WO1998021446A1 - Inhibiteurs et leurs applications dans des huiles - Google Patents

Inhibiteurs et leurs applications dans des huiles Download PDF

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Publication number
WO1998021446A1
WO1998021446A1 PCT/GB1997/003076 GB9703076W WO9821446A1 WO 1998021446 A1 WO1998021446 A1 WO 1998021446A1 GB 9703076 W GB9703076 W GB 9703076W WO 9821446 A1 WO9821446 A1 WO 9821446A1
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WIPO (PCT)
Prior art keywords
ester
alcohol
carbons
polymer
aliphatic
Prior art date
Application number
PCT/GB1997/003076
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English (en)
Inventor
Simon Neil Duncum
Philip Kenneth Gordon Hodgson
Keith James
Christopher George Osborne
Original Assignee
Bp Exploration Operating Company Limited
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 GBGB9623742.5A external-priority patent/GB9623742D0/en
Priority claimed from GBGB9623736.7A external-priority patent/GB9623736D0/en
Priority claimed from GBGB9626443.7A external-priority patent/GB9626443D0/en
Priority claimed from GBGB9709064.1A external-priority patent/GB9709064D0/en
Priority claimed from GBGB9713709.5A external-priority patent/GB9713709D0/en
Application filed by Bp Exploration Operating Company Limited filed Critical Bp Exploration Operating Company Limited
Priority to GB9911074A priority Critical patent/GB2334258B/en
Priority to AU48778/97A priority patent/AU4877897A/en
Publication of WO1998021446A1 publication Critical patent/WO1998021446A1/fr
Priority to NO992310A priority patent/NO992310L/no

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    • 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
    • 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
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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    • C10L1/192—Macromolecular compounds
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    • 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
    • C10L1/1963—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 mono-carboxylic
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    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
    • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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    • C10L1/18—Organic compounds containing oxygen
    • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
    • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
    • C—CHEMISTRY; METALLURGY
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    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
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    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
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    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C10L1/2235—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom hydroxy containing
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    • C10L1/224—Amides; Imides carboxylic acid amides, imides
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
    • C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
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Definitions

  • the present invention relates to wax inhibitors especially wax deposition inhibitors and their use, particularly in petroleum industry pipelines.
  • Crude oils are complex mixtures comprising hydrocarbons of varying types and molecular weights.
  • One class of hydrocarbon present in the oils is paraffins which are linear, branched chain or cyclic hydrocarbons having at least 18 carbons which can form waxy solids.
  • the solubility of these waxy solid forming components in the crude oils is predominantly temperature-dependant. They are usually soluble in the crude oil under down-hole conditions i.e. high pressures or high temperatures. However as the oil is brought to the surface its temperature and pressure are reduced. As a result the wax may begin to precipitate out and may form deposits on any cooler surface with which it comes into contact. These wax deposits can cause problems, such as blockage of pipelines, valves and other process equipment.
  • the wax may also deposit in pipelines subsequently used to transport crude oil or fractions derived from the total product brought up from down-hole, such as fractions comprising gas, e.g. natural gas, and/or water, as well as a liquid hydrocarbon body, e.g. crude (or black) oil or "condensate"; the pipelines may thus be hydrocarbon lines or multi phase transportation lines with oil, gas and/or water.
  • the wax may deposit on surfaces of metare.g. of ferrous metal.
  • the contents of the transport pipelines are often cooler than the contents of lines on oil platforms or in refineries. This cooling is especially critical in respect of lines from offshore oil fields to the land and land lines in cold territories such as Alaska.
  • Wax deposition may be reduced in a number of ways, including keeping the lines hot, diluting the oil with solvent, use of special additives which interfere with wax crystal growth. We have discovered how to reduce the tendency to deposit wax from waxy oils.
  • the present invention provides a polymer of a monomer with structural units derived from an ester (1) of an aliphatic carboxylic acid with an aliphatic alcohol, wherein one of the acid and alcohol is ethylenically unsaturated and the other of the acid and alcohol has a long chain group e.g. of 14-40 carbons, and optionally at least one monomer, which is a monomer with structural units derived from a different ester (2) within the same definition as ester 1, such that the mole average carbon content of the long chain group is 15-35 preferably 16.5-24 especially 17.5-22 or that 30% e.g. at least 50% of the long chain groups have 15-35 carbons preferably 16.5-24 especially 18-22 carbons.
  • the polymers or copolymers may be made by direct (Co)polymerisation, but are preferably polymers obtainable by or obtained by transesterification of at least one polymer of an ester (3) with an aliphatic alcohol or carboxylic acid having an aliphatic group of 14-40 or 15-35 e.g. 16-24 carbons (depending on whether the acid or alcohol in ester 1 is unsaturated or aliphatic); the conversion may be substantially complete, but preferably is only 30-90% e.g. 40-90% or 50-90%.
  • the present invention also provides said transesterification process.
  • the present invention provides a blend of at least two different polymers selected from homopolymers (A) with structural units derived from an ester (1) and copolymers (B) thereof with structural units derived from a different ester (2) within the same definition as ester 1, such that the mole average carbon content of the long chain group is 15-35 preferably 16.5-24 especially 17.5-22 or that at least 30% e.g. at least 50% of the long chain groups have 15-35 carbons preferably 16.5-24 especially 18-22 carbons, and copolymers (C) of said ester (1) and optionally ester (2) with a corresponding ester (3) such that at least 30% e.g.
  • the present invention also provides at least one copolymer C.
  • the present invention also provides a blend of components selected from:- a) component (I), which is at least one N-substituted polyalkyleneimine compound with chain nitrogen atoms, which has at least one organic substituent of at least 6 carbon atoms on at least one nitrogen atom and b) component (II) selected from at least one polymer of said homopolymers (A), copolymers (B) and copolymers (C) with the proviso that the blend comprises at least 2 components of which at least one is a component (I).
  • the blends of the invention may comprise at least two components (I) or may comprise at least one component (I) together with at least one component (II).
  • the blend comprises a component (I) with at least one component (II) which is preferably copolymer (C) and at least one of polymer (A) and (C).
  • the present invention also provides a composition
  • a composition comprising at least one polymer A, B or C or said blend, together with at least one monomeric additive, which has an aliphatic group of at least 14 carbons and a polar group, preferably a group containing one or more nitrogen atoms, especially with at least one tertiary or secondary amino nitrogen (and optionally in addition a primary) amino nitrogen atom, in particular in a heterocyclic group containing at least 1 nitrogen atom.
  • the present invention also provides a method of reducing wax formation and/or deposition in a wax-containing oil, preferably in a pipeline containing said oil, while flowing, which comprises mixing with said oil at least one polymer A, copolymer B or C, blend or composition of the invention.
  • Ester 1 may be derived from an ethylenically unsaturated carboxylic acid and a long chain alcohol, whether saturated or unsaturated and in this case ester 2 and/or ester 3 (if present) are of this same type with a long chain alcohol or short chain alcohol whether saturated or unsaturated.
  • ester 1 may be derived from an ethylenically unsaturated alcohol e.g. "vinyl alcohol” and a long chain aliphatic carboxylic acid whether saturated or unsaturated, and in this case ester 2 and/or ester 3 if present are of this same type with a long chain acid or shor chain acid whether saturated or unsaturated.
  • blends of the invention of at least 2 polymers selected from homopolymers A, copolymers B and copolymers C, ones with copolymer C and at least one of A, B and C are preferred .
  • Preferred blends have a bimodal distribution of carbon numbers in the 14-40 region for alcohols when the acid is unsaturated or for acids the "alcohol" is unsaturated.
  • the above copolymers C are preferably obtainable by or obtained by transesterification of at least one polymer of an ester (3) with an aliphatic alcohol or carboxylic acid having an aliphatic group of 14-40 e.g.
  • the transesterification product may be used as such i.e. containing any unreacted polymer of ester (3) and/or unreacted alcohol or acid (respectively) with a 14-40 e.g. 16-24 carbon group, e.g. in amount of 1-50% e.g. 10-50% (by weight, based on the weight of polymer 3) especially for unreacted alcohol.
  • the unreacted alcohol or acid respectively may be substantially removed so the product may be in the substantial absence of said alcohol or acid.
  • the acid may be a mono, di or tricarboxylic acid, examples of the diacid being fumaric, maleic and crotonic acids.
  • each of the long chain groups may be saturated or ethylenically unsaturated, but are preferably all saturated or all unsaturated, though at least one may be unsaturated and the rest saturated.
  • the long chain aliphatic alcohol for use in the ester polymers is preferably linear, but may be branched (e.g. with a branch methyl group).
  • the alcohol may be saturated i.e. an alkanol in which case preferably at least 40% of the saturated aliphatic groups have 15-35 carbons in particular when the copolymer consists essentially of units of esters 1 and 3.
  • the alcohol may be ethylenically unsaturated i.e. an alkenol in which case preferably at least 50% of the aliphatic groups in the copolymer have 15-35 carbons and the molecular weight is at least 5000, e.g.
  • the alcohol may contain at least one unsaturated group e.g 1-4 such as 1 or 2 or 3 or 4, especially 1 unsaturated group.
  • the unsaturated group may be beta, gamma, or in another location, to the alcohol group.
  • at least one unsaturated group is a non-terminal unsaturated group, wherein each unsaturated group may be spaced from the alcohol group by 2-16 carbons, in particular 4-10 carbons and spaced from the terminal carbon by 2-16 carbons, in particular by 4-10 carbons.
  • the unsaturated group may have a cis or trans configuration or when more than one unsaturated group is present each may have a cis or trans configuration; the unsaturated groups may be conjugated or non-conjugated, especially separated by 1-3 e.g 1 carbon atom.
  • the alcohol usually contains 14-40 carbons such as 15-25 carbons, especially 16, 18, 20, 22 or 24 carbons.
  • the alcohol may be natural or synthetic e.g. from oxo or ALFOL processes.
  • suitable alcohols are palmityl, hexadecyl, stearyl, octadecyl, eicosyl, docosyl, tetracosyl, hexacosyl, octacosyl and triacontyl alcohols, as well as oleyl alcohol and branched alcohols such as oxo alcohols e.g. 2-methyl eicosyl alcohol.
  • suitable unsaturated alcohols are palmitoleyl alcohol, hexadecenoyl alcohol, oleyl alcohol, linolenyl alcohol, linoleyl alcohol, ricinoleyl, octadecenoyl alcohol, docosenyl alcohol, arachidonyl alcohol and tetracosenyl alcohol.
  • the alcohols saturated or unsaturated may be substantially pure, but are preferably mixtures of alcohols, e.g. as in tallow alcohol or mixtures of alkanols or alkenols of even carbon number, with one carbon number predominating with decreasing proportions of alkanols or alkenols of lower and higher carbon number (e.g.
  • Such mixtures may contain at least 50% e.g. at least 80 or 90% (by mole) of one alkanol or alkenol.
  • Examples of such mixtures are unsaturated alcohols e.g of 16 or 18 carbon atoms containing in wt % 50-100% of cis-alkenol, 1-15% e.g. 5-15% of trans-alkenol, 1-15% e.g. 5-15% of non-conjugated dieneols, 0.1-5% e.g. 1-5% of conjugated dieneols and optionally 1-20% e.g.
  • saturated alkanols especially C14, C16 or C18 saturated alkanols (such as in commercial oleyl alcohol), and/or saturated alcohols e.g. commercial behenyl alcohol with a majority of a 22 carbon alkanol and smaller amounts of 16, 18, 20 and 24 carbon alkanols.
  • ester polymer there may also be used a mixture of alcohols (saturated or unsaturated) with a bimodal distribution of the carbon number content, e.g. with at least 25% moles of each of 2 alcohols, especially alcohols different in at least 1, or at least 3 carbons, such as 1-9 e.g. 2 or especially 3-7 e.g. 4 or 6 carbons.
  • Such mixtures are for alkanols palmityl/stearyl alcohols and mixtures of hexadecyl/octadecyl, hexadecyl/eicosyl, hexadecyl/docosyl, octadecyl/eicosyl, octadecyl/docosyl, octadecyl/tetracosyl and eicosyl/dosocyl and eicosyl/tetracosyl alcohols.
  • mixtures are oleyl/linoleyl alcohols and mixtures of oleyl/linolenyl, linoleyl/linolenyl, oleyl/ricinoleyl, linolenyl/ricinoleyl, linoleyl/ricinoleyl, palmitoleyl/oleyl, palmitoleyl/linolenyl, palmitoleyl linoleyl, palmitoleyl/ricinoleyl, oleyl/arachidonyl, linolenyl/arachidonyl, linoleyl/arachidonyl, ricinoleyl/arachidonyl, and palmitoleyl/arachidonyl, hexadecenoyl/octadecenoyl, hexadecenoyl/eicosenoyl, hexadecenoyl/
  • Mixtures of alcohols may also contain at least 20% ⁇ of each of 2 alcohols and usually at least 30% of at least one alcohol; examples of these are mixtures of 16/28, 16/18/20, 18/20/22, 20/22/24 alkanols, e.g. as sold by Condea Germany.
  • the polymers and copolymers consist essentially of structural units derived from the esters 1 and/or 2, but they may also contain structural units derived from esters(3) from a short chain aliphatic alcohol, such as a linear or branched one and saturated or unsaturated in which case the copolymers consist essentially of units derived from esters 1 and/or 2 with 3 especially units derived from esters 1 and 3.
  • a short chain aliphatic alcohol such as a linear or branched one and saturated or unsaturated
  • the copolymers consist essentially of units derived from esters 1 and/or 2 with 3 especially units derived from esters 1 and 3.
  • alkanols of 1-6 carbons such as methanol, ethanol, n-propanol, n-butanol, iso, sec. and tert. butanol, pentanol and hexanols; methanol or t-butanol are preferred.
  • the long chain aliphatic acid for use in the ester polymers is preferably linear, but may be branched (e.g. with a branch methyl group).
  • the acid may be saturated i.e. an alkanoic acid or ethylenically unsaturated i.e. an alkenoic acid. It may contain at least one unsaturated group e.g 1-4 such as 1 or 2 or 3 or 4, especially 1 unsaturated group.
  • the unsaturated group may be beta, gamma, or in another location, to the carboxylic group or when more than one ethylenically unsaturated group is present, a mixture therof.
  • At least one unsaturated group is a non-terminal unsaturated group, wherein each unsaturated group may be spaced from the alcohol group by 2-16 carbons, in particular 4-10 carbons and spaced from the terminal carbon by 2-16 carbons, in particular by 4-10 carbons.
  • the unsaturated group may have a cis or trans configuration or when more than one ethylenically unsaturated group is present each may have a cis or trans configuration; the unsaturated group may be conjugated or non-conjugated, especially separated by 1-3 e.g. 1 carbon atom.
  • the acid usually contains 14-40 carbons such as 15-25 carbons, especially 16, 18, 20, 22, or 24 carbons.
  • the saturated or unsaturated acid may be natural or synthetic e.g.
  • suitable unsaturated acids are palmitoleic, hexadecenoic, oleic, octadecenoic, eicosenoic, docosenoic, tetracosenoic, linoleic, linolenic and arachidonoic acids.
  • suitable saturated acids are palmitic, hexadecanoic, stearic, octadecanoic, eicosanoic, docosanoic, tetracosanoic, hexacosanoic, octacosanoic and triacontanoic.
  • the saturated or unsaturated acids may be substantially pure, but are preferably mixtures of acids, e.g. as in tallow acid or mixtures of acids of even carbon number with one carbon number predominating with decreasing proportions or acids or lower and higher carbon number (e.g. of Gaussian distribution) i.e. with carbon numbers distributed on either side of the major one.
  • Such mixtures may contain at least 50% e.g. at least 80 or 90%) (by mole) of one alkanoic or alkenoic acid and smaller amount(s) of other alkanoic or alkenoic acid(s).
  • Examples of such mixtures are unsaturated acids e.g of 16 or 18 carbons containing (in wt %) 50-100 % cis-acid, 1-15% e.g. 5-15%) of trans-acid, 1-15%> e.g. 5-15% non-conjugated diacids, 0.1-5%) e.g. 1-5% of conjugated diacids (such as in commercial oleic acid) or saturated acids e.g. behenic acid with a majority of 22 carbon alkanoic acid and smaller amounts of 16, 18, 20 and 24 carbon alkanoic acids.
  • conjugated diacids such as in commercial oleic acid
  • saturated acids e.g. behenic acid with a majority of 22 carbon alkanoic acid and smaller amounts of 16, 18, 20 and 24 carbon alkanoic acids.
  • ester polymer there may also be used a mixture of acids with a bimodal distribution of the carbon number content, e.g.
  • long chain ester monomer units in the polymers and copolymers there may also be short chain ester monomer units.
  • the polymers and copolymers consist essentially of structural units derived from the esters 1 and/or 2, but they may also contain structural units derived from esters (3) from a short chain aliphatic acid, such as a linear or branched one, and saturated or unsaturated, in which case the copolymers consist essentially of units derived from esters 1 and/or 2 with 3 especially units derived from esters 1 and 3.
  • Examples of such acids are alkanoic acids of 1-6 carbons, such as formic, acetic, propionic, butyric/isobutyric, pentanoic and n-hexanoic acids; acetic and propionic acids are preferred.
  • polymers B structural units from alcohols or acids of different carbon number may be present in the same polymer, especially those with a bimodal distribution of alcohol/acid carbon number.
  • Blends of 2 of these unimodal polymers may contain them in a 10-90:90-10 e.g. 20-80:80-20 molar ratio e.g.
  • the average carbon chain length of the long chain aliphatic groups is 14-25 or 15-24 preferably 15.5-22.5 (or 16.5-22.5) particularly 16.5-22.0 (or 17.5-22.0) especially 17.5-21.0 (or 18.5-21.5) (in particular for oils of WAT 20-50°C and pour point -20 to +20°C); the ranges in brackets are particularly preferred for ester polymer derived from long chain alcohols. Pour points were measured as defined in the ASTM Standard.
  • the polymers may also contain structural units from alcohols or acids of 1-6 carbons, so the distribution may be trimodal or higher modal e.g.
  • the polymers when the polymers contain units from esters 1, 2 and 3; in this case the average carbon chain of the aliphatic side chains is 11-18 (or 12-18) e.g. 1 1.5-17.5 (or 13.0-16.0) especially 12.5-17.0 (or 13.5-15.5) particularly for oils of WAT 20-45°C and pour point -20 to +20°C; the ranges in brackets are particularly preferred for ester polymer derived from long chain alcohols, whether saturated or unsaturated.
  • Preferred polymers A and B are those from acrylates of eicosyl alcohol and behenyl alcohol, especially with at least 80% of 20 and/or 22 carbon alcohols respectively and at most 10% molar of any alcohol with 2 or 4 carbons higher or lower than 20 or 22 respectively, and from acrylates of oleyl alcohol, and linoleyl alcohol, especially with at least 70%> of the 18 carbon alcohol and at most 20% molar of any alcohol with the same number of carbons or 2 or 4 carbons higher or lower than 18 carbons.
  • Preferred copolymers C are those D with structural units from the above acrylates and structural units from at least one acrylate of an alcohol of 1-6 carbons, such as methanol or ethanol.
  • the preferred copolymers C contain 50- 90% molar of units from alcohols of 14-40 e.g. 16-24 carbons and 10-50% molar of units from the alcohol of 1-6 carbons. Of these 14-40 e.g. 16-24 carbon alcohols, at least 80%> are preferably of 1 particular carbon number especially 16, 18, 20 or 22 in particular 20.
  • Particularly preferred are blends of copolymers C e.g.
  • At least 2C particularly the above copolymers D especially blends of polymer of unimodal distribution (with respect to 14-40 carbon alcohols content) with a molar ratio of structural units derived primarily from alcohols of a higher carbon number to those of the lower of 10-90:90-10 e.g. 30-70:70-30.
  • Preferred polymers A 1 and B 1 are those from the vinyl esters of stearic, octadecanoic or eicosanoic and behenic acids, especially with at least 80%> of 20 or 22 carbon acids and at most 5% molar of any alkanoic acid with 2 or 4 carbons higher or lower than 20 or 22 respectively, and those from the vinyl esters of oleic, and linoleic acids, especially with at least 80%o of 18 carbon acids and at most 5% molar of any alkenoic acid with the same number of carbons or 2 or 4 carbons higher or lower than 18 carbons.
  • Preferred copolymers C 1 are those D 1 with structural units from the above vinyl esters and structural units from at least one vinyl ester of an acid of 1-6 carbons, such as acetic.
  • the preferred copolymer C 1 contain 50-90% molar of units from alkanoic or alkenoic acids of 14-40 carbons and 10-50%o molar of units from the acid of 1-6 carbons. Of these 14-40 carbon acids, at least 80% are preferably of 1 particular carbon number.
  • Particularly preferred are blends of copolymers C 1 e.g.
  • the polymers and copolymers A, B, C, D, A*, B ⁇ , C* and D ⁇ may contain structural units from other unsaturated monomers e.g. ones monomers containing at least one N and/or S atom or O atom in an ether linkage, e.g. an amount of up to 10%) by weight based on the total weight of structural units, but preferably structural units from such monomers are substantially absent.
  • the polymers and copolymers may be made directly from the corresponding ester(s) and polymerisation e.g. ester 1 alone or with ester 2 and/or 3 especially esters 1 and 3.
  • the polymers and coppolymers may be made by transesterification of the corresponding ester polymers (3) from an alcohol or acid of 1-13 carbons e.g. 1-6 with the long chain aliphatic alcohol (saturated or unsaturated) or mixture thereof, or long chain aliphatic acid (saturated or unsaturated) or mixture thereof.
  • the ester polymers used as feed for the transesterification preferably consist essentially of structural units from said ester
  • the polymerisation may be performed in a conventional manner e.g. with or without a diluent e.g. a hydrocarbon solvent, such as hexane, heptane, or a higher boiling hydrocarbon oil, at a temperature of 25-120°C, such as 60-100°C, and optionally in the presence of a free radical catalyst, such as a peroxide (e.g. benzoyl peroxide) or azo catalyst such as azobis isobutyronitrile.
  • a free radical catalyst such as a peroxide (e.g. benzoyl peroxide) or azo catalyst such as azobis isobutyronitrile.
  • the polymerisation is usually performed under inert conditions e.g. under nitrogen or argon.
  • the polymerisation time may be 0.5-40hr, preferably 5-25hr at 60-100°C.
  • the reaction product may be purified by evaporation under vacuum to remove unreacted monomer, and/or precipitation of the product with methanol from a liquid aromatic or aliphatic hydrocarbon solution of the product.
  • the copolymerisation may be performed with monomer of ester 1 and monomer of ester 3 in a mole ratio of 30-90:10-70 e.g. 50-90: 10-50 e.g. such as 55-75:45-25 or 70-90:10-30.
  • the transesterification may be performed in the absence of but preferably in the presence of a liquid aromatic or aliphatic hydrocarbon solvent, by reaction of a lower alkyl ester polymer(or lower alkanoic acid ester polymer) with the higher alcohol or alcohols ( or higher acid or acids respectively).
  • the transesterification may be performed with an amount of the long chain alcohol (or acid) substantially corresponding to the amount needed for the degree of conversion required, or an amount in excess of this e.g. substantially corresponding to an equimolar amount (based on the units of ester 3 in the starting polymer) may be used and the reaction stopped when the desired degree of transesterification has occurred e.g. as found from the amount of distilled by product lower alcohol or acid.
  • the reaction may be performed at 50-150°C e.g. 60-120°C for 1-30 e.g. 5-20 hours, in the absence or presence of a catalyst e.g. an organic soluble strong acid such as an aromatic sulphuric acid e.g. p-toluene sulphonic acid or a basic catalyst, such as an alkali metal alkoxide e.g. sodium methoxide or ethoxide (added as such or prepared in situ from alkali metal and by product lower alkanol) or a polyvalent metal alkoxide such as tetra methyl or tetra ethyl titanate. Amounts of the basic catalyst e.g.
  • alkali metal alkoxide may be 0.05-5%> e.g. 0.1-1%> by weight of the feed polymer.
  • the by product lower alcohol or lower acid is preferably evaporated.
  • any solvent is advantageously evaporated, while optionally unreacted higher alcohol or acid may be evaporated e.g. under reduced pressure.
  • the transesterification may be performed substantially to completion e.g. 90-100% especially 95%- 100%, with substantially no unreacted starting polymer e.g. 0-10% especially 0-5%, but advantageously the amount of reaction is 50-90% e.g. 55- 75% or 70-90%.
  • the copolymer product whether of the direct copolymerisation or transesterification can contain (in relation to the aliphatic side chains) 10-70% or 10-60% e.g. 10-50% short chain e.g. methyl ester groups and 30-90% or 40-90% e.g. 50-90% long chain chain e.g. 25-45% or 10-30% short and 55-75% or 70- 90%) long chain.
  • Preferred products whether of a direct copolymerisation or transesterification are ones with an average aliphatic side chain length of 12-19 carbons e.g. 14.5-18.5 or 15.5-18 especially for alkyl and alkenyl esters and advantageously for oils of WAT 20-45°C and pour point -20 to +20°C.
  • ester 3 which was the lower alkyl ester (or lower alkanoic ester) e.g. (m)ethyl (meth)acrylate with the long chain aliphatic alcohol of 14-40 carbons, or of vinyl acetate with the long chain aliphatic carboxylic acid of 14-40 carbons respectively
  • the transesterification is performed to 30-90%, 40-90 or preferably 50-90% completion, with evaporation of by product alcohol or acid, and with or without removal of unreacted higher alcohol or acid.
  • the preferred copolymers, especially each transesterification product comprise a mixture of polymers with (as far as the aliphatic side chains are concerned) 30-90%> e.g. 50-90%> of long chain groups (whether saturated or ethylenically unsaturated) and 10-70% e.g. 10-50% of unreacted short chain e.g. lower alkyl ester groups; especially preferred are mixtures with 60-80% or 75-95% long chain groups and 40-20% or 5-25% unreacted short chain groups.
  • blends of copolymers of esters 1 and 3 in particular partial transesterification products with side chains of methyl and C20, and also methyl and Ci ⁇ or Cjs or 22> especially with average alkyl or alkenyl side chain lengths of 15.5-19 especially 16-18, in particular with esters from long chain alcohols (saturated or unsaturated).
  • the blends of polymers involve at least two polymers selected from A, B and C and include blends of polymers differing in the nature and/or proportion of their structural units and/or in their molecular weight especially blends of polymers C differing in the length of the chains in their structural units.
  • the polymers, especially polymer C may also differ in their manufacturing route, i.e. direct or transesterification but both are preferably the same, especially transesterification.
  • the polymers of the present invention may have a molecular weight of 500 to 200,000, e.g.
  • 500 to 39,999, preferably 5,000 to 35,000 and especially 20,000 to 30,000 or for example 40,000 to 200,000, preferably 80,000 to 160,000(Mw, weight average molecular weight) and the molecular weight distribution (Mw/Mn) may be 1.2-20 e.g. 1.2-10, preferably, 1.4-2 or 2-20 e.g. 5-15.
  • the term "Molecular Weight" of an ester polymer produced by transesterification of the corresponding precursor ester polymer means the weight average molecular weight of the ester polymer obtained by calculation from the percentage conversion (based on spectroscopic analysis) and the molecular weight of the precursor ester polymer or the weight average molecular weight of the ester polymer itself, the molecular weight being determined by gel permeation chromatography (GPC) against polystyrene standards as described in the Aldrich Chemical Company's Standard Test Method for GPC;
  • GPC gel permeation chromatography
  • the term "Molecular Weight" of an ester polymer produced by direct polymerisation of the corresponding ester means the weight average molecular weight of the ester polymer determined by gel permeation chromatography (GPC) against polystyrene standards as described in the Aldrich Chemical Company's Standard Test Method for GPC
  • compositions of the invention usually contains the polymer A B and/or C and/or component I and at least one monomeric additive with a long chain hydrocarbyl group and a polar group.
  • the additive is oil soluble e.g. soluble in diesel oil at 25°C to at least lg/l e.g. at least lOg/l.
  • the additive preferably has surfactant activity and especially surface wetting activity.
  • the hydrocarbyl group in the additive may be linear or branched aliphatic, e.g. alkyl or alkenyl with at least 10 carbons such as 14-30 e.g. 16-24; examples are dodecyl, cetyl, stearyl, palmityl, tallyl, and hydrogenated tallyl and oleyl.
  • the polar group may contain at least one oxygen atom e.g. in an ether or alcohol group such as a hydroxyl or 2-hydroxyethyl group, and/or at least 1 e.g. 1-4 nitrogen atoms e.g.
  • a primary secondary and/or tertiary amine or amide group especially one nitrogen atom in a primary amine and one nitrogen atom in a secondary or tertiary amine or amide in particular in a non cyclic structure, or with one nitrogen atom in a primary amine and/or 2 nitrogen atoms in a tertiary amine, in particular in a heterocyclic compound.
  • the additive may be a long chain substituted amine with 2 or more nitrogens, in particular ones with the long chain hydrocarbyl group attached directly to one nitrogen atom, preferably in an NH group, and with a primary amine NH2 group elsewhere in the molecule, especially separated from the long chain group by the NH group.
  • Such additives may be of formula
  • Preferred additives are mono N-terminal hydrocarbyl derivatives of 1,2- ethylene diamine, 1,2- and 1,3-propylenediamine and 1,2-, 1,3-- or 1,4- butylenediamine, as well as diethylene triamine and triethylene tetramine.
  • Examples of such compound are mono- terminal N hydrocarbyl derivatives of 1,3- propylene diamine and diethylenetriamine, in particular where the aliphatic group is alkyl or alkenyl e.g. stearyl, oleyl, "tallyl” (i.e. a mixture of stearyl, palmityl and oleyl) and hydrogenated tallyl (a mixture of stearyl and palmityl); mono terminal N- hydrogenated tallyl-l,3-propylene diamine is preferred.
  • the aliphatic group is alkyl or alkenyl e.g. stearyl, oleyl, "tallyl” (i.e. a mixture of stearyl, palmityl and oleyl) and hydrogenated tallyl (a mixture of stearyl and palmityl)
  • mono terminal N- hydrogenated tallyl-l,3-propylene diamine is preferred.
  • the additive may also be the corresponding long chain amido amine e.g. of formula
  • RCO NH C n H 2n NH
  • m CpH 2 pNH2
  • R, n, m and p are as defined above.
  • Preferred are the amido analogues of the above amines, especially N-tallowyl-l,3-propylene diamine.
  • the additive may also be a hydroxy alkyl or amino alkyl derivative of either the long chain amine or long chain amido amine.
  • Such additives may be of formula R-(CO) a -N(Rl)-(C n H 2n NR2.
  • Such additives are mono or poly alkoxylated or amino alkylated derivatives of the additives of formula I.
  • the additive may be a long chain aliphatic hydrocarbyl N- heterocyclic compound, which is not quaternised.
  • the aliphatic hydrocarbyl group in the heterocyclic compound usually has 8-24 carbons in the hydrocarbyl group, preferably a linear saturated or mono or diethylenically unsaturated hydrocarbyl group; cetyl-, stearyl and especially oleyl- groups are preferred.
  • the N- heterocyclic compound usually has 1-3 ring N atoms, especially 1 or 2, which compound usually has 5-7 ring atoms in each of 1 or 2 rings; imidazole and imidazoline rings are preferred.
  • the heterocyclic compound may have the aliphatic hydrocarbyl group on an N or preferably C atom in the ring; the ring may also have an amino-alkyl (e.g. 2-amino ethyl) or hydroxyalkyl (e.g. 2-hydroxyethyl) substituent, especially on an N atom.
  • N-2-aminoethyl-2-oleyl-imidazoline is preferred.
  • the long chain amine usually contains 8-24 carbons and preferably is an aliphatic primary amine, which is especially saturated or mono ethylenically unsaturated; an examples is dodecylamine and oleylamine. Mixtures of any of the above additives with each other may be used.
  • the additive e.g. a long chain amine may also comprise a phosphate ester salt, especially one with surface wetting activity.
  • phosphate esters are anionic surfactants, which are salts of alkali metals e.g. sodium or a quaternary ammonium e.g. tetra methyl ammonium or tetrabutyl ammonium salts of acid phosphate esters, e.g. with 1 or 2 organic groups and 2 or 1 acidic hydrogen atoms; examples of the organic groups are alkyl or alkenyl groups as described for R above.
  • examples of such phosphate ester salts are mono and dioctyl acid phosphate salts and mixtures thereof.
  • a preferred blend comprises a long chain alkylamine and a phosphate ester salt e.g. as sold as NAL 1272 by Nalco.
  • the amount of additive is usually in a weight ratio of 1 :500 to 1:10 e.g. 1:50 to 1: 15 by weight based on the total dry weight of the polymer.
  • each alkylene group usually has 2-4 carbons, eg 2, 3 or 4 especially 2 carbons.
  • the substituted polyalkyleneimine compound or polyalkyleneimine backbone thereof may have a molecular weight of 600-1000000 eg 800-100000 such as 1300-3000 but may be 200,000-500,000.
  • the polyalkyleneimine backbone may be linear or branched; the back bone usually has linear and branched sections with branching on each 1-10 nitrogen atoms e.g. 2-5 N atoms.
  • the compound is usually oil soluble to an extent of at least 0.05%> w/w in decane at 0°C, preferably at least 1% w/w; it is usually water insoluble, eg with a solubility in water at 25°C of less than 1% w/w, especially less than 0.05%> w/w.
  • the compound is usually a waxy solid, eg of softening point 20-1 OOX e.g. 40-80° C.
  • the organic substituent in the substituted polyalkyleneimine may be of 6-40 carbon atoms, preferably with a continuous chain of at least 6, eg at least 12, such as 6-24 or 12-20 or 12-24 carbon atoms.
  • the chain, and especially the organic substituent may be branched but is especially linear.
  • the organic substituent may have such a chain bonded directly to a chain or terminal nitrogen atom of the polyalkylene imine or preferably bonded via an intermediate group usually a polar group.
  • the intermediate group which is usually divalent may be inorganic eg an ether oxygen atom or sulphonyl SO 2 group, or the intermediate group may be a functional group containing C and at least one O and/or N atom and optionally at least one hydrogen atom.
  • Examples of such groups are carbonyl (-CO), including 2 hydroxycarbonyleth-1-yl- 1 -carbonyl (derived from a succinic acid group), a 2- hydroxy (or amino) alkylidene (1,1)- group, or 2-hydroxy (or amino) alkylene (1,2)- group (each alkylidene or alkylene having 2-4 e.g. 2 carbons) such as 2- hydroxy ethylidene HOCH2-CH ⁇ or 2 hydroxyethylene -(HO)CH-CH2- (or mixtures thereof) and the corresponding amino compounds (or mixtures thereof).
  • the organic substituent may also comprise a group A of at least 6 carbons which may be an alkyl group of 6-30 eg 12-24 carbon atoms, such as octyl, decyl, dodecyl/lauryl, tetradecyl, hexadecyl/palmityl, octadecyl/stearyl or may be an alkenyl group of 6-30 eg 12-24 carbon atoms such as octadecenyl, hexadecenyl or dodecenyl.
  • a group A of at least 6 carbons which may be an alkyl group of 6-30 eg 12-24 carbon atoms, such as octyl, decyl, dodecyl/lauryl, tetradecyl, hexadecyl/palmityl, octadecyl/stearyl or may be an alkenyl group of 6-30 e
  • the organic substituent may also comprise an aryl group A, eg an aromatic hydrocarbyl group, which may be optionally substituted by at least one ether group, eg alkoxy of 1-6 carbons such as methoxy or ethoxy; the aryl group may contain 6-30 carbons, such as 6-14 and especially 6-9 carbon atoms, preferably phenyl, tolyl, xylyl dodecyl-phenyl or naphthyl or methoxy phenyl.
  • aryl group A eg an aromatic hydrocarbyl group, which may be optionally substituted by at least one ether group, eg alkoxy of 1-6 carbons such as methoxy or ethoxy; the aryl group may contain 6-30 carbons, such as 6-14 and especially 6-9 carbon atoms, preferably phenyl, tolyl, xylyl dodecyl-phenyl or naphthyl or methoxy phenyl.
  • the organic substituent may also comprise a cycloalkyl group A eg of 5-10 carbons such as cyclopentyl or cyclohexyl, either of which may be substituted by at least one hydrocarbyl group eg alkyl of 1-6 carbons such as methyl, or alkoxy eg of 1-6 carbons such as methoxy or ethoxy.
  • a cycloalkyl group A eg of 5-10 carbons such as cyclopentyl or cyclohexyl, either of which may be substituted by at least one hydrocarbyl group eg alkyl of 1-6 carbons such as methyl, or alkoxy eg of 1-6 carbons such as methoxy or ethoxy.
  • the organic substituent may also comprise an arylalkylene group A or cycloalkylalkylene group A each of 7 to 30 carbons eg 7- 12 or 14-20 carbons, in which the aryl group and cycloalkyl groups may be as defined above and the alkylene group may contain 1-4 carbons, especially methylene and 1,2-ethylene, such as benzyl, 2-phenylethyl or cyclohexylmethyl.
  • the organic substituent may also comprise an arylalkenylene group A, wherein aryl is as defined above and alkenylene has 2-4 carbons such as 1,2-ethylene as in 2- phenyleth-1-enyl.
  • the organic substituent preferably consists of said intermediate group and said group A or consists of said group A.
  • the organic substituent may also be a group B of formula R 7 -C-(R 8 )-R 9 , wherein R comprises an optionally hydroxy or amino substituted organic group (eg with at least one carbon atom, particularly as defined for A above), especially with the HO or H 2 N group in the 2 or 1 position to the free valency such as hydroxy methyl or amino methyl and R ⁇ may be hydrogen or an organic group (eg as defined for A above) and R ⁇ may be hydrogen or an organic group (eg as defined for A above).
  • Component (I) are polyethyleneimines with at least one N- substituent which is a 1 -alkyl or aryl 1 -hydroxymethyl 1 -methyl group eg 1- hexadecyl-1 -hydroxymethyl 1 -methyl group, 1 -phenyl- 1 -hydroxymethyl- 1 -methyl group, or 2-alkyl or aryl- 2 hydroxy ethyl- 1- group such as 2-hexadecyl-2 hydroxy ethyl (2 -hydroxy octadecyl) or 2-phenyl 2 hydroxy ethyl group, a fatty acid acyl group eg stearoyl or lauroyl, or arylacyl group eg benzoyl or arylalkylene acyl group e.g.
  • N- substituent is a 1 -alkyl or aryl 1 -hydroxymethyl 1 -methyl group eg 1- hexadecyl-1 -hydroxymethyl 1 -
  • cinnamoyl aryl sulphonyl group eg benzene- or toluene sulphonyl group, 1 -alkyl or aryl-1 aminomethyl-1 -methyl group, or alkenyl succinyl group, eg fatty alkenyl succinyl group eg octadecenyl succinyl group.
  • Component (I) contains at least one alkyleneimine with an above substituent eg 0.1-1 substituent per nitrogen atom in the polyalkyleneimine chain, especially 0.5-1 per secondary nitrogen atom in the polyalkylene imine chain, and/or per primary nitrogen atom in said chain.
  • Component (I) may have at least one alkyleneimine unit, eg at least one repeating unit of formula -C n H 2n -N-(X)f-R 10 where f is 0 or 1, n is 2-5 or 2 - 4, eg 2, X is an inorganic or organic intermediate group (eg as defined above) and R 10 is an organic group, eg as described for R or A above.
  • the compounds may contain 10-100 of such units and/or -CH 2 CH 2 -NH- units.
  • the compounds may have NH 2 or -NH-(X)f-R 10 or HO termination groups.
  • Component (I) may be prepared by reacting a polyalkyleneimine with a compound of formula R 10 -(X)f-Y, wherein R 10 , X and f are as defined above and Y is a nucleophilic leaving group such as a halide eg chloride or bromide or hydroxy group or ester thereof, eg a sulphonate ester, such as one of 1-10 carbons eg methane-, benzene-, toluene- or xylene-sulphonate ester group.
  • R 10 -(X)f-Y wherein R 10 , X and f are as defined above and Y is a nucleophilic leaving group such as a halide eg chloride or bromide or hydroxy group or ester thereof, eg a sulphonate ester, such as one of 1-10 carbons eg methane-, benzene-, toluene- or xylene-
  • Examples of compounds of formula R 10 (X)fY are acid chlorides (or the acids themselves) from lauric, palmitic, stearic, oleic acids benzoic or cinnamic acids or sulphonyl chlorides from benzene, toluene or xylene sulphonic acids, or an acid anhydride (or acid itself) such as a substituted succinic acid e.g.
  • the polyalkyleneimine may be of a structure as described for the polyalkyleneimine back bone above; the polyalkylene imine usually has secondary or tertiary internal chain N atoms and usually primary terminal N atoms; the ratio of primary to secondary to tertiary N atoms is usually 0.5-2: 1-4:0.5-2 e.g. about 1:2: 1.
  • the reaction may be performed with heating usually at 30-250°C such as 100-200°C and may be in the presence of a base eg an acid acceptor (for HY); examples are particulate inorganic hydroxides and carbonates, such as calcium carbonate and organic tertiary bases such as NN dimethylaniline.
  • a base eg an acid acceptor (for HY); examples are particulate inorganic hydroxides and carbonates, such as calcium carbonate and organic tertiary bases such as NN dimethylaniline.
  • the reaction may be performed with continuous removal of by product water eg azeotroping in a Dean and Stark apparatus, or by evaporation under vacuum; the latter may also be used when Y is a halide.
  • the reaction may be performed with a molar ratio of R 10 (X)f-Y compound to NH group in the polyalkyleneimine of 0.1- 10: 1.
  • Component (I) may also be prepared by reacting a polyalkyleneimine with an epoxide or a mixture of at least two epoxides, or an imine eg with a terminal epoxy or imine group.
  • epoxides or imines are those which are R substituted ethylene oxides or ethylene imines such as 1,2-epoxy octadecane, 1,2- epoxy eicosane, 1,2-epoxy docosane and mixtures thereof.
  • the epoxide or imine may also have an internal epoxy or imine group as in epoxidised internal alkadienes or alkenes, eg octadiene or epoxidised ricinoleic acid.
  • the reaction conditions, proportions etc may be as described above.
  • the products are ones in which the organic substituent is bonded to the polyethylene imine by an intermediate group, which is a hydroxy (or amino) alkylene or alkylidene group (or a mixture thereof).
  • the acyl substituted polyethylene imines which are predominantly linear may also be made by cationic polymerisation of 2-alkyl oxazolines, while other N- organo substituted polyethylene imines may be made by cationic polymerisation of the corresponding N-substituted aziridines.
  • the products may be used as such or after working up, eg by filtration or extraction of any products from the acid acceptor, and optionally evaporation of any solvent or diluent.
  • the blends may comprise at least 2 different components (I). They may differ in respect of different organic substituents especially different alkyl chain lengths, different numbers of carbon atoms between the nitrogen atoms of the polyalkylene imine. Thus the organic substituents especially the alkyl chain length may differ by at least 1, e.g. 1-9 such as 3-7 carbon atoms.
  • the ratio of the weights of the 2 different components I may be 10-90:90-10 e.g. 25-75:75-25.
  • the oil whose flow characteristics are to be improved usually comprise a liquid hydrocarbon.
  • the hydrocarbon is usually primarily aliphatic in nature, but may contain up to 50% w/w liquid aromatic compounds.
  • the hydrocarbon may be a crude or black oil or non volatile fraction from a distillation of crude oil, such as a vacuum or thermal residue.
  • the hydrocarbon is an oil field product, e.g. either a whole well product, the multiphase mixture in or from the well bore, or one at the well head after at least partial separation of gas and/or water (and may be a condensate), and may be flowing up a well bore, or on a production platform or between platforms or from a platform to a collection or storage facility e.g. from offshore to onshore.
  • Particularly of interest are hydrocarbons moved in pipelines under the sea under low temperature conditions e.g. in latitudes of greater than 50° N or S or in Gulf of Mexico.
  • the hydrocarbon may contain up to 50% by weight of wax usually
  • the wax may contain 20-100 e.g. 20-60 or 30-60 or 40-70 carbon atoms; the hydrocarbon may contain 0.1-5% e.g. 0.2-1%) of waxes of 20-60 carbons.
  • the hydrocarbons may contain dissolved gas (e.g. with amounts of up to 10%> gas) or water or water droplets e.g. with 5-40% water (e.g. as in water in oil emulsions, so called "chocolate mousse"). There may also be gas and/or water as a physically separate phase.
  • the hydrocarbons may in the absence of the compounds of the invention, have a wax appearance temperature (WAT) value which approximates the cloud point value of at least 0°C e.g.
  • WAT wax appearance temperature
  • pour point of such hydrocarbons may be 10-50°C e.g. 20-50°C lower than the WAT value and may be - 30°C to 20°C e.g. -20°C to +10°C.
  • the polymers, blends and compositions of the invention may reduce the WAT value of the liquid hydrocarbon by at least 2°C e.g. 2-20°C such as 5-15°C, and can reduce the rate of wax deposition per unit time.
  • the compounds may also delay the onset of wax nucleation e.g. as shown by light scattering and they may also reduce the pour point and/or modify the wax crystals or disperse the wax.
  • the compounds may reduce the weight of wax deposition either by reducing the rate of deposition and/or by reducing the temperature of onset of deposition.
  • the reduced wax deposition may be associated with reduced wax in suspension (i.e. reduced total wax formation) or the same or an increased amount of wax in suspension (i.e. the altering distribution of wax between suspension and deposition).
  • the polymers, blends and compositions may be mixed in a portion with the hydrocarbon to be protected or may be mixed batchwise, continually o ⁇ continuously with a moving usually liquid body of that oil e.g. hydrocarbon, preferably added to a line containing flowing liquid hydrocarbon to be protected, upstream of a cooler location where wax deposition may occur in the absence of said compound.
  • the polymers blends and compositions may be added to a tank of the oil e.g. to inhibit deposition of wax.
  • the amount of polymer or polymer blend added may be 10-10,000 ppm e.g. 100-5000 ppm based on the weight of oil e.g. hydrocarbon, while the weight of additive may be 1-1000 e.g.
  • 5- 100 ppm such as 20-60 ppm on the same basis; there may also be present 5-2000 ppm e.g. 30-1000 ppm (on the same basis) of long chain alcohol, e.g. of 14-40 or 15-25 carbons, such as described for use in the preparation of the ester polymer.
  • 5-2000 ppm e.g. 30-1000 ppm (on the same basis) of long chain alcohol, e.g. of 14-40 or 15-25 carbons, such as described for use in the preparation of the ester polymer.
  • the amount of component (I) or component (II) present in the oil may each be 5-2000 ppm e.g. 10-500 or 20-250 such as 100-1000 ppm; the ratio of component (I) : component (II) may be 10-90:90-10 e.g. 25-75 :75-25.
  • the invention is illustrated in the following Examples:- Coaxial S earine Cell Wax Deposition test
  • the test apparatus comprised an internally water cooled stationary cylinder which was fitted with upper inlet and outlet tubes for coolant, and a rotatable drum coaxial with the cylinder and spaced from it by an annulus, which in this test contains the fluid to be tested.
  • the drum fitted with a motor, is immersed in a water bath (at about 38°C).
  • the drum was mounted for rotation in the bath, a thermal insulator pad laid in the bottom of the drum and the liquid to be tested poured into the drum.
  • the cylinder was then lowered into the liquid down to the pad.
  • the drum was rotated at 150 rpm to effect shearing in the liquid.
  • the coolant flow was then started and the flow rate and temperatures of coolant, cylinder and drum monitored.
  • the temperature of the cylinder was kept at a fixed temperature in the 15-20°C region, which caused wax to be deposited on the outer surface of the cylinder.
  • the U tubes were kept vertical at a constant depth in the fluid.
  • Each bottle contained a magnetic stirrer follower (operating at 700rpm).
  • the stainless steel (4.6mm id) U tubes (Cold Fingers) were cleaned with toluene to remove any adherent organic soluble chemicals, after which they were cleaned with a fine grade emery paper then rinsed, wiped and dried.
  • the stirrer pellets were washed in toluene and dried before use.
  • the test was on the rate of build up of wax deposits in a pipeline as evidenced by the temperature at which blockage occurs.
  • the apparatus comprised in a stainless steel coil of 1.88mm internal diameter tube 3.2m long which was maintained in a constant temperature bath and the solution at 55°C containing liquid to be tested was passed through this coil at 5ml/min, giving a 2 minute retention time. Initially the bath was at 40°C and then the temperature of the bath was reduced to 10°C, well below the temperature at which wax would deposit and block the tube in the absence of inhibitor. The liquid exiting the coil was recycled through a heating bath at 55° to melt any wax crystals in it and then returned to the cold coil. In this way the only solid involved in the experiment was that deposited in the coil. The pressure difference across the coil was monitored to determine the build up of deposit and the temperature for complete blockage noted; this was deemed to occur when the pressure difference across the coil was greater than 12.5psi. Wax Appearance Temperature (WAT) Test
  • test fluid was loaded by capillary action into a flat cross-section microscope capillary tube.
  • the contents were then sealed in place with rapid drying epoxy cement.
  • the capillary tube was then loaded into a temperature- controlled microscope stage and the contents monitored and recorded by video.
  • the fluid was heated up to 85°C and kept at this temperature for fifteen minutes to dissolve any crystals and ensure liquid homogeneity.
  • the temperature was then reduced at a rate of 5°C/min down to a temperature which is about 10°C above the WAT of the blank and then cooled at a rate of 0. l°C/min to determine accurately the WAT i.e. the highest temperature at which wax crystals deposited
  • the morphology of the wax crystals was also studied. Wax Nucleation Test
  • Proton nmr spectroscopy showed the degree of transesterification to be 14 %.
  • a polyethyleneimine of molecular weight 1800 obtained from Polysciences
  • Example 1 A series of blends were made by mixing the polymer and/or another polymer and/or additive AJ, and the appropriate oil. The natures and amounts of the polymers or additive expressed as ppm in the total oil were as given in Table 1. The oil containing the blends was then tested in the Coaxial Shearing Cell Wax Deposition Test with 14°C of subcooling below the WAT; and the results were as given below.
  • the wax was easy to remove with polymers B, C, D and the blank , had a microcrystalline structure for polymers B and Commercial 2, was sticky and difficult to remove with commercial 1 and polymer A, and was granular for the blank.
  • C x is a repeat preparation of C.
  • Example 8 The coaxial shear test was performed on the Oil 2 with the Polymer F in amount of 1 SOppm, and Additive AJ in amount of 20ppm.
  • the WAT was 35.2°C, a depression of 2.8°C on the blank results with Oil 2.
  • the coaxial shear test was performed for 330min, with a cold plate average temperature of 15.7°C, an oil bath temperature of 29.2°C and a coolant temperature of 5.90°C.
  • the weight of wax deposited was 0.0563g, corresponding to an amount per day of 0.246g, (compared to 3.98g from a cold plate temperature of 14.55°C for Oil 2 without the Polymer).
  • the wax deposit was soft, smoth and easily removed.
  • the coaxial shear test was performed on the Oil 2 with the Polymer F in amount of 800ppm.
  • the WAT was 35.6°C, a depression of 2.4°C on the blank results with Oil 2.
  • the coaxial shear test was performed for 290min, with a cold plate average temperature of 19.6°C, an oil bath temperature of 30.0°C and a coolant temperature of 7.94°C.
  • the weight of wax deposited was 0.0910g, corresponding to an amount per day of 0.452g, (compared to 3.98g from a cold plate temperature of 14.55°C for Oil 2 without the Polymer).
  • the wax deposit was of small irregular shaped plates.
  • Example 10 The Coaxial Shear test was performed on Oil 4 with the Polymer F in amount of 800ppm.
  • the WAT was 24.2°C, a depression of 6.1°C on the blank results with Oil 4.
  • the Coaxial test was performed for 290 min, with cold plate average temperature of 20.0°C an oil bath temperatures of 38°C and a coolent temperature of 13.0°C.
  • the weight of wax deposited per day was 11.14g/day compared to 72.09g/day with cold plate temperature of 20.3°C with Oil 4 and no Polymer F.
  • a blend was made by mixing polymer K and polymer L in oil 7. The amounts of the polymers expressed as ppm in the total oil are given below. The oil containing the blend was then tested according to the cold finger test procedure described above except that the cold finger temperature was maintained at 5.0 °C and the stirrer operated at 300 rpm. The results are given in below.
  • Polymers B8 and B12 were purified by solution of the product and precipitation of the polymer for recovery and use, leaving the unreacted fatty alcohol and possibly low molecular weight polymer in the solution Example 14
  • Polymer D4 was purified by solution, and then precipitation of polymer Example 15
  • a fresh batch of Polymer L (called polymer B 13) was prepared to give a product with 68% conversion and calculated Molec Wt of 1 15440 (Mw/Mn 2.6) This product was compared with polymer N at 400ppm in oil 3.
  • the WAT results were as follows Polymer B 13, 21 8°C, Polymer N 22 1°C, Blank 24.3°C
  • the cold finger 10°C results were Polymer B13 0 377g, Polymer N 0 139g, Blank 0 779g
  • polymer B 14 A fresh batch of Polymer L (called polymer B 14) was prepared to give a product with 69% conversion This and polymer N were tested in Oil 3 in the cold finger test 10°C and compared to the same polymer oil blend mixed also with 40ppm of Additive AJ The results were as follows
  • C2-4 and D6 Various C 2 o chain length polymers and blends were tested in oil 1 in the cold finger test with the finger at 17°C and the oven at 35°C.
  • Some of the polymers (hereinafter C2-4 and D6) were prepared by the general procedure for that of polymer L but applied to 1-eicosonol (or docosanol) and use of different amounts of catalyst to give different degrees of conversion.
  • Polymers C3, C2, C4 were based on eicosanol with 79%>, 81%> and 65% conversion.
  • Polymer D6 was based on docosanol with 65%> conversion.
  • Polymer D7 and D8 were repeats of the process to make polymer L with docosanol to 64%o and 82% conversion, respectively (and D8 used the catalyst for polymer F).

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Abstract

Ces inhibiteurs du dépôt de cire pour huiles brutes sont des polymères issus, d'une part, d'un monomère à motifs structuraux dérivé d'au moins un ester (i) d'un acide carboxylique aliphatique et d'un alcool aliphatique, l'un de ces deux éléments, l'acide ou l'alcool, étant insaturé à l'éthylène et l'autre étant pourvu d'un groupe à chaîne longue comportant de 14 à 40 atomes de carbone et, d'autre part, d'un monomère à motifs structuraux dérivé d'un ester correspondant (3) à motifs structuraux dérivé d'un acide carboxylique aliphatique et d'un alcool aliphatique, l'un de ces deux éléments, l'acide ou l'alcool, étant insaturé à l'éthylène et l'autre possédant un groupe aliphatique comportant de 1 à 13 atomes de carbone, de sorte que 30 % au moins, de préférence entre 50 et 90 %, desdits groupes aliphatiques comportent de 15 à 35 atomes de carbone. On obtient, de préférence, ces inhibiteurs par interestérification. On peut utiliser comme inhibiteurs des mélanges de ces polymères et/ou les homopolymères ou copolymères correspondants de l'ester 1 et/ou de polyacoylène-imines à longues chaînes latérales, comportant éventuellement, des produits d'addition monomères polaires.
PCT/GB1997/003076 1996-11-14 1997-11-07 Inhibiteurs et leurs applications dans des huiles WO1998021446A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB9911074A GB2334258B (en) 1996-11-14 1997-11-07 Inhibitors and their uses in oils
AU48778/97A AU4877897A (en) 1996-11-14 1997-11-07 Inhibitors and their uses in oils
NO992310A NO992310L (no) 1996-11-14 1999-05-12 Inhibitorer og deres anvendelse i oljer

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
GBGB9623742.5A GB9623742D0 (en) 1996-11-14 1996-11-14 Inhibitors
GBGB9623736.7A GB9623736D0 (en) 1996-11-14 1996-11-14 Compounds
GB9623736.7 1996-11-14
GB9623742.5 1996-11-14
GBGB9626443.7A GB9626443D0 (en) 1996-12-20 1996-12-20 Inhibitor blends
GB9626443.7 1996-12-20
GB9709064.1 1997-05-02
GBGB9709064.1A GB9709064D0 (en) 1997-05-02 1997-05-02 Inhibitors
GB9713709.5 1997-06-27
GBGB9713709.5A GB9713709D0 (en) 1997-06-27 1997-06-27 Inhibitors

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034733A1 (fr) * 1999-11-12 2001-05-17 The Lubrizol Corporation Compositions contenant des agents modificateurs de cire
WO2001048032A1 (fr) * 1999-12-23 2001-07-05 Bp Chemicals Limited Esters de polyacrylate, preparations et utilisations comme agents d'amelioration de l'ecoulement a basse temperature dans des hydrocarbures de distillat moyen
WO2004048502A1 (fr) * 2002-11-22 2004-06-10 Basf Aktiengesellschaft Utilisation d'homopolymeres d'esters ethyleniquement insatures pour ameliorer l'action d'ameliorants de fluage a froid
WO2008113757A1 (fr) * 2007-03-22 2008-09-25 Basf Se Mélange d'agents qui améliorent l'écoulement à froid et d'amines
CN102876308A (zh) * 2012-10-16 2013-01-16 东莞优诺电子焊接材料有限公司 水基型无闪点亲蜡剂及其制备方法
RU2671198C1 (ru) * 2018-07-04 2018-10-30 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" Ингибитор асфальтосмолопарафиновых отложений для парафинистых и высокопарафинистых смолистых нефтей
US11292952B2 (en) 2016-05-04 2022-04-05 Cameron International Corporation Encapsulated production chemicals

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US3347789A (en) * 1966-03-04 1967-10-17 Petrolite Corp Treatment of oil wells
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GB1158603A (en) * 1967-02-03 1969-07-16 Exxon Research Engineering Co Fuel Oil Compositions
GB1161188A (en) * 1967-07-07 1969-08-13 Shell Int Research Crude Oil with improved Flow Properties
AT322716B (de) * 1971-02-22 1975-06-10 Shell Int Research Rohöl und kraft-oder brennstoff auf mineralölbasis
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GB2160536A (en) * 1984-06-21 1985-12-24 Elf Aquitaine Polymeric additives usable for inhibition of the deposit of paraffins in crude oils
EP0306290A1 (fr) * 1987-09-02 1989-03-08 Exxon Chemical Patents Inc. Produits améliorant l'écoulement, et produits abaissant le point de trouble
EP0344644A2 (fr) * 1988-05-31 1989-12-06 Röhm Gmbh Huile minérale à comportement modifié à l'écoulement
EP0407906A1 (fr) * 1989-07-14 1991-01-16 Röhm Gmbh Huiles minérales à comportement modifié à l'écoulement
DE4236337C1 (de) * 1992-10-28 1994-01-27 Goldschmidt Ag Th Verwendung von Polyacrylsäureestern als Dispergiermittel
WO1995009220A1 (fr) * 1993-09-30 1995-04-06 Elf Antar France Composition d'additifs d'operabilite a froid des distillats moyens

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001034733A1 (fr) * 1999-11-12 2001-05-17 The Lubrizol Corporation Compositions contenant des agents modificateurs de cire
WO2001048032A1 (fr) * 1999-12-23 2001-07-05 Bp Chemicals Limited Esters de polyacrylate, preparations et utilisations comme agents d'amelioration de l'ecoulement a basse temperature dans des hydrocarbures de distillat moyen
WO2004048502A1 (fr) * 2002-11-22 2004-06-10 Basf Aktiengesellschaft Utilisation d'homopolymeres d'esters ethyleniquement insatures pour ameliorer l'action d'ameliorants de fluage a froid
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