective composition).

[0024] The term“inhibiting” is used herein in a broad and general sense to mean any improvement in preventing, controlling, delaying, reducing or mitigating the formation or growth of asphaltene and/or paraffin wax precipitates in any manner, including, but not limited to, kinetically, thermodynamically, by dissolution, by breaking up or any combination thereof. Although the term“inhibiting” is not intended to be restricted to the complete cessation of asphaltene and/or paraffin wax precipitate formation, it may include the possibility that formation of any asphaltene and/or paraffin wax precipitate is entirely prevented.

[0025] The term "enhanced" refers to an improvement or increase over an original observation or function.

[0026] The term "effective amount" refers to that amount of a composition necessary to bring about a desired result, for example, the amount needed to reduce the viscosity of heavy crude oil.

[0027] The term“optional” or“optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the phrase “the composition may optionally comprise an oil field additive” means that the oil field additive may or may not be included in the composition and that the description includes both a composition that includes an oil field additive and a composition that does not include an oil field additive. [0028] The term “liquid”, “flows”, “flowable” or "flow" when referring to a composition of the present disclosure means that 10 mL of the composition vertically at rest on a substantially horizontal surface in a cylindrical container having dimensions of radius 1 inch and height 2 inches flows observably within about 10 seconds when tipped to a substantially horizontal position. In some embodiments, "liquid”,“flows”,“flowable” or“flow” when referring to a composition of the present disclosure means a composition that has a Brookfield viscosity at 10s 1 of about 5 cP to 1000 cP.

[0029] The term "stable", "freeze-thaw stable" or the like indicates that the composition being discussed is not subject to phase separation for an extended period of time (for e.g. at least 1 hour or at least 6 hours or at least 12 hours, or at least 24 hours, or at least 2 weeks, or at least 1 month, or at least 6 months, or at least one year) and/or passes the hereinafter set forth freeze-thaw test.

[0030] According to one embodiment, the present disclosure provides a liquid treatment composition comprising a solvent package and a chemical treatment agent. The solvent package may include a mixture of two or more of: an aromatic solvent; an alcohol; a saturated hydrocarbon solvent; an ether solvent; a ketone solvent; a glycol solvent; an ester solvent; an aldehyde solvent; a nitrogen-containing solvent; a sulfur-containing solvent and a terpene solvent.

[0031] In one embodiment, the solvent package may comprise an aromatic solvent. The aromatic solvent may be a monoaromatic solvent, a polycyclic aromatic solvent or a mixture thereof. Examples of monoaromatic solvents include benzene and alkylbenzenes where the alkyl substituents can have 1 to about 10 carbon atoms, such as, but not limited to, mesitylene, 1 ,2,4-trimethylbenzene, tetramethylbenzene, ethylbenzene, n-propylbenzene, i-propylbenzene, n- butylbenzene, s-butylbenzene, i-butylbenzene, t-butylbenzene, n-pentylbenzene, n- hexylbenzene, n-heptylbenzene, n-octylbenzene, n-nonylbenzene, n-decylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1 ,2,4-triethylbenzene, 1 ,3,5- triethylbenzene, tetraethylbenzene, o-ethylmethylbenzene, p-ethylmethylbenzene, m- ethylmethylbenzene, di-n-propylbenzene, di-i-propylbenzene, tri-n-propylbenzene, ethyl-n-propylbenzene, ethyl-i-propylbenzene, ethyl-n-propylbenzene, methyl-i- propylbenzene, methyl-n-propylbenzene, cyclohexylbenzene, tetralin, methyltetralin, indene and mixtures thereof. Examples of polycyclic aromatic solvents include, but are not limited to, naphthalene, alkylnaphthalenes where the alkyl substituents can have 1 to about 10 carbon atoms, such as, but not limited to, a-methylnaphthalene, b-methylnaphthalene, a-ethylnaphthalene, b-ethylnaphthalene, n-propylnaphthalene, and 1 ,4-dimethylnaphtalene, anthracene, phenanthrene, fluorene and mixtures thereof.

[0032] In another embodiment, the solvent package may comprise an alcohol. Examples of alcohols include, but are not limited to: straight chain or branched aliphatic alcohols, such as, but not limited to, methanol, ethanol, i-propanol, n- propanol, i-butanol, n-butanol, t-butanol, s-butanol, 3-methoxy-1 -butanol, n-pentanol, 3-methyl-1 -butanol, n-hexanol, n-heptanol, n-octanol, 2-ethyl-1 ,3-hexyldiol, 2-ethyl-1 - hexanol, n-nonylalcohol, n-decanol, isodecylalcohol, isotridecylalcohol, 4-hydroxy-4- methyl-2-pentanone, methylisobutylcarbinol, cyclopentanol, cyclohexanol, methylcyclohexanol, cyclohexenol, cyclohexylmethanol, tetrahydrofurfurylalcohol, furfuryl alcohol or mixtures thereof; and, aromatic alcohols such as, but not limited to, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3- xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 4-methoxyphenol, o-t-butylphenol, p-t- butylphenol, 2,4-di-t-butylphenol, 2,6-di-t-butylphenol, 2-methyl-6-t-butylphenol, o- phenylphenol, m-phenylphenol, p-phenylphenol, a-naphthol, b-naphthol, benzylalcohol or mixtures thereof; and mixtures of aliphatic and aromatic alcohols.

[0033] In another embodiment, the solvent package may comprise a saturated hydrocarbon solvent. Saturated hydrocarbon solvents include linear or branched C5- C20 alkane-based or unsubstituted or lower alkyl branched C5-C20 cycloalkane-based solvents and mixtures thereof. Examples include, but are not limited to, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, nonane, n-decane, n-undecane, n-dodecane, isododecane, n-tridecane, n- tetradecane, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, cyclohexene, cycloheptane, decalin, norbornane and mixtures thereof.

[0034] In another embodiment, the solvent package may comprise an ether solvent. Ether solvents can include aliphatic ether solvents, aromatic ether solvents and mixtures thereof. The aliphatic ether solvents include, but are not limited to, methyl-t-butyl ether, diethyl ether, propyl ether, isopropyl ether, dibutyl ether, diisoamyl ether, 2,2-dimethoxy propane, propyleneglycolmonomethyl ether, dioxane, 1 ,3-dioxolane, cyclohexeneoxide, 2,3-dihydropyrane, tetrahydrofuran, and tetrahydropyrane. The aromatic ether solvents can include, but are not limited to, anisole, ethoxyphenol, o-dimethoxybenzene, p-dimethoxybenzene, and benzyl ether.

[0035] In another embodiment, the solvent may comprise a ketone. The ketone solvent may be a Ci -5 alkyl-Ci- 5 alkyl ketone, diacetone alcohol, trimethyl heptanone, cyclohexanone, propiophenone, benzophenone and mixtures thereof. In another embodiment, the ketone solvent may also be a C 1 -3 alkyl-Ci_ 3 alkyl ketone, such as, but not limited to, acetone, methyl-ethyl ketone, methyl-n-propyl ketone, methyl- isopropyl ketone, methyl isobutyl ketone, methyl heptyl ketone, diethyl ketone, ethyl- n-propyl ketone, ethyl-isopropyl ketone, di-n-propyl ketone, di-isopropyl ketone, n- propyl-isopropyl ketone, diisobutyl ketone, methyl isoamyl ketone and methyl amyl ketone.

[0036] In another embodiment, the solvent package may comprise a glycol solvent. Examples of glycol solvents include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, ethyleneglycol dimethyl ether, ethyleneglycol mono-butylether, ethyleneglycol mono-t-butylether, propylene glycol, isoprene glycol, dipropylene glycol, tripropylene glycol, 1 ,3-butanediol, 1 ,4-butanediol, neopentyl glycol, 1 ,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1 ,5- pentanediol and mixtures thereof.

[0037] In another embodiment, the solvent package may comprise an ester solvent, including aliphatic ester solvents, aromatic ester solvents and mixtures thereof. The aliphatic ester solvents can include, but are not limited to, methyl formate, ethyl formate, n-butyl formate, n-propyl formate, methyl acetate, ethyl acetate, allyl acetate, isopropyl acetate, n-butyl acetate, n-propyl acetate, diethyl succinate, dimethyl succinate, dimethyl carbonate, propylene carbonate, diethyl oxalate, dimethyl oxalate, methyl lactate, ethyl lactate, butyl lactate, methyl pyruvate, ethyl pyruvate, dimethyl malonate, diethyl malonate, y-butyrolactone, propyleneglycolmonomethylether acetate, 3-methoxybutyl acetate, and 3-methoxy-3- methylbutyl acetate. The aromatic ester solvents can include, but are not limited to, diallyl isophthalate, dimethyl isophthalate, diethyl isophthalate, dimethyl terephthalate, diethyl terephthalate, methyl benzoate, ethyl benzoate, n-propyl benzoate, and n-butyl benzoate.

[0038] In another embodiment, the solvent package may comprise an aldehyde solvent. Examples of aldehyde solvents include aliphatic aldehyde solvents, such as acetaldehyde, propione aldehyde, and furfural, and aromatic aldehyde solvents, such as benzaldehyde, and mixtures thereof.

[0039] In another embodiment, the solvent package may comprise a nitrogen- containing solvent. Such nitrogen-containing solvents may include aliphatic nitrogen- containing solvents, aromatic nitrogen-containing solvents and mixtures thereof. The aliphatic nitrogen-containing solvents include, but are not limited to, acetonitrile, amyl acetate, acetic acid amide, N,N-diisopropylethyl amine, cyclohexylamine, N,N- dimethylacetamide, N,N-dimethylformamide, and imidazole. The aromatic nitrogen- containing solvents include, but are not limited to, o-anisidine, p-anisidine, m- anisidine, aniline, p-aminoacetanilide, o-aminophenol, m-aminophenol, p- aminophenol, o-toluidine, m-toluidine, p-toluidine, N-methylaniline, N,N- dimethylaniline, N-ethylaniline, N,N-diethylaniline, diphenylamine, N,N-dimethyl-p- toluidine, pyridine, and quinoline.

[0040] In another embodiment, the solvent package may comprise a sulfur- containing solvent, including aliphatic sulfur-containing solvents, aromatic sulfur- containing solvents and mixtures thereof. The aliphatic sulfur-containing solvents include, but are not limited to, dimethyl sulfoxide and thiodiglycol. The aromatic sulfur-containing solvents include, but are not limited to, diphenylsulfide, diphenylsulfone, and benzylmercaptan.

[0041 ] In another embodiment, the solvent package may comprise a terpene solvent. Examples of terpene solvents include, but are not limited to, pinene isomers comprising one or more of the following structures:

(lR)-(+)-a- (lSM-)-a- (lR)-(+)-P- (ISH-)-p- pinene pinene pinene pinene

terpineol comprising one or more of the following structures:

a-terpineol, b-terpmeol g-terpineol , 4-terpineol ; D-limonene having the formula:

dipentene; pine oil and mixtures thereof.

[0042] In one particular embodiment, the liquid treatment composition is substantially free of a paraffinic hydrocarbon solvent. Paraffinic hydrocarbon solvents may include one or more petroleum distillates having boiling points above 130°C. For example, the paraffinic hydrocarbon may include one or more mineral spirits, kerosene, naphtha, diesel fuels, gas oils, fuel oils or any combination thereof.

[0043] According to one particular embodiment, the solvent package comprises an aromatic solvent and at least one of an alcohol, a saturated hydrocarbon solvent, an ether solvent, a ketone solvent, a glycol solvent, an ester solvent, an aldehyde solvent, a nitrogen-containing solvent, a sulfur-containing solvent and a terpene solvent. In such embodiments, the solvent package may comprise at least about 10% by weight, or at least about 20% by weight, or at least about 30% by weight, or at least about 40% by weight or at least about 50% by weight or at least about 60% by weight or at least about 70% by weight, or even at least about 80% by weight of the aromatic solvent, where the % by weight is based on the total weight of the solvent package. In other embodiments, the solvent package may comprise less than about 95% by weight, or less than about 85% by weight, or less than about 75% by weight, or less than about 45% by weight, or less than about 25% by weight or even less than about 10% by weight of the aromatic solvent, where the % by weight is based on the total weight of the solvent package. [0044] According to another embodiment, the solvent package may comprise an aromatic solvent, an alcohol and optionally a glycol. In one embodiment, the solvent package may comprise:

(i) about 50%-99% by weight, or about 55%-95% by weight or about 60%-90% by weight, or about 65%-85% by weight of the aromatic solvent,

(ii) about 1 %-50% by weight, or about 5%-45% by weight, or about 10%-40% by weight, or about 15%-35% by weight of the alcohol, and

(iii) 0-10% by weight, or about 0.5%-5% by weight of the glycol, where the % by weight is based on the total weight of the solvent package.

[0045] In one embodiment, the liquid treatment composition may include at least about 45% by weight of the solvent package, where the % by weight is based on the total weight of the liquid treatment composition. In other embodiments, the liquid treatment composition may include at least about 50% by weight, or at least 60% by weight or at least 70% by weight, or at least 80% by weight or even at least 85% by weight of the solvent package, where the % by weight is based on the total weight of the liquid treatment composition. In further embodiments, the liquid treatment composition may include less than about 99% by weight of the solvent package, where the % by weight is based on the total weight of the liquid treatment composition. In still other embodiments, the liquid treatment composition may include less than about 90% by weight, or less than about 80% by weight, or less than about 70% by weight, or less than about 60% by weight or even less than about 50% by weight of the solvent package, where the % by weight is based on the total weight of the liquid treatment composition.

[0046] The liquid treatment composition of the present disclosure also includes a chemical treatment agent which is the active ingredient in the liquid treatment composition. According to one embodiment, the chemical treatment agent comprises a mixture of a strong acid, a fatty acid, an amine, an oxidizing agent and an aliphatic alcohol. One example of such a chemical treatment agent is described in WO 2016/089230, the contents of which are incorporated herein by reference.

[0047] In one embodiment, the strong acid may be an acid that dissociates completely in an aqueous solution with a pH£2. The strong acids which may be used include, but are not limited to: sulphuric acid (H 2 S0 4 ), hydrohalogenic acid (i.e. HX" wherein X" is I, Br, Cl or F), nitric acid (HN0 3 ), phosphoric acid (H 3 P0 4 ) and combinations thereof. In one embodiment, the strong acid is a mixture of HCI and H 3 P0 4 .

[0048] In one embodiment, the fatty acid may be a straight chain or branched saturated, mono-unsaturated or poly-unsaturated fatty acid and can include between about 14 and about 30 carbon atoms. Examples of fatty acids include, but are not limited to, myristic acid (C14), pentadecylic acid (C15), palmitic acid (C16), palmitoleic acid (C16), stearic acid (C18), isostearic acid (C18), oleic acid (C18), vaccenic acid (C18), linoleic acid (C18), alpha-linolenic acid (C18), gamma-linolenic acid (C18), arachidic acid (C20), gadoleic acid (C20), arachidonic acid (C20), eicosapentaenoic acid (C20), behenic acid (C22), erucic acid (C22), docosahexaenoic acid (C22), lignoceric acid (C24) and hexacosanoic acid (C26), heptacosylic acid (C27), montanic acid (C28), nonacocylic acid (C29), melissic acid (C30) and mixtures thereof.

[0049] In one embodiment, the amine may be an organic amine, such as, but not limited to, triethylamine, isopropyl ethylamine, diisopropyl amine, diisopropylethyl amine tributyl amine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and piperidine, pyridine, a quaternary ammonium salt of the general formula Ri R 2 R 3 R NOhr (where R r R 4 each independently represent a C r C 3 straight-chain alkyl group), including, but are not restricted to, tetramethylammonium hydroxide, trimethylethylammonium hydroxide and dimethyldiethylammonium hydroxide and mixtures thereof.

[0050] In one embodiment, the oxidizing compound may be a persulfate compound, peroxy acid, permanganate compound, periodic acid, ozone, and derivatives and combinations thereof. Examples of oxidizing agents include, but are not limited to, potassium permanganate, cerium compounds, chromate compounds, dichromate compounds, peroxide compounds, ozone, tetroxide compounds, nitrate compounds, nitrite compounds, persulfate compounds, peroxy acids, halogen- containing compounds (e.g., hypochlorite, chlorite, chlorate, perchlorate and analogous halogen-containing compounds) and derivatives and combinations thereof

[0051] In one embodiment, the aliphatic alcohol may be a linear or branched, saturated or unsaturated, short chain or long chain, aliphatic alcohol or mixture thereof. Examples of short chain aliphatic alcohols include, but are not limited to, methanol, ethanol, n-propanol, n-butanol, iso-, sec- and tert-butanol, pentanol and hexanol. Examples of long chain aliphatic alcohols include, but are not limited to, saturated alcohols such as palmityl, hexadecyl, stearyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl and triacontyl alcohols, as well as oleyl alcohol and branched alcohols such as oxo alcohols, for example, 2-methyl eicosyl alcohol and unsaturated alcohols such as palmitoleyl alcohol, hexadecenoyl alcohol, oleyl alcohol, linolenyl alcohol, linoleyl alcohol, ricinoleyl, octadecenoyl alcohol, docosenyl alcohol, arachidonyl alcohol and tetracosenyl alcohol.

[0052] In one embodiment, the chemical treatment agent includes from about 0.1 % by weight to about 10% by weight of a strong acid, from about 5% by weight to about 80% by weight of a fatty acid, from about 0.1 % by weight to about 20% by weight of an amine, from about 2% by weight to about 30% by weight of an oxidizing agent and from about 0.1 % by weight to about 30% by weight of an aliphatic alcohol, where the % by weight is based on the total weight of the chemical treatment agent.

[0053] In one embodiment, the liquid treatment composition may include at least about 5% by weight of the chemical treatment agent, where the % by weight is based on the total weight of the liquid treatment composition. In other embodiments, the liquid treatment composition may include at least about 10% by weight, or at least about 15% by weight, or at least about 20% by weight, or at least about 25% by weight, or at least about 30% by weight, or at least about 35% by weight or even at least about 40% by weight of the chemical treatment agent, where the % by weight is based on the total weight of the liquid treatment composition. In still other embodiments, the liquid treatment composition may include less than about 45% by weight, or less than 40% by weight, or less than about 30% by weight, or less than 20% by weight of the chemical treatment composition, where the % by weight is based on the total weight of the liquid treatment composition.

[0054] According to another embodiment, the liquid treatment composition may include the solvent package and the chemical treatment agent at a ratio of about 90 parts by weight solvent package:about 10 parts by weight chemical treatment agent to about 55 parts by weight solvent package:about 45 parts by weight chemical treatment package. In another embodiment, the liquid treatment composition may include the solvent package and the chemical treatment agent at a ratio of about 85 parts by weight solvent package:about 15 parts by weight chemical treatment agent to about 60 parts by weight solvent package:about 40 parts by weight chemical treatment agent.

[0055] In addition to the solvent package and chemical treatment agent, the liquid treatment composition may include one or more oil field additives typically used in connection with oil and gas production including: a cationic surfactant, an anionic surfactant, a pour point depressant, a paraffin inhibitor, an asphaltene inhibitor, an emulsifier, a demulsifier, a dispersing agent, a corrosion inhibitor, a scale inhibitor, a C0 2 scavenger, a hydrogen sulfide scavenger, an oxygen scavenger, a lubricating agent, a dehazer, a cetene number improver, a weighting agent, a fluoride, a fluid loss control additive, gas, nitrogen, carbon dioxide, a surface modifying agent, a tackifying agent, a foamer, a catalyst, a clay control agent, a biocide, a friction reducer, an antifoam agent, a bridging agent and a flocculant. When present, the one or more oil field additives may be included in the liquid treatment composition in an amount from about 0.01 % by weight to about 20% by weight, or from about 0.1 % by weight to about 10% by weight, or from about 0.5% by weight to about 5% by weight or from about 1 % by weight to about 3% by weight, where the % by weight is based on the total weight of the liquid treatment composition. [0056] Examples of cationic and anionic surfactants include, but are not limited to, quaternary ammonium compounds, oxy and ethoxylated amines, linear diamines, amide, ester and ether-amines, alkanol amides, and amino acids, alkyl ether sulfates, sulfated alkanolamides, glyceride sulfates, alky benzenesulphonic acids and their salts, a-olefin sulphonates, lignosulphonates, and phosphate esters.

[0057] Examples of pour point depressants include, but are not limited to, an ethylene-unsaturated ester copolymer; a comb polymer; a polar nitrogen compound; a sulphur carboxy compound; a hydroxylated aromatic compound and mixtures thereof.

[0058] In one embodiment, the liquid treatment composition can comprise a paraffin inhibitor and/or asphaltene inhibitor known in the art, such as, an aliphatic sulphonic acid, an alkyl aryl sulphonic acid, an aryl sulfonate, lignosulfonate, an alkylphenol/aldehyde resin and similar sulfonated resin, a polyolefin ester, a polyolefin imide, a polyolefin ester with alkyl, alkylenephenyl or alkylenepyridyl functional groups, a polyolefin amide, a polyolefin amide with alkyl, alkylenephenyl or alkylenepyridyl functional groups, a polyolefin imide with alkyl, alkylenephenyl or alkylenepyridyl functional groups, an alkenyl/vinyl pyrrolidone copolymer, a graft polymer of polyolefins with maleic anhydride or vinyl imidazole, a hyperbranched polyester amide, a polyalkoxylated asphaltene, an amphoteric fatty acid, a salt of an alkyl succinate, sorbitan monooleate, polyisobutylene succinic anhydride, an alkyl acrylate copolymer, an alkyl acrylate vinylpyridine copolymer, an ethylene vinyl acetate copolymer, a maleic anhydride ester copolymer, a branched polyethylene, dodecyl benzene sulfonate, an oxyalkylated alkylphenol, and an oxyalkylated alkylpnenolic resin. In other embodiments, the liquid treatment composition is substantially free of such paraffin inhibitors and/or asphaltene inhibitors.

[0059] The liquid treatment composition of the present disclosure may be prepared by admixing the maximum amount of chemical treatment agent with the solvent package (and optional oil field additive(s)) that can be maintained in a flowable state at the intended use temperatures and pressures. The liquid treatment compositions of the present disclosure can be prepared by admixing the components of the liquid treatment composition together at ambient conditions or such mixing can be done at reduced or elevated temperatures. The admixing can be done using active stirring or static mixers. In some embodiments, the chemical treatment agent may be heated and homogenized before being admixed with the solvent package (and optional oil field additive(s)). In other embodiments, once the solvent package, chemical treatment agent (and optional oil field additive(s)) have been admixed, the mixture may be homogenized.

[0060] According to one embodiment, the liquid treatment composition may include from about 45% by weight to about 99% by weight of the solvent package, from about 1 % by weight to about 55% by weight of the chemical treatment agent and from 0 to about 20% by weight of the oil field additive(s), where the % by weight is based on the total weight of the liquid treatment composition. In other embodiments, the liquid treatment composition may include: from about 50% by weight to about 97.5% by weight, or from about 55% by weight to about 95% by weight, or from about 60% by weight to about 90% by weight, or from about 65% by weight to about 85% by weight of the solvent package; from about 2.5% by weight to about 50% by weight, or from about 5% by weight to about 45% by weight, or from about 10% by weight to about 40% by weight, or from about 15% by weight to about 35% by weight of the chemical treatment agent and from 0 to about 20% by weight of the oil field additive(s), where the % by weight is based on the total weight of the liquid treatment composition.

[0061] In another embodiment, there is provided a packaged product comprising: a) a container having at least an outlet; and b) a liquid treatment composition described above. In an additional embodiment, there is provided the packaged product and further where the liquid treatment composition is freeze-thaw stable when subjected to a temperature as low as about 0 °C, or as low as about -10°C, or as low as about -20 °C, or as low as about -30 °C or as low as about -35 °C or even as low as about -40 °C. [0062] In one embodiment, the packaged product of the present disclosure comprises a container having a closure means, such as a lid, cover, cap, or plug to seal the container. The sealed container may be a storage tank, drum or vessel and may have the shape of a cylinder, an oval, a circle, a rectangle, a canister, a tub or a square and contains the liquid treatment composition of the present disclosure.

[0063] According to another embodiment, the present disclosure provides a method for winterizing or freeze protecting the chemical treatment agent described above by admixing the chemical agent with the solvent package (and optionally one or more oil field additives) to form a liquid treatment composition wherein the liquid treatment composition remains liquid and flowable at a temperature as low as about - 40 °C to about 80 °C. The liquid treatment composition may also have a pour point that is at least 1 °C lower than the pour point of the chemical treatment agent, or it may have a pour point that is at least 2°C lower, or at least 3 °C lower, or at 4°C lower, at least 5°C lower, or at least 6°C or at least 7°C lower or at least 8°C or at least 10°C lower than pour point of the chemical treatment agent. In embodiments, the liquid treatment composition is stored or otherwise located in the container.

[0064] A principal benefit of the solvent package is its ability to allow the chemical treatment agent to be a stable mixture and flow at temperatures as low as about -40 °C. Such stable mixtures and flow properties facilitate pouring or pumping of the liquid treatment composition from a storage container, drum or vessel into contact with a hydrocarbon composition requiring treatment. Thus, in one embodiment, a method of the present disclosure includes storing the liquid treatment composition in an enclosed container at a first temperature between about -40 °C and about 60 °C; removing the liquid treatment composition from the container at a second temperature between about -40 °C and about 60 °C; and applying the liquid treatment composition to a hydrocarbon composition (for e.g. crude oil). In embodiments, the removing and the applying are accomplished using a mechanical pump and/or gravity. In some embodiments, the first temperature, the second temperature, or both are between about -40 °C and about 0 °C, or between about -40 °C to about -10°C, or between about -40 °C to about -20 °C, or between about -40 °C to about -30 °C. It will be understood that storing and removing are carried out over a variable range of temperatures, and in particular storage temperatures often vary during the storage period. The duration of storage may also vary from about 1 day to five years, such as about 2 days to 1 year, or about 1 week to 6 months, or about 2 weeks to 4 months, or about 1 to 2 months. Such storage may take place under various temperature conditions. Storage may take place under sustained temperature conditions for various durations. For example, storing may extend through the winter and/or summer season. Accordingly, storage may take place at about -40 °C to about 0°C for months (for e.g., 1 hour to 6 months or 1 week to 5 months) in some regions, or may take place at temperatures of as high as about 40 °C for months (for e.g., 1 hour to 7 months or 1 week to 3 months) in some regions. Thus, the first temperature of the method is suitably measured at any point during storage, wherein the temperature during at least some period of storage is within the stated range. In some embodiments the applying is sufficient to contact the hydrocarbon composition with about 10 ppm or more, or about 100 ppm or more of the liquid treatment composition, such as from about 100 ppm to 20,000 ppm of the liquid treatment, or from about 500 ppm to about 10,000 ppm of the liquid treatment composition, or from about 1000 ppm to about 5000 ppm of the liquid treatment composition.

[0065] Thus, according to another embodiment, the present disclosure provides a method for improving the cold flow properties of a hydrocarbon composition which comprises adding an effective amount of the liquid treatment composition to the hydrocarbon composition. “Cold flow properties” encompasses one or more performance properties such as, but not limited to, cloud point, pour point, viscosity, density, API gravity, shear behavior, etc. For example, after addition of the liquid treatment composition, the hydrocarbon composition may exhibit a significantly reduced viscosity and/or a lower point as compared to a hydrocarbon composition in the absence of the liquid treatment composition.

[0066] The liquid treatment composition described herein may be added to the hydrocarbon composition after its extraction from a well in a subterranean formation, prior to the hydrocarbon composition being extracted from the well, or a combination thereof. In one embodiment, the well is located underwater, for example, the well may be a deep water well located at least 1000 meters below the surface of the water. In another embodiment, the well is located on land. In still another embodiment, the liquid treatment composition may be added downhole at or near the producing section of the well, near the top of the well or even into a separation device used to separate hydrocarbons from aqueous components of the hydrocarbon composition, or any other location in flowlines or pipelines conveying the hydrocarbon composition. In still another embodiment, the liquid treatment composition may be added to the hydrocarbon composition in a storage tank, drum, vessel, reservoir, sump, rail car, tank truck, barge, ocean going vessel or any combination thereof.

[0067] The liquid treatment composition may be added to the hydrocarbon composition by any known means, such as by batch treatment, continuous injection, squeezing or any combination thereof, using available production equipment including for example, pipes, mixers, pumps, tanks, injection ports, and the like.

[0068] It will be appreciated that there are a number of complex and interrelated factors which would determine the effective amount of the liquid treatment composition that is added to a particular hydrocarbon composition, including, but not necessarily limited to, the chemical composition of the hydrocarbon composition, the temperature and pressure of the hydrocarbon composition stream and the nature of any mechanical or physicochemical process the hydrocarbon composition stream will be subjected to. The latter includes, but is not limited to, depressurization, cooling or heating, mixing with other produced fluids, shearing, the use of other oil field additives, and the like. While it is impossible to generalize the effective amount because of these complex factors, it will be appreciated that in one non-limiting example, the effective amount of liquid treatment composition that is added to the hydrocarbon composition is at least about 10 ppm or at least about 100 ppm or at least about 500 ppm or at least about 1000 ppm or at least about 2000 ppm or at least about 3000 ppm or at least about 5000 ppm. In another embodiment, the effective amount of the liquid treatment composition that is added to the hydrocarbon composition may be less than about 20,000 ppm. In a further embodiment, the effective amount of the liquid treatment that is added to the hydrocarbon composition may be between about 100 to about 20,000 ppm, or between about 200 ppm to about 10,000 ppm or between about 500 ppm to about 5000 ppm or between about 1000 ppm to about 4000 ppm. The effective amount employed may also be dependent on the paraffin wax and asphaltene content of the hydrocarbon composition.

[0069] In one embodiment, the hydrocarbon composition may comprise at least about 0.1 % by weight of paraffin wax, or at least about 3 % by weight, or at least 5% by weight, or at least 10% by weight or at least 15% by weight of paraffin wax, where the % by weight is based on the total weight of the hydrocarbon composition. In other embodiments, the paraffin wax may be present in the hydrocarbon composition in an amount from about 0.01 % by weight to about 50% by weight, or from about 0.5% by weight to about 30% by weight or about 1 % by weight to about 15% by weight, where the % by weight is based on the total weight of the hydrocarbon composition.

[0070] In another embodiment, the hydrocarbon composition may contain at least about 0.01 % by weight of asphaltene, or at least about 3% by weight, or at least about 15% by weight or even at least about 35% by weight of asphaltene, where the % by weight is based on the total weight of the hydrocarbon composition. In other embodiments, the amount of asphaltene present in the hydrocarbon composition may include from about 0.01 % by weight to about 40% by weight or from about 1 % by weight to about 35% by weight or from about 2% by weight to about 30% by weight, or from about 3% by weight to about 25% by weight, where the % by weight is based on the total weight of the hydrocarbon composition.

[0071] In still another embodiment, the hydrocarbon composition can be a component of a fluid mixture that further comprises a non-hydrocarbon fluid and/or a non-liquid phase. In one embodiment, the non-hydrocarbon fluid can comprise water, and the non-liquid phase can comprise natural gas. Additionally, when the hydrocarbon composition is a component of a fluid mixture, the liquid hydrocarbon can account for at least about 50% by weight, at least about 60% by weight, or at least 70% by weight of the fluid mixture.

[0072] According to one embodiment, the present disclosure provides a method comprising adding an effective amount of the liquid treatment composition described above to a hydrocarbon composition to form a treated hydrocarbon composition and subjecting the treated hydrocarbon composition to a temperature of between about - 40 °C to about 80 °C or between about -40 °C to about 0 °C. “Subjecting the treated hydrocarbon composition to a temperature of” means adding and/or transferring the treated hydrocarbon composition to a location where the temperature of the treated hydrocarbon composition decreases until the temperature of the treated hydrocarbon composition is between a certain range. The method may further comprise the step conveying the treated hydrocarbon composition through a flowline, a pipeline, a capillary string, an umbilical, an annulus, a pump, a valve, a flowmeter, a pressure gauge, a heat exchanger, a separator or any combination thereof.

[0073] According to another embodiment there is provided a method for recovering a hydrocarbon composition from a subterranean formation having at least one well penetrating the formation and in fluid communication therewith, comprising the steps of: (a) injecting into the well and the formation an effective amount of the liquid treatment composition described above; (b) allowing the liquid treatment composition to disperse into the formation; and (c) recovering the reduced viscosity hydrocarbon composition. In some embodiments, the hydrocarbon composition is crude oil. In another embodiment, the crude oil may comprise a super light, light, medium, heavy, extra heavy crude oil or any mixture thereof.

[0074] According to another embodiment, the present disclosure is also directed to a method for reducing the viscosity of a hydrocarbon composition in a significantly non-reversible manner, comprising the steps of: (i) adding an effective amount of the liquid treatment composition as described above to the hydrocarbon composition, and (ii) dispersing the liquid treatment composition throughout a portion of the hydrocarbon composition. This is in contrast to methods of treatment with only the chemical treatment agent or during heating or steam injection methods where the physical properties of the hydrocarbon composition can return to their initial conditions. In some embodiments, the hydrocarbon composition comprises crude oil. The crude oil may comprise a super light, light, medium, heavy, extra heavy crude oil or any mixture thereof. Generally, the viscosity of the crude oil can be reduced by an amount in the range of from about 1 % to about 60%, or from about 10% to about 55%, based on the initial viscosity of the crude oil prior to treatment with the liquid treatment composition.

[0075] According to another embodiment, the present disclosure provides a method for reducing or inhibiting paraffin wax and/or asphaltene precipitate blockage in a flowline transporting a hydrocarbon composition, the method comprising adding the liquid treatment composition to the hydrocarbon composition containing to produce a treated hydrocarbon composition; and transporting the treated hydrocarbon composition through the flowline under conditions that would be conducive for the formation of paraffin wax and/or asphaltene precipitate in the original hydrocarbon composition; whereby paraffin wax and/or asphaltene precipitate is inhibited from forming within the flowline by the addition of the liquid treatment composition. In some embodiments, the hydrocarbon composition is crude oil. In another embodiment, the crude oil may comprise a super light, light, medium, heavy, extra heavy crude oil or any mixture thereof.

[0076] According to another embodiment, the present disclosure provides a system for preventing the formation of paraffin wax and/or asphaltene precipitate blockage in flowlines. The system includes a flowline for transporting a hydrocarbon composition and an injection conduit fluidly connected to the flowline to add the liquid treatment composition to the flowline. The flowline should be connected to a hydrocarbon composition source and the injection conduit fluidly connected to a liquid treatment composition source. The system may be operable in an environment sufficiently cool such that paraffin wax and/or asphaltene precipitate blockage might form absent the addition of the liquid treatment composition to the hydrocarbon composition from the injection conduit. The hydrocarbon composition source may be a well bore from which hydrocarbons are produced. The liquid treatment composition source may be a storage tank or vessel. The system may be used on land where hydrocarbon compositions are to be transported in flowlines and the flowlines are exposed to cold temperatures as low as about -40 °C.

[0077] In another embodiment, the present disclosure provides a method of modifying the behavior of paraffin and/or asphaltene in a hydrocarbon composition, the method comprising: adding to the hydrocarbon composition comprising paraffin and asphaltene an effective amount of the liquid treatment composition described above to modify the behavior of paraffin and/or asphaltene therein, where the modification of paraffin and/or asphaltene behavior is at least one of: inhibiting or preventing the deposition of paraffin and/or asphaltene; modifying the crystal structure of the paraffin; lowering the viscosity of the hydrocarbon composition; lowering the pour point of the hydrocarbon composition; lowering the cloud point of the hydrocarbon composition; and dispersing the paraffin and/or asphaltene in the hydrocarbon composition, as compared to the paraffin and/or asphaltene behavior in the absence of the liquid treatment composition. In some embodiments, the hydrocarbon composition is crude oil. In another embodiment, the crude oil may comprise a super light, light, medium, heavy, extra heavy crude oil or any mixture thereof.

EXAMPLES

[0078] Example 1 : Viscosity reduction and cold flow improvement

A liquid treatment composition of the present disclosure was prepared comprising about 80% by weight to about 90% by weight of a solvent package containing an aromatic solvent, an alcohol and optionally a glycol solvent and about 10% by weight to about 20% by weight of a chemical treatment agent (hereinafter referred to as“Liq. Treatment Composition 1”). Liq. Treatment Composition 1 was then used to treat hydrocarbon composition samples obtained from a production formation. The samples obtained from the production formation were first homogenized at a temperature of about 70 °C and then either not treated or treated with 5000 ppm or 10,000 ppm of Liq. Treatment Composition 1 . The untreated and treated samples (containing 0.5% by weight or 1 % by weight of Liq. Treatment Composition 1 ) were held at a temperature of about 70 °C for 25 minutes before being injected into a viscometer. The dynamic viscosity of the untreated sample and treated samples was then measured twice at a range from 70 °C to 40 °C, in steps of 10 °C, based on ASTM D7042 Standard Test Method for Dynamic Viscosity, the contents of which are incorporated herein by reference. The results are shown below in Tables 1 and 2:

Table 1

Table 2

As shown above, the liquid treatment composition according to the present disclosure significantly reduced the dynamic viscosity of the hydrocarbon compositions as compared to an untreated hydrocarbon composition, especially at lower temperatures, thereby demonstrating its ability to improve the cold flow properties of the hydrocarbon composition.

[0079] Example 2: Maturation over time

In a manner similar to Example 1 , Liq. Treatment Composition 1 was used to treat hydrocarbon composition samples obtained from a production formation. The samples obtained from the production formation were first homogenized at a temperature of about 70 °C and then either not treated or treated with 20,000 ppm of the Liq. Treatment Composition 1. The untreated and treated samples (containing 2% by weight of Liq. Treatment Composition 1 ) were held at a temperature of about 70 °C for 25 minutes before being injected into a viscometer. The dynamic viscosity of the untreated and treated samples was measured at a range from 70 °C to 40 °C, in steps of 10°C, based on ASTM D7042. The samples were then held at ambient conditions for 48 hours and the dynamic viscosity of the samples was measured again as above. The results are shown below in Table 3:

Table 3

As shown above, the liquid treatment composition according to the present disclosure was again able to significantly reduce the dynamic viscosity of the hydrocarbon composition as compared to the untreated hydrocarbon composition (especially at lower temperatures). In addition, the reduction in dynamic viscosity was shown to be irreversible and even evolved over the 48 hour period of time (i.e. maturation of the oil) whereas the untreated hydrocarbon composition did not.

[0080] Example 3: Viscosity reduction and cold flow improvement

In a manner similar to Example 1 , Liq. Treatment Composition 1 was used to treat hydrocarbon composition samples obtained from a production formation. The samples obtained from the production formation were first homogenized and then either not treated or treated with 3000 ppm or 10,000 ppm of the Liq. Treatment Composition 1. The untreated and treated samples (containing 0.3% by weight or 1 % by weight of Liq. Treatment Composition 1 ) were held at a temperature of about 60 °C for 30 minutes before being injected into a viscometer. The dynamic viscosity of the samples was then measured at a range from 60 °C to 20 °C, in steps of 20 °C, based on ASTM D7042. The results are shown below in Table 4:

Table 4

As shown above, the liquid treatment composition according to the present disclosure again reduced the dynamic viscosity of the hydrocarbon composition samples as compared to the untreated hydrocarbon composition sample, with the largest reduction occurring at the lower temperature, thus demonstrating its ability to improve the cold flow properties of the hydrocarbon composition.

[0081] Example 4: Viscosity reduction, flow improvement and wax temperature appearance reduction

In a manner similar to Example 1 , Liq. Treatment Composition 1 was used to treat hydrocarbon composition samples obtained from a production formation. The well was first sampled prior to treatment with Liq. Treatment Composition 1. The untreated crude oil sample was heated in a water bath at 40 °C until the paraffin solids disappeared and then added to separate 100 mL volumes of condensate. The 100 mL volumes of condensate were either treated with 1500 ppm of Liq. Treatment Composition or not treated. The 100 mL volumes of condensate were then heated to 40 °C and stirred for 180 minutes before being taken out and allowed to cool to reduce the loss of lighter ends. The dynamic viscosity of each of the 100 ml. volume condensates was then measured at a range from 60 °C to 20 °C based on ASTM D7042 and the results are shown in Figure 1 .

In addition, the well at the production formation was treated with Liq. Treatment Composition 1 and samples of the treated crude oil were obtained at the separator. These samples were processed and their dynamic viscosity was measured similar to the samples above. The results for these treated crude oil samples are also shown in Figure 1 .

From Figure 1 , it is apparent that dynamic viscosity and the appearance of wax in the treated crude oil samples was clearly reduced as compared to the untreated crude oil sample thus demonstrating an improvement in flow properties at low temperatures.

[0082] Example 5: Reduction of salts in crude oil

Crude oil condensate samples were obtained from the inlet separator at a production formation over a period of several weeks and the concentrations of calcium and sodium were determined using Inductively Coupled Plasma Mass Spectroscopy. The results are shown in Figure 2. The baseline sample refers to untreated condensate prior to the injection of Liq. Treatment Composition 1 into the well. The well was then treated continuously with Liq. Treatment Composition 1 and samples were taken approximately every 3 weeks and analyzed. At the initial start up of this test, the production site was salting off its condensate stabilizer every 2 to 3 weeks due to plugging. However, as this test continued, the frequency of plugging of the condensate stabilizer was significantly reduced. In fact, the frequency was reduced to a period of 8 weeks, thus saving operational costs and increasing throughput of the production site. [0083] Example 6: Viscosity reduction, cold flow improvement and wax temperature appearance reduction

Liq. Treatment Composition 1 was used to continuously treat a well located at a production formation. The well was first treated with 3000 ppm of Liq. Treatment Composition 1 and a treated hydrocarbon composition sample was obtained at the well head (the sampling point was first purged to remove stagnant fluid). The well was then treated over a period of several weeks at different treatment levels and additional treated samples were obtained as above. Each of the treated samples were heated in a water bath at 45 °C to homogenize precipitated paraffins and the dynamic viscosity of each sample was measured at a range from 15°C to -1 °C based on ASTM D7042 and the results are depicted in Figure 3. The wax appearance temperature and dynamic viscosity of the treated crude oil samples were again clearly reduced thus improving the flow properties of such samples as compared to the untreated sample. Surprisingly, even when the amount of Liq. Treatment Composition 1 used to treat the crude oil sample was reduced, it was still able to effectively improve the cold flow properties of the crude oil sample.

[0084] Example 7. Freeze-Thaw Stability

Liquid treatment compositions according to the present disclosure were prepared and the freeze-thaw stability was measured according to the method described below:

1 ) A sample was placed in a screw-top glass vial and capped;

(2) The vial was placed in a freezing compartment overnight for 16 hours at - 37°C to -40 °C. It was then removed and allowed to sit at ambient temperature during the day for 8 hours;

(3) Step 2 was repeated twice more (to give a total of 3 cycles);

(4) The sample was then examined for visual signs of separation or solidification (the sample should move and flow as freely with minimal hand stirring as it did before the test). Unless all of these requirements were satisfied, the sample is not freeze-thaw stable.

Samples containing up to 25% by weight of the chemical treatment agent, based on the total weight of the sample, were unexpectedly found to be freeze-thaw stable when combined with a solvent package according to the present disclosure containing an aromatic solvent and an alcohol.

[0085] Example 8. Pour point depressant

The pour points of liquid treatment compositions according to the present disclosure were determined using ASTM D-97 Standard Test Method for Pour Point of Petroleum Products, the contents of which are incorporated herein by reference. In general, samples were cooled to about 9 °C above the expected pour point, and for every subsequent 3°C interval thereafter, the sample was removed, tilted and checked for surface movement. When the sample did not flow after tilting, the sample was held horizontally for 5 seconds, and if it still did not flow, 3°C was added to the corresponding temperature with the result being its pour point temperature. Various liquid treatment compositions were prepared as shown in Table 5 and subsequently tested with the results shown in Table 6:

Table 5

1 RDV-00 or RDV-01 Hydrocarbon Treatment composition (GlobalQuimica Partners LLC). Table 6

As shown above, the liquid treatment compositions exhibited pour points of at least -20 °C and in some instances, at least -40 °C. [0086] While the foregoing is directed to embodiments of the present disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.