KR20230090515A - Composition for preventing pour point deterioration of crude oil - Google Patents

Abstract

The present invention relates to a composition for preventing reduction in fluidity of crude oil. The present invention provides a composition for preventing reduction in fluidity of crude oil including: an oil-soluble aliphatic compound; one or more oil-soluble nitrogen compounds capable of interacting with paraffin crystals contained in crude oil; and a remaining solvent. The fluidity characteristics of crude oil can be improved by adding the mixture of the present invention to the crude oil.

Description

Composition for preventing pour point deterioration of crude oil}

It relates to a composition for preventing a decrease in fluidity of crude oil.

Crude oil derived from fossil sources has different contents of paraffins, particularly n-paraffins, depending on the origin of the crude oil. At low temperatures, solid paraffin composed of n-paraffin starts to separate at the wax appearance temperature (WAT).

Upon further temperature reduction, the platelet-like n-paraffin crystals form a "house of cards structure" and the crude oil, even as a liquid, stops flowing.

The precipitated n-paraffin lowers the flow of crude oil within the temperature range between the wax formation temperature and the pour point (PP), and thus the paraffin precipitate interferes with the normal operation of the crude oil transfer facility.

It has long been known that suitable additives can modify the crystal growth of n-paraffins in crude oil.

Additives with excellent efficacy prevent paraffin from solidifying at a temperature lower than the temperature at which the first paraffin crystals crystallize in crude oil. The efficacy of pour point depressants can be determined indirectly by measuring the pour point (PP) of crude oil.

Ethylene-vinyl carboxylate copolymers have been used as pour point improvers for a long time. A disadvantage of these additives is that the precipitated paraffin crystals, compared to the liquid fraction, tend to precipitate more in the lower part of the plant due to their high density.

As a result, a uniform low-paraffinic phase is formed at the top of the equipment and a paraffin-rich layer is formed at the bottom. In general, during transportation of crude oil, fluidity is lowered by high concentration paraffin, and the risk increases as the outdoor temperature decreases. The reason is that the amount of precipitated paraffin increases as the temperature decreases.

An object of the present invention is to provide a product as a high-performance pour point lowering agent, wherein the lowering agent effectively lowers the pour point (PP) measured in unadded crude oil compared to unadded crude oil in a normal capacity, that is, lowers by 10 ° C or more By doing so, it is intended to improve the fluidity performance of crude oil having a high pour point of about PP 35 ° C before the addition of the degrading agent.

In one embodiment of the present invention, oil-soluble aliphatic compounds; one or more oil-soluble nitrogen compounds capable of interacting with paraffin crystals contained in crude oil; And it provides a composition for preventing the decrease in fluidity of crude oil containing a solvent as the balance.

The oil-soluble nitrogen compound may be included in an amount of 10-90% by weight based on 100% by weight of the total composition.

The oil-soluble aliphatic compound may be included in an amount of 10-90% by weight based on 100% by weight of the total composition.

The oil-soluble aliphatic compound is an aliphatic monocarboxylic acid or dicarboxylic acid having 4 to 200 carbon atoms or a monoamine or polyamine derivative thereof, or at least one straight acid having 8 or more carbon atoms obtained by reacting with an alcohol. It may contain one or more oil-soluble aliphatic compounds comprising chain or branched alkyl or alkenyl chains.

The oil-soluble nitrogen compound is an oil-soluble polar nitrogen compound and may have one or more, particularly two or more amine-based nitrogen radicals having C ₈ to C ₄₀ hydrocarbon radicals in each case as substituents on a nitrogen atom.

The composition may additionally contain an inert polar diluent.

The composition may additionally contain an inert, non-polar diluent.

Due to the composition, the pour point (PP) of crude oil can be lowered by 10 ° C or more.

The composition may be added at 100-1000 ppm by weight of crude oil.

The flow properties of crude oil can be improved by adding the mixture of the present invention to crude oil.

A significant drop in the PP value is observed when the mixture used in the present invention is used in a crude oil having a high pour point (PP) of 35°C.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

The pour point depressant is a mixture comprising component (A) and component (B).

Component (A) is preferably an aliphatic mono- or dicarboxylic acid in which the parent carboxylic acid unit of the oil-soluble aliphatic compound has 4 to 75 carbon atoms, in particular 4 to 30 carbon atoms.

Dicarboxylic acids mentioned with respect to the position of the two carboxyl functional groups typically have an α, β-structure. The parent monoamine of component (A) may be a primary or secondary monoamine having 1 to 30 carbon atoms, the hydrocarbon radical of which is an alkyl, alkenyl, or cycloalkyl substituent.

The parent polyamines of component (A) may be those having 2 to 1000, particularly 2 to 500, specifically 2 to 100 nitrogen atoms in the molecule, wherein useful hydrocarbon radicals and bridging members are alkyl, alkenyl radicals, respectively; and alkylene and alkenylene radicals.

The parent alcohol may be an aliphatic or cycloaliphatic monoalcohol, di-alcohol or polyalcohol having from 1 to 30 carbon atoms. Accordingly, the oil-soluble aliphatic compounds of component (A) are generally carboxamides, carboxylic acid monoamides, carboximides or carboxylic acid esters.

In a preferred embodiment, the at least one oil-soluble aliphatic compound (A) comprises an aliphatic α, β-dicarboxylic acid or derivative thereof having 4 to 300 carbon atoms and a primary C ₈ to C ₃₀ -alkylmonoamine or -alkenylmonoamine. It can be a reaction product with an amine.

The parent α, β-dicarboxylic acid of the oil-soluble reaction product of component (A) having 4 to 300, in particular 4 to 75, in particular 4 to 12 carbon atoms, is in particular succinic acid, maleic acid, fumaric acid or derivatives thereof. , which may have, on the bridging ethylene or enenylene groups, relatively short-chain or relatively long-chain hydrocarbyl substituents that may or may contain heteroatoms and functional groups.

For reactions with primary alkylamines or alkenylamines, the acids are generally used in the free dicarboxylic acid form or in the form of reactive derivatives thereof. Reactive derivatives used herein may be carbonyl halides, carboxylic acid esters or especially carboxylic acid anhydrides.

In a preferred embodiment the oil-soluble aliphatic compound (A) is the reaction product of maleic anhydride with a primary C ₉ to C ₁₅ -alkylamine.

The parent primary alkylamine of the oil-soluble reaction product of component (A) is typically preferably 8 to 30, in particular 8 to 22, in particular 9 to 15 carbon atoms, and linear or branched, saturated or unsaturated aliphatic Hydrocarbon chains such as dorsal octyl-, nonyl-, isononyl-, decyl-, undecyl-, tridecyl-, isotridecyl-, tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl, octadecyl- or medium to long chain alkylmonoamines or alkenylmonoamines with oleylamines and mixtures of these amines.

If the primary alkylamines or alkenylamines of this type used are naturally occurring fatty amines, suitable examples are in particular cocoamine, tallowamine, oleylamine, arachidylamine or behenylamine and mixtures thereof. The reaction products of component (A) are typically - depending on the stoichiometry and type of reaction - in the form of monoamides or bisamides of dicarboxylic acids, and the products may also contain trace amounts of the corresponding ammonium salts. .

A typical example of an oil-soluble reaction product of component (A) is the reaction product of 1 mol of maleic anhydride and 1 mol of isotridecylamine, the product existing predominantly as a monoamide of maleic acid.

Component (B) is an oil-soluble polar nitrogen compound, which may be ionic or nonionic in nature, having as substituents on the nitrogen atom at least one, in particular at least two, amine-based nitrogen radicals having in each case C ₈ to C ₄₀ hydrocarbon radicals. it is desirable These nitrogen radicals can also exist in quaternized form, ie in cationic form. Examples of such nitrogen compounds are ammonium salts and/or amides, which can be obtained by the reaction of one or more amines substituted by one or more hydrocarbon radicals with one to four carboxylic acids or with suitable derivatives of these carboxylic acids. can The amine preferably contains one or more linear C ₈ to C ₄₀ alkyl radicals.

In a preferred embodiment the mixture of the present invention may contain as component (B) at least two of the compounds exemplified below.

B1 : reaction products of aromatic or cycloaliphatic dicarboxylic acids or succinic acids substituted by C ₈ to C ₃₀ -hydrocarbon radicals with 2 mol of primary or secondary amines having at least 8 carbon atoms and

B2: Reaction product of 1 mol of alkenylspirobislactone with 2 mol of primary or secondary amines having 8 or more carbon atoms

Preferred components (B1) are dicarboxylic acids such as cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalendica carboxylic acids such as naphthalene-1,2-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid and naphthalene-1,8-dicarboxylic acid, phthalic acid , isophthalic acid, terephthalic acid, and long-chain hydrocarbon radicals such as octyl, 2-ethylhexyl, nonyl, isononyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, Reaction products of succinic acid substituted by octadecyl or eicosyl. In the context of the text, the aromatic dicarboxylic acids listed are particularly preferred.

Primary and secondary amines having at least 8 carbon atoms as specific reaction partners for the polycarboxylic acids or alkenylspirobislactones forming component (B) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines may be selected from a plurality of amines having hydrocarbon radicals, optionally linked to one another. In a preferred embodiment, such amines are secondary amines and have the general formula HNR ₂ , wherein the two R variables are each independently straight or branched C ₈ to C ₃₀ -alkyl or -alkenyl radicals, in particular a C ₄ to C ₂₄ -alkyl radical, specifically a C ₁₆ to C ₂₀ alkyl radical.

Preferably, such relatively long-chain alkyl or alkenyl radicals are straight-chain or branched-chain with only minimal branching. In general, the secondary amines mentioned, with respect to relatively long-chain alkyl and alkenyl radicals, are derived from naturally occurring fatty acids or from derivatives of these fatty acids.

It is preferred that the two R radicals are the same. Suitable primary amines are, for example, octylamine, 2-ethylhexylamine, nonylamine, decylamine, 2-propylheptyl, undecylamine, dodecylamine, tridecylamine, isotridecylamine, tetradecylamine, hexadecylamine, octadecylamine (stearylamine), oleylamine or behenylamine.

Suitable secondary amines are, for example, dioctadecylamine (distearylamine) and methylbehenylamine. For example, amine mixtures, in particular amine mixtures obtainable on an industrial scale, such as fatty amines or hydrogenated or unhydrogenated tallow amines, for example hydrogenated or unhydrogenated tallow fatty amines, are also suitable.

Incidentally, the aforementioned long-chain secondary amines, such as distearylamines, may also be part of mixtures suitable as additive concentrates for crude oil, in free form, ie in a form that does not react with carboxyl functional groups.

A typical example of component (B1) is a N,N-dialkylammonium salt of 2-N',N'-dialkylamidobenzoate, for example the reaction product of 1 mol of phthalic anhydride with 2 mol of ditallow fatty amine. including, in which case the latter may be hydrogenated or unhydrogenated.

A typical example of component (B2) is the reaction product of 1 mol of an alkenylspirobislactone with 2 mol of a dialkylamine, for example ditallowamine and/or tallowamine, in which case the latter two substances may be hydrogenated. or may be unhydrogenated.

Furthermore, the oil-soluble polar nitrogen compound (B) is, in a preferred embodiment, an amide, an amide ammonium salt or an ammonium salt in which a carboxylic acid group is not converted to an amide group, or at least one carboxylic acid group is converted to an amide group. The secondary amines mentioned above may be bound to the polycarboxylic acid in the form of an amide structure or in the form of an ammonium salt, and it is also possible that only part of it is in the form of an amide structure or another part is in the form of ammonium. It is preferred that only a few or zero free acid groups are present. The reaction product of such a dicarboxylic acid with a secondary amine is preferably in the form of a hybridized amide ammonium salt.

In a preferred embodiment, the mixture used according to the invention comprises, as further components, C ₈ to C ₃₀ -alkanols, aryl-substituted C ₁ to C 6 -alkanols, C ₆ to _{C 20 -phenols} , 8 to C 20 -alkanols, at least one inert selected from monoalkyl monocarboxylates having at least one hydrocarbyl chain of 30 carbon atoms and dialkyl dicarboxylates having at least one hydrocarbyl chain of 8 to 30 carbon atoms. A polar diluent (C) is included in an amount effective to further lower the pour point.

This is because, in many cases, such inert polar diluents, when combined with components (A) and (B), result in a further lowering or enhanced lowering of the pour point in the crude oil upon addition of the cold flow improver.

Examples of C ₈ to C ₃₀ -alkanols useful for component (C) are n-octanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, 2-propylheptanol, n- Undecanol, n-dodecanol, n-tridecanol, isotridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n -Includes nonandecanol and eicosanol. Among these, the branched alcohols 2-ethylhexanol, isononanol, 2-propyleneheptanol, isotridecanol, and the linear alkanols n-heptadecanol and n-octadecanol show particularly excellent action.

Examples of aryl-substituted C ₁ to C ₆ alkanols useful for component (C) include benzyl alcohol, 2-phenylethanol, 3-phenylpropanol, 4-phenylbutanol and 6-phenylhexanol.

Examples of C ₆ to C ₂₀ phenols useful for component (C) include unsubstituted phenols, α-naphthol, β-naphthol, o-, m- and p-cresols, 2-tert-butylphenol, 4-tert-butyl phenol, 2,4-di-tert-butylphenol and 2,6-di-tert-butylphenol.

Monoalkyl monocarboxylates having at least one hydrocarbyl chain of 8 to 30 carbon atoms useful for component (C) are primarily esters of relatively short-chain carboxylic acids with relatively long-chain alcohols, such as formic acid, acetic acid, propionic acid , n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl of butyric acid, isobutyric acid, valeric acid, cyclohexanecarboxylic acid and benzoic acid yl, n-tridecyl, isotridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and eicosyl esters. In this case, it is preferred that the carboxylic acid unit has 1 to 12, in particular 1 to 8, in particular 1 to 6 carbon atoms. Very good action here is exhibited by esters of C ₄ to C ₆ -monocarboxylic acids with the branched relatively long-chain alkanols 2-ethylhexanol, isononanol, 2-propylheptanol and isotridecanol.

Secondarily useful as monoalkyl monocarboxylates having at least one hydrocarbyl chain of 8 to 30 carbon atoms in component (C) are concomitantly esters of relatively long-chain carboxylic acids with relatively short-chain alcohols, such as C methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl esters of ₁₂ to C ₂₀ fatty acids. In this context, both pure fatty acids and industrially customary fatty acid mixtures are useful, such mixtures comprising for example stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid and/or linolenic acid, for example mixtures tallow fatty acid, coconut oil fatty acid, fish oil fatty acid, coconut palm kernel oil fatty acid, soybean oil fatty acid, colza oil fatty acid, peanut oil fatty acid or palm oil fatty acid, which contain oleic acid and palmitic acid as main components.

Examples of dialkyl dicarboxylates having at least one hydrocarbyl chain of 8 to 30 carbon atoms useful for component (C) are oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid , pimelic acid, suberic acid, azelic acid, sebacic acid, cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid , di-n-octyl, di-2-ethylhexyl, di-n-nonyl, di-isononyl, di-n-decyl, di-2-propylheptyl, di-n- of phthalic acid, isophthalic acid, and terephthalic acid Undecyl, di-n-dodecyl, di-n-tridecyl, di-isotridecyl, di-n-tetradecyl, di-n-pentadecyl, di-n-hexadecyl, di-n-heptadecyl , di-n-octadecyl, di-n-nonadecyl and dieicosyl esters. It is preferred here that the dicarboxylic acid contains 2 to 20, in particular 2 to 12, in particular 2 to 8 carbon atoms. The two ester alcohol units may also be different, but preferably the same. Very good action here is shown by the diesters of the branched alkanols 2-ethylhexanol, isononanol, 2-propylheptanol and isotridecanol with C ₄ to C ₆ -dicarboxylic acids. A typical example of such a dicarboxylic acid diester is diisononyl cyclohexane-1,2-dicarboxylate.

Here, "hydrocarbyl chain" is to be understood as meaning a linear or branched structural element in the esters mentioned, which is formed essentially of carbon and hydrogen. Provided that its predominantly hydrocarbon character is not impaired, the hydrocarbyl chain may contain, to a minimal extent, heteroatoms such as oxygen, nitrogen and/or sulfur, or may contain functional groups such as hydroxyl or amino. may contain. It is also possible to use unsaturations, such as ethylenic double bonds and/or C≡C bonds. These hydrocarbyl chains are either the backbone of a monocarboxylic acid or the backbone of an ester alcohol, or a bridging unit between two carboxylic acid functional groups.

Besides the inert polar diluents (C) mentioned, it is also possible that inert, non-polar diluents (D) are present in the mixtures used according to the invention. The proportion of the inert polar diluent (C) in the total amount of the inert diluent, i.e. the total amount of (C) and (D), when used, may be 20% by weight or more, particularly 40% by weight or more, specifically 50% by weight or more. Such inert, non-polar diluents here include in particular aliphatic and aromatic hydrocarbons, for example xylenes or high-boiling aromatic mixtures, such as Solvent Naphtha. Here, it is also possible to use middle distillate fuel itself as diluent.

The mixture used according to the present invention can be mixed in the following quantitative ratio.

- component (A), 3 to 70% by weight, in particular 10 to 40% by weight, in particular 15 to 30% by weight,

- component (B), 5 to 60% by weight, in particular 10 to 50% by weight, in particular 20 to 40% by weight,

- from 0 to 75% by weight, in particular from 5 to 75% by weight, in particular from 30 to 60% by weight of components (C) + (D)

The total amount of all components mentioned herein is 100% by weight.

The mixture according to the invention can be prepared by simple mixing of the components mentioned, with or without the use of diluents (C) and/or (D) and without supplying heat.

The mixture used according to the present invention is an additive for crude oil which already has a high PP of 20° C. or more, in particular 35° C. or more, before the addition of the additive, for lowering the pour point of the crude oil upon addition of the cold flow improver, as a pour point inhibitor. functionally works.

The mixture used according to the invention may be added to crude oil. The dose of the mixture of components effective to lower the pour point of crude oil, i.e. the mixture of components (A) and (B) or (A), (B) and (C), in each case based on the total amount of crude oil, is generally 5 to 10000 ppm by weight, particularly 10 to 5000 ppm by weight, specifically 25 to 3000 ppm by weight, for example 100 to 1000 ppm.

Preferred examples and comparative examples of the present invention are described below. However, the following example is only a preferred embodiment of the present invention, but the present invention is not limited to the following example.

Example

The components used in the mixtures used according to the present invention or in the specific mixtures of the present invention are as follows.

A1: maleic anhydride reacted with 1 mol of tridecylamine

B1: phthalic anhydride reacted with 2 mol of hydrogenated ditallowamine

C1: heptadecanol

C2: 2-Propylceptanol

D1: solvent naphtha 150

Certain mixtures P1 to P3 of the present invention were prepared using the above-mentioned ingredients and they are listed in Table 1 below. (% by weight)

P1 P2 P3 A1 15 15 15 B1 35 35 35 C1 0 20 0 C2 0 0 20 D1 50 30 30

In order to measure the PP value, crude oil obtained from K oil field was used.

Crude Oil: PP (According to ISO 3016): 35℃

API degree: 32

In each case, 1000 ppm of mixtures P1 to P3 were added to crude oil, stirred at 45 ° C for 30 minutes in each case, and then the pour point of the crude oil with the mixture was measured according to ISO 3016, and the pour point was also measured for the crude oil without the mixture. did

The pour point measurement results in each case are shown in Table 2.

PP(℃) Unadded Crude Oil 35 Crude Oil+P1 25 Crude Oil+P2 24 Crude Oil+P3 23

The present invention is not limited to the above embodiments, but can be manufactured in a variety of different forms, and those skilled in the art to which the present invention pertains may take other specific forms without changing the technical spirit or essential features of the present invention. It will be understood that it can be implemented as. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting.

Claims (9)

oil soluble aliphatic compounds;
one or more oil-soluble nitrogen compounds capable of interacting with paraffin crystals contained in crude oil; and
A composition for preventing deterioration in fluidity of crude oil containing a solvent as the remainder.
According to claim 1,
The oil-soluble nitrogen compound is contained in 10-90% by weight based on 100% by weight of the total composition, the composition for preventing the decrease in fluidity of crude oil.
According to claim 1,
The oil-soluble aliphatic compound is contained in 10-90% by weight based on 100% by weight of the total composition, the composition for preventing the decrease in fluidity of crude oil.
According to claim 1,
The oil-soluble aliphatic compound,
one or more straight-chain or branched-chain alkyls having at least 8 carbon atoms obtainable by reaction with monoamines or polyamines which are aliphatic mono- or dicarboxylic acids or derivatives thereof having 4 to 200 carbon atoms or with alcohols; or A composition for preventing a decrease in fluidity of crude oil comprising at least one oil-soluble aliphatic compound containing an alkenyl chain.
According to claim 1,
The oil-soluble nitrogen compound is an oil-soluble polar nitrogen compound and has one or more, particularly two or more amine-based nitrogen radicals having C ₈ to C ₄₀ hydrocarbon radicals in each case as substituents on nitrogen atoms.
According to claim 1,
The composition further comprises an inert polar diluent in addition to the crude oil fluidity reduction preventing composition.
According to claim 1,
The composition further comprises an inert non-polar diluent in addition to the composition for preventing the decrease in fluidity of crude oil.
According to claim 1,
Due to the composition, the pour point (PP) of crude oil is lowered by 10 ° C or more.
According to claim 1,
The composition is a crude oil fluidity reduction prevention composition that is added at 100-1000 ppm relative to the weight of crude oil.