EP3445837A1 - Composition de pétrole brut, comprenant un additif pour améliorer les propriétés d'écoulement de pétrole brut contenant de la paraffine. - Google Patents

Composition de pétrole brut, comprenant un additif pour améliorer les propriétés d'écoulement de pétrole brut contenant de la paraffine.

Info

Publication number
EP3445837A1
EP3445837A1 EP17718899.2A EP17718899A EP3445837A1 EP 3445837 A1 EP3445837 A1 EP 3445837A1 EP 17718899 A EP17718899 A EP 17718899A EP 3445837 A1 EP3445837 A1 EP 3445837A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
crude oil
comonomers
mol
additive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17718899.2A
Other languages
German (de)
English (en)
Inventor
Artem UCHAEV
Alisa GAPCHENKO
Hans-Ulrich Moritz
Werner Pauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universitaet Hamburg
Original Assignee
Universitaet Hamburg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from LU93040A external-priority patent/LU93040B1/de
Application filed by Universitaet Hamburg filed Critical Universitaet Hamburg
Publication of EP3445837A1 publication Critical patent/EP3445837A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • C10L10/16—Pour-point depressants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0453—Petroleum or natural waxes, e.g. paraffin waxes, asphaltenes
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • 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
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/04—Additive or component is a polymer
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index

Definitions

  • the invention relates to a crude oil composition
  • a crude oil composition comprising an additive for improving the flow properties of paraffinic crude oil, a process for producing a crude oil composition having a reduced pour point compared to the crude oil, and the use of an additive for improving the flow properties of paraffinic crude oil.
  • Crude oil is a mixture of substances consisting mainly of hydrocarbons.
  • crude oil contains oxygen and sulfur containing compounds such as naphthenic acids, phenol, aldehydes, thioesters and various heterocyclic compounds.
  • a majority of the hydrocarbons is a mixture of straight-chain unbranched paraffins having 1 to 30 carbon atoms, wherein gaseous and solid hydrocarbons are dissolved in the liquid hydrocarbons.
  • paraffins in the crude oil cause particular problems in terms of flow properties.
  • paraffins With pure crude oil, paraffins begin to crystallize out and agglomerate at temperatures around 40 to 50 ° C, which significantly worsens the flow properties of the crude oil.
  • the temperature at which crude oil loses its flowing properties is referred to as pour point, which leads to deposits on the inner walls of the pipes during transport of the crude oil through pipelines, especially in winter, in some cases even to complete blockage (eg in case of a temporary stoppage of crude oil in a pipeline).
  • paraffin inhibitors are macromolecular substances which by physical interaction with paraffins modify their size, shape and adsorption properties. This leads to the formation of smaller paraffin crystals, which no longer aggregate and the
  • Paraffin inhibitors are predominantly paraffin-like in structure and generally have polar groups in the side chains. Among other things, these branches have the task of countering the crystal formation of the paraffins. The additives lead to a lowering of the pour point of crude oil.
  • paraffin inhibitors polymers, copolymers and terpolymers having an average molecular weight of 3,000 to 100,000 g / mol are known.
  • the effectiveness of the additives depends on their chemical composition and their concentration.
  • US 3 735 770 discloses a process for improving the flow properties of crude oils. This process involves the addition of copolymers of ethylene with unsaturated ones
  • US 3,393,057 discloses a terpolymer as a pour point depressant consisting of 10 to 90% by weight of C10-C24a olefins, 2.5 to 35% by weight of butadiene and 2.5 to 35 Wt% styrene or indene and has a kinematic viscosity of 35 to 600 centistokes at 210 ° F.
  • US 3,951,929 discloses a pour point improver comprising an interpolymeric acrylic ester having an average molecular weight of 3,000 to 100,000.
  • EP 1 086 964 B2 discloses a pour point improver of (meth) acrylic acid copolymer.
  • the poly (meth) acrylic acid ester copolymer consists of 5 to 60 wt .-% (meth) acrylic acid esters of alcohols having 11 to 15 carbon atoms, and 95 to 40 wt .-% of (meth) acrylic acid esters of
  • DE 2048308 Al discloses as a paraffin inhibitor a mixture of ethylene-vinyl ester copolymer having a molecular weight of 3,000 and 9,000. From 0.01% to 0.5% by weight of the mixture is added to the crude to reduce the pour point.
  • EA 012243 Bl discloses a pour point improver consisting of a product
  • WO 2001/096503 A2 discloses an additive for improving the flowability of mineral oil. This contains: a) Copolymers of 80 to 96.5 mol% of ethylene and 3.5 to 20 mol%
  • No. 7,790,821 B2 discloses a process for producing a stable latex dispersion consisting of (co) polymers with one or more (meth) acrylic acid ester monomers of alcohols having from 6 to 40 carbon atoms, optionally with one or more monomers, of non-water-soluble (meth) acrylic and / or vinyl type, and optionally one or more polar monomers selected from (meth) acrylamides and their derivatives, and optionally one or more monomers selected from the ethylenically unsaturated mono- and / or dicarboxylic acids or their anhydrides are selected.
  • the latex dispersion inhibits the separation of paraffins in the crude oil.
  • EP 0 120 512 A2 discloses a pour point improver comprising a minor amount of a polymer having predominantly aliphatic hydrocarbon side chains of at least 14 carbon atoms, the polymer having a branched carbon backbone.
  • EP 0 332 000 A2 discloses the use of copolymers of acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts having at least 16 carbon atoms in the alcohol radical and not more than 5 wt .-% maleic anhydride as flow improvers in paraffin-rich crude oils and / or petroleum fractions with Eigenfmonyddlingen above 25 ° C to lower their pour points to values below 15 ° C.
  • monohydric alcohols with interpolymers derived from (i) ⁇ , ⁇ -unsaturated dicarboxylic acids or derivatives thereof, and (ii) vinyl aromatic monomers having up to 12 carbon atoms.
  • Object of the present invention is therefore to provide a way to favorably influence the pour point of crude oil and thus to improve the flow properties of crude oil.
  • the invention provides a crude oil composition
  • a paraffin-containing crude oil and an amount of an additive which causes a lowering of the pour point of the crude oil
  • the additive comprising at least one copolymer composed of at least two comonomers, all of which being the copolymer comonomers are selected from the groups (a) and (b) of comonomers, and wherein the group (a) consists of comonomers of acrylic acid and methacrylic acid, and the group (b) consists of comonomers of styrene and a styrene derivative.
  • a copolymer of at least two comonomers wherein the comonomers are selected from groups (a) consisting of acrylic acid and methacrylic acid, and (b) consisting of styrene and a styrene derivative, improve the cold properties of crude oil can.
  • corresponding copolymers are acrylic acid / styrene, methacrylic acid / styrene or (meth) acrylic acid / styrene derivative, or else Mixed polymers of a mixture of acrylic acid and methacrylic acid and styrene or styrene derivative.
  • paraffine-containing crude oil a crude oil (crude petroleum) containing hydrocarbons in the form of paraffins.
  • paraffins as used herein are acyclic, saturated, straight-chain or branched hydrocarbons (alkanes) having 1 to 33
  • Carbon atoms in particular having 12 to 33 carbon atoms or 16 to 20
  • paraffin-containing crude oil is used here in particular when the paraffin content is at least 10%.
  • styrene phenylethene, CAS number 100-42-5) is understood as meaning a compound of the following formula:
  • styrene derivative is understood here to mean a compound according to the following formula:
  • R 2 , R 3 , R 4 , R 5 and R 6 are each independently H, or alkyl, preferably H, methyl, or C 2 -C 12 alkyl, with the proviso that not all R 2 to R 6 are H are.
  • the formulation according to which the comonomers of the at least one copolymer are selected from groups (a) and (b) of comonomers wherein group (a) consists of comonomers of acrylic acid and methacrylic acid and group (b) of comonomers of styrene and a styrene derivative "or the formulation according to which the at least one
  • Copolymer "composed of at least two comonomers, all of which
  • Copolymer composing comonomers are selected from the groups (a) and (b) of comonomers, wherein the group (a) of comonomers of acrylic acid and
  • Methacrylic acid and the group (b) of comonomers of styrene and a
  • Styrene derivative "means that the copolymer is in any case composed of at least one type of comonomer from group (a) and at least one type of comonomer from group (b). Examples of copolymers would therefore be those of two comonomers, for example the comonomers acrylic acid (cf.
  • mixed polymers of more than four comonomers are also suitable, for example a copolymer of acrylic acid and methacrylic acid (Group
  • the formulation according to which "the additive comprises at least one copolymer of at least two comonomers” or “the additive comprises at least one copolymer composed of at least two comonomers” includes, besides additives, a copolymer having a substantially uniform comonomer composition, i. a copolymer of two particular comonomers (e.g., acrylic acid and styrene), also mixtures of copolymers of different comonomer composition, as long as the copolymers of the copolymer blend have the composition specified above, i. are composed of at least two comonomers selected from comonomers of groups a and b.
  • the copolymer mixture may contain, for example, copolymers of acrylic acid and styrene, methacrylic acid and styrene and / or acrylic acid, methacrylic acid and styrene.
  • the term "improving the flow properties of paraffinic crude oil” is understood here to mean a reduction in the pour point of the crude oil, the pour point being the temperature at which crude oil loses its flowing properties.
  • the pour point can be determined, for example, according to ASTM D5853. A that
  • Crude oil composition containing additive according to the invention thus has a lower pour point compared to crude oil.
  • a crude oil may have a pour point of 12 ° C while the crude oil composition has a pour point of -5 ° C.
  • pour point improver is understood here to be an additive which lowers the pour point of a crude oil, preferably by at least 1 ° C., more preferably by at least 2 ° C., by at least 3 ° C., by at least 4 ° C, at least 5 ° C, at least 6 ° C, at least 7 ° C, at least 8 ° C, at least 9 ° C or at least 10 ° C.
  • alkyl includes saturated and unsaturated aliphatic (non-aromatic)
  • C 2 -C 2 alkyl means an alkyl group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12 carbon atoms.
  • An arbitrary smaller area of the area should also be disclosed, wherein the smaller area also includes areas which do not include any of the limit values of the area.
  • an indication such as "10,000 to 30,000” includes not only areas such as “10,000 to 29,000” or “15,000 to 30,000” but also ranges of "15,000 to 28,000” or “20,000 to 29,000” or “12,000 to 27,000” individual values within the range are expressly included, and not just its limits.
  • a copolymer used according to the invention has the general structure according to the following formula I:
  • R 1 is H or methyl, R 2, R 3, R 4, R 5 and R 6, each independently, H or alkyl, preferably H, methyl, or C 2 -C 2 are alkyl, and m is the number of the comonomer (s) of group (a) (acrylic acid, methacrylic acid) and n indicates the number of comonomers or comonomers of group (b) (styrene, styrene derivative) in the copolymer.
  • the above formula indicates schematically only a general structure and is in particular not to be understood that this must be an alternating copolymer or block copolymer. Rather, it may also be a random copolymer. As already indicated, the formula is also not to be understood that only two comonomers, eg
  • Acrylic acid and styrene in which copolymer is present are suitable (for example acrylic acid, methacrylic acid and styrene), but with the proviso that always at least one comonomer from group a and at least one comonomer from group b is present.
  • copolymers are basically known (see, for example, Ullmanns Enzyklopadie der Technischen Chemie, Vol. 21, pages 305 to 403).
  • monomers are dissolved in an organic solvent and polymerized in the presence of a radical initiator at temperatures in the range of, for example, 30 to 150 ° C.
  • the additive comprises 0.05 to 50% by weight, preferably 0.5 to 50% by weight, 1 to 50% by weight, 2.5 to 50% by weight or 5 up to 50% by weight, more preferably 5 to 45% by weight, 10 to 45% by weight, 15 to 45% by weight or 15 to 40% by weight, particularly preferably 20 to 40% by weight of the at least one copolymer.
  • the at least one copolymer used in the additive is in a preferred
  • Embodiment composed of two comonomers, wherein the comonomer from group (a) of comonomers is acrylic acid or methacrylic acid, preferably acrylic acid, and the comonomer from group (b) of comonomers is styrene or a styrene derivative, preferably styrene.
  • the molecular weight or molecular weight distributions (MWD) of the copolymers used according to the invention in the crude oil composition can be in a range from 2,000 to
  • the molecular weight distribution can be determined, for example, by means of gel permeation chromatography against polystyrene standards.
  • the conversion of acrylic acid for example, after the reaction by
  • Reverse phase high performance liquid chromatography RP-HPLC
  • acetonitrile as the eluent.
  • the conversions of styrene can be determined, for example, after the reaction by means of gas chromatography (GC).
  • GC gas chromatography
  • the average molecular weight or molecular weight distribution of the copolymer or copolymer mixture in the additive is preferably that used to prepare the
  • Crude oil of the invention used crude oil, in particular the
  • the at least one copolymer has an average molecular weight of 2,000 to 30,000 g / mol, preferably 5,000 to 30,000 g / mol, more preferably 10,000 to 30,000 g / mol, 10,000 to ⁇ 30,000 g / mol, 10,000 to 29,000 g / mol, 10,000 to 28,000 g / mol, 10,000 to 27,000 g / mol, 10,000 to 26,000 g / mol or 10,000 to 25,000 g / mol.
  • Crude oil composition is in the additive, the proportion of the comonomer (a) to the at least one copolymer, based on the comonomer mixture, 0.6 to ⁇ 10.0 wt .-%, preferably 1.0 to ⁇ 10.0 wt .-%, more preferably 1.0 to 9.0% by weight, 2.0 to 9.0% by weight, 3.0 to 9.0% by weight, 4.0 to 9.0% by weight, 5.0 to 9.0 wt% or 5.0 to 8.0 wt%.
  • the at least one copolymer has an average molecular weight of 10,000 to 30,000 g / mol, and a proportion of acrylic acid of 1.0 to
  • ⁇ 10.0 wt% preferably from 2.0 to 9.0 wt%, more preferably from 3.0 to 9.0 wt%, 4.0 to 9.0 wt%, 5.0 to 9.0 Wt .-% or 5.0 to 8.0 wt .-%, for example, 5 wt .-%, on.
  • the additive preferably also comprises at least one organic solvent in addition to the at least one copolymer, wherein the organic solvent is preferably an aromatic solvent, and is more preferably selected from aromatic
  • Hydrocarbons such as toluene, xylene, trimethylbenzene, ethylbenzene, dimethylnaphthalene or a mixture thereof.
  • the organic solvent is preferably chosen so that it is readily soluble in crude oil and at the same time the copolymer or
  • Copolymer mixture dissolves well.
  • the additive may be composed of the at least one copolymer and the at least one organic solvent. The share of
  • Solvent on the additive may in this case, depending on the proportion of at least one Copolymer, for example 50 to 99.95% by weight, 50 to 99.5% by weight, 50 to 97.5% by weight, 50 to 95% by weight, 55 to 95% by weight. %, 55 to 90 wt .-%, 55 to 85 wt .-%, 60 to 85 wt .-% or 60 to 80 wt .-% amount.
  • the additive may be composed of 20% by weight of the at least one copolymer and 80% by weight of the at least one solvent.
  • radical initiators e.g. Azo-bis-isobutyronitrile
  • esters of peroxycarboxylic acid such as t-butyl perprivalate and t-butyl-per-2-ethylxeanoate or dibenzoyl peroxide or other peroxides and azo compounds
  • the initiators can be added to the comonomer mixture, for example, in an amount of 0.05 to 10 wt .-%.
  • the desired properties of the copolymer can be determined, for example, by varying the reaction parameters pressure and temperature and by the ratio of initiator to
  • Monomer (s) can be adjusted.
  • a preferred crude oil composition of the invention comprises an amount of the additive containing a pour point depression of the crude oil of at least 1 ° C, preferably at least 2 ° C, at least 3 ° C, at least 4 ° C, at least 5 ° C, at least 6 ° C, at least 7 ° C, at least 8 ° C, at least 9 ° C or at least 10 ° C causes.
  • Crude oil composition for example, 1 to 1000 ppmw, preferably 5 to 1000 ppmw or 5 to 750 ppmw, particularly preferably 5 to 500 ppmw, 10 to 500 ppmw, 10 to 300 ppmw or 15 to 250 ppmw of the at least one copolymer.
  • the present invention also relates to a process for preparing a crude oil composition having a pour point lowered from the crude oil, comprising adding an additive to the crude oil in an amount effective to lower the pour point, the additive comprising at least one copolymer, which is composed of at least two comonomers, all of which is the copolymer
  • comonomers are selected from groups (a) and (b) of Comonomers, and wherein the group consists of (a) of comonomers of acrylic acid and methacrylic acid, and the group (b) of comonomers of styrene and a
  • an additive is added to the crude oil, which is 0.05 to 50 wt .-%, preferably 0.5 to 50 wt .-%, 1 to 50 wt .-%, 2.5 to 50 wt .-% or 5 bis 50 wt .-%, more preferably 5 to 45 wt .-%, 10 to 45 wt .-%, 15 to 45 wt .-% or 15 to 40 wt .-%, particularly preferably 20 to 40 wt .-% of comprises at least one copolymer.
  • an additive is added to the crude oil,
  • the at least one copolymer has a weight average molecular weight of 2,000 to 30,000 g / mol, preferably 5,000 to 30,000 g / mol, more preferably 10,000 to ⁇ 30,000 g / mol, 10,000 to 30,000 g / mol, 10,000 to 29,000 g / mol, 10,000 to 28,000 g / mol, 10,000 to 27,000 g / mol, 10,000 to 26,000 g / mol or 10,000 to 25,000 g / mol or 10,000 to 25,000 g / mol, and / or
  • the at least one copolymer is composed of two comonomers, and wherein the comonomer from group (a) of comonomers is acrylic acid or methacrylic acid, preferably acrylic acid, and the comonomer from group (b) of comonomers is styrene or a styrene derivative, preferably Styrene is, and / or
  • Solvent preferably an aromatic solvent, more preferably one
  • an amount of the additive which reduces the pour point by at least 1 ° C., preferably at least 2 ° C., at least 3 ° C., at least 4 ° C., at least 5, is added to the crude oil ° C, at least 6 ° C, at least 7 ° C, at least 8 ° C, at least 9 ° C or at least 10 ° C.
  • an amount of the additive is added to the crude oil such that the resulting
  • Crude oil composition 1 to 1000 ppmw, preferably 5 to 1000 ppmw or 5 to 750 ppmw, particularly preferably 5 to 500 ppmw, 10 to 500 ppmw, 10 to 300 ppmw or 15 to 250 ppmw of the at least one copolymer.
  • the present invention relates to the use of a copolymer or mixture of copolymers composed of at least two comonomers, wherein all comonomers of the copolymer or copolymer mixture are selected from groups (a) and (b) of comonomers, and wherein the group (a) consists of comonomers of acrylic acid and methacrylic acid, and group (b) of
  • Comonomers of styrene or a styrene derivative as an additive for improving the flow properties of paraffinic crude oil.
  • the invention relates to the use of the additive for lowering the pour point of paraffinic crude oil, preferably by at least 1 ° C, preferably at least 2 ° C, at least 3 ° C, at least 4 ° C, at least 5 ° C, at least 6 ° C, at least 7 ° C, at least 8 ° C, at least 9 ° C or at least 10 ° C.
  • a copolymer or copolymer mixture is used which is dissolved in an organic solvent, wherein the copolymer or copolymer mixture 0.05 to 50 wt .-%, preferably 0.5 to 50 wt .-%, 1 to 50 wt. -%, 2.5 to 50 wt .-% or 5 to 50 wt .-%, more preferably 5 to 45 wt .-%, 10 to 45 wt .-%, 15 to 45 wt .-% or 15 to 40 Wt .-%, particularly preferably 20 to 40 wt .-% of the solution of copolymer or copolymer mixture and organic solvent.
  • the copolymer or copolymer mixture is in an aromatic
  • Solvent preferably in a solvent of one or more aromatic Hydrocarbons, for example, from toluene, xylene, trimethylbenzene, ethylbenzene, dimethylnaphthalene or a mixture thereof.
  • aromatic Hydrocarbons for example, from toluene, xylene, trimethylbenzene, ethylbenzene, dimethylnaphthalene or a mixture thereof.
  • the amount of acrylic acid was 0.6 to 10.0 wt .-%, based on the comonomer mixture. Thereafter, initiator (dibenzoyl peroxide) was used in an amount of 0.1 to 3.0 wt .-%, based on the comonomer mixture. The metering of the initiator was carried out at intervals of 40 minutes (4 to 6 times) (ratio of initiator to monomers: 0.1 to 3.0% by weight) to full conversion after about 160 to 240 minutes. Solubility of copolymers with different acrylic acid content.
  • Tab. 1 Influence of the amount of acrylic acid in the formulation on the solubility of the copolymer in hydrocarbons (diesel fraction). Amount of acrylic acid in the recipe
  • Copolymers made with 10% or more by weight of acrylic acid did not dissolve in hydrocarbons.
  • the effectiveness of the prepared copolymers as paraffin inhibitor was determined by measuring the pour point, determined according to ASTM D5853, to give the Saharan blend (Saharan Blend) grade with a pour point of +12.0 ° C (see Table 2).
  • Tab. 2 Influence of the amount of acrylic acid in the recipe on the pour point of "Sahara” crude oil.
  • Example 1 0.25 30.040 150 +12.0
  • Example 2 0.5 21.750 150 -20.0
  • Example 3 1.0 17.990 150 -21.0
  • Example 4 2.0 11.580 150 -12.0
  • Ex. 5 2.5 10.510 150 -10.0
  • Example 3 The additive prepared in Example 3 was added to "Sibir” (pour point +17.0 ° C) and “Sahara” (pour point +12.0 ° C) crude at different concentrations, and the pour point of the resulting crude oil compositions was determined (see Tab. 4, 5).

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Emergency Medicine (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'amélioration des propriétés d'écoulement de pétrole brut contenant de la paraffine. La présente invention vise à fournir une possibilité pour influencer favorablement le point d'écoulement de pétrole brut et améliorer ainsi les propriétés d'écoulement de pétrole brut contenant de la paraffine. Selon un aspect, l'invention concerne une composition de pétrole brut qui comprend un pétrole brut contenant de la paraffine et une quantité d'un additif qui provoque un abaissement du point d'écoulement du pétrole brut, l'additif comprenant au moins un copolymère, qui est constitué par au moins deux comonomères et l'ensemble des comonomères composant le copolymère étant choisi dans les groupes (a) et (b) de comonomères, le groupe (a) étant constitué de comonomères d'acide acrylique et d'acide méthacrylique et le groupe (b) étant constitué de comonomères de styrène et d'un dérivé de styrène.
EP17718899.2A 2016-04-21 2017-04-20 Composition de pétrole brut, comprenant un additif pour améliorer les propriétés d'écoulement de pétrole brut contenant de la paraffine. Withdrawn EP3445837A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102016107426 2016-04-21
LU93040A LU93040B1 (de) 2016-04-21 2016-04-21 Additiv zur Verbesserung der Fliesseigenschaften von paraffinhaltigen Rohölen
PCT/EP2017/059408 WO2017182574A1 (fr) 2016-04-21 2017-04-20 Composition de pétrole brut, comprenant un additif pour améliorer les propriétés d'écoulement de pétrole brut contenant de la paraffine.

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EP3445837A1 true EP3445837A1 (fr) 2019-02-27

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Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3393057A (en) 1963-04-11 1968-07-16 Sinclair Research Inc Mineral oil pour point depressor
US3574575A (en) * 1969-04-21 1971-04-13 Mobil Oil Corp Liquid hydrocarbon oil compositions containing esters of styrene-maleic anhydride copolymers as fluidity improvers
DE2048308A1 (en) 1970-10-01 1972-04-06 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Pour point depressants - for paraffinic crude oils consisting of mixed ethylene-vinyl acetate copolymers
GB1337288A (en) * 1971-05-13 1973-11-14 Ici Ltd Polymer solution
US3735770A (en) 1972-02-09 1973-05-29 Gulf Research Development Co Method for increasing the mobility of waxy crude oils
US3904385A (en) 1972-05-08 1975-09-09 Texaco Inc Polyacrylates and waxy residual fuel compositions thereof
DE2345814A1 (de) * 1973-09-11 1975-03-20 Bp Benzin Und Petroleum Ag Verfahren zur herstellung von styrolacrylsaeure-copolymerisaten und ihre verwendung
US4284414A (en) * 1980-10-14 1981-08-18 The Lubrizol Corporation Mixed alkyl esters of interpolymers for use in crude oils
GB8307522D0 (en) 1983-03-18 1983-04-27 Shell Int Research Wax-containing crude oil
SU1102900A1 (ru) * 1983-03-21 1984-07-15 Сибирский научно-исследовательский институт нефтяной промышленности Способ предотвращени образовани парафиновых отложений в нефтепромысловом оборудовании
DE3807394A1 (de) 1988-03-07 1989-09-21 Henkel Kgaa Verwendung ausgewaehlter copolymertypen der acryl- und/oder methacrylsaeureester als fliessverbesserer in paraffinreichen erdoelen und erdoelfraktionen (i)
US6255261B1 (en) 1999-09-22 2001-07-03 Ethyl Corporation (Meth) acrylate copolymer pour point depressants
CA2412740A1 (fr) 2000-06-15 2002-12-13 Clariant International Ltd Additif pour ameliorer la fuidite a froid et la stabilite au stockage du petrole brut
FR2828494B1 (fr) 2001-08-08 2005-06-03 Ceca Sa Dispersions de latex de polymeres acryliques comme additifs pour l'inhibition du depot de paraffines dans les huiles brutes et compositions les contenant
US7417009B2 (en) * 2004-03-26 2008-08-26 Nalco Company Paraffin inhibitors
EA012243B1 (ru) 2006-03-03 2009-08-28 Галина Ильясовна Бойко Депрессорная присадка для высокопарафинистых нефтей и нефтепродуктов и способ ее получения

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RU2740208C2 (ru) 2021-01-12
RU2018135050A (ru) 2020-05-21
RU2018135050A3 (fr) 2020-06-04
US20190062660A1 (en) 2019-02-28

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