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
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
  • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
• • 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
  • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
  • C10L1/224—Amides; Imides carboxylic acid amides, imides
• • 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

Definitions

• This invention relates generally to a method or dispersing asphaltenes 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 5% of at least one reaction product of: (i) an amine; and (ii) a carboxylic, phosphonic or sulfonic acid; and (b) crude oil; provided that the reaction product has a hydrogen bond donor group located two to eight chemical bonds from either: (i) a carbonyl carbon of a carboxylic acid, a phosphorus atom of a phosphonic acid or a sulfur atom of a sulfonic acid; or (ii) a nitrogen atom of an amino group.
• This invention is directed further to a method for dispersing asphaltenes in a petroleum product by adding to the petroleum product 0.001% to 5% of at least one reaction product of: (i) an amine; and (ii) a carboxylic, phosphonic or sulfonic acid; and (b) crude oil; provided that the reaction product has a hydrogen bond donor group located two to eight chemical bonds from either: (i) a carbonyl carbon of a carboxylic acid, a phosphorus atom of a phosphonic acid or a sulfur atom of a sulfonic acid; or (ii) a nitrogen atom of an amino group.
• a “hydrogen bond donor group” is a group capable of forming a hydrogen bond with an oxygen or nitrogen atom, e.g., a hydroxy, oxime, amide, or alkyl amide functional group.
• 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.
• 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.
• 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.
• reaction product of an amine and an acid is added to a petroleum product, with the total amount of said reaction product(s) being from 0.001% to 5%, preferably from 0.01% to 5%, more preferably from 0.01% to 1%, more preferably from 0.01% to 0.2%, and most preferably from 0.02% to 0.2%.
• the reaction product has no new covalent bonds, i.e., bonds not present in the amine or the acid.
• the reaction product is either a salt or a physical mixture or complex of the amine 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 has a cation and an anion, and is not zwitterionic.
• 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 hydrogen bond donor group and the carboxylic, phosphonic or sulfonic acid or the amine is measured by the number of covalent chemical bonds intervening between either: (i) an oxygen of a hydroxy group; or (ii) a carbonyl or imine carbon of amide or oxime; and one of: the carboxylic acid carbonyl carbon, the phosphorus atom of a phosphonic acid, the sulfur atom of a sulfonate and the amine nitrogen atom.
• 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 six chemical bonds from a carboxylic acid carbonyl carbon, the phosphorus atom of a phosphonic acid, the sulfur atom of a sulfonate or the amine nitrogen atom; and most preferably two, three, four or five chemical bonds from a carboxylic acid carbonyl carbon, the phosphorus atom of a phosphonic acid, the sulfur atom of a sulfonate or the amine nitrogen atom.
• 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 hydrogen bond donor group is a hydroxy or amide functional group. Most preferably, a hydrogen bond donor group is a hydroxy group.
• the salt has formula (I), R 1 R 2 R 3 N+ R 4 COO- wherein R 1 , R 2 , R 3 independently are hydrogen or organic functional groups, provided that at least one is not hydrogen; and R 4 is an organic functional group.
• 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.
• one of R 1 , R 2 and R 3 is C 10 -C 22 alkyl, more preferably C 12 -C 22 alkyl, and most preferably, C 16 -C 22 alkyl.
• the protonated amine part of the compound of formula (I) is derived from an unsubstituted C 10 -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 alkyl.
• 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 16 -C 22 alkyl.
• the carboxylate ion of formula (II) occurs in a salt with at least one protonated amine.
• the amine is an unsubstituted alkyl amine, preferably a C 16 -C 22 alkyl amine.
• the carboxylate ion of a salt is selected from the group consisting of: and R 12 COO- wherein R 9 is hydrogen or C 1 -C 22 alkyl; R 10 and R 11 independently are hydrogen or C 1 -C 22 alkyl; R 12 is C 16 -C 22 alkyl; and n is one or two.
• R 9 is hydrogen or C 1 -C 6 alkyl.
• R 10 and R 11 independently are hydrogen or C 1 -C 6 alkyl, most preferably hydrogen, methyl or ethyl.
• the ammonium ion of a salt used in the invention has the formula R 13 R 14 R 15 NH+, wherein R 13 is C 2 -C 6 alkyl, or C 2 -C 6 heteroalkyl with one or two carbon atoms replaced by oxygen atoms, and in either case substituted by one or two hydroxy groups; and R 14 and R 15 independently are hydrogen, methyl or ethyl.
• R 13 is 2-hydroxyethyl or 3-hydroxypropyl.
• R 14 and R 15 are hydrogen.
• the carboxylate ion of the salt is selected from the group consisting of: and
• 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.
• Salts of hydroxy acids and amines 1 salicylic acid/oleylamine (1:1) salt hexanes; treat rate: 1000 ppm 2+ 2 oleylamine/2-hydroxyisobutyric acid salt hexanes; treat rate: 1000 ppm 2+ 3 oleylamine/3,4-dihydroxybenzoic acid salt hexanes; treat rate: 1000 ppm 2+ 4 oleylamine/bicine salt hexanes; treat rate: 1000 ppm 2+ 5 oleylamine/citric acid; 2:1 salt hexanes; treat rate: 1000 ppm 2+ 6 oleylamine/citric acid; 3:1 salt hexanes; treat rate: 1000 ppm 2+ Salts of hydroxy amines and acids 7 SylfatTM FA-1/ethanolamine salt hexanes; 1000 ppm 2+ 8 SylfatTM FA-1/diethanolamine salt hexanes; 1000 ppm 1 9 N-Methyl-N-o
• the treat rate is the concentration of the salt in the crude oil.
• AROMATIC 150 SOLVENT is a solvent mixture with a boiling range of 184-204°C which contains xylene isomers, and which is available from Exxon Mobil Chemical Co., Houston TX; this solvent, at a treat rate of 10,000 ppm has a rating of 0.
• 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.
• SylfatTM FA-1 is a naturally-occurring mixture of unsaturated C 18 aliphatic acids, available from Arizona Chemicals Co., Jacksonville, FL.

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• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Citations (9)

• 2003
  • 2003-04-09 CA CA 2424903 patent/CA2424903A1/fr not_active Abandoned
  • 2003-04-09 NO NO20031605A patent/NO20031605L/no not_active Application Discontinuation
  • 2003-04-10 EP EP03252268A patent/EP1359208A3/fr not_active Withdrawn
  • 2003-04-15 MX MXPA03003370 patent/MXPA03003370A/es unknown

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