WO2015044905A1 - Traitement du pétrole et/ou de résidus de pétrole - Google Patents

Traitement du pétrole et/ou de résidus de pétrole Download PDF

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Publication number
WO2015044905A1
WO2015044905A1 PCT/IB2014/064863 IB2014064863W WO2015044905A1 WO 2015044905 A1 WO2015044905 A1 WO 2015044905A1 IB 2014064863 W IB2014064863 W IB 2014064863W WO 2015044905 A1 WO2015044905 A1 WO 2015044905A1
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WIPO (PCT)
Prior art keywords
petroleum
residues
organic component
additive composition
oil
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PCT/IB2014/064863
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English (en)
Inventor
John Toft
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Pme Enterprises Company Limited
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Publication of WO2015044905A1 publication Critical patent/WO2015044905A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • 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
    • 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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
    • 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
    • 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic 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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/302—Viscosity

Definitions

  • This invention relates to compositions and methods of processing petroleum and/or petroleum-based residues, particularly where said petroleum and/or petroleum-based residues are difficult to extract or obtain.
  • the compositions of the invention generally help to reduce the viscosity of petroleum and/or petroleum-based residues, such as crude oil (especially heavy crudes prone to precipitating waxy deposites), and thereby enhance its ability to flow.
  • paraffin waxes are generally at least partially soluble in light oil fractions of petroleum (e.g. oil fractions with boiling points less than 150°C), whereas asphaltenes are not.
  • alternative sources such as, for example, tar sand.
  • compositions which facilitate the separation of oil from oil-water mixtures are provided.
  • a method of processing petroleum and/or petroleum-based residues comprising mixing the petroleum and/or petroleum-based residues with a petroleum additive composition or with the individual components of the petroleum additive composition; wherein the petroleum additive composition comprises:
  • a method of extracting, storing and/or transporting petroleum and/or petroleum-based residues comprising: i) mixing the petroleum and/or petroleum-based residues with a petroleum additive composition, or with the individual components of the petroleum additive composition, to produce a treated petroleum-based composition; and ii) extracting, storing and/or transporting the treated petroleum-based composition; wherein the petroleum additive composition comprises: - A non-fatty acid-based unsaturated organic component; and
  • a petroleum additive composition or a kit comprising the individual components of the petroleum additive composition to modify the viscosity of petroleum and/or petroleum-based residues; wherein the petroleum additive composition comprises:
  • a petroleum additive composition or a kit comprising the individual components of the petroleum additive composition to extract, store and/or transport petroleum and/or petroleum-based residues; wherein the petroleum additive composition comprises:
  • a petroleum additive composition comprising:
  • kits of parts comprising: - A non-fatty acid-based unsaturated organic component;
  • a treated petroleum-based composition comprising:
  • a method of recovering a petroleum additive composition from a treated petroleum-based composition comprising separating the petroleum additive composition from the treated petroleum-based composition by centrifugation and/or distillation; wherein the treated petroleum-based composition comprises:
  • the petroleum additive composition comprises: - A non-fatty acid-based unsaturated organic component;
  • a petroleum additive composition obtainable by, obtained by, or directly obtained by the method of recovering a petroleum additive composition of the eighth aspect.
  • a petroleum- based product obtainable by, obtained by, directly obtained by the method of the first, second, or eighth aspects.
  • a method of separating water from an oil-water mixture comprising: (a) providing a treated oil-water mixture comprising:
  • a method of disposing of water from an oil-water mixture comprising separating water from an oil-water mixture as defined in the eleventh aspect to thereby provide a clean water phase, and thereafter disposing of some or all of the clean water phase.
  • the compositions of the present invention have surprisingly been found to possess a number of advantageous properties. Firstly, the additive compositions have been found to uniformly penetrate throughout (heterogeneous) crude oil fractions and thereby effectively reduce viscosity or otherwise mobilize said crude oil to enable the oil to flow. The additive compositions also typically act as plasticizers for waxy petroleum-based residues.
  • compositions of the invention act synergistically: to mobilize the paraffin waxes through effective penetration, lubrication, and solubilisation thereof; to mobilize the asphaltenes through the plasticization and solubilisation thereof; and to stabilize the resulting mobile fluid.
  • the compositions of the invention represent broad spectrum mobilizing agents having the flexibility and versatility required to cope with the diverse range of residues within crude oil.
  • the skilled person can easily adapt the compositions of the invention, for instance, by judiciously varying (e.g. increasing) the proportions of any aromatic hydrocarbons (e.g. with a phenyl ring) or aromatic organic compounds (e.g.
  • the additive compositions of the present invention are relatively inexpensive and are acceptable from an environmental perspective (e.g. biodegradable).
  • the specific gravity of the composition can be controlled so that it is sufficiently different to that of the petroleum or residues thereof to enable it to be easily recovered from the petroleum/residues by centrifugation when desired.
  • Such compositions may also be recovered or otherwise separated from the petroleum/residues by distillation, including during an oil refining process.
  • compositions of the present invention can inhibit corrosion in pipelines. This "anti-corrosive" property reduces the need for corrosion inhibitors to be added to the petroleum/residues.
  • compositions of the present invention can facilitate extraction/separation of the petroleum/residues from aqueous mixtures, whether via standard heterogeneous liquid-liquid phase separations (i.e. separation of layers) or via centrifugation.
  • aqueous mixtures whether via standard heterogeneous liquid-liquid phase separations (i.e. separation of layers) or via centrifugation.
  • the compositions of the invention can facilitate formation of polyphasic (e.g. biphasic or triphasic) mixtures that can be more easily handled to extract petroleum/residues therefrom.
  • cleaner interfaces between aqueous and oil phases can be obtained.
  • compositions of the invention can facilitate demulsification to some extent, thereby increasing the amount of the oil phase that can be simply "tapped/skimmed off".
  • compositions of the invention facilitate centrifugation of oil-water mixtures thereby allowing oil and water phases to be effectively separated from one another.
  • the compositions of the invention allow for such clean separations that the water phase can be easily purified to allow for its safe discharge into the natural environment.
  • Using petroleum additive compositions of the invention can conveniently avoid the need for heat to mobilize or otherwise fluidize petroleum and/or petroleum-based residues.
  • Petroleum additive compositions of the invention conveniently can facilitate filtration of fluidized or partially fluidized petroleum and/or petroleum-based residues, and may in some cases facilitate nanofiltrations that would otherwise be impossible.
  • Using petroleum additive compositions of the invention conveniently can facilitate rapid processing of petroleum and/or petroleum-based residues which could otherwise only be processed at a slow flow rate due to their relative high viscosity.
  • using petroleum additive compositions of the invention may allow petroleum and/or petroleum-based residues obtained from oil reservoirs to be directly centrifuged without the need for pre-treatments.
  • Petroleum additive compositions of the invention can help to revolutionize the safety of what are otherwise highly dangerous operations.
  • the petroleum additive compositions of the invention can be used to either prevent or reduce waxy deposits forming in the first place, or to mobilize waxy deposits in situ to facilitate their facile removal in safe manner (e.g. via pumping).
  • the term "petroleum” is well understood in the art and generally refers to synthetic or naturally occurring complex mixtures of hydrocarbons of various molecular weights and optionally other organic compounds.
  • the petroleum may include unprocessed (i.e. unrefined) crude oil, but in some cases includes petroleum products derived from refined crude oil.
  • the "petroleum” referred to herein is naturally occurring petroleum or petroleum-based residues, or are otherwise petroleum-based residues (e.g. waste or otherwise disgarded products) derived from naturally occurring petroleum (e.g. following initial refinement of naturally occurring petroleum).
  • the petroleum may include crude oil from crude oil reservoirs, or otherwise petroleum and/or petroleum residues from oil sands or oil shales, etc.
  • viscosities are generally quoted in “centistokes” (cSt) at 25°C as measured using a Brookfield Viscometer.
  • a “non-fatty acid-based unsaturated organic component” is an organic compound (or mixture of one or more such compounds), suitably an organic solvent, which is not derived from fatty acids, and which comprises at least one unsaturated carbon-carbon bond (e.g. a double bond).
  • the unsaturated organic component may comprise one or more alkenyl groups and/or aromatic groups.
  • a "fatty acid-based organic component” is an organic compound (or mixture of one or more such compounds), suitably an organic solvent, which is derived from fatty acids (e.g. fatty acids, fatty acid esters, etc.).
  • fatty acids e.g. fatty acids, fatty acid esters, etc.
  • free-flowing liquid has its ordinary dictionary meaning, and refers to a liquid that can be readily poured.
  • standard ambient temperature and pressure SATP
  • STP standard temperature and pressure
  • extracting when used in relation to the extraction of petroleum and/or petroleum-based residues refers to any form of extraction, including extraction of said petroleum/residues from a reservoir (e.g. underground or underwater oil reservoir), from oil sands or shale, or even from a mixture with other components (e.g. from mono, bi-, or tri-phasic mixtures with water).
  • a reservoir e.g. underground or underwater oil reservoir
  • oil sands or shale e.g. from oil sands or shale
  • mixture with other components e.g. from mono, bi-, or tri-phasic mixtures with water.
  • the term "transporting” when used in relation to the transport of petroleum and/or petroleum-based residues may include any movement of said petroleum/residues, in particular through pipework or in tankers (marine or road-based).
  • processing when used in relation to the processing of petroleum and/or petroleum-based residues, may include any form of processing known in the art, for example, extracting, transporting, or simple treating. In a particular embodiment, the "processing” refers to extracting and/or transporting of petroleum and/or petroleum-based residues.
  • a specific gravity is suitably calculated by first measuring the density of the material using either a hydrometer (e.g. as detailed in ASTM D1298) or with an oscillating U-tube as per ASTM D4052. The density may be established at standard ambient temperature and pressure by making the appropriate corrections if required. Specific gravity may then be calculated as:
  • API gravity of a petroleum sample is quoted in degrees (i.e. °) and is suitably measured at 60°F (i.e. 15.55°C) and is derivable from the specific gravity of the petroleum sample via the following formula:
  • API gravity (141 .5/SG) - 131 .5 [0045]
  • parts e.g. parts by weight, pbw
  • pbw parts by weight
  • a composition said to "consist essentially of" a particular set of one or more components suitably comprises at least 80% w/w of said component(s), more suitably at least 90% w/w of said components, more suitably at least 95% w/w of said components, and most suitably at least 98% w/w of said components.
  • alkyl includes both straight and branched chain alkyl groups. References to individual alkyl groups such as “propyl” are specific for the straight chain version only and references to individual branched chain alkyl groups such as “isopropyl” are specific for the branched chain version only.
  • (1 -6C)alkyl includes (1 -4C)alkyl, (1 - 3C)alkyl, propyl, isopropyl and f-butyl.
  • phenyl(1 -6C)alkyl includes phenyl(1 -4C)alkyl, benzyl, 1 -phenylethyl and 2-phenylethyl.
  • (m-nC) or "(m-nC) group” used alone or as a prefix, refers to any group having m to n carbon atoms.
  • (3-8C)cycloalkyl means a hydrocarbon ring containing from 3 to 8 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or bicyclo[2.2.1 ]heptyl.
  • (3-8C)cycloalkenyl means a hydrocarbon ring containing at least one double bond, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl or cycloheptenyl, such as 3-cyclohexen-1 - yl, or cyclooctenyl.
  • aryl means a cyclic or polycyclic aromatic ring having from 5 to 12 carbon atoms.
  • aryl includes both monovalent species and divalent species. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl and the like. In particular embodiment, an aryl is phenyl.
  • aryl(1 -6C)alkyl means an aryl group covalently attached to a (1 -6C)alkylene group, both of which are defined herein.
  • aryl-(1 -6C)alkyl groups include benzyl, phenylethyl, and the like
  • arylalcohol such as an “aryl(m-nC)alcohol” refers to an alkyl alcohol bonded to an aryl group, such as an (m-nC)alkyl alcohol.
  • aryl group such as an (m-nC)alkyl alcohol.
  • acylated species is a species which is bonded to an acyl group (i.e. a carbonyl). Examples are acetylated species, which are bonded to an acetate group.
  • benzyl acetate is an example of an acylated arylalcohol since it is acetylated benzyl alcohol.
  • the present invention provides a petroleum additive composition comprising:
  • the petroleum additive composition is suitably for reducing the viscosity of petroleum and/or petroleum-based residues.
  • the petroleum additive composition is suitably a free-flowing liquid at standard ambient temperature and pressure.
  • the petroleum additive composition is suitably for facilitating extraction of petroleum and/or petroleum-based residues.
  • the petroleum additive composition is suitably for reducing the viscosity of petroleum and/or petroleum-based residues, especially of petroleum and/or petroleum residues comprising significant quantities of heavy oil fractions.
  • the synergistic interaction between the non-fatty acid-based unsaturated organic component and the fatty-acid based organic component affords many advantages, and enables the almost universal extraction of petroleum and/or petroleum-based residues over a range of specific gravities.
  • the additive compositions of the invention facilitate mobilization and/or extraction of heavy oil, such as bitumen, which is a sticky, black, tar-like form of crude oil which is so thick and heavy that it must usually be heated and/or diluted before it can flow.
  • heavy oil such as bitumen
  • compositions of the present invention are suitably biodegradable, suitably comprising greater than 98% w/w biodegradable ingredients, suitably greater than 99%.
  • compositions of the present invention are suitably recoverable from petroleum and/or petroleum-based residues after mixing therewith. Such recovery may suitably be effected by centrifugation and/or distillation.
  • compositions of the present invention suitably have a specific gravity that is sufficiently lower than that of the petroleum and/or petroleum-based residues to enable the composition of the invention to be separated from the petroleum and/or petroleum-based residues by centrifugation.
  • the specific gravity of the composition of the invention is at least 10% less than that of the petroleum and/or petroleum-based residues.
  • the specific gravity of the composition is within the range 0.8 to 0.89.
  • the specific gravity of the composition is within the range 0.84 to 0.88.
  • the specific gravity of the composition is within the range 0.86 to 0.88.
  • the flash point of the composition of the invention i.e. the lowest temperature at which it can vaporise to form an ignitable mixture in air
  • the constituents making up the composition of the invention can be varied in order to optimise its properties for the particular petroleum and/or petroleum- based residues concerned.
  • the specific gravity of the composition may need to be optimised for a particular application.
  • the relative amounts of the constituents may be varied to optimise the viscosity lowering effect of the composition for a particular petroleum and/or petroleum-based residues.
  • the non-fatty acid-based unsaturated organic component and the fatty-acid based organic component account for greater than or equal to 50% w/w of the total composition, suitably greater than or equal to 70% w/w of the total composition, suitably greater than or equal to 85% w/w of the total composition.
  • the non-fatty acid-based unsaturated organic component and the fatty-acid based organic component account for less than or equal to 98% w/w of the total composition, suitably less than or equal to 95% w/w of the total composition, suitably less than or equal to 92% w/w of the total composition.
  • the non-fatty acid-based unsaturated organic component suitably constitutes 5 to 95% w/w of the petroleum additive composition, suitably 15 to 90% w/w, suitably 30 to 85% w/w, more suitably 40 to 80% w/w, most suitably 55 to 65% w/w.
  • the fatty-acid based organic component suitably constitutes 5 to 95% w/w of the petroleum additive composition, suitably 10 to 60% w/w, suitably 15 to 45% w/w, more suitably 20 to 40% w/w, most suitably 25 to 35% w/w.
  • the petroleum additive composition comprises: - 30-120 parts non-fatty acid-based unsaturated organic component;
  • the petroleum additive composition comprises:
  • the petroleum additive composition may suitably comprise one or more additional constituents.
  • the petroleum additive composition may comprise 2-20 parts additional constituents relative to the abovementioned amounts of non-fatty acid-based unsaturated organic component and fatty-acid based organic component.
  • the petroleum additive composition may comprise a non-fatty acid-based unsaturated organic component, a fatty-acid based organic component, and one or more one or more additional constituents in a weight ratio of 30-120 : 15-60 : 2-20 respectively.
  • the petroleum additive composition may comprise 5-15 parts additional constituents relative to the abovementioned amounts of non-fatty acid- based unsaturated organic component and fatty-acid based organic component.
  • the additional constituents may comprise, consist of, or consist essentially of a hydrophilic component, suitably a hydrophilic organic component (which is suitably not derived from petroleum and/or petroleum-based residues). In some embodiments, the additional constituents may comprise, consist of, or consist essentially of an additional hydrophobic component (which is suitably not derived from petroleum and/or petroleum-based residues).
  • the petroleum additive composition consists of or consists essentially of a non-fatty acid-based unsaturated organic component, a fatty-acid based organic component, and optionally one or more one or more additional constituents as defined herein.
  • the petroleum additive composition may comprise a further diluent. Such a diluents may optionally be derived from petroleum and/or petroleum-based residues.
  • any such diluent suitably constitutes less than or equal to 90% w/w of the petroleum additive composition, suitably less than or equal to 70% w/w, suitably less than or equal to 50% w/w, suitably less than or equal to 20% w/w, most suitably less than or equal to 10% w/w.
  • Non-fatty acid-based unsaturated organic component is N-fatty acid-based unsaturated organic component
  • compositions of the invention may suitably comprise one or more non-fatty acid- based unsaturated organic components, suitably selected from any of the non-fatty acid-based unsaturated organic components hereindescribed.
  • the non-fatty acid-based unsaturated organic component is not derived from fatty acids.
  • the non-fatty acid-based unsaturated organic component comprises at least one unsaturated carbon-carbon bond, which may be a double bond or triple bond, most suitably a double bond.
  • the non-fatty acid-based unsaturated organic component is suitably substantially immiscible with water.
  • the non-fatty acid-based unsaturated organic component is suitably miscible with light oil fractions of petroleum (e.g. oil fractions with boiling points less than 150°C), such as gasoline.
  • the non-fatty acid-based unsaturated organic component may also suitably be miscible with heavy oil fractions.
  • the non-fatty acid-based unsaturated organic component suitably penetrates heavy oil fractions.
  • the non-fatty acid-based unsaturated organic component suitably lowers the surface tension of petroleum and/or petroleum-based residues when mixed therewith.
  • the non-fatty acid-based unsaturated organic component suitably lowers the viscosity of petroleum and/or petroleum-based residues when mixed therewith.
  • the non-fatty acid-based unsaturated organic component is a hydrocarbon (i.e. an unsaturated hydrocarbon) or an oxygen-containing derivative thereof, suitably that is miscible with light oil fractions of petroleum, such as gasoline.
  • the non-fatty acid-based unsaturated organic component is a hydrocarbon.
  • the non-fatty acid-based unsaturated organic component is a (5-35C)hydrocarbon (i.e. C5-C35 hydrocarbon).
  • the non-fatty acid-based unsaturated organic component is a (6-22C)hydrocarbon.
  • the non-fatty acid-based unsaturated organic component is a (8-12C)hydrocarbon.
  • the non-fatty acid-based unsaturated organic component suitably comprises at least one alkenyl moiety, suitably at least two.
  • the non-fatty acid-based unsaturated organic component is or comprises a terpene.
  • the non-fatty acid-based unsaturated organic component is or comprises an aromatic hydrocarbon (e.g. with a phenyl ring, e.g. toluene) and/or an aromatic organic compound (e.g. benzyl acetate).
  • the non-fatty acid-based unsaturated organic component may be or comprise toluene and/or benzyl acetate.
  • the fatty acid-based unsaturated organic component is suitably selected from terpenes (or derivatives thereof - e.g. terpenoids, terpene alcohols such as terpeneol, or acylated derivatives thereof), acylated arylalkyl alcohols (e.g. benzyl acetate), or a mixture thereof.
  • terpenes or derivatives thereof - e.g. terpenoids, terpene alcohols such as terpeneol, or acylated derivatives thereof), acylated arylalkyl alcohols (e.g. benzyl acetate), or a mixture thereof.
  • terpenes or derivatives thereof - terpenoids, terpene alcohols such as terpeneol, or acylated derivatives thereof
  • acylated arylalkyl alcohols e.g. benzyl acetate
  • the fatty acid-based unsaturated organic component may be any one of the compounds defined herein in relation to the fatty acid-based unsaturated organic component or any suitable mixtures thereof.
  • the fatty acid-based unsaturated organic component may comprise a mixture of a terpene (e.g. D-limonene) and benzyl acetate.
  • the fatty acid-based unsaturated organic component is or comprises a terpene.
  • the fatty acid-based unsaturated organic component is or comprises benzyl acetate (i.e. the condensation product of benzyl alcohol and acetic acid).
  • compositions of the invention may suitably comprise one or more non-fatty acid- based unsaturated organic components, suitably selected from any of the non-fatty acid-based unsaturated organic components hereindescribed.
  • the compositions of the invention may suitably comprise two or more non-fatty acid-based unsaturated organic components, suitably selected from any of the non-fatty acid-based unsaturated organic components hereindescribed.
  • the non-fatty acid-based unsaturated organic component(s) may include both a (5-35C)hydrocarbon (e.g. a terpene or derivative thereof) and an aromatic hydrocarbon (e.g. with a phenyl ring) or an aromatic organic compound (e.g. benzyl acetate).
  • the proportions of aromatic hydrocarbon or aromatic organic compound may be increased within the composition to cater for high-asphaltene containing petroleum and/or petroleum-based residues.
  • the one or more non-fatty acid-based unsaturated organic component(s) comprises or consists of a terpene (or derivative thereof) and benzyl acetate and/or toluene.
  • the one or more non-fatty acid-based unsaturated organic component(s) comprises or consists of a terpene (or derivative thereof), benzyl acetate and toluene.
  • the fatty acid-based unsaturated organic component is suitably biodegradable.
  • the fatty acid-based unsaturated organic component is suitably recoverable from petroleum and/or petroleum-based residues when mixed therewith, suitably via centrifugation and/or distillation.
  • the terpene may be or include a (5-35C)terpene (i.e. C5-C35 terpene).
  • the non-fatty acid-based unsaturated organic component is a (6-20C)terpene.
  • the non-fatty acid-based unsaturated organic component is a (8- 12C)terpene.
  • the non-fatty acid-based unsaturated organic component is a C10 terpene.
  • the terpene is selected from the groups consisting of limonene, pine oil, diterpene, turpentine, dipentene and other cyclohexene derivatives.
  • the terpene is monoterpene.
  • the terpene is a monocyclic terpene.
  • the terpene is limonene.
  • the terpene is D-limonene.
  • the amount of the terpene present in the composition of the invention is suitably 5 to 95% w/w of the total composition.
  • the terpene is present in the composition at a concentration of 15 to 90% w/w of the total composition.
  • the terpene is present in the composition at a concentration of 30 to 85% w/w of the total composition.
  • the terpene is present in the composition at a concentration of 40 to 80% w/w of the total composition. [0099] In a further embodiment of the invention, the terpene is present in the composition at a concentration of 55 to 65% w/w of the total composition.
  • the terpene is present in the composition at a concentration of 60% w/w of the total composition.
  • any suitable acylated arylalkyl alcohol may be employed.
  • the acylated arylalkyl alcohol is an acylated aryl(1 -2C)alkyl alcohol, suitably an acylated benzyl alcohol.
  • the acyl group of the acylated arylalkyl alcohol is suitably a (1 -6C)alkanoyl group, suitably an acetyl group.
  • the acylated arylalkyl alcohol is benzyl acetate.
  • the amount of the acylated arylalkyl alcohol present in the composition of the invention is suitably 5 to 95% w/w of the total composition.
  • the acylated arylalkyl alcohol is present in the composition at a concentration of 15 to 90% w/w of the total composition.
  • the acylated arylalkyl alcohol is present in the composition at a concentration of 30 to 85% w/w of the total composition.
  • the acylated arylalkyl alcohol is present in the composition at a concentration of 40 to 80% w/w of the total composition.
  • the acylated arylalkyl alcohol is present in the composition at a concentration of 55 to 65% w/w of the total composition. [00108] In a particular embodiment of the invention, the acylated arylalkyl alcohol is present in the composition at a concentration of 60% w/w of the total composition.
  • the fatty-acid based organic component is suitably substantially immiscible with water.
  • the fatty-acid based organic component is suitably miscible with heavy oil fractions of petroleum (e.g. oil fractions with boiling points greater than 300°C), such as bitumen.
  • the fatty- acid based organic component may also suitably be miscible with light oil fractions.
  • the fatty- acid based organic component suitably dissolves heavy oil fractions and thereby mobilizes them.
  • the fatty-acid based organic component suitably lowers the viscosity of petroleum and/or petroleum-based residues when mixed therewith.
  • the fatty-acid based organic component suitably serves as a plasticizer for heavy oil fractions (e.g. bitumen).
  • the fatty-acid based organic component is derived from one or more fatty acids.
  • the fatty-acid based organic component suitably is or comprises one or more fatty acids or esters thereof, suitably greater than or equal to 80% w/w one or more fatty acids or esters thereof, more suitably greater than or equal to 90% w/w one or more fatty acids or esters thereof, suitably greater than 95% w/w one or more fatty acids or esters thereof.
  • the fatty acids or esters thereof suitably comprise a hydrocarbyl group attached to a carboxylate group.
  • the carboxylate group is suitably either a carboxylic acid or carboxylate ester (e.g. optionally substituted alkyl ester).
  • the fatty-acid based organic component suitably comprises a mixture of different fatty acids or esters thereof.
  • the one or more fatty acids or esters thereof of the fatty- acid based organic component are selected from compounds of Formula I:
  • RiC(0) 2 R 2 (Formula I) wherein Ri is hydrocarbyl, and R 2 is hydrogen or optionally substituted hydrocarbyl.
  • Ri may be a saturated or unsaturated hydrocarbyl.
  • the one or more fatty acids or esters thereof comprise a mixture of saturated or unsaturated Ri moieties.
  • Ri is suitably (2-40C)hydrocarbyl, more suitably (4-30C) hydrocarbyl, most suitably (7- 25C) hydrocarbyl.
  • the one or more fatty acids or esters thereof comprise a mixture of Ri moieties.
  • R 2 may be hydrogen (i.e. so that the fatty acid derivative is a carboxylic acid).
  • R 2 may be a saturated or unsaturated hydrocarbyl (optionally substituted), most preferably optionally substituted saturated hydrocarbyl.
  • R 2 may be optionally substituted alkyl (i.e. a fatty acid alkyl ester).
  • the alkyl groups of said optionally substituted alkyl ester may comprise 1 to 20 carbon atoms.
  • the ester will be an alkyl ester comprising 1 to 10 or, more typically, 1 to 3 carbon atoms. Methyl or ethyl esters are generally preferred.
  • the one or more fatty acids or esters thereof of the fatty-acid based organic component comprise greater than or equal to 80% w/w fatty acid esters, suitably greater than or equal to 90% w/w fatty acid ester, suitably greater than or equal to 95% w/w fatty acid ester.
  • the fatty-acid based organic component comprises greater than or equal to 80% w/w fatty acid esters, suitably greater than or equal to 90% w/w fatty acid ester, suitably greater than or equal to 95% w/w fatty acid ester.
  • Fatty acid esters are generally preferred in the additive compositions of the present invention because fatty acid ester mixtures are typically more consistent in terms of their distribution of fatty acids.
  • the fatty-acid based organic component may suitably be or comprise vegetable oil or an esterified form thereof.
  • the vegetable oil is in the form of a vegetable oil ester.
  • the esterified vegetable oil may be an alkyl or substituted alkyl ester as defined above.
  • the vegetable oil is soya bean oil, sunflower oil or rapeseed oil or an ester thereof.
  • the vegetable oil is soya bean oil methyl ester.
  • the vegetable oil suitably constitutes 5 to 95% w/w of the petroleum additive composition, suitably 10 to 60% w/w, suitably 15 to 45% w/w, more suitably 20 to 40% w/w, most suitably 25 to 35% w/w.
  • the amount of the vegetable oil present in the composition is less than the amount of the terpene.
  • the additional constituent(s) may comprise, consist of, or consist essentially of a hydrophilic component, suitably a hydrophilic organic component (which is suitably not derived from petroleum and/or petroleum-based residues).
  • a hydrophilic component may facilitate clarification (e.g. demulsification) of a water-oil phase interface when extracting petroleum and/or petroleum-based residues from aqueous mixtures thereof. It may also help the general physical form of aqueous petroleum mixtures to facilitate extraction of the petroleum therefrom.
  • the hydrophilic component may assist the separation of water and oil into separate phases and thereby provide an increased quantity of oil in the oil phase which can be easily separated without further processing.
  • the additional constituent(s) may comprise, consist of, or consist essentially of an additional hydrophobic component (which is suitably not derived from petroleum and/or petroleum-based residues).
  • the hydrophobic component may facilitate clarification (e.g. demulsification) of a water-oil phase interface when extracting petroleum and/or petroleum- based residues from aqueous mixtures thereof. It may also help the general physical form of aqueous petroleum mixtures to facilitate extraction of the petroleum therefrom.
  • the additional constituent(s) may comprise, for example, bulking agents, agents that modify the specific gravity of the composition, agents that modify the flash point of the composition, demulsifying agents, coagulants, flocculating agents, corrosion inhibitors, and/or agents that function as penetration enhancers (to enable the composition to effectively break up high viscosity lumps that are present in the petroleum-based fluid and thereby uniformly reduce the viscosity).
  • These additional constituents may typically be present in range of 0 to 40% w/w of the total petroleum additive composition. Suitably, these additional constituents together account for 5 to 40% w/w of the total composition. More suitably, these additional constituents account for 5 to 25% w/w of the total composition. Even more suitably, these additional constituents account for 5 to 20% w/w of the total composition.
  • the additional constituents may be selected from one or more of the following:
  • the petroleum additive composition may suitably comprise a glycol (or derivative thereof).
  • glycols is used herein to refer to one or more glycol containing compounds.
  • a glycol is an ethylene or propylene glycol compound.
  • the glycol is an ethylene of propylene glycol ether.
  • the glycol has the formula:
  • R 3 -0-CH 2 -CHR 4 -0-R 5 wherein: R 3 is alkyl, hydroxyalkyl or alkanoyl;
  • R 4 is hydrogen or methyl; and R 5 is alkyl, hydroxyalkyl or alkanoyl. [00128] Suitably, any R 3 or R 5 group comprises 1 to 5 carbon atoms.
  • the glycol is an ethylene or propylene glycol ether acetate.
  • the glycol may be propylene glycol methyl ether acetate or ethoxy diglycol, or a mixture thereof.
  • Suitable glycol is Dowanol PMA (Dow Chemical Company; propylene glycol methyl ether acetate)
  • a glycol if present, may constitute 1 to 25% w/w of the total composition. More typically, a glycol, if present, may constitute 5 to 25% w/w of the total composition. In an embodiment, a glycol is present at 5 to 20% w/w of the total composition.
  • glycol may be used as an additional aid to reduce the viscosity of the composition of the invention.
  • a higher alcohol, alkane or alkyl acetate will typically comprise 8 to 13 carbon atoms.
  • a single alkyl chain length may be present in the composition or the higher alcohol, alkane or alkyl acetate may be a broad cut mixture comprising a range of different alkyl chain lengths.
  • a higher alcohol, alkane and/or alkyl acetate, if present, may constitute 1 to 25% w/w of the total composition. More typically, a higher alcohol, alkane and/or alkyl acetate, if present, may constitute 5 to 25% w/w of the total composition. In an embodiment, a higher alcohol, alkane and/or alkyl acetate is present at 5 to 20% w/w of the total composition.
  • the composition of the invention comprises 0.5 to 5% w/w of ethoxy diglycol.
  • the composition of the invention comprises 2 to 5% w/w of ethoxy diglycol.
  • the composition of the invention comprises 0.5 to 5% w/w of triacetin.
  • the composition of the invention comprises 2 to 5% w/w of triacetin.
  • the composition of the invention comprises 0.5 to 5% w/w of an alkoxylated alcohol.
  • the composition of the invention comprises 2 to 5% w/w of alkoxylated alcohol.
  • the alkoxylated alcohol is an ethoxylated C 8 to Ci 3 alcohol.
  • Sorbitan ester is an ethoxylated C 8 to Ci 3 alcohol.
  • the composition of the invention comprises 0.5 to 5% w/w of sorbitan ester.
  • the composition of the invention comprises 2 to 5% w/w of sorbitan ester.
  • the composition of the invention comprises 0.5 to 5% w/w of sulphosuccinate. [00146] In an embodiment, the composition of the invention comprises 2 to 5% w/w of sulphur suxonate.
  • the composition of the invention comprises 0.5 to 20% w/w of octyl acetate.
  • the composition of the invention comprises 5 to 15% w/w of octyl acetate.
  • the present invention provides a petroleum additive composition for reducing the viscosity of crude oil, the composition comprising:
  • the terpene and the vegetable oil account for greater than 50% w/w of the total composition. More suitably, the terpene and the vegetable oil account for greater than 70% w/w of the total composition. Even more suitably, the terpene and the vegetable oil account for greater than 75% w/w of the total composition and most suitably more than 80% w/w of the total composition.
  • the present invention provides a petroleum additive composition for reducing the viscosity of crude oil, the composition comprising: (i) benzyl acetate; and
  • the benzyl acetate and the vegetable oil account for greater than 50% w/w of the total composition. More suitably, the benzyl acetate and the vegetable oil account for greater than 70% w/w of the total composition. Even more suitably, the benzyl acetate and the vegetable oil account for greater than 75% w/w of the total composition and most suitably more than 80% w/w of the total composition.
  • the present invention provides a petroleum additive composition for reducing the viscosity of crude oil, the composition comprising:
  • the present invention provides a petroleum additive composition for reducing the viscosity of crude oil, the composition comprising:
  • the present invention provides a petroleum additive composition for reducing the viscosity of crude oil, the composition comprising:
  • the present invention provides a kit of parts comprising:
  • kits of parts of the invention suitably form a free-flowing liquid at standard temperature and pressure.
  • the kit may suitably comprise any of the components described herein in relation to the petroleum additive composition, and any of said components may be provided within the kit as separate components (e.g. separately packaged) or mixed together with one or more other components.
  • the kit may be used in the same manner as described herein in relation to the petroleum additive compositions. Some or all of the components of the kit may be pre-mixed prior to use in the methods of the invention, or alternatively some or all of the components may be added separately (whether sequentially or simultaneously) to the petroleum and/or petroleum-based residues in question.
  • the petroleum and/or petroleum-based residues may suitably possess a high viscosity.
  • the or some of the petroleum and/or petroleum-based residues may be a petroleum fluid at standard ambient temperature and pressure.
  • the or some of the petroleum and/or petroleum-based residues may be substantially non-flowing at standard ambient temperature and pressure, for instance, in the form of a solid or wax.
  • the petroleum and/or petroleum- based residues will possess a specific gravity of greater than 0.88.
  • the petroleum and/or petroleum-based residues will possess a specific gravity within the range 0.88 to 0.98.
  • the petroleum and/or petroleum-based residues is crude oil, for example, heavy crude oil (or extra heavy crude oil) which suitably does not readily flow.
  • Heavy crude oil is closely related to bitumen and is associated with oil or tar sand reserves.
  • the heavy crude oil suitably has an API gravity less than 20°.
  • Extra heavy oil is defined with a gravity of less than 10° API (i.e. with density greater than 1000 kg/m 3 or, equivalently, a specific gravity greater than 1 and a reservoir viscosity of no more than 10,000 cSt.
  • the petroleum and/or petroleum-based resides is a petroleum-based fluid, in that it is a free-flowing fluid at standard ambient temperature and pressure.
  • the petroleum and/or petroleum-based residues may be selected from any one of the following:
  • Petroleum and/or petroleum-based residues causing a blockage e.g. in a pipeline
  • Waste petroleum and/or petroleum-based residues e.g. waste products from refineries
  • Petroleum and/or petroleum-based residues mixed with water e.g. such as mixtures obtained from extracting petroleum/residues using water or steam.
  • Petroleum and/or petroleum residues from oil shale e.g. kerogen
  • a treated petroleum- based composition comprising:
  • Such a treated petroleum-based composition may be petroleum and/or petroleum- based residues that has been treated with the petroleum additive composition of the invention or with the components of the kit of parts of the invention.
  • the presence of the abovementioned components of the petroleum additive composition(s) of the invention within petroleum and/or petroleum-based residues indicates that the methods of the present invention have been employed.
  • Such treated petroleum-based compositions may be processed so as to recover some or all of the components of the petroleum additive composition therefrom (e.g. via centrifugation and/or distillation).
  • such treated petroleum-based compositions may be transported for later processing or use.
  • the present invention provides a method of processing petroleum and/or petroleum- based residues as defined herein.
  • the "processing” may refer to or result in any one or more of the following: i) mobilizing the petroleum and/or petroleum-based residues; reducing the viscosity of the petroleum and/or petroleum-based residues; reducing surface tension of the petroleum and/or petroleum-based residues; plasticizing waxy petroleum and/or petroleum-based residues; extracting or facilitating extraction of the petroleum and/or petroleum- based residues; vi) storing or facilitating storage of the petroleum and/or petroleum-based residues (especially without unwanted settling out of petroleum residues) vii) transporting or facilitating transportation of the petroleum and/or petroleum-based residues; viii) separating or facilitating separation of aqueous and oil phases in aqueous mixtures of the petroleum and/or petroleum-based residues; ix) clarifying interfaces between aqueous and oil phases in aqueous mixtures of the petroleum and/or petroleum-based residues; increasing the extraction yields of petroleum and/or petroleum-based residues; xi) reducing the amount of
  • the "processing” comprises extracting, storing and/or transporting petroleum and/or petroleum-based residues.
  • the method of processing is suitably a method of reducing the viscosity of petroleum and/or petroleum-based residues.
  • the processing involves mixing the petroleum and/or petroleum-based residues with the petroleum additive composition or individual components thereof to form treated petroleum and/or petroleum-based residues (i.e. treated petroleum-based composition). Such mixing may occur at any point in the overall process.
  • the processing may involve extracting, storing and/or transporting the treated petroleum-based composition.
  • the processing may involve treating petroleum and/or petroleum-based residues so as to prevent or reduce precipitation or settling of waxy deposits therefrom.
  • the processing may involve treating waxy deposits that have already precipitated or settled out from petroleum and/or petroleum-based residues, for instance, to solubilise or otherwise mobilize said waxy deposits.
  • This is particularly useful where waxy deposits need to be removed from a vessel (e.g. oil tank) or from pipes (e.g. in a pipeline, e.g. a blocked or partially blocked pipeline).
  • the processing may involve adding the petroleum additive composition or individual components thereof directly to a relevant vessel, pipelines, or flowlines.
  • the processing may involve adding adding the petroleum additive composition or individual components thereof to the flowlines of a wellhead.
  • the process may furthermore involve eventually recovering the petroleum additive composition, or some or all of the individual components thereof, from the treated petroleum- based composition.
  • the process may involve separating water from an oil-water mixture, such as via a method defined herein, and optionally further disposing of a clean water phase obtained therefrom, again via a method defined herein.
  • the petroleum additive composition or individual components thereof may be mixed with the petroleum and/or petroleum-based residues at any stage in the processing, though most suitably at a stage when its effects are most advantageous (e.g. where the petroleum/residues need mobilizing to enable the transport/movement thereof; and/or where the petroleum/residues need to be more clearly or cleanly separated from an aqueous phase).
  • the amount of petroleum additive composition (or individual components thereof) mixed with petroleum and/or petroleum-based residues is suitably less than or equal to 30% w/w of the petroleum and/or petroleum-based residues, suitably less than or equal to 20% w/w of the petroleum and/or petroleum-based residues, suitably less than or equal to 10% w/w of the petroleum and/or petroleum-based residues.
  • T he amount of petroleum additive composition (or individual components thereof) mixed with petroleum and/or petroleum-based residues is suitably greater than or equal to 0.5% w/w of the petroleum and/or petroleum-based residues, suitably greater than or equal to 1% w/w of the petroleum and/or petroleum-based residues, suitably greater than or equal to 2% w/w of the petroleum and/or petroleum-based residues.
  • the step of mixing suitably reduces the viscosity of the petroleum and/or petroleum- based residues.
  • the petroleum additive composition or individual components thereof are added to and mixed with petroleum and/or petroleum-based residues in situ.
  • “In situ” ma refer to the original source of the petroleum and/or petroleum-based residues, e.g. where they naturally occur (e.g. at source within natural oil reservoirs, lagoons, oil sands, or oil shale, especially in oil reservoirs) or where they occur artificially (e.g. as a result of waste disposal of petroleum residues - e.g. oil slops).
  • “in situ” may refer to a site at which the relevant petroleum and/or petroleum-based residues have been partially or fully immobilized, such as in an oil tank (e.g.
  • Such in situ treatment of the petroleum and/or petroleum- based residues may suitably precede (and suitably facilitates) extraction (e.g. pumping) of the treated petroleum and/or petroleum-based residues from source. Thus, this may be considered a pre-treatment regime.
  • extraction is suitably facilitated by the mobilizing/fluidizing effect of the petroleum additive composition upon petroleum and/or petroleum-based residues in question.
  • compositions of the invention to viscous, waxy, or solid petroleum and/or petroleum-based residues reduces the viscosity of the petroleum and/or petroleum-based residues and enables the treated petroleum and/or petroleum-based residues to be transported/moved and optionally subsequently processed.
  • Such treatment may reduce the viscosity of the petroleum and/or petroleum-based residues. This may facilitate "natural lift” (i.e. natural reservoir pressure to force the treated petroleum and/or petroleum-based residues to the surface) or “artificial lift” (i.e. where artificial pressure is applied to force the treated petroleum and/or petroleum-based residues to the surface - e.g. via waterflooding, injecting steam, carbon dioxide, or other pressurising gases into the reservoir).
  • natural lift i.e. natural reservoir pressure to force the treated petroleum and/or petroleum-based residues to the surface
  • artificial lift i.e. where artificial pressure is applied to force the treated petroleum and/or petroleum-based residues to the surface - e.g. via waterflooding, injecting steam, carbon dioxide, or other pressurising gases into the reservoir.
  • the petroleum additive composition or individual components thereof are added to and mixed with petroleum and/or petroleum-based residues that have been already removed from source (e.g. their naturally occurring environment, or oil waste disposal zone). Such a process may be considered a post-treatment regime.
  • the petroleum and/or petroleum-based residues prior to mixing, is first removed or extracted from source and thereafter transferred into an appropriate vessel for subsequent mixing with the petroleum additive composition (or components thereof).
  • Such a process is particularly appropriate for extracting petroleum and/or petroleum-based residues from oil/tar sand and oil shale deposits, since oil/tar sand and oil shale deposits are typically first mined before they are subsequently treated to extract the petroleum and/or petroleum-based residues therein.
  • the petroleum additive compositions of the invention can be added directly to said oil/tar sands and oil shale deposits and suitably mixed therewith and the mixture subsequently processed (e.g. filtered, decanted, or otherwise separated) to isolate treated petroleum and/or petroleum-based residues.
  • Such post-treatments are also appropriate to facilitate extraction/separation of petroleum and/or petroleum-based residues from aqueous mixtures thereof (e.g. oil-in-water emulsions).
  • aqueous mixtures of petroleum and/or petroleum-based residues may arise from the "artificial lift" process, which involves water or steam pressurized removal of the petroleum and/or petroleum-based residues from their natural environment (e.g. oil reservoirs).
  • aqueous mixtures may arise naturally (e.g. within the natural environment), such that the water carries through with the petroleum and/or petroleum-based residues as the petroleum and/or petroleum-based residues are removed from their natural environment.
  • Post- treatment with compositions of the invention can facilitate separation of the oil and water phases.
  • treatment with compositions of the invention can facilitate direct centrifugation of oil/water mixtures, for example, by sufficiently reducing the viscosity to aid efficient centrifugation.
  • treatment with compositions of the invention may allow for more facile separation of an oil layer (e.g. by "skimming off") from a heterogeneously partitioned oil/water phase mixture.
  • Such post-treatments may also help to clarify oil/water phase interfaces or minimize interfacial oil/water emulsion layers.
  • the method may involve both "pre-treatment” and "post- treatment” as described above.
  • the method may additionally involve mixing additional ingredients with the petroleum and/or petroleum-based residues, for example, any one or more of the additional constituents as define herein, or one or more additional bulking agents, agents that modify the specific gravity of the composition, agents that modify the flash point of the composition, demulsifying agents, coagulants, flocculating agents, corrosion inhibitors, and/or agents that function as penetration enhancers (to enable the composition to effectively break up high viscosity lumps that are present in the petroleum-based fluid and thereby uniformly reduce the viscosity).
  • additional ingredients for example, any one or more of the additional constituents as define herein, or one or more additional bulking agents, agents that modify the specific gravity of the composition, agents that modify the flash point of the composition, demulsifying agents, coagulants, flocculating agents, corrosion inhibitors, and/or agents that function as penetration enhancers (to enable the composition to effectively break up high viscosity lumps that are present in the petroleum-based fluid and thereby uniformly reduce the viscosity).
  • Extracting or extraction may refer to and/or include the removal of petroleum and/or petroleum-based residues from their source (whether natural or otherwise) or from a site at which the relevant petroleum and/or petroleum-based residues are partially or fully immobilized (e.g. tanker, pipeline, or wellhead). Such extraction may merely require pumping (using natural or artificial pressure) of the relevant petroleum and/or petroleum-based residues, where they are sufficiently fluid or otherwise mobilized through pre-treatments with compositions of the invention. As aforementioned, mixing of the petroleum and/or petroleum-based residues with the petroleum additive composition or individual components thereof may precede such extraction, especially if such a pre-treatment helps to mobilize the petroleum and/or petroleum- based residues to facilitate what would otherwise be a difficult extraction process.
  • Extracting or extraction may also refer to and/or include the separation/extraction of petroleum and/or petroleum-based residues from water and/or other unwanted residues in aqueous mixtures of the petroleum and/or petroleum-based residues.
  • aqueous mixtures may arise naturally at source of may arise artificially during the process of initially extracting the petroleum and/or petroleum-based residues from source.
  • Extractions of petroleum and/or petroleum-based residues from aqueous mixtures thereof may typically involve allowing an aqueous mixture to settle/partition into a polyphasic mixture.
  • a polyphasic mixture suitably comprises a plurality of liquid layers, suitably at least an oil phase (suitably an upper layer) and an aqueous phase (a lower layer), but may also comprise a mixed phased comprising both water and oil (e.g. an oil/water emulsion).
  • the interfaces between the liquid layers may lack clarity through being partially emulsified.
  • the oil layer may be "skimmed off” or “tapped off”, and thereby suitably separated from all other liquid layers and emulsified layer interfaces.
  • the oil/water mixed emulsion layer may be processed to separate the petroleum and/or petroleum-based residues therein from the water and other unwanted residues, typically via centrifugation.
  • the aqueous layer is suitably mixed with dense petroleum residues, which may be recovered (e.g. for us or reprocessing, optionally extracting again in accordance with the invention) or discarded.
  • separation/extraction of petroleum and/or petroleum-based residues from water and/or other unwanted residues in aqueous mixtures of the petroleum and/or petroleum- based residues may involve centrifugation (possible direct centrifugation of the entire oil-water mixture without any partition-separation of phases).
  • the petroleum additive compositions of the invention allow oil-water mixtures to be centrifuged at a rate of 200 gallons per minute (gpm) or more, suitably a rate of 500 gallons per minute (gpm) or more.
  • Centrifugation may be employed to separate aqueous mixtures of the petroleum and/or petroleum-based residues into three distinct phases: i) an oil phase; ii) a slurry phase; and iii) solids.
  • the oil phase is essentially a petroleum-based product, which may be subsequently refined or optionally subsequently processed as defined anywhere herein.
  • the slurry phase is typically a mixture of oil, water, and fine suspended solids. Water is typically separated from the slurry phase by techniques well known in the art, and the resulting clean water optionally disposed of (e.g. through discharge into the natural environment).
  • the solids are suitably disposed of (e.g. in landfill sites) or otherwise used as fuel, for example, in concrete works.
  • the extracted petroleum and/or petroleum-based residues may then be stored (e.g. in an oil tank), used, transported, and/or subsequently processed (e.g. refined and/or have the petroleum additive composition removed therefrom).
  • the present invention provides a method of separating water from an oil-water mixture, such as the oil-water mixtures defined herein, which may for example arise during extraction of petroleum and/or petroleum-based residues from source.
  • the method suitably comprises: (a) providing a treated oil-water mixture comprising:
  • the treated oil-water mixture may be provided as a result of any "mixing" as defined herein in relation to the processing of the petroleum and/or petroleum-based residues. This may therefore involve mixing the petroleum and/or petroleum-based residues with the petroleum additive composition or individual components thereof prior to, after, or during bringing the petroleum and/or petroleum-based residues into contact with water.
  • Separating the water from the oil-water mixture may comprise any suitable method of separating, including any such method described herein in relation to the separation of petroleum and/or petroleum-based residues from water, including heterogeneous liquid-liquid phase separations and centrifugation.
  • separating involves the use of centrifugation.
  • at least 20 wt% of the total water content of the original oil-water mixture is separated to provide a clean water phase, more suitably at least 50 wt%, more suitably at least 70 wt%.
  • the separating may involve further treatments to clean the water thereby obtained, but in preferred embodiments requires no further cleaning steps.
  • a particular advantage of the petroleum additive compositions of the invention is that they facilitate the separation of clean water which can then be optionally disposed of as defined herein, most preferably discharged into the natural environment.
  • the present invention provides a method of disposing of water from an oil- water mixture, wherein the method comprises separating water from an oil-water mixture as described above, to thereby provide a clean water phase, and thereafter disposing of some or all of the clean water phase, suitably into the natural environment.
  • Storing or storage refers to storing petroleum and/or petroleum-based residues, especially treated petroleum and/or petroleum-based residues in vessels such as containers or oil tankers.
  • Transporting or transportation may refer to either transporting petroleum and/or petroleum-based residues in a vessel (e.g. container) upon a vehicle (e.g. marine or land-going oil tanker) or via pipework or a pipeline.
  • Pre-treatments, as described above, of petroleum and/or petroleum-based residues with petroleum additive composition of the invention or individual components thereof suitably facilitates transport of said petroleum and/or petroleum-based residues through pipework and pipelines.
  • compositions of the invention facilitate storage and/or transport of petroleum and/or petroleum-based residues.
  • the present invention may be employed to extract the "settled-out" viscous deposits from the vessel by: i) first extracting from the vessel the most mobile/free-flowing portion of the petroleum and/or petroleum-based residues; ii) then treating the viscous deposits left within the vessel with the petroleum additive composition of t e invention or individual components thereof to produce a treated petroleum-based composition; iii) extracting the treated petroleum-based composition from the vessel; iv) optionally removing the petroleum additive composition or individual components thereof from the treated petroleum-based composition; and v) optionally combining it with the mobile petroleum and/or petroleum-based residues removed in step i).
  • compositions of the present invention may be recovered from the petroleum and/or petroleum-based residues.
  • recovery involves centrifugation and/or distillation.
  • Compositions of the present invention (and individual components thereof) are or may be readily tuned (e.g. by adjusting the ingredients or relative amounts thereof) to have a specific gravity that differs from the petroleum and/or petroleum-based residues with which they are mixed, so that centrifugation can be used to recover said compositions. This allows compositions of the invention to be used to perform their role and subsequently recovered and thereby recycled.
  • compositions of the invention are or may be readily tuned (e.g. by adjusting the ingredients or relative amounts thereof) to have a boiling points that differ from the petroleum and/or petroleum-based residues with which they are mixed, so that distillation can be used to recover said compositions.
  • This allows compositions of the invention to be used to perform their role and subsequently recovered and thereby recycled.
  • This also allows compositions of the invention to be employed and subsequently removed during the oil refining process, to thereby reduce additional processing steps.
  • greater than 70% of the composition of the invention can be recovered by centrifugation and/or distillation. More preferably, greater than 85% and even more preferably greater than 90% of the composition is recovered by centrifugation and/or distillation.
  • the present invention further provides a process for reducing the viscosity of a petroleum based fluid, such as crude oil, the process comprising adding a composition as defined herein to the fluid.
  • the present invention provides a process for extracting and/or transporting a petroleum based fluid, the process comprising the steps of:
  • composition as defined herein optionally separating the composition as defined herein from the petroleum based fluid by centrifugation and/or distillation.
  • composition of the invention required to adequately lower the viscosity of the petroleum-based fluid will be determined by experimentation for the particular fluid concerned. For adequate flow properties, a viscosity of below 350 centistokes is desirable.
  • the petroleum and/or petroleum-based residues may be pre-treated prior to performing any of the methods of the present invention.
  • the petroleum and/or petroleum-based residues or aqueous mixtures thereof may be demulsified, for example, through the addition of a demulsifier.
  • a first composition according to the present invention is prepared by mixing the following constituents in the proportions stated:
  • a composition according to the present invention is prepared by mixing the following constituents in the proportions stated:
  • a composition according to the present invention is prepared by mixing the following constituents in the proportions stated:
  • Example 4 The effect of the composition of Example 1 on the viscosity of Venezuelan Crude Oil
  • Example 1 Varying amounts of the composition of Example 1 is added to a representative heavy fuel oil, Venezuelan Crude Oil at 50 °C and 35 °C and the viscosity was measured using a Brookfield Viscometer. The temperatures of the experiments were maintained by the use of water baths. The results are shown in Table 1 below.
  • a composition according to the present invention is prepared by mixing the following constituents in the proportions stated: 60% w/w D-limonene
  • a composition according to the present invention is prepared by mixing the following constituents in the proportions stated:
  • a composition according to the present invention is prepared by mixing the following constituents in the proportions stated: 60% w/w Benzyl acetate
  • Example 5 50g of the composition of Example 5 (i.e. 5% w/w relative to oil) was added to and mixed with (using a mechanical stirrer) 1 kg of a representative heavy fuel oil, Venezuelan Crude Oil. [00221] The heavy fuel oil became significantly more mobile and less viscous, and thereby easier to handle, extract, and transport.
  • the treated heavy fuel oil was then thoroughly mixed with 1 kg of water in a separating funnel.
  • the mixture was left to separate into layers over a 24 hour period, after which time a triphasic mixture formed consisting of a top oil layer, a bottom aqueous layer mixed with solid residues, and a middle mixed emulsified oil/water layer.
  • the oil phase yielded clean heavy oil mixed with the petroleum additive composition.
  • the middle layer was a slurry of water, fine particulates, and some oil. This aqueous slurry could be filtered to afford sufficiently clean water for discharging back into the natural environment.
  • the solids could be disposed of.
  • the clean heavy oil phase was further processed to remove the additive composition itself via further centrifugation.
  • compositions of the invention can be used to reduce viscosity of petroleum and petroleum-based residues to facilitate the transport and extraction thereof, and also to facilitate separation from water in aqueous mixtures. It is has also been demonstrated that the composition may be subsequently recovered and reused.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Cette invention concerne des compositions et des procédés de traitement du pétrole et/ou de résidus à base de pétrole, en particulier là où ledit pétrole et/ou lesdits résidus à base de pétrole sont difficiles à extraire ou à obtenir. De manière générale, les compositions selon l'invention contribuent à réduire la viscosité du pétrole et/ou des résidus à base de pétrole, tels que le pétrole brut, et à améliorer ainsi son aptitude à l'écoulement. Les compositions selon l'invention comprennent un composant organique insaturé à base d'un acide non gras et un composant organique à base d'acide gras.
PCT/IB2014/064863 2013-09-26 2014-09-26 Traitement du pétrole et/ou de résidus de pétrole WO2015044905A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2017214345A1 (fr) * 2016-06-08 2017-12-14 M-I L.L.C. Agent d'amélioration d'écoulement pour pétroles bruts lourds et extralourds
CN110452676A (zh) * 2018-05-08 2019-11-15 中国石油化工股份有限公司 用于降低稠油粘度的组合物和稠油降粘剂及其制备方法和应用及稠油降粘的方法
CN114174476A (zh) * 2019-07-30 2022-03-11 国际壳牌研究有限公司 具有增强稳定性的燃料组合物及其制造方法

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US5549839A (en) * 1995-04-21 1996-08-27 Chandler; William C. Industrial solvent based on a processed citrus oil for cleaning up petroleum waste products
US6260620B1 (en) * 1995-10-03 2001-07-17 Nor Industries, Inc. Process of separating excess water or sludge from recovered crude petroleum oil
USRE37629E1 (en) * 1994-05-04 2002-04-09 Joe S. Wilkins, Jr. Engine fuels
JP2012017483A (ja) * 2010-07-06 2012-01-26 Softard Kogyo Kk 石油精製プラントの洗浄方法
US20130228329A1 (en) * 2011-10-04 2013-09-05 Biospan Technologies, Inc. Oil Thinning Compositions And Retrieval Methods

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USRE37629E1 (en) * 1994-05-04 2002-04-09 Joe S. Wilkins, Jr. Engine fuels
US5549839A (en) * 1995-04-21 1996-08-27 Chandler; William C. Industrial solvent based on a processed citrus oil for cleaning up petroleum waste products
US6260620B1 (en) * 1995-10-03 2001-07-17 Nor Industries, Inc. Process of separating excess water or sludge from recovered crude petroleum oil
JP2012017483A (ja) * 2010-07-06 2012-01-26 Softard Kogyo Kk 石油精製プラントの洗浄方法
US20130228329A1 (en) * 2011-10-04 2013-09-05 Biospan Technologies, Inc. Oil Thinning Compositions And Retrieval Methods

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017214345A1 (fr) * 2016-06-08 2017-12-14 M-I L.L.C. Agent d'amélioration d'écoulement pour pétroles bruts lourds et extralourds
CN110452676A (zh) * 2018-05-08 2019-11-15 中国石油化工股份有限公司 用于降低稠油粘度的组合物和稠油降粘剂及其制备方法和应用及稠油降粘的方法
CN110452676B (zh) * 2018-05-08 2022-01-04 中国石油化工股份有限公司 用于降低稠油粘度的组合物和稠油降粘剂及其制备方法和应用及稠油降粘的方法
CN114174476A (zh) * 2019-07-30 2022-03-11 国际壳牌研究有限公司 具有增强稳定性的燃料组合物及其制造方法

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