EP1357172A2 - Oil-soluble imine-acid reaction products as asphaltene dispersants in crude oil - Google Patents
Oil-soluble imine-acid reaction products as asphaltene dispersants in crude oil Download PDFInfo
- Publication number
- EP1357172A2 EP1357172A2 EP03252271A EP03252271A EP1357172A2 EP 1357172 A2 EP1357172 A2 EP 1357172A2 EP 03252271 A EP03252271 A EP 03252271A EP 03252271 A EP03252271 A EP 03252271A EP 1357172 A2 EP1357172 A2 EP 1357172A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- imine
- salt
- alkyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2493—Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2691—Compounds of uncertain formula; reaction of organic compounds (hydrocarbons acids, esters) with Px Sy, Px Sy Halz or sulfur and phosphorus containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1608—Well defined compounds, e.g. hexane, benzene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
- C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
Definitions
- This invention relates generally to oil-soluble imine-acid reaction products useful in processing of crude oil.
- the problem addressed by this invention is to find materials suitable for improving processing of petroleum products.
- This invention is directed to a composition
- 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.
- 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
- 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.
- alkyl groups are 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.
- an organic functional group is an alkyl, heteroalkyl, aryl, aralkyl, heterocyclic or heterocyclic-alkyl group.
- At least one of the organic functional groups is a C 2 -C 22 alkyl or heteroalkyl group, more preferably a C 7 -C 22 alkyl or heteroalkyl group, more preferably a C 9 -C 22 alkyl or heteroalkyl group, and most preferably, a C 15 -C 22 alkyl group.
- alkyl and heteroalkyl groups are unsubstituted.
- 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.
- a reaction product used in this invention is a salt, preferably one that is soluble in oil at least at the aforementioned levels.
- the salt has at least ten carbon atoms, more preferably at least 15 carbon atoms.
- a salt used in this invention is aliphatic.
- a salt used in this invention is acyclic.
- a 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.
- the acid is a carboxylic acid having no other acidic functional groups, i.e., groups having pK a ⁇ 6.
- the acid is a phosphonic acid having no other acidic functional groups.
- the acid is a sulfonic acid having no other acidic functional groups.
- the separation between a polar group and a carboxylate, phosphonate or sulfonate ion 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.
- conjuggate base group e.g., the oxygen of hydroxy; the nitrogen of amino or nitroso; or the sulfur of sulfur-containing groups
- a carbonyl or imine carbon of the polar group e.g., the carbonyl carbon of amide or the imine carbon of oxime
- the oxygen of the hydroxy group is two bonds from the carbonyl carbon of the carboxylate group.
- 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.
- the compound has one conjugate acid group and one conjugate base group.
- 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.
- the salt has formula (I), wherein R 1 , R 2 , R 3 and R 4 independently are hydrogen or organic functional groups. Other carboxylate groups or other protonated imine groups optionally are present on R 1 , R 2 , R 3 or R 4 .
- R 1 , R 2 , R 3 and R 4 independently are hydrogen, alkyl, heteroalkyl, aryl, aralkyl or heterocyclic.
- R 1 , R 2 , R 3 and R 4 do not contain other carboxylate groups.
- R 2 is C 2 -C 22 alkyl, more preferably C 7 -C 22 alkyl, more preferably C 9 -C 22 alkyl, and most preferably, C 15 -C 22 alkyl.
- the imine part of the compound of formula (I) is derived from an unsubstituted C 15 -C 22 alkyl amine, R 2 NH 2 , preferably one which is an oil-soluble amine.
- 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.
- tertiary alkyl primary amines examples include the PrimeneTM amines available from Rohm and Haas Company, Philadelphia, PA.
- 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.
- the carboxylate ion of a salt used in this invention has formula (II) wherein R 5 and R 6 independently are hydrogen, alkyl or hydroxy; X is O - or R 7 R 8 N; and R 7 and R 8 independently are hydrogen, alkyl, aryl, aralkyl or heteroalkyl.
- R 7 is hydrogen and R 8 is 2-hydroxyethyl.
- R 5 and R 6 both are hydroxy and X is O - .
- R 5 is alkyl
- X is R 7 R 8 N
- R 6 is hydrogen; preferably, at least one of R 5 , R 7 and R 8 is C 8 -C 22 alkyl, more preferably C 15 -C 22 alkyl.
- the carboxylate ion of formula (II) occurs in a salt with at least one protonated imine.
- the carboxylate ion of a salt is selected from the group consisting of: and wherein R 9 , R 10 , R 11 , and R 12 independently are alkyl, aryl, aralkyl or heteroalkyl; m is zero or one; and n is one, two or three.
- the composition of the present invention typically also increases demulsibility, reduces sediment formation, reduces surface fouling and reduces corrosion.
- 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.
- 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 toluen
- 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 %.
- 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.
- asphaltenic stock solution 0.1 mL
- 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.
- 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.
- 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.
- PrimeneTM amines are tertiary alkyl primary amines in which the alkyl groups are a mixture of isomers.
- the alkyl group is a mixture of C 10 -C 15 alkyl groups; and in PrimeneTM JM-T amine, of C 16 -C 22 alkyl groups.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
- 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.
- The problem addressed by this invention is to find materials suitable for improving processing of petroleum products.
- 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.
- 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
- 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. Preferably, a 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. Preferably a salt used in this invention has a cation and an anion, and is not zwitterionic.
- Preferably, 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 pKa<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 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 %.
- 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.
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 (10)
- 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.
- The composition of claim 1 in which 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.
- The composition of claim 2 in which said polar group is hydroxy, oxime, nitro, ester, amide or alkyl amide.
- The composition of claim 3 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 4 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 6 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 7 in which said polar group is hydroxy, oxime, nitro, ester, amide or alkyl amide.
- The method of claim 8 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 9 in which said at least one salt is a salt of an imine and a carboxylic acid, and has no other acidic functional groups.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37487702P | 2002-04-23 | 2002-04-23 | |
US374877P | 2002-04-23 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1357172A2 true EP1357172A2 (en) | 2003-10-29 |
EP1357172A3 EP1357172A3 (en) | 2004-03-17 |
EP1357172B1 EP1357172B1 (en) | 2006-07-05 |
Family
ID=29270560
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20030252271 Expired - Lifetime EP1357172B1 (en) | 2002-04-23 | 2003-04-10 | Oil-soluble imine-acid reaction products as asphaltene dispersants in crude oil |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1357172B1 (en) |
CA (1) | CA2424915A1 (en) |
DE (1) | DE60306574D1 (en) |
MX (1) | MXPA03003359A (en) |
NO (1) | NO20031602L (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1357171A2 (en) * | 2002-04-23 | 2003-10-29 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
US7097759B2 (en) | 2003-05-23 | 2006-08-29 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
US10125306B2 (en) | 2014-10-02 | 2018-11-13 | Croda, Inc. | Asphaltene inhibition |
GB2573348A (en) * | 2018-05-05 | 2019-11-06 | Innospec Ltd | Method |
US10717917B2 (en) | 2016-06-24 | 2020-07-21 | Croda, Inc. | Method and composition for asphaltene dispersion |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3326975A (en) * | 1963-02-11 | 1967-06-20 | Eastman Kodak Co | Amide or imine hydrocarbon fuel stabilizers |
GB1506786A (en) * | 1976-02-20 | 1978-04-12 | Shell Int Research | Oil compositions |
US6140276A (en) * | 1995-12-22 | 2000-10-31 | Bp Exploration Operating Company Limited | Wax deposit inhibitors |
US6171521B1 (en) * | 1998-11-09 | 2001-01-09 | Nalco/Exxon Energy Chemicals, L.P. | Zwitterionic water-soluble substituted imine corrosion inhibitors |
EP1357171A2 (en) * | 2002-04-23 | 2003-10-29 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
EP1359208A2 (en) * | 2002-04-23 | 2003-11-05 | Rohm And Haas Company | Amine-acid reaction products as asphaltene dispersants in crude oil |
-
2003
- 2003-04-09 CA CA 2424915 patent/CA2424915A1/en not_active Abandoned
- 2003-04-09 NO NO20031602A patent/NO20031602L/en unknown
- 2003-04-10 EP EP20030252271 patent/EP1357172B1/en not_active Expired - Lifetime
- 2003-04-10 DE DE60306574T patent/DE60306574D1/en not_active Expired - Lifetime
- 2003-04-15 MX MXPA03003359 patent/MXPA03003359A/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3326975A (en) * | 1963-02-11 | 1967-06-20 | Eastman Kodak Co | Amide or imine hydrocarbon fuel stabilizers |
GB1506786A (en) * | 1976-02-20 | 1978-04-12 | Shell Int Research | Oil compositions |
US6140276A (en) * | 1995-12-22 | 2000-10-31 | Bp Exploration Operating Company Limited | Wax deposit inhibitors |
US6171521B1 (en) * | 1998-11-09 | 2001-01-09 | Nalco/Exxon Energy Chemicals, L.P. | Zwitterionic water-soluble substituted imine corrosion inhibitors |
EP1357171A2 (en) * | 2002-04-23 | 2003-10-29 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
EP1359208A2 (en) * | 2002-04-23 | 2003-11-05 | Rohm And Haas Company | Amine-acid reaction products as asphaltene dispersants in crude oil |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1357171A2 (en) * | 2002-04-23 | 2003-10-29 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
EP1357171A3 (en) * | 2002-04-23 | 2004-03-17 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
US7097759B2 (en) | 2003-05-23 | 2006-08-29 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
US10125306B2 (en) | 2014-10-02 | 2018-11-13 | Croda, Inc. | Asphaltene inhibition |
US10717917B2 (en) | 2016-06-24 | 2020-07-21 | Croda, Inc. | Method and composition for asphaltene dispersion |
GB2573348A (en) * | 2018-05-05 | 2019-11-06 | Innospec Ltd | Method |
Also Published As
Publication number | Publication date |
---|---|
DE60306574D1 (en) | 2006-08-17 |
CA2424915A1 (en) | 2003-10-23 |
NO20031602D0 (en) | 2003-04-09 |
EP1357172A3 (en) | 2004-03-17 |
MXPA03003359A (en) | 2005-08-16 |
NO20031602L (en) | 2003-10-24 |
EP1357172B1 (en) | 2006-07-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1666570B1 (en) | Formulations useful as asphaltene dispersants in petroleum products | |
US20070124990A1 (en) | Asphaltene dispersants for petroleum products | |
US7122112B2 (en) | Compounds containing amide and carboxyl groups as asphaltene dispersants in crude oil | |
US20170022109A1 (en) | Polyphosphoric acid resistant hydrogen sulfide scavenger for use in asphalt applications | |
CA2991180C (en) | Hydrogen sulfide scavenging additive compositions, and medium comprising the same | |
US9150472B2 (en) | Method and composition for inhibiting asphaltene deposition in a hydrocarbon mixture | |
EP1357172B1 (en) | Oil-soluble imine-acid reaction products as asphaltene dispersants in crude oil | |
US7097759B2 (en) | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil | |
US20040232044A1 (en) | Oil-soluble imine-acid reaction products as asphaltene dispersants in crude oil | |
EP1359208A2 (en) | Amine-acid reaction products as asphaltene dispersants in crude oil | |
US20040232042A1 (en) | Amine-acid reaction products as asphaltene dispersants in crude oil | |
EP1357171A2 (en) | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil | |
US20040232043A1 (en) | Amine-unsaturated acid adducts as asphaltene dispersants in crude oil | |
US10617994B2 (en) | Amine based hydrogen sulfide scavenging additive compositions of copper salts, and medium comprising the same | |
EP1359206A1 (en) | Amine-unsaturated acid adducts as asphaltene dispersants in crude oil | |
US20070074449A1 (en) | Additive concentrate | |
EP1359209A2 (en) | Compounds containing amide and carboxyl groups as asphaltene dispersants in crude oil | |
US20150218434A1 (en) | Method and composition for inhibiting wax in a hydrocarbon mixture | |
EP0744453B1 (en) | Fuel compositions containing organic molybdenum complexes | |
WO2005085396A1 (en) | Method for corrosion control of refining units by acidic crudes | |
CN114292205A (en) | Marine fuel oil stability additive and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20030426 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
17Q | First examination report despatched |
Effective date: 20040427 |
|
AKX | Designation fees paid |
Designated state(s): DE FR GB |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60306574 Country of ref document: DE Date of ref document: 20060817 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061006 |
|
EN | Fr: translation not filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070410 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20070410 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070511 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070410 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060705 |