WO2024236268A1 - Procédé de désémulsification - Google Patents

Procédé de désémulsification Download PDF

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Publication number
WO2024236268A1
WO2024236268A1 PCT/GB2024/051167 GB2024051167W WO2024236268A1 WO 2024236268 A1 WO2024236268 A1 WO 2024236268A1 GB 2024051167 W GB2024051167 W GB 2024051167W WO 2024236268 A1 WO2024236268 A1 WO 2024236268A1
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WIPO (PCT)
Prior art keywords
additive composition
hydrocarbon
amine compounds
aldehyde
alkylphenol
Prior art date
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Ceased
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PCT/GB2024/051167
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English (en)
Inventor
Romain DESNOS
Elise GUIMARD
Hubert Jungbluth
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Innospec Ltd
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Innospec Ltd
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Application filed by Innospec Ltd filed Critical Innospec Ltd
Priority to MX2025013154A priority Critical patent/MX2025013154A/es
Priority to CN202480044043.1A priority patent/CN121443706A/zh
Priority to EP24726695.0A priority patent/EP4705409A1/fr
Publication of WO2024236268A1 publication Critical patent/WO2024236268A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/682—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of chemical compounds for dispersing an oily layer on water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981—Condensation polymers of aldehydes or ketones
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/32—Hydrocarbons, e.g. oil
    • C02F2101/325—Emulsions

Definitions

  • the present invention relates to a method of demulsifying a hydrocarbon emulsion and to the use of an additive composition to demulsify a hydrocarbon emulsion.
  • the present invention relates to a method of demulsifying a hydrocarbon emulsion using an additive composition comprising one or more alkoxylated amine compounds and one or more aldehyde alkylphenol copolymers.
  • Hydrocarbons such as crude oil (produced from geological formations) typically contain inorganic salts, such as calcium, sodium and magnesium chlorides. These salts may cause precipitate and emulsion formation, which can lead to operational problems such as the obstruction of flow through pipes, corrosion, increased heat capacity, fouling of equipment, and/or poisoning of catalysts. Such salts are therefore removed before processing of the hydrocarbons.
  • Inorganic salts are typically removed from the hydrocarbons by washing with an aqueous component such as water.
  • an aqueous component such as water.
  • water washing produces undesirable water-hydrocarbon emulsions and if not removed, the water may cause corrosion to equipment, such as processing and distillation equipment.
  • Water may also be introduced into hydrocarbons during processing and/or storage, again leading to the formation of undesirable emulsions.
  • An aqueous component such as water may be separated from an emulsion using an appropriate emulsion-breaking additive (also termed an emulsion breaker) or demulsifier, and following separation, the aqueous component such as water may be removed by a suitable method.
  • an appropriate emulsion-breaking additive also termed an emulsion breaker
  • demulsifier demulsifier
  • a method of demulsifying a hydrocarbon emulsion comprising adding an additive composition to the hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • an additive composition to demulsify a hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • a method of improving the demulsification of a hydrocarbon emulsion comprising adding an additive composition to the hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • an additive composition to improve the demulsification of a hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde- alkylphenol copolymers.
  • a method of improving the demulsification action of one or more alkoxylated amine compounds in a hydrocarbon emulsion comprising admixing the one or more alkoxylated amine compounds with one or more aldehyde-alkylphenol copolymers to provide an additive composition, and adding the additive composition to the hydrocarbon emulsion.
  • a sixth aspect of the present invention there is provided the use of one or more aldehyde-alkylphenol copolymers to improve the demulsification action of one or more alkoxylated amine compounds in a hydrocarbon emulsion.
  • an additive composition comprising a combination of (I) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers has been found to provide unexpected advantages.
  • alkoxylated amine compounds are known as demulsifiers
  • the addition of one or more aldehyde-alkylphenol copolymers (which are known to be dispersants) to one or more alkoxylated amine compounds improves the demulsification action of the one or more alkoxylated amine compounds, such as by accelerating the speed of separation, improving clean separation of the aqueous component (for example water) from the hydrocarbon component, increasing the volume of water separated and/or minimising residual (or unresolved) emulsion.
  • aqueous component for example water
  • alkyl and alkylene include both straight and branched chain alkyl and alkylene groups respectively unless otherwise stated.
  • aryl refers to an organic moiety derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic.
  • aralkyl refers to alkyl moieties substituted with an aryl group, wherein the aryl group is an organic moiety derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic.
  • An example of an aralkyl group is a benzyl group.
  • hydrocarbyl is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
  • the term “comprising” or “comprises” means including the component(s) specified but not to the exclusion of the presence of other components.
  • the term “consisting essentially of’ or “consists essentially of’ means including the components specified but excluding other components except for components added for a purpose other than achieving the technical effect of the invention.
  • the term “consisting of or “consists of” means including the components specified but excluding other components.
  • endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.70 and 3.80, when referring to, for example, measurements).
  • the recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • the term "and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a list is described as comprising group A, B, and/or C, the list can comprise A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.
  • a method of demulsifying a hydrocarbon emulsion comprising adding an additive composition to the hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • an additive composition to demulsify a hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • hydrocarbon emulsion would be well understood by a person skilled in the art to mean an emulsion comprising a hydrocarbon component and an aqueous component.
  • the hydrocarbon emulsion will comprise an aqueous component dispersed in a hydrocarbon component, such as droplets of the aqueous component dispersed throughout the hydrocarbon component wherein the aqueous component is not soluble in or miscible with the hydrocarbon component.
  • the hydrocarbon emulsion may be known as a water in hydrocarbon, or a water in oil, emulsion.
  • demulsifying a hydrocarbon emulsion we mean to separate an aqueous component from a hydrocarbon component of the hydrocarbon emulsion.
  • this provides the hydrocarbon in a form that is substantially free or is free of the aqueous component such that no emulsion is provided (i.e. such that demulsification occurs).
  • the amount of separation can be termed the level of demulsification, by which we mean the volume of the aqueous component that is separated from the hydrocarbon component of the hydrocarbon emulsion.
  • the level of demulsification (or separation) may be measured using any suitable method, such as the method described in the examples provided herein.
  • references herein to “demulsifying”, “demulsification”, “demulsify” and suchlike would be well understood by persons skilled in the art.
  • these terms would be well understood to refer to separating, or improving the separation of, an emulsion, for example to substantially or completely separate the components of the emulsion.
  • the demulsification provides a clean interface between the aqueous and the hydrocarbon components of the emulsion.
  • substantially free of the aqueous component we mean that any aqueous component (or water) that is present, if any, is present as an incidental impurity.
  • free of the aqueous component we mean that no aqueous component (or water) is present.
  • the method of the first aspect of the invention comprises adding an additive composition to the hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • the use of the second aspect of the invention refers to the use of an additive composition to demulsify a hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • both the method and use of the invention make use of an additive composition that comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • the additive composition acts to demulsify a hydrocarbon emulsion.
  • the additive composition may suitably improve or enhance the demulsifying effect compared to the use of an alkoxylated amine compound alone.
  • the demulsifying effect may be enhanced by accelerating the demulsification, providing a clean interface between the aqueous and the hydrocarbon components and/or minimising residual emulsion in the aqueous component.
  • the additive composition may accelerate the demulsification of a hydrocarbon emulsion compared to the use of an alkoxylated amine compound alone and/or may provide complete demulsification of a hydrocarbon emulsion in a time period of 10 to 60 minutes, for example 10 to 45 or 10 to 40 minutes, such as 10 to 20 minutes.
  • the additive composition may, for example, improve the level of demulsification (or separation) of a hydrocarbon emulsion compared to a hydrocarbon emulsion without the additive composition at intervals after addition of the additive composition (when present), for example after 10 minutes, after 15 minutes or after 60 minutes.
  • the level of demulsification (or separation) of a hydrocarbon emulsion may be measured 10 minutes after addition of the additive composition thereto and compared to the hydrocarbon emulsion without the additive composition. After 10 minutes, an improvement (or increase) in the level of demulsification (or separation) of at least 500%, for example at least 750%, suitably at least 1000% or at least 1500% may be achieved for the hydrocarbon emulsion with the additive composition added compared to the hydrocarbon emulsion without the additive composition.
  • the level of demulsification (or separation) of a hydrocarbon emulsion may be measured 60 minutes after addition of the additive composition thereto and compared to the hydrocarbon emulsion without the additive composition. After 60 minutes, an improvement (or increase) in the level of demulsification (or separation) of at least 0.5%, for example at least 1 .0%, or at least 1.5% or at least 2.0%, suitably at least 2.5 % or at least 10% may be achieved for the hydrocarbon emulsion with the additive composition added compared to the hydrocarbon emulsion without the additive composition.
  • the additive composition comprises one or more alkoxylated amine compounds.
  • the additive composition may comprise one alkoxylated amine compound.
  • the additive composition may comprise two or more alkoxylated amine compounds.
  • the additive composition may comprise any alkoxylated amine compound(s).
  • an “alkoxylated amine compound” we mean to include any compound including one or more amine functional groups which has been reacted with at least one alkylene oxide moiety, i.e. such that the compound comprises one or more amine functional groups and at least one alkylene oxide residue. Such compounds will be known to persons skilled in the art.
  • the alkoxylated amine compounds include more than one alkylene oxide residue.
  • Suitable alkylene oxide residues include ethylene oxide residues, propylene oxide residues, butylene oxide residues and mixtures thereof.
  • the alkoxylated amine compounds include ethylene oxide residues, propylene oxide residues, or mixtures thereof.
  • the one or more alkoxylated amine compounds may each comprise one or more alkylene oxide residues independently selected from ethylene oxide residues, propylene oxide residues and butylene oxide residues.
  • the one or more alkoxylated amine compounds are independently selected from one or more of an alkoxylated monoamine and one or more of an alkoxylated polyamine (which may be an alkoxylated diamine).
  • polyamine we mean a compound including two or more amine groups (including a diamine compound).
  • Some preferred alkoxylated amine compounds for use herein have the formula A-(RO)n-H wherein A is the residue of an amine and RO is an alkylene oxide residue (i.e. wherein R represents an alkylene moiety) and n is at least one.
  • R is preferably an ethylene, propylene or butylene group.
  • R may be an n-propylene or n-butylene group or an isopropylene or isobutylene group.
  • R may be - CH 2 CH 2 -, -CH 2 CH(CH 3 )-, - CH 2 C(CH 3 )2, -CH(CH 3 )CH(CH 3 )- or -CH 2 CH(CH 2 CH 3 )-.
  • R may comprise a mixture of isomers.
  • the alkylene oxide residue may include the moieties -CH 2 CH(CH 3 )- and -CH(CH 3 )CH 2 - in any order within the chain.
  • R may be the same or different.
  • R may comprise a mixture of different alkylene moieties, for example ethylene, propylene or butylene moieties. Block copolymer units are preferred in this case.
  • R is ethylene and/or propylene. More preferably R is -CH 2 CH 2 - and/or -CH(CH 3 )CH 2 -, such as -CH 2 CH 2 - or -CH(CH 3 )CH 2 -.
  • the one or more alkoxylated amine compounds comprise a mixture of ethylene oxide residues and propylene oxide residues.
  • n is at least 1.
  • n is from 5 to 1000, preferably from 5 to 500, more preferably from 10 to 400, more preferably from 15 to 300, preferably from 20 to 250, suitably from 30 to 200, preferably from 50 to 150.
  • A is the residue of an amine.
  • A is the residue of an amino or polyamino compound having at least one NH group.
  • Suitable amino compounds include primary, secondary, and tertiary monoamines having hydrocarbon substituents of 1 to 30 carbon atoms or hydroxyl-substituted hydrocarbon substituents of 1 to about 30 carbon atoms.
  • the ammo compounds include tertiary monoamines haying hydroxyi-substituted alky! substituents of 1 to 5 carbon atoms.
  • each substituent is the same.
  • Suitable monoamines may, for example, be selected from triethanolamine, diethanolamine, ethanolamlne, tri-n-propanoiamine, dl-n-propanolamlns, n-propanolamine, triisopropanolamfh®, diisopfopanolamine, and isopropanolamine.
  • a preferred monoamine is triethanolamine.
  • A is the residue of a polyamine.
  • Poiyamlnes may be selected from any compound including two or more amine groups.
  • the polyamine is a (poiy)alkylene polyamine (by Which is meant an alkylene polyamine or a poiyalkylene polyamine: including in each case a diamine, within the meaning of “polyamine”).
  • the polyamine is a (polyjalkylene polyamine in which the alkylene component has 1 to 6, preferably 1 to 4. most preferably 2 to 3, carbon atoms.
  • the polyamine is a (poly)ethylene polyamine (that. is an ethylene polyamine or a polyethylene polyamine).
  • the polyamine has 2 to 15 nitrogen atoms, preferably 2 to TO nitrogen atoms, more preferably 2 to 8 nitrogen atoms.
  • the poiyamine may, for example, be selected from ethytenediamine. diethyienetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene-hexamine. hexaethyieneheptamine, heptaethyleneoctamine, propane ⁇ 1,2*diamine, 2(2-amino-ethyiamino)ethanol, N’.N ⁇ bis (2- aminoethyl) ethylenediamine (NCCHaCHaNHaJs), diphenyl 4, 4’-diamtne, diamino naphthalene, phenylene diamine, xylene diamine, 1,2-diaminopropane and 1 ,3-diaminopropane, 1,4- diaminobutane, 1,5-diamsno pentane and 1 ,6-diamino hexane.
  • a preferred polyamine is ethylenediamine
  • A is the residue of ethyienediamine or triethanolamine.
  • the one or more alkoxy lated amine compounds may be selected f rom one or more oom pounds of formula (IA): wherein EO represents an ethylene oxide residue, PO represents a propylene oxide residue and at least one of a, b, c, d, e, f, g and h Is not 0.
  • the compounds of formula (IA) way be prepared by reaction of ethylene diamine with ethylene oxide and propylene oxide (when both present) in any combination thereof and in any order, i.e. so as to provide compounds of formula (IA) in which the ethylene oxide and propylene oxide residues may be present in any combination and in any order as bonded to the nitrogen of the amine group.
  • the compounds of formula (I A) are prepared by reaction of ethylene diamine with ethylene oxide, removal of residual ethylene oxide, followed by subsequent reaction with propylene oxide, such that a block copolymer is formed.
  • each of a, b. c, d, e, f , g and h is at least one.
  • the sum of a , b, c, d, e ⁇ f, g and h is from 10 to 500, suitably from 20 to 250, preferably from 40 to 200, more preferably from 50 to 150.
  • the one or more alkoxylated amine compounds may be selected from one or more compounds of formula (IB): wherein EO represents an ethylene oxide residue, PO represents a propylene oxide residue and at least one of a', b’, c' t d’> a', and f is not 0.
  • the campounds of formula (IB) may be prepared by reaction of triethanolamine with ethylene oxide and propylene oxide (when both present) in any combination thereof and in any order, i.e. so as to provide compounds of formula (IB) in which the ethylene oxide and propylene oxide residues may be present in any combination and in any order as bonded to the oxygen of the ethoxy group.
  • the compounds of formula (IB) are prepared by reaction of triethanolamine with ethylene oxide, removal of residual ethylene oxide, followed by subsequent reaction with propylene oxide, such that a block copolymer is formed.
  • each of a’, b', o’, d', e f , and f is at least one.
  • the sum of a ⁇ b . c ⁇ d’. e’, and f is from 10 to 500, suitably from 20 to 250, preferably from 40 to 200, more preferably from 50 to 150.
  • polymeric compounds of formulae (IA) and (IB) are usually in the form of mixtures.
  • the ethylene oxide and propylene oxide residues may be present in any combination and in any order as bonded to the nitrogen or oxygen of the amine or ethoxy groups respectively.
  • the one or more alkoxylated amine compounds may be selected from one or more compounds of formula (IA) and/or one or more compounds of formula (IB).
  • the one or more alkoxylated amine compounds have a number average molecular weight of from 500 to 20000, preferably from 1000 to 15000, more preferably from 2000 to 12000, for example from 2500 to 10000.
  • the additive composition may comprise the one or more alkoxylated amine compounds in any suitable amount.
  • the additive composition may comprise at least 5 wt%, such as at least 10 wt% or at least 15 wt% of the one or more alkoxylated amine compounds, and/or the additive composition may comprise up to 45 wt%, such as up to 40 wt% or up to 35 wt% of the one or more alkoxylated amine compounds.
  • the additive composition may, for example, comprise from 5 to 45 wt%, or from 10 to 40 wt%, such as from 15 to 35 wt%, of the one or more alkoxylated amine compounds.
  • the additive composition comprises one or more aldehyde-alkylphenol copolymers.
  • the additive composition may comprise two or more aldehyde-alkylphenol copolymers.
  • the additive composition may comprise any aldehyde-alkylphenol copolymer(s). Such copolymers will be known to persons skilled in the art.
  • the aldehyde-alkylphenol copolymer(s) do not comprise any alkoxy groups or residues, i.e. the aldehyde-alkylphenol copolymer(s) are non-alkoxylated.
  • the aldehyde-alkylphenol copolymers may be prepared by copolymerising an aldehyde compound and an alkylphenol compound.
  • the aldehyde compound used to prepare the aldehyde-alkylphenol copolymers is selected from formaldehyde or a reactive equivalent thereof (for example paraformaldehyde), C2 to C10 aldehydes and aromatic aldehydes (for example benzaldehyde).
  • Preferred aldehyde-alkylphenol copolymers are copolymers of formaldehyde and an alkylphenol compound.
  • the one or more aldehyde-alkylphenol copolymers may be selected from one or more copolymers of formaldehyde and an alkylphenol.
  • the alkylphenol compound used to prepare the aldehyde-alkylphenol copolymers is mono- substituted with an alkyl group, preferably at the para position.
  • Preferred alkyl groups have 1 to 40 carbon atoms, preferably 2 to 36 or 9 to 36 carbon atoms, more preferably 4 to 30 carbon atoms, for example 4 to 28 or 4 to 24 carbon atoms, or for example 6 to 28 or 6 to 24 carbon atoms.
  • the alkylphenol compound may suitably be a C2- C36 or a C9- C36 or a C4- C28 alkyl substituted phenol.
  • the alkylphenol compound may suitably be a polyisobutenyl (PIB) substituted phenol.
  • Polyisobutenyl (PIB) substituted phenols include a hydrocarbyl chain having the repeating unit: wherein m is from 3 to 54.
  • polyisobutenes and so-called "highly-reactive" polyisobutenes are suitable for use in preparing the alkylphenol compounds.
  • Highly reactive polyisobutenes in this context are defined as polyisobutenes wherein at least 50 mol%, preferably 70 mol% or more, of the terminal olefinic double bonds are of the vinylidene type as described in EP0565285.
  • Particularly preferred polyisobutenes are those having more than 80 mol% and up to 100 mol% of terminal vinylidene groups such as those described in EP1344785.
  • alkylphenol compounds for example polyisobutene substituted phenols, are known to the person skilled in the art, and include the methods described in EP831141 .
  • the PIB substituent of a suitable polyisobutene substituted phenol may preferably have an average molecular weight of 200 to 3000.
  • the PIB substituent has a molecular weight of at least 225, suitably at least 250, preferably at least 275, suitably at least 300, for example at least 325 or at least 350.
  • the PIB substituent may have an average molecular weight of at least 375, preferably at least 400, suitably at least 475, for example at least 500.
  • the PIB substituent may have an average molecular weight of up to 2800, preferably up to 2600, for example up to 2500 or up to 2400.
  • the PIB substituent may have an average molecular weight of from 240 to 2500, for example from 450 to 2400, preferably from 500 to 1500, suitably from 550 to 1300.
  • a suitable polyisobutene substituted phenyl may include a PIB substituent having an average molecular weight of from 200 to 600.
  • a suitable polyisobutene substituted phenyl may include a PIB substituent having an average molecular weight of from 500 to 1000.
  • a suitable polyisobutene substituted phenyl may include a RIB substituent having an average molecular weight of from 700 to 1300.
  • a suitable poly isobutene substituted pheny l may include a RIB substituent having an average molecular weight of from 1000 to 2000.
  • a suitable polyisobutene substituted phenyl may include a RIB substituent having an average molecular weight of from 1700 to 2600. for example 2000 to .2500,
  • the one or more atdehyde-alkylphenoi copolymers may be selected from one or more compounds Of formula (il) and/or (Hi): wherein each R 1 independently represents hydrogen or a hydrocarbyi group and q is at least 1 .
  • q is from 2 to 12, preferably from 5 to 9; and R 1 is C3-C25 such as C3-C24, preferably C1- C12, alkyl (for example isononyl, isobutyl or. amyl), C6-C12 aryi or hydroxyaryl, or C2-C12 aralkyl
  • aldehyde-alkylphenol copolymers may be prepared from mixtures of monomers, in particular compounds in which R 1 comprises a mixture of alkyl groups.
  • Further suitable aldehyde-alkylphenol copolymers for use herein include compounds of formula (II) in which the terminal phenol groups are further functionalised, for example by reaction with a fatty acid or an amine and an aldehyde via a Mannich reaction. Compounds of this type are described, for example, in US2007/221539.
  • the aldehyde-alkylphenol copolymer(s) have a number average molecular weight of from 400 to 20000 or from 500 to 20000, preferably from 400 to 10000 or from 1000 to 10000, more preferably from 400 to 1500 or from 1500 to 5000, for example from 400 to 3500 or from 2000 to 3500 g/mol.
  • the additive composition may comprise the one or more aldehyde-alkylphenol copolymer(s) in any suitable amount.
  • the additive composition may comprise at least 5 wt%, such as at least 10 wt% or at least 15 wt% of the one or more aldehyde-alkylphenol copolymers, and/or the additive composition may comprise up to 45 wt%, such as up to 40 wt% or up to 35 wt% of the aldehyde-alkylphenol copolymer(s).
  • the additive composition may, for example, comprise from 5 to 45 wt%, or from 10 to 40 wt%, such as from 15 to 35 wt%, of the aldehyde-alkylphenol copolymers.
  • the additive composition may comprise from 10 to 40 wt% of the one or more alkoxylated amine compounds and from 10 to 40 wt% of the one or more aldehyde-alkylphenol copolymers.
  • the additive composition may comprise from 15 to 35 wt% of the one or more alkoxylated amine compounds and from 15 to 35 wt% of the one or more aldehyde-alkylphenol copolymers.
  • the additive composition may comprise one or more additional components in any suitable amount.
  • the additive composition may further comprise a solvent.
  • the additive composition may comprise any suitable solvent.
  • the additive composition may comprise one or more solvents selected from an aromatic hydrocarbon (such as benzene, toluene, xylene or a C11-C14 aromatic hydrocarbon), a light or heavy aromatic naphtha, an aliphatic hydrocarbon (such as n-alkanes, isoalkanes, cyclic alkanes), a paraffin (which may be a long-chain paraffin or a mixture of paraffins such as kerosene) a heterocyclic compound with high boiling point and combinations thereof.
  • a preferred solvent may be kerosene.
  • the additive composition may comprise a solvent in any suitable amount.
  • the additive composition may comprise at least 10 wt%, such as at least 15 wt% or at least 20 wt% of the solvent, and/or the additive composition may comprise up to 50 wt%, such as up to 30 wt%, or such as up to 25 wt% of the solvent.
  • the additive composition may, for example, comprise from 10 to 50 wt% or from 20 to 50 wt%, for example from 10 to 30 wt%, such as from 15 to 25 wt%, of the solvent.
  • the additive composition may comprise from 10 to 40 wt% of the one or more alkoxylated amine compounds, from 10 to 40 wt% of the one or more aldehyde-alkylphenol copolymers and from 20 to 50 wt% of a solvent.
  • the additive composition may comprise from 10 to 40 wt% of the one or more alkoxylated amine compounds, from 10 to 40 wt% of the one or more aldehyde-alkylphenol copolymers and from 10 to 30 wt% of a solvent.
  • the additive composition may comprise from 15 to 35 wt% of the one or more alkoxylated amine compounds, from 15 to 35 wt% of the one or more aldehyde-alkylphenol copolymers and from 20 to 50 wt% of a solvent.
  • the additive composition may comprise from 15 to 35 wt% of the one or more alkoxylated amine compounds, from 15 to 35 wt% of the one or more aldehyde-alkylphenol copolymers and from 10 to 25 wt% of a solvent.
  • the additive composition may further comprise an additional additive selected from one or more of a conductivity improver, a combustion improver, an asphaltene dispersant, a fuel antioxidant, a cold flow improver, a wax anti-setting agent, a biofuel instability inhibitor, a blended fuel separation inhibitor, a detergent and a dispersant.
  • additional additives selected from one or more of a conductivity improver, a combustion improver, an asphaltene dispersant, a fuel antioxidant, a cold flow improver, a wax anti-setting agent, a biofuel instability inhibitor, a blended fuel separation inhibitor, a detergent and a dispersant.
  • the additive composition may be added to the hydrocarbon emulsion in any suitable manner.
  • the additive composition may be dispersed within the hydrocarbon emulsion.
  • the method or use of the present invention may be used with any hydrocarbon emulsion from which it is desired to separate an aqueous component (e.g. water) from the hydrocarbon component of the emulsion.
  • an aqueous component e.g. water
  • Suitable hydrocarbon emulsions include those in which the hydrocarbon is selected from a residual fuel oil (such as high sulfur fuel oil, very low sulfur fuel oil and ultra low sulfur fuel oil), a distillate fuel oil, a bio-derived fuel oil, a cracked process stream, a synthetic fuel, a gas oil (such as B7 gasoil, vacuum gas oil, light heating oil, diesel, biodiesel and middle distillate) and a plastic pyrolysis oil.
  • the hydrocarbon may be selected from crude oil, heavy fuel oil, gasoline, kerosenes, diesel fuels, transformer oils, turbine oils, heating oils, marine fuels, bunker oils, lubricating oils and mixtures thereof.
  • the hydrocarbon may be crude oil.
  • the hydrocarbon emulsion has formed by addition of an aqueous component (e.g. water) to the hydrocarbon component so as to form an emulsion.
  • an aqueous component e.g. water
  • the hydrocarbon emulsion may comprise a hydrocarbon component and an aqueous component.
  • the hydrocarbon emulsion may comprise an aqueous component, for example wherein the aqueous component may be present in an amount of less than 95 vol%, less than 90 vol%, less than 80 vol%, for example less than 60 vol%, or less than 40 vol%, suitably less than 30%, or less than 20 vol%, or less than 15 vol%.
  • the aqueous component of the hydrocarbon emulsion may be selected from one or more of fresh water, waste-water, sour-water, brine and saline solution.
  • the aqueous component may have been added to the hydrocarbon component for processing purposes, such as for the removal of inorganic salts.
  • the additive composition may be added to the hydrocarbon emulsion in any suitable amount.
  • the additive composition may be added to the hydrocarbon emulsion at a concentration of from 0.1 ppm to 10000 ppm, for example from 1 ppm to 5000 ppm, or from 10 ppm to 1000 ppm, suitably from 30 to 500 ppm, or from 50 to 300 ppm.
  • the additive composition may be added to the hydrocarbon emulsion in an amount wherein the concentration of the one or more alkoxylated amine compounds is from 0.025 ppm to 2500 ppm, for example from 0.25 ppm to 1250 ppm, or from 2.5 ppm to 250 ppm, suitably from 7 to 125 ppm, or from 12 to 75 ppm.
  • the additive composition may be added to the hydrocarbon emulsion in an amount wherein the concentration of the one or more aldehyde-alkylphenol copolymers is from 0.025 ppm to 2500 ppm, for example from 0.25 ppm to 1250 ppm, or from 2.5 ppm to 250 ppm, suitably from 7 to 125 ppm, or from 12 to 75 ppm.
  • the additive composition may be added to the hydrocarbon emulsion in an amount wherein the concentration of the active components (i.e. the one or more alkoxylated amine compounds and the one or more aldehyde-alkylphenol copolymers) is from 0.05 ppm to 5000 ppm, for example from 0.5 ppm to 2500 ppm, or from 5 ppm to 500 ppm, suitably from 15 to 250 ppm, or from 25 to 150 ppm.
  • the concentration of the active components i.e. the one or more alkoxylated amine compounds and the one or more aldehyde-alkylphenol copolymers
  • the additive composition may comprise the one or more alkoxylated amine compounds and the one or more aldehyde-alkylphenol copolymers in a weight ratio in the range of 1 :2 to 2:1 , such as a weight ratio of about 1 :1.
  • a method of improving the demulsification of a hydrocarbon emulsion comprising adding an additive composition to the hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde-alkylphenol copolymers.
  • an additive composition to improve the demulsification of a hydrocarbon emulsion, wherein the additive composition comprises (i) one or more alkoxylated amine compounds and (ii) one or more aldehyde- alkylphenol copolymers.
  • a method of improving the demulsification action of one or more alkoxylated amine compounds in a hydrocarbon emulsion comprising admixing the one or more alkoxylated amine compounds with one or more aldehyde-alkylphenol copolymers to provide an additive composition, and adding the additive composition to the hydrocarbon emulsion.
  • a sixth aspect of the present invention there is provided the use of one or more aldehyde-alkylphenol copolymers to improve the demulsification action of one or more alkoxylated amine compounds in a hydrocarbon emulsion.
  • references to improving the demulsification or demulsification action may refer to improvements such as by accelerating the speed of separation, improving clean separation of the aqueous component (for example water) from the hydrocarbon component, increasing the volume of water separated and/or minimising residual (or unresolved) emulsion, as discussed herein.
  • aqueous component for example water
  • the one or more aldehyde-alkylphenol copolymer(s) will be known to persons skilled in the art and are as discussed above.
  • the aldehyde-alkylphenol copolymer(s) do not comprise any alkoxy groups or residues, i.e. the aldehyde-alkylphenol copolymer(s) are non-alkoxylated.
  • the one or more aldehyde-alkylphenol copolymers may be selected from one or more compounds of formula (II) and/or (III) as discussed above.
  • Figure 1 shows the results of the demulsification tests of Example 1 , in which different additives were tested for their demulsifying properties.
  • FIG. 2 shows a photograph of the demulsification test tubes taken at 60 minutes after each additive of Example 1 was added.
  • An additive composition 1 comprising an alkoxylated amine compound (wherein EO represents an ethylene oxide residue and PO represents a propylene oxide residue), an aldehyde-alkylphenol copolymer and a solvent was provided as shown in Table 1 :
  • the demulsification tests follow the commonly known “bottle test”, based on the BS&W test as described in ASTMD4007 - 11 :
  • Figure 1 shows the demulsifying performance of an alkoxylated amine compound alone, an aldehyde-alkylphenol copolymer alone, and an additive composition comprising both an alkoxylated amine compound and an aldehyde-alkylphenol copolymer, compared to when no additive is present.
  • the aldehyde-alkylphenol copolymer (Tube 4 in Table 3) provides a deficient demulsification effect, even outperformed by the blank test (Tube 1 in Table 3) after 60 minutes.
  • the additive composition used in the method of the present invention (Tube 2 in Table 3) outperformed all tests in separation efficiency and speed, by completely separating the 20 mL of water initially added after 15 minutes.
  • Figure 2 is a visual assessment of the demulsification tests at 60 minutes after each additive from Table 2 was added.
  • the additive composition used in the method of the present invention (Tube 2 in Table 3) had no observable crude oil trace on the walls of the tube and displayed the best results in achieving a clean water-hydrocarbon interface (as assessed visually).
  • the invention is not restricted to the details of the foregoing embodiment(s).
  • the invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

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Abstract

L'invention concerne un procédé de désémulsification d'une émulsion d'hydrocarbure, le procédé consistant en l'ajout d'une composition d'additif à l'émulsion d'hydrocarbure, la composition d'additif comprenant (i) un ou plusieurs composés d'amine alcoxylés et (ii) un ou plusieurs copolymères d'aldéhyde-alkylphénol.
PCT/GB2024/051167 2023-05-03 2024-05-03 Procédé de désémulsification Ceased WO2024236268A1 (fr)

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MX2025013154A MX2025013154A (es) 2023-05-03 2024-05-03 Metodo de desmulsificacion
CN202480044043.1A CN121443706A (zh) 2023-05-03 2024-05-03 破乳方法
EP24726695.0A EP4705409A1 (fr) 2023-05-03 2024-05-03 Procédé de désémulsification

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GB2306540.2 2023-05-03
GBGB2306540.2A GB202306540D0 (en) 2023-05-03 2023-05-03 Demulsifying method

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Citations (7)

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US4209422A (en) * 1977-02-04 1980-06-24 Exxon Research & Engineering Co. Multicomponent demulsifier, method of using the same and hydrocarbon containing the same
DE3002111A1 (de) * 1980-01-22 1981-07-23 Exxon Research And Engineering Co., Florham Park, N.J. Mehrkomponentiger entemulgator
EP0565285A1 (fr) 1992-04-10 1993-10-13 BP Chemicals Limited Compositions de combustible contenant un détergent polyisobutene succinimide
EP0831141A1 (fr) 1996-09-05 1998-03-25 BP Chemicals (Additives) Limited Détergents pour combustibles hydrocarbures
EP1344785A1 (fr) 2002-03-15 2003-09-17 Bayer Ag Procédé de préparation de polyisobutylene hautement reactif
US6838422B2 (en) 2000-08-03 2005-01-04 Ecolab Inc. Plastics compatible detergent composition and method of cleaning plastics
US20070221539A1 (en) 2005-09-22 2007-09-27 Clariant Produkte (Deutschland) Gmbh) Additives for crude oils

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Publication number Priority date Publication date Assignee Title
RU2139317C1 (ru) * 1998-10-27 1999-10-10 Гречухина Алевтина Анатольевна Композиция для обезвоживания и обессоливания нефти "полинол-д"

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4209422A (en) * 1977-02-04 1980-06-24 Exxon Research & Engineering Co. Multicomponent demulsifier, method of using the same and hydrocarbon containing the same
DE3002111A1 (de) * 1980-01-22 1981-07-23 Exxon Research And Engineering Co., Florham Park, N.J. Mehrkomponentiger entemulgator
EP0565285A1 (fr) 1992-04-10 1993-10-13 BP Chemicals Limited Compositions de combustible contenant un détergent polyisobutene succinimide
EP0831141A1 (fr) 1996-09-05 1998-03-25 BP Chemicals (Additives) Limited Détergents pour combustibles hydrocarbures
US6838422B2 (en) 2000-08-03 2005-01-04 Ecolab Inc. Plastics compatible detergent composition and method of cleaning plastics
EP1344785A1 (fr) 2002-03-15 2003-09-17 Bayer Ag Procédé de préparation de polyisobutylene hautement reactif
US20070221539A1 (en) 2005-09-22 2007-09-27 Clariant Produkte (Deutschland) Gmbh) Additives for crude oils

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GB202306540D0 (en) 2023-06-14
GB2629678B (en) 2026-03-04
MX2025013154A (es) 2026-02-03
GB202406227D0 (en) 2024-06-19
AR132613A1 (es) 2025-07-16
EP4705409A1 (fr) 2026-03-11
CN121443706A (zh) 2026-01-30

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