EP1357172B1

EP1357172B1 - Oil-soluble imine-acid reaction products as asphaltene dispersants in crude oil

Info

Publication number: EP1357172B1
Application number: EP20030252271
Authority: EP
Inventors: Ravindranath Mukkamala
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 2002-04-23
Filing date: 2003-04-10
Publication date: 2006-07-05
Anticipated expiration: 2023-04-10
Also published as: MXPA03003359A; EP1357172A3; NO20031602L; DE60306574D1; NO20031602D0; EP1357172A2; CA2424915A1

Description

Background

This invention relates generally to oil-soluble imine-acid reaction products useful in processing of crude oil.
Certain petroleum products, including heavy crude oils, which include materials referred to as "tars," "petroleum tars" or "tar sands," are rich in asphaltenes, metals and resins. The presence of these types of compounds can lead to various problems in the recovery, transportation, treatment and refining of crude oils, including increased viscosity, formation of stable emulsions, fouling and corrosion. U.S. Pat. No. 6,168,702 discloses a particular class of mixed sulfonic-carboxylic acid salts with amines as demulsifiers for crude oil. However, this reference does not disclose useful compounds that are not amine salts, or compounds that disperse asphaltenes.
GB-A-1 506 786 discloses an oil composition comprising a major proportion of an oil and 0.01-15% by weight of a basic dispersant. Said dispersant is the reaction product of an alkyl or alkenyl succinic acid or anhydride with a polymer of an alkylene imine.
US-A-6 140 276 discloses a method of reducing the deposition of wax from crude oil containing wax, which comprises adding thereto at least one N-substituted polyalkylene imine which has at least one organic substituent that is a hydroxy-substituted alkyl group of 12-24 carbon atoms.
US-A-6171 521 teaches a zwitterionic water-soluble imine.
The problem addressed by this invention is to find materials suitable for improving processing of petroleum products.

Statement of Invention

This invention is directed to a composition comprising: (a) 0.001% to 20% of at least one reaction product of (i) an imine; and (ii) an organic acid; and (b) crude oil wherein said reaction product is a salt of a carboxylic, phosphonic or sulphonic acid, and the salt has a polar group located two to ten chemical bonds from either : (i) a carbonyl carbon of a carboxylate group, a phosphorus atom of a phosphonate group or a sulfur atom of a sulfonate group; or (ii) a nitrogen atom of a protonated imine group; further wherein the salt has cation and an anion and is not zwitterionic.
This invention is directed further to a method for dispersing asphaltenes in a petroleum product by adding to the petroleum product 0.001% to 20% of at least one reaction product of: (a) an imine; and (b) an organic acid.

Detailed Description

All percentages are weight percentages based on the entire composition, unless otherwise indicated. A "polar" group is a functional group selected from among the following: hydroxy, oxime, amide, alkyl amide, ester, ammonium, alkylammonium, nitroso, mercapto, alkylthio, alkylsulfonyl, alkylsulfenyl, and alkylsulfinyl. An "organic acid" is an acid which is not a mineral acid. An "alkyl" group is a hydrocarbyl group having from one to twenty-two carbon atoms in a linear, branched or cyclic arrangement. Alkyl groups optionally have one or more double or triple bonds. Substitution on alkyl groups of one or more of halo, cyano, alkyl, alkoxy, or the aforementioned polar groups is permitted; alkoxy groups may in turn be substituted by one or more halo substituents. A "heteroalkyl" group is an alkyl group in which at least one carbon has been replaced by O, NR, or S, wherein R is hydrogen, alkyl, heteroalkyl, aryl or aralkyl. An "aryl" group is a substituent derived from an aromatic hydrocarbon compound. An aryl group has a total of from six to twenty ring atoms, and has one or more rings which are separate or fused. An "aralkyl" group is an "alkyl" group substituted by an "aryl" group. A "heterocyclic" group is a substituent derived from a heterocyclic compound having from five to twenty ring atoms, at least one of which is nitrogen, oxygen or sulfur. Preferably, heterocyclic groups do not contain sulfur. Substitution on aryl or heterocyclic groups of one or more of halo, cyano, alkyl, heteroalkyl, alkoxy or the aforementioned polar groups is permitted, with substitution by one or more halo groups being possible on alkyl, heteroalkyl or alkoxy groups. An "aromatic heterocyclic" group is a heterocyclic group derived from an aromatic heterocyclic compound. Preferably, heterocyclic groups in compounds used in this invention are aromatic heterocyclic groups.
An "organic functional group" is a functional group which does not contain metal atoms, and which has from one to twenty-two carbon atoms, hydrogen atoms, and optionally, contains heteroatoms, including but not limited to: nitrogen, oxygen, sulfur, phosphorus and halogen atoms. An organic functional group optionally contains double and/or triple bonds; rings, which are linked or fused; and if it is wholly or partly acyclic, the acyclic part can be linear or branched. Preferably, an organic functional group is an alkyl, heteroalkyl, aryl, aralkyl, heterocyclic or heterocyclic-alkyl group. In a preferred embodiment of this invention, at least one of the organic functional groups is a C₂-C₂₂ alkyl or heteroalkyl group, more preferably a C₇-C₂₂ alkyl or heteroalkyl group, more preferably a C₉-C₂₂ alkyl or heteroalkyl group, and most preferably, a C₁₅-C₂₂ alkyl group. Preferably, alkyl and heteroalkyl groups are unsubstituted.
In the present invention, at least one reaction product of an imine and an acid is added to a petroleum product, with the total amount of said reaction product(s) being from 0.001% to 20%, preferably from 0.001% to 10%, more preferably from 0.01% to 10%, more preferably from 0.01% to 1%, and most preferably from 0.02% to 0.2%. The reaction product has no new covalent bonds, i.e., bonds not present in the imine or the acid. The reaction product is either a salt or a physical mixture or complex of the imine and the acid. The reaction product used in this invention is a salt, preferably one that is soluble in oil at least at the aforementioned levels. Preferably, the salt has at least ten carbon atoms, more preferably at least 15 carbon atoms. Preferably, a salt used in this invention is aliphatic. Preferably, a salt used in this invention is acyclic. The salt used in this invention has a cation and an anion, and is not zwitterionic.
The organic acid used in this invention is a carboxylic, phosphonic or sulfonic acid. In a preferred embodiment of this invention, the acid is a carboxylic acid having no other acidic functional groups, i.e., groups having pK_a<6. In another preferred embodiment of this invention, the acid is a phosphonic acid having no other acidic functional groups. In another preferred embodiment of this invention, the acid is a sulfonic acid having no other acidic functional groups.
In an embodiment of the present invention in which the organic acid is a carboxylic, phosphonic or sulfonic acid, the separation between a polar group and a carboxylate, phosphonate or sulfonate ion (collectively: "conjugate base group"); or a protonated imine ("conjugate acid group"); is measured by the number of covalent chemical bonds intervening between either: (i) the atom of the polar group through which it is attached (e.g., the oxygen of hydroxy; the nitrogen of amino or nitroso; or the sulfur of sulfur-containing groups); or (ii) a carbonyl or imine carbon of the polar group (e.g., the carbonyl carbon of amide or the imine carbon of oxime); and one of: the carboxylate carbon, the phosphorus atom of a phosphonate, the sulfur atom of a sulfonate and the imine nitrogen atom. For example, in an imine salt of glycolic acid (hydroxyacetic acid), the oxygen of the hydroxy group is two bonds from the carbonyl carbon of the carboxylate group. Preferably, at least one polar group in a compound of this invention is located two to eight chemical bonds from either a conjugate acid or base functional group, more preferably from two to seven chemical bonds, and most preferably two, three, four, five or six chemical bonds from either a conjugate acid or base functional group.
A compound used in this invention optionally contains other carboxylate, phosphonate, sulfonate or protonated imine functional groups on one or more of the organic functional groups, preferably for a total of one to five conjugate acid functional groups and one to five conjugate base functional groups. Preferably, the compound has one conjugate acid group and one conjugate base group. Preferably, a polar group is a hydrogen bond donor, e.g., a hydroxy, oxime, amide, or alkyl amide functional group; or a nitro group. More preferably, a polar group is a hydroxy or amide functional group. Most preferably, a polar group is a hydroxy group.
In a preferred embodiment of the invention in which a salt of an imine and a carboxylic acid is added to crude oil, the salt has formula (I),
wherein R¹, R², R³ and R⁴ independently are hydrogen or organic functional groups. Other carboxylate groups or other protonated imine groups optionally are present on R¹, R², R³ or R⁴. Preferably, R¹, R², R³ and R⁴ independently are hydrogen, alkyl, heteroalkyl, aryl, aralkyl or heterocyclic. Preferably, R¹, R², R³ and R⁴ do not contain other carboxylate groups. Preferably, R² is C₂-C₂₂ alkyl, more preferably C₇-C₂₂ alkyl, more preferably C₉-C₂₂ alkyl, and most preferably, C₁₅-C₂₂ alkyl. Preferably, the imine part of the compound of formula (I) is derived from an unsubstituted C₁₅-C₂₂ alkyl amine, R²NH₂, preferably one which is an oil-soluble amine. In one embodiment, the alkyl amine is a tertiary alkyl primary amine, i.e., a primary amine in which the alkyl group is attached to the amino group through a tertiary carbon. Examples of commercially available tertiary alkyl primary amines are the Primene^™ amines available from Rohm and Haas Company, Philadelphia, PA. Preferably, a polar group is present and is located two to ten chemical bonds from either: a carbonyl carbon of a carboxylate group; or a nitrogen atom of a protonated imine group.
In one preferred embodiment of the invention, the carboxylate ion of a salt used in this invention has formula (II)
wherein R⁵ and R⁶ independently are hydrogen, alkyl or hydroxy; X is O^- or R⁷R⁸N; and R⁷ and R⁸ independently are hydrogen, alkyl, aryl, aralkyl or heteroalkyl. Preferably, R⁷ is hydrogen and R⁸ is 2-hydroxyethyl. In one preferred embodiment, R⁵ and R⁶ both are hydroxy and X is O^-. In another preferred embodiment, R⁵ is alkyl, X is R⁷R⁸N, and R⁶ is hydrogen; preferably, at least one of R⁵, R⁷ and R⁸ is C₈-C₂₂ alkyl, more preferably C₁₅-C₂₂ alkyl. The carboxylate ion of formula (II) occurs in a salt with at least one protonated imine.
In a preferred embodiment of this invention, the carboxylate ion of a salt is selected from the group consisting of:

and
wherein R⁹, R¹⁰, R¹¹, and R¹² independently are alkyl, aryl, aralkyl or heteroalkyl; m is zero or one; and n is one, two or three.
In addition to dispersing asphaltenes, the composition of the present invention typically also increases demulsibility, reduces sediment formation, reduces surface fouling and reduces corrosion. For crude oil recovery, the composition of the present invention can be injected directly into an injection well, or preferably diluted with solvent prior to injection. Suitable solvents include but are not limited to: petroleum distillates such as kerosene and gas oil; linear and branched aliphatic solvents such as pentane, hexanes, mixtures of nonanes and 2-ethylhexanes; cycloaliphatic mixtures commonly known as naphtha; aromatic solvents such as toluene, xylenes and commercial aromatic solvent mixtures; esters; ethers; alcohols such as ethanol, isopropanol, octanol and dodecanol; ketones such as acetone, cyclohexanone and acetophenone; and other polar solvents. Preferred dilutions are 0.01 to 50 wt% of the compound in the solvent, more preferred dilutions being 0.01 to 20 wt%, more preferred dilutions being 0.1 to 10%, and most preferred dilutions being 1 to 10 wt %.

Examples

Performance Criteria and Test Methods:

Asphaltene Dispersancy-test tube method: This test requires a previously made dispersion of asphaltene in xylenes (Aromatic 150 solvent) or asphaltenic heavy crude diluted in xylenes (Aromatic 150 solvent) at a known concentration. A solution of an additive formulation (0.1 mL, the active ingredient was typically at 5-10 wt%, making the treat rate 500-1000 ppm) was taken in to a 15.0 mL graduated glass centrifuge tube, and hexanes added such that the total volume in the tube became 10.0 mL. To this mixture of additive and hexanes, asphaltenic stock solution (0.1 mL) was added. The test tube was then capped, shaken vigorously for about a minute or 40-60 times by hand and allowed to stand. The volume of any precipitated asphaltenes settled at the bottom of the tube was recorded at 10, 30, 60, 90 and 1440 (24 h) min intervals. When no additive was used, the volume of asphaltenes precipitated in the first 0.5-1 h was 0.4-0.5 mL (4-5%); in fact, it was important to initially adjust the concentration of the asphaltene stock in such a way that under these conditions of dilution with paraffinic solvents, a 4-5 vol% of asphaltenic precipitation occurred. When the additive was an effective dispersant of asphaltene, then no precipitate was formed up to 24 h (Rating = 2; good). In some cases, no precipitation was observed in over 24 h to several days (Rating = 2+; excellent). If the additive was not a dispersant, then an almost immediate precipitation of asphaltenes occurred (Rating = 0; poor). Results for several imine salts are reported in the Table.

Table

1)	methylene imine of Primene^™ 81-R amine/3-hydroxyisobutyric acid salt
	formulated in hexanes (treat rate in oil: 1000 ppm)	2+

2)	methylene imine of Primene^™ JM-T amine/3-hydroxyisobutyric acid salt
	formulated in hexanes (treat rate in oil: 1000 ppm)	2+

3)	methylene imine of n-dodecylamine/glycolic acid salt
	formulated in hexanes (treat rate in oil: 1000 ppm)	2+

4)	methylene imine of Primene^™ JM-T amine/glycolic acid salt
	formulated in hexanes (treat rate in oil: 1000 ppm)	2+

The methylene imines were prepared by treating the indicated amine with formaldehyde.
The treat rate is the concentration of the salt in the crude oil.
Primene^™ amines are tertiary alkyl primary amines in which the alkyl groups are a mixture of isomers. In Primene^™ 81-R amine, the alkyl group is a mixture of C₁₀-C₁₅ alkyl groups; and in Primene^™ JM-T amine, of C₁₆-C₂₂ alkyl groups.

Claims

A composition comprising:
(a) 0.001% to 20% of at least one reaction product of (i) an imine; and (ii) an organic acid; and

(b) crude oil,
wherein said reaction product is a salt of a carboxylic, phosphonic or sulfonic acid, and the salt has a polar group located two to ten chemical bonds from either: (i) a carbonyl carbon of a carboxylate group, a phosphorus atom of a phosphonate group or a sulfur atom of a sulfonate group; or (ii) a nitrogen atom of a protonated imine group further wherein the salt has a cation and an anion and is not zwitterionic.
The composition of claim 1 in which said polar group is hydroxy, oxime, nitro, ester, amide or alkyl amide.
The composition of claim 4 in which said polar group is hydroxy, and is located two to six chemical bonds from either: (i) a carbonyl carbon of a carboxylate group, a phosphorus atom of a phosphonate group or a sulfur atom of a sulfonate group; or (ii) a nitrogen atom of an imine group.
The composition of claim 3 in which said at least one salt is a salt of an imine and a carboxylic acid, and has no other acidic functional groups.
A method for dispersing asphaltenes in a petroleum product; said method comprising adding to the petroleum product 0.001% to 20% of at least one salt of:
(a) an imine; and

(b) an organic acid.
The method of claim 5 in which said reaction product is a salt of a carboxylic, phosphonic or sulfonic acid, and the salt has a polar group located within two to ten chemical bonds of either: (i) a carbonyl carbon of a carboxylate group, a phosphorus atom of a phosphonate group or a sulfur atom of a sulfonate group; or (ii) a nitrogen atom of a protonated imine group.
The method of claim 6 in which said polar group is hydroxy, oxime, nitro, ester, amide or alkyl amide.
The method of claim 7 in which said polar group is located two to six chemical bonds from either: (i) a carbonyl carbon of a carboxylate group, a phosphorus atom of a phosphonate group or a sulfur atom of a sulfonate group; or (ii) a nitrogen atom of an imine group.
The method of claim 8 in which said at least one salt is a salt of an imine and a carboxylic acid, and has no other acidic functional groups.