EP0721492B2 - Additifs et compositons de combustibles - Google Patents

Additifs et compositons de combustibles Download PDF

Info

Publication number
EP0721492B2
EP0721492B2 EP94924280A EP94924280A EP0721492B2 EP 0721492 B2 EP0721492 B2 EP 0721492B2 EP 94924280 A EP94924280 A EP 94924280A EP 94924280 A EP94924280 A EP 94924280A EP 0721492 B2 EP0721492 B2 EP 0721492B2
Authority
EP
European Patent Office
Prior art keywords
fuel oil
acid
carbon atoms
composition
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.)
Expired - Lifetime
Application number
EP94924280A
Other languages
German (de)
English (en)
Other versions
EP0721492B1 (fr
EP0721492A1 (fr
Inventor
Brian William Davies
Allessandro Lombardi
Dhanesh Gordon Goberdhan
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.)
Infineum USA LP
Original Assignee
Infineum USA LP
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10739263&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0721492(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Infineum USA LP filed Critical Infineum USA LP
Priority to EP98204020A priority Critical patent/EP0908507A1/fr
Priority to EP98202903A priority patent/EP0885948B1/fr
Publication of EP0721492A1 publication Critical patent/EP0721492A1/fr
Publication of EP0721492B1 publication Critical patent/EP0721492B1/fr
Application granted granted Critical
Publication of EP0721492B2 publication Critical patent/EP0721492B2/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1811—Organic compounds containing oxygen peroxides; ozonides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/28—Organic compounds containing silicon
    • C10L1/285—Organic compounds containing silicon macromolecular compounds

Definitions

  • This invention relates to the use of additives for improving the cold flow properties of fuel oil, for example distillate petroleum fuel such as middle distillate fuel oil boiling within the range of 110°C to 500°C.
  • fuel oil for example distillate petroleum fuel such as middle distillate fuel oil boiling within the range of 110°C to 500°C.
  • wax may separate out from the fuel and impair the flow properties of the oil.
  • middle distillate fuels contain wax which precipitates at low temperatures to form large waxy crystals which tend to plug the small pore openings of fuel filters. This problem is particularly acute when the fuel is a diesel fuel because the nominal apertures in the fuel filter of diesel engines are typically of diameter between about 5 and 50 micrometers.
  • Additives are known in the art for overcoming the above problem and are called Flow Improvers.
  • Such additives may act as wax crystal modifiers when blended with waxy mineral oil by modifying the shape and size of crystals of the wax therein and reducing the adhesive forces between the crystals and between the wax and the oil to permit the oil to remain fluid at a lower temperature than in the absence of the additive.
  • additives are described in the art for improving the cold-flow properties of oils, for example in the form of oil-soluble addition products or condensates that may be polymeric or monomeric and as described, for example, in US-A-3,048,479; GB-A-1,263,152; US-A-3,961,961; and EP-A-0,261,957.
  • Some of the above additives have been and are used commercially as Cold Flow Improvers.
  • GB-A-1,112,808 describes ethylene-vinyl acetate copolymers in combination with rust inhibitors, anti-emulsifying agents, corrosion inhibitors, anti-oxidants, dispersants, dyes, dye-stabilisers, haze-inhibitors, and anti-static additives.
  • a first aspect of the invention is the use of a co-additive (A) which comprises an oil-soluble lubricity additive comprising a glycerol monoester of an unsaturated mono-carboxylic acid wherein the acid has from 2 to 50 carbon atoms; said use being in a composition comprising a major proportion of a fuel oil and a minor proportion of component (B) which comprises a cold flow improver additive comprising an ethylene/unsaturated ester copolymer having a number-average molecular weight, as measured by vapour phase osmometry, of 1,000 to 5,000, and being to enhance the cold flow properties of the composition.
  • A oil-soluble lubricity additive comprising a glycerol monoester of an unsaturated mono-carboxylic acid wherein the acid has from 2 to 50 carbon atoms
  • component (B) which comprises a cold flow improver additive comprising an ethylene/unsaturated ester copolymer having a number-average molecular weight
  • a second aspect of the invention is a process for blending additives with a fuel oil comprising
  • the invention also includes a fuel oil composition comprising a major proportion of fuel oil and a combination of:
  • the invention further includes an additive concentrate containing component (A) and component (B) as defined above, and optionally other additives.
  • Component (A) may additionally comprise
  • the fuel oil is preferably in the form of a flowing stream wherein step (i) takes places at a first station and step (ii) takes place at a second station, though the first and second stations may be co-terminous and injection be via a common injector.
  • the process can be automated so that a sensor can carry out step (iii), e.g. by measuring the cold filter plugging point (CFPP), and the information fed via a controller to control injection of one or both of components (B) and (A).
  • CFPP cold filter plugging point
  • the invention surprisingly enables less of component (B) to be used to achieve a desired cold flow improvement performance.
  • hydrocarbyl refers to a group having a carbon atom directly attached to the rest of the molecule and having a hydrocarbon or predominantly hydrocarbon character.
  • hydrocarbon groups including aliphatic (e. g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl or cycloalkenyl), aromatic, and alicyclic-substituted aromatic, and aromatic-substituted aliphatic and alicyclic groups.
  • Aliphatic groups are advantageously saturated. These groups may contain non-hydrocarbon substituents provided their presence does not alter the predominantly hydrocarbon character of the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If the hydrocarbyl group is substituted, a single (mono) substituent is preferred.
  • substituted hydrocarbyl groups examples include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl, and propoxypropyl.
  • the groups may also or alternatively contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms include, for example, nitrogen, sulphur, and, preferably, oxygen.
  • esters prepared from one or more of the above-mentioned unsaturated carboxylic acids such as glycerol monooleate.
  • Such polyhydric esters may be prepared by esterification as described in the art and/or may be commercially available.
  • the ester has more than are free hydroxy groups. Examples are described in WO-PCT/EP 94/00148.
  • Ethylene/unsaturated ester copolymer flow improvers have a polymethylene backbone divided into segments by oxyhydrocarbon side chains.
  • the copolymer may comprise an ethylene copolymer having, in addition to units derived from ethylene, units of the formula -CR 5 R 6 -CHR 7 - wherein R 6 represents hydrogen or a methyl group; R 5 represents a -OOCR 8 or -COOR 8 group wherein R 8 represents hydrogen or a C 1 to C 28 , preferably C 1 to C 9 , straight or branched chain alkyl group, provided that R 8 does not represent hydrogen when R 5 represents -COOR 8 ; and R 7 is hydrogen or -COOR 8 .
  • ethylene with an ethylenically unsaturated ester, or derivatives thereof.
  • An example is a copolymer of ethylene with an ester of an unsaturated carboxylic acid, but the ester is preferably one of an unsaturated alcohol with a saturated carboxylic acid.
  • An ethylene-vinyl ester copolymer is advantageous; an ethylene-vinyl acetate, ethylene vinyl propionate, ethylene-vinyl hexanoate, or ethylene-vinyl octanoate copolymer is preferred.
  • the copolymers contain from 1 to 25, e.g.
  • the vinyl ester 1 to 20 mole % of the vinyl ester, more preferably from 3 to 17 mole % vinyl ester. They may also be in the form of mixtures of two copolymers such as those described in US-A3,961,916.
  • the number average molecular weight, as measured by vapour phase osmometry, of the copolymer is 1,000 to 5,000.
  • the copolymers may be derived from additional comonomers, e.g. they may be terpolymers or tetrapolymers or higher polymers, for example where the additional comonomer is isobutylene or diisobutylene.
  • the copolymers may be made by direct polymerisation of comonomers. Such copolymers may also be made by transesterification, or by hydrolysis and reesterification, of an ethylene unsaturated ester copolymer to give a different ethylene unsaturated ester copolymer.
  • ethylene vinyl hexanoate and ethylene vinyl octanoate copolymers may be made in this way, e. g. from an ethylene vinyl acetate copolymer.
  • Component (B) may be used with co-components such as one or more of the following:
  • Comb polymers are discussed in "Comb-Like Polymers. Structure and Properties", N. A. Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs., 8, p 117 to 253 (1974).
  • comb polymers have one or more long chain branches such as hydrocarbyl branches, such as oxyhydrocarbyl branches, having from 10 to 30 carbon atoms, pendant from a polymer backbone, said branch or branches being bonded directly or indirectly to the backbone.
  • long chain branches such as hydrocarbyl branches, such as oxyhydrocarbyl branches, having from 10 to 30 carbon atoms, pendant from a polymer backbone, said branch or branches being bonded directly or indirectly to the backbone.
  • indirect bonding include bonding via interposed atoms or groups, which bonding can include covalent and/or electrovalent bonding such as in a salt.
  • the comb polymer is a homopolymer having, or a copolymer at least 25 and preferably at least 40, more preferably at least 50, molar per cent of the units of which have, side chains containing at least 6, and preferably at least 10, atoms, selected from for example carbon, nitrogen and oxygen, in a linear chain.
  • the comb polymer may contain units derived from other monomers if desired or required. It is within the scope of the invention to include two or more different comb copolymers.
  • These comb polymers may be copolymers of maleic anhydride or fumaric acid and another ethylenically unsaturated monomer, e.g. an ⁇ -olefin or an unsaturated ester, for example, vinyl acetate. It is preferred but not essential that equimolar amounts of the comonomers be used although molar proportions in the range of 2 to 1 and 1 to 2 are suitable.
  • olefins that may be copolymerized with e.g. maleic anhydride, include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.
  • the copolymer may be esterified by any suitable technique and although preferred it is not essential that the maleic anhydride or fumaric acid be at least 50% esterified.
  • examples of alcohols which may be used include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, and n-octadecan-1-ol.
  • the alcohols may also include up to one methyl branch per chain, for example, 1-methylpentadecan-1-ol, 2-methyltridecan-1-ol.
  • the alcohol may be a mixture of normal and single methyl branched alcohols.
  • R 12 refers to the average number of carbon atoms in the alkyl group; if alcohols that contain a branch at the 1 or 2 positions are used R 12 refers to the straight chain backbone segment of the alcohol.
  • These comb polymers may especially be fumarate or itaconate polymers and copolymers such as for example those described in European Patent Applications EP-A-153 176, EP-A-153 177 and EP-A-225 688, and WO-A-91 16407.
  • Particularly preferred fumarate comb polymers are copolymers of alkyl fumarates and vinyl acetate, in which the alkyl groups have from 12 to 20 carbon atoms, more especially polymers in which the alkyl groups have 14 carbon atoms or in which the alkyl groups are a mixture of C 14 /C 16 alkyl groups, made, for example, by solution copolymerizing an equimolar mixture of fumaric acid and vinyl acetate and reacting the resulting copolymer with the alcohol or mixture of alcohols, which are preferably straight chain alcohols.
  • the mixture it is advantageously a 1:1 by weight mixture of normal C 14 and C 16 alcohols.
  • mixtures of the C 14 ester with the mixed C 14 /C 16 ester may advantageously be used.
  • the ratio of C 14 to C 14 /C 16 is advantageously in the range of from 1:1 to 4: 1, preferably 2:1 to 7:2, and most preferably about 3:1, by weight.
  • the particularly preferred fumarate comb polymers may, for example, have a number average molecular weight in the range of 1,000 to 100,000, preferably 1,000 to 30,000, as measured by Vapour Phase Osmometry (VPO).
  • comb polymers are the polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride, and esterified copolymers of styrene and fumaric acid; mixtures of two or more comb polymers may be used in accordance with the invention and, as indicated above, such use may be advantageous.
  • comb polymers are hydrocarbon polymers such as copolymers of ethylene and at least one ⁇ -olefin, preferably the ⁇ -olefin having at most 20 carbon atoms, examples being n-decene-1 and n-dodecene-1.
  • the number average molecular weight of such a copolymer is at least 30,000.
  • the hydrocarbon copolymers may be prepared by methods known in the art, for example using a Ziegler type catalyst.
  • Such compounds comprise a compound in which at least one substantially linear alkyl group having 10 to 30 carbon atoms is connected to a non-polymeric organic residue to provide at least one linear chain of atoms that includes the carbon atoms of said alkyl groups and one or more non-terminal oxygen atoms.
  • substantially linear is meant that the alkyl group is preferably straight chain, but that essentially straight chain alkyl groups having a small degree of branching such as in the form of a single methyl group may be used.
  • the compound has a least two of said alkyl groups when the linear chain may include the carbon atoms of more than one of said alkyl groups.
  • the linear chain or chains may provide part of a linking group between any two such alkyl groups in the compound.
  • the oxygen atom or atoms are preferably directly interposed between carbon atoms in the chain and may, for example, be provided in the form of a mono- or poly-oxyalkylene group, said oxyalkylene group preferably having 2 to 4 carbon atoms, examples being oxyethylene and oxypropylene.
  • chain or chains include carbon and oxygen atoms. They may also include other heteroatoms such as nitrogen atoms.
  • the compound may be an ester where the alkyl groups are connected to the remainder of the compound as -O-CO n alkyl, or -CO-O n alkyl groups, in the former the alkyl groups being derived from an acid and the remainder of the compound being derived from a polyhydric alcohol and in the latter the alkyl groups being derived from an alcohol and the remainder of the compound being derived from a polycarboxylic acid.
  • the compound may be an ester where the alkyl groups are connected to the remainder of the compound as -O-n-alkyl groups.
  • the compound may be both an ester and an ether or it may contain different ester groups.
  • Examples include polyoxyalkylene esters, ethers, ester/ethers and mixtures thereof, particularly those containing at least one, preferably at least two, C 10 to C 30 linear alkyl groups and a polyoxyalkylene glycol group of molecular weight up to 5,000, preferably 200 to 5,000, the alkylene group in said polyoxyalkylene glycol containing from 1 to 4 carbon atoms, as described in EP-A-61 895 and in US-A-4,491,455.
  • esters, ethers or ester/ethers which may be used may be structurally depicted by the formula R 23 OBOR 24
  • R 23 and R 24 are the same or different and may be
  • Suitable glycols generally are substantially linear polyethylene glycols (PEG) and polypropylene glycols (PPG) having a molecular weight of about 100 to 5,000, preferably about 200 to 2,000.
  • Esters are preferred and fatty acids containing from 10 to 30 carbon atoms are useful for reacting with the glycols to form the ester additives, it being preferred to use C 18 to C 24 fatty acid, especially behenic acid.
  • the esters may also be prepared by esterifying polyethoxylated fatty acids or polyethoxylated alcohols.
  • Polyoxyalkylene diesters, diethers, ether/esters and mixtures thereof are suitable as additives, diesters being preferred when the petroleum based component is a narrow boiling distillate, when minor amounts of monoethers and monoesters (which are often formed in the manufacturing process) may also be present. It is important for active performance that a major amount of the dialkyl compound is present In particular, stearic or behehic diesters of polyethylene glycol, polypropylene glycol or polyethylene/polypropylene glycol mixtures are preferred.
  • Examples of other compounds in this general category are those described in Japanese Patent Publication Nos. 2-51477 and 3-34790, and EP-A-117,108 and EP-A-326,356, and cyclic esterified ethoxylates such as described EP-A-356,256.
  • These polymers may be made directly from ethylenically unsaturated monomers or indirectly by hydrogenating the polymer made from monomers such as isoprene and butadiene.
  • Preferred hydrocarbon polymers are copolymers of ethylene and at least one ⁇ -olefin, having a number average molecular weight of at least 30,000.
  • the ⁇ -olefin has at most 20 carbon atoms.
  • examples of such olefins are propylene, 1 -butene, isobutene, n-octane-1, isooctene-1, n-decene-1, and n-dodecene-1.
  • the copolymer may also comprise small amounts, e.g. up to 10% by weight of other copolymerizable monomers, for example olefins other than ⁇ -olefins, and non-conjugated dienes.
  • the preferred copolymer is an ethylene-propylene copolymer. It is within the scope of the invention to include two or more different ethylene- ⁇ -olefin copolymers of this type.
  • the number average molecular weight of the ethylene- ⁇ -olefin copolymer is, as indicated above, at least 30,000, as measured by gel permeation chromatography (GPC) relative to polystyrene standards, advantageously at least 60,000 and preferably at least 80,000. Functionally no upper limit arises but difficulties of mixing result from increased viscosity at molecular weights above about 150,000, and preferred molecular weight ranges are from 60,000 and 80,000 to 120,000.
  • GPC gel permeation chromatography
  • the copolymer has a molar ethylene content between 50 and 85 per cent. More advantageously, the ethylene content is within the range of from 57 to 80%, and preferably it is in the range from 58 to 73%; more preferably from 62 to 71%, and most preferably 65 to 70%.
  • Preferred ethylene- ⁇ -olefin copolymers are ethylene-propylene copolymers with a molar ethylene content of from 62 to 71% and a number average molecularweight in the range 60,000 to 120,000, especially preferred copolymers are ethylene-propylene copolymers with an ethylene content of from 62 to 71% and a molecular weight from 80,000 to 100,000.
  • the copolymers may be prepared by any of the methods known in the art, for example using a Ziegler type catalyst.
  • the polymers are substantially amorphous, since highly crystalline polymers are relatively insoluble in fuel oil at low temperatures.
  • the additive composition may also comprise a further ethylene- ⁇ -olefin copolymer, advantageously with a number average molecular weight of at most 7500, advantageously from 1,000 to 6,000, and preferably from 2,000 to 5,000, as measured by vapour phase osmometry.
  • ⁇ -olefins are as given above, or styrene, with propylene again being preferred.
  • the ethylene content is from 60 to 77 molar per cent although for ethylene-propylene copolymers up to 86 molar per cent ethylene may be employed with advantage. Examples of hydrocarbon polymers are described in WO-A-9 111 488.
  • the oil-soluble polar nitrogen compound is either ionic or non-ionic and is capable of acting as a wax crystal growth inhibitor in fuels. It comprises for example one or more of the compounds (i) to (iii) as follows:
  • Ester/amides may be used containing 30 to 300, preferably 50 to 150 total carbon atoms. These nitrogen compounds are described in US-A-4 211 534. Suitable amines are usually long chain C 12 -C 40 primary, secondary, tertiary or quaternary amines or mixtures thereof but shorter chain amines may be used provided the resulting nitrogen compound is oil soluble and therefore normally contains about 30 to 300 total carbon atoms.
  • the nitrogen compound preferably contains at least one straight chain C 8 to C 40 , preferably C 14 to C 24 , alkyl segment.
  • Suitable amines include primary, secondary, tertiary or quaternary, but preferably are secondary. Tertiary and quaternary amines can only form amine salts. Examples of amines include tetradecyl amine, cocoamine, and hydrogenated tallow amine. Examples of secondary amines include dioctadecyl amine and methylbehenyl amine. Amine mixtures are also suitable such as those derived from natural materials.
  • a preferred amine is a secondary hydrogenated tallow amine of the formula HNR 1 R 2 wherein R 1 and R 2 are alkyl groups derived from hydrogenated tallow fat composed of approximately 4% C 14 , 31% C 16 , 59% C 18 .
  • suitable carboxylic acids and their anhydrides for preparing the nitrogen compounds include cyclohexane 1,2 dicarboxylic acid, cyclohexene 1,2 dicarboxylic acid, cyclopentane 1,2 dicarboxylic acid and naphthalene dicarboxylic acid, and 1,4-dicarboxylic acids including dialkyl spirobislactone. Generally, these acids have about 5-13 carbon atoms in the cyclic moiety.
  • Preferred acids useful in the present invention are benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. Phthalic acid or its anhydride is particularly preferred.
  • the particularly preferred compound is the amide-amine salt formed by reacting 1 molar portion of phthalic anhydride with 2 molar portions of dihydrogenated tallow amine. Another preferred compound is the diamide formed by dehydrating this amide-amine salt.
  • Examples are long chain alkyl or alkylene substituted dicarboxylic acid derivatives such as amine salts of monoamides of substituted succinic acids, examples of which are known in the art and described in US-A-4 147 520, for example. Suitable amines may be those described above. Other examples are condensates such as described in EP-A-327,423.
  • a chemical compound comprising or including a cyclic ring system, the compound carrying at least two substituents of the general formula (I) below on the ring system -A-NR 1 R 2 where A is an aliphatic hydrocarbyl group that is optionally interrupted by one or more hetero atoms and that is straight chain or branched, and R 1 and R 2 are the same or different and each is independently a hydrocarbyl group containing 9 to 40 carbon atoms optionally interrupted by one or more hetero atoms, the substituents beingthe same or different and the compound optionally being in the form of a salt thereof.
  • A has from 1 to 20 carbon atoms and is preferably a methylene or polymethylene group.
  • hydrocarbyl refers to a group having a carbon atom directly attached to the rest of the molecule and having a hydrocarbon or predominantly hydrocarbon character.
  • hydrocarbon groups including aliphatic (e. g. alkyl or alkenyl), alicyclic (e.g. cycloalkyl or cycloalkenyl), aromatic, and alicyclic-substituted aromatic, and aromatic-substituted aliphatic and alicyclic groups.
  • Aliphatic groups are advantageously saturated. These groups may contain non-hydrocarbon substituents provided their presence does not alter the predominantly hydrocarbon character of the group. Examples include keto, halo, hydroxy, nitro, cyano, alkoxy and acyl. If the hydrocarbyl group is substituted, a single (mono) substituent is preferred.
  • substituted hydrocarbyl groups examples include 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl, and propoxypropyl.
  • the groups may also or alternatively contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Suitable hetero atoms include, for example, nitrogen, sulphur, and, preferably, oxygen.
  • the cyclic ring system may include homocy- such as hexane, pentane and isoparaffins, and includes mixtures of the above.
  • the carrier liquid must, of course, be selected having regard to its compatibility with the additive and with the fuel.
  • the additives of the invention may be incorporated into bulk oil by other methods such as those known in the art. If others are required, they may be incorporated into the bulk oil at the same time as the additives of the invention or at a different time.
  • additives include antioxidants, corrosion inhibitors, dehazers, metal deactivators, cosolvents, package compatibilisers, reodorants, antistatic additives (conductivity improvers), biocides, dyes, smoke reducers, catalyst life enhancers, power boosters, additives for fuel economy, demulsifiers, and spray modifiers.
  • the test was carried out by the procedure substantially as described in EP-A-0,403,097 and is a variation of the CFPP test.
  • a sample of the oil to be tested (40 ml) is cooled in a bath which is maintained at about -34°C to give non-linear cooling at about 1°C/min.
  • the cooled oil tested for its ability to flow through a fine screen in a prescribed time period using a test device which is a pipette to whose lower end is attached an inverted funnel which is positioned below the surface of the oil to be tested. Stretched across the mouth of the funnel is a 350 mesh screen having an area defined by a 12 millimetre diameter.
  • the periodic tests are each initiated by applying a vacuum to the upper end of the pipette whereby oil is drawn through the screen up into the pipette to a mark indicating 20 ml of oil. After each successful passage, the oil is returned immediately to the CFPP tube. The test is repeated with each one degree drop in temperature until the oil fails to fill the pipette within 60 seconds, the temperature at which failure occurs being reported as the CFPP temperature.
  • the additive combinations of the invention may also be effective in reducing the tendency of wax in the fuel to settle (i.e. they may be wax anti-settling additives) and may exhibit activity in slow cooling tests such as the Extended Programmed Cooling Test (XPCT) which is known in the art.
  • XPCT Extended Programmed Cooling Test
  • the concentrations of the constituents of Components BX and BY in the fuels are given in parentheses as weight per cent of fuel.
  • the constituents, identified by reference numbers 3 and 5 to 7 above, are as follows (additional to constituents already defined herein)
  • an itaconate polymer of number average molecular weight about 4000 as measured by GPC prepared by polymerising a monomer in cyclohexane solvent using a free radical catalyst, the monomer containing linear alkyl groups of 18 carbon atoms.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (23)

  1. Utilisation d'un co-additif (A) qui comprend un additif d'onctuosité, soluble dans l'huile, comprenant un mono-ester de glycérol d'un acide monocarboxylique insaturé, dans lequel l'acide a 2 à 50 atomes de carbone ; ladite utilisation consistant en une utilisation dans une composition comprenant une proportion dominante d'un fuel-oil et une petite proportion d'un constituant (B) qui comprend un additif améliorant l'écoulement à froid comprenant un copolymère éthylène/ester insaturé ayant une moyenne en nombre du poids moléculaire mesurée par osmométrie en phase vapeur, de 1000 à 5000, et étant destiné à améliorer les propriétés d'écoulement à froid de la composition.
  2. Utilisation suivant la revendication 1, dans laquelle l'additif d'onctuosité comprend l'ester d'un acide monocarboxylique de formule : R'(COOH) dans laquelle R' représente un groupe alcényle ayant 10 à 30 atomes de carbone.
  3. Utilisation suivant la revendication 2, dans laquelle le groupe alcényle a une, deux ou trois doubles liaisons.
  4. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle l'acide est l'acide oléique, élaïdique, palmitoléique, pétrosélinique, ricinoléique, éléostéarique, linoléique, linolénique, gadoléique, érucique ou hypogaéique.
  5. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le monoester de glycérol consiste en mono-oléate de glycérol.
  6. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le constituant (B) comprend un copolymère éthylène/ester insaturé.
  7. Utilisation suivant la revendication 6, dans laquelle l'ester insaturé est un ester d'un alcool insaturé avec un acide carboxylique saturé.
  8. Utilisation suivant l'une quelconque des revendications précédentes, comprenant en outre, comme co-additif, un composé azoté polaire, soluble dans l'huile, portant un ou plusieurs substituants de formule -NR1-, dans laquelle R1 représente un groupe hydrocarbyle contenant 8 à 40 atomes de carbone, ledit substituant ou bien un ou plusieurs desdits substituants étant facultativement sous forme d'un cation qui en est dérivé.
  9. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle le fuel-oil consiste en un fuel-oil distillé moyen.
  10. Utilisation suivant l'une quelconque des revendications précédentes, dans laquelle la concentration totale des constituants (A) et (B) dans le fuel-oil est comprise dans l'intervalle de 25 à 500 ppm d'ingrédient actif en poids, par poids du fuel-oil.
  11. Composition de fuel-oil comprenant une proportion dominante d'un fuel-oil et une association :
    d'un constituant (A) qui comprend un additif d'onctuosité, soluble dans l'huile, comprenant un mono-ester de glycérol d'un acide monocarboxylique insaturé, dans lequel l'acide a 2 à 50 atomes de carbone ; et
    d'un constituant (B) qui comprend un additif améliorant l'écoulement à froid, comprenant un copolymère éthylène/ester insaturé ayant une moyenne en nombre du poids moléculaire mesurée par osmométrie en phase vapeur, de 1000 à 5000 ; et
    facultativement, d'autres additifs.
  12. Concentré d'additifs contenant :
    un constituant (A) qui comprend un additif d'onctuosité, soluble dans l'huile, comprenant un ester de glycérol d'un acide monocarboxylique insaturé, dans lequel l'acide a 2 à 50 atomes de carbone ; et
    un constituant (B) qui comprend un additif améliorant l'écoulement à froid, comprenant un copolymère éthylène/ester insaturé ayant une moyenne en nombre du poids moléculaire mesurée par osmométrie en phase vapeur, de 1000 à 5000 ; et
    facultativement, d'autres additifs.
  13. Composition suivant la revendication 11 ou 12, dans laquelle l'additif d'onctuosité comprend l'ester d'un acide monocarboxylique de formule : R'(COOH) dans laquelle R' représente un groupe alcényle ayant 10 à 30 atomes de carbone.
  14. Composition suivant la revendication 13, dans laquelle le groupe alcényle a une, deux ou trois doubles liaisons.
  15. Composition suivant la revendication 11 à 14, dans laquelle l'acide est l'acide oléique, élaïdique, palmitoléique, pétrosélinique, ricinoléique, éléostéarique, linoléique, linolénique, gadoléique, érucique ou hypogaéique.
  16. Composition suivant l'une quelconque des revendications 11 à 15, dans laquelle le monoester de glycérol consiste en mono-oléate de glycérol.
  17. Composition suivant l'une quelconque des revendications 11 à 16, dans laquelle le constituant (B) comprend un copolymère éthylène/ester insaturé, dans lequel l'ester insaturé est un ester d'un alcool insaturé avec un acide carboxylique saturé.
  18. Composition suivant l'une quelconque des revendications 11 à 17, comprenant en outre, comme co-additif, un composé azoté polaire, soluble dans l'huile, portant un ou plusieurs substituants de formule -NR1-, dans laquelle R1 représente un groupe hydrocarbyle contenant 8 à 40 atomes de carbone, ledit substituant ou bien un ou plusieurs desdits substituants étant facultativement sous forme d'un cation qui en est dérivé.
  19. Composition suivant la revendication 11, ou suivant l'une quelconque des revendications 13 à 18 lorsqu'elles dépendent de la revendication 11, dans laquelle le fuel-oil est un fuel-oil distillé moyen.
  20. Composition suivant la revendication 11, ou suivant l'une quelconque des revendications 13 à 19 lorsqu'elles dépendent de la revendication 11, dans laquelle la concentration totale de constituants (A) et (B) dans le fuel-oil est comprise dans l'intervalle de 25 à 500 ppm d'ingrédient actif en poids, par poids de fuel-oil.
  21. Procédé pour mélanger des additifs à un fuel-oil, comprenant les étapes consistant :
    (i) à injecter le constituant (B) répondant à la définition suivant la revendication 1 dans le fuel-oil ;
    (ii) à injecter le constituant (A) répondant à la définition suivant la revendication 1 dans le fuel-oil ;
    (iii) à mesurer les propriétés d'écoulement à froid du fuel-oil après les injections des étapes (i) et (ii) ; et
    (iv) à ajuster les vitesses relatives d'injection des constituants (B) et (A) et, ainsi, leurs proportions relatives pour tenir compte des résultats de l'étape (iii) et conférer les propriétés désirées d'écoulement à froid au fuel-oil.
  22. Procédé suivant la revendication 21, dans lequel le fuel-oil comprend un courant en mouvement de ce fuel-oil, l'étape (i) s'effectuant à un premier poste et l'étape (ii) s'effectuant à un second poste.
  23. Procédé suivant la revendication 21 ou 22, dans lequel un capteur met en oeuvre l'étape (iii) et l'information est amenée par un régulateur pour commander l'injection de l'un des ou des deux constituants (B) et (A).
EP94924280A 1993-07-22 1994-07-22 Additifs et compositons de combustibles Expired - Lifetime EP0721492B2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP98204020A EP0908507A1 (fr) 1993-07-22 1994-07-22 Additifs et compositions de combustible
EP98202903A EP0885948B1 (fr) 1993-07-22 1994-07-22 Utilisation de compositions d'additifs dans un combustible

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9315205 1993-07-22
GB939315205A GB9315205D0 (en) 1993-07-22 1993-07-22 Additives and fuel compositions
PCT/EP1994/002432 WO1995003377A1 (fr) 1993-07-22 1994-07-22 Additifs et compositons de combustibles

Related Child Applications (2)

Application Number Title Priority Date Filing Date
EP98204020A Division EP0908507A1 (fr) 1993-07-22 1994-07-22 Additifs et compositions de combustible
EP98202903A Division EP0885948B1 (fr) 1993-07-22 1994-07-22 Utilisation de compositions d'additifs dans un combustible

Publications (3)

Publication Number Publication Date
EP0721492A1 EP0721492A1 (fr) 1996-07-17
EP0721492B1 EP0721492B1 (fr) 1999-09-15
EP0721492B2 true EP0721492B2 (fr) 2002-06-19

Family

ID=10739263

Family Applications (3)

Application Number Title Priority Date Filing Date
EP98204020A Withdrawn EP0908507A1 (fr) 1993-07-22 1994-07-22 Additifs et compositions de combustible
EP98202903A Revoked EP0885948B1 (fr) 1993-07-22 1994-07-22 Utilisation de compositions d'additifs dans un combustible
EP94924280A Expired - Lifetime EP0721492B2 (fr) 1993-07-22 1994-07-22 Additifs et compositons de combustibles

Family Applications Before (2)

Application Number Title Priority Date Filing Date
EP98204020A Withdrawn EP0908507A1 (fr) 1993-07-22 1994-07-22 Additifs et compositions de combustible
EP98202903A Revoked EP0885948B1 (fr) 1993-07-22 1994-07-22 Utilisation de compositions d'additifs dans un combustible

Country Status (8)

Country Link
EP (3) EP0908507A1 (fr)
JP (1) JPH09503530A (fr)
KR (1) KR100325574B1 (fr)
CA (1) CA2167672C (fr)
DE (2) DE69420736T3 (fr)
GB (1) GB9315205D0 (fr)
NO (1) NO321605B1 (fr)
WO (1) WO1995003377A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023247973A1 (fr) * 2022-06-24 2023-12-28 Innospec Limited Compositions de carburant comprenant un additif, et procédés et utilisations associés

Families Citing this family (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9410820D0 (en) * 1994-05-31 1994-07-20 Exxon Chemical Patents Inc Oil additives and compositions
GB2289287A (en) * 1994-05-04 1995-11-15 Ethyl Petroleum Additives Ltd Fuel foam control additive
CA2183180C (fr) * 1994-12-13 2003-06-24 Brian William Davies Compositions de fuel-oil
GB9502041D0 (en) * 1995-02-02 1995-03-22 Exxon Chemical Patents Inc Additives and fuel oil compositions
CH689981A5 (de) * 1995-07-25 2000-02-29 Midt Gmbh K Schwefelarmer, additivierter Diesel Kraftstoff mit verbesserter Schmierwirkung und erhöhter Dichte.
US5968211A (en) * 1995-12-22 1999-10-19 Exxon Research And Engineering Co. Gasoline additive concentrate
DE69613549T2 (de) * 1995-12-22 2001-10-25 Exxon Mobil Research And Engineering Co., Annandale Benzinzusatzkonzentrat
DE19614722A1 (de) * 1996-04-15 1997-10-16 Henkel Kgaa Kältestabiles Schmier- und Kraftstoffadditiv
GB9610363D0 (en) 1996-05-17 1996-07-24 Ethyl Petroleum Additives Ltd Fuel additives and compositions
US6001141A (en) * 1996-11-12 1999-12-14 Ethyl Petroleum Additives, Ltd. Fuel additive
GB2322138A (en) * 1997-02-17 1998-08-19 Ethyl Petroleum Additives Ltd Foam reducing fuel additive
DE19739271A1 (de) † 1997-09-08 1999-03-11 Clariant Gmbh Additiv zur Verbesserung der Fließfähigkeit von Mineralölen und Mineralöldestillaten
FR2772784B1 (fr) * 1997-12-24 2004-09-10 Elf Antar France Additif d'onctuosite pour carburant
FR2772783A1 (fr) * 1997-12-24 1999-06-25 Elf Antar France Additif d'onctuosite pour carburant
EP1116780B1 (fr) 2000-01-11 2005-08-31 Clariant GmbH Additif polyfonctionnel pour huiles combustibles
DE10136828B4 (de) 2001-07-27 2005-12-15 Clariant Gmbh Schmierverbessernde Additive mit verminderter Emulgierneigung für hochentschwefelte Brennstofföle
DE10356595A1 (de) 2003-12-04 2005-06-30 Basf Ag Brennstoffölzusammensetzungen mit verbesserten Kaltfließeigenschaften
US20050132641A1 (en) * 2003-12-23 2005-06-23 Mccallum Andrew J. Fuel lubricity from blends of lubricity improvers and corrosion inhibitors or stability additives
DE102005002700A1 (de) 2005-01-19 2006-07-27 Cognis Deutschland Gmbh & Co. Kg Zusammensetzungen verwendbar als Biotreibstoff
DE102005002711A1 (de) 2005-01-19 2006-07-27 Cognis Deutschland Gmbh & Co. Kg Herstellung und Verwendung von Monoglyceriden
EP1866397A2 (fr) 2005-03-29 2007-12-19 Arizona Chemical Company Compositions renfermant des acides gras et/ou leurs derives et un stabilisateur a basse temperature
EP1801187B2 (fr) 2005-12-22 2022-03-23 Clariant Produkte (Deutschland) GmbH Huiles minérales contenant des additifs détergents avec capacité de fluidité au froid améliorée
JP5854581B2 (ja) * 2006-04-18 2016-02-09 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎｖｅｎｎｏｏｔｓｈａｐ 燃料組成物
EP1923454A1 (fr) 2006-11-17 2008-05-21 Basf Se Agent d'amélioration de l'écoulement à froid.
EP1947161A1 (fr) 2006-12-13 2008-07-23 Infineum International Limited Compositions de carburant
US20080141579A1 (en) * 2006-12-13 2008-06-19 Rinaldo Caprotti Fuel Oil Compositions
EP1935968B1 (fr) * 2006-12-13 2009-02-25 Infineum International Limited Améliorations de compositions de carburant
EP1932899A1 (fr) * 2006-12-13 2008-06-18 Infineum International Limited Améliorations de compositions de carburant
DE102007028306A1 (de) 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
DE102007028304A1 (de) * 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
DE102007028307A1 (de) 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
DE102007028305A1 (de) * 2007-06-20 2008-12-24 Clariant International Limited Detergenzadditive enthaltende Mineralöle mit verbesserter Kältefließfähigkeit
EP2025737A1 (fr) 2007-08-01 2009-02-18 Afton Chemical Corporation Compositions de combustibles sans danger pour l'environnement
FR2947558B1 (fr) 2009-07-03 2011-08-19 Total Raffinage Marketing Terpolymere et ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles
US20110192076A1 (en) 2010-02-05 2011-08-11 Evonik Rohmax Additives Gmbh Composition having improved filterability
US20130219868A1 (en) 2010-10-29 2013-08-29 Evonik Oil Additives Gmbh Diesel motor having improved properties
CA2846371A1 (fr) 2011-08-26 2013-03-07 Evonik Oil Additives Gmbh Procede de reduction de la teneur en halogene d'un polymere
GB201810852D0 (en) * 2018-07-02 2018-08-15 Innospec Ltd Compositions, uses and methods

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3031344A1 (de) † 1980-08-20 1982-04-08 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von polymerisat-sekundaerdispersionen und die verwendung der sekundaerdispersionen als stockpunktserniedriger fuer mineraloele
EP0085803A1 (fr) † 1982-02-10 1983-08-17 Nippon Oil And Fats Company, Limited Méthode pour améliorer l'écoulement à froid d'huiles combustibles
JPS5953594A (ja) † 1982-09-22 1984-03-28 Dai Ichi Kogyo Seiyaku Co Ltd 燃料油用流動性向上剤
DD215803A5 (de) † 1982-12-22 1984-11-21 Voest Alpine Ag Verfahren zur durchfuehrung von metallurgischen oder chemischen prozessen und niederschachtofen
EP0183447A1 (fr) † 1984-11-15 1986-06-04 Exxon Research And Engineering Company Polyesters comme agents améliorateurs de l'écoulement pour hydrocarbures
JPS61213292A (ja) † 1985-03-19 1986-09-22 Kao Corp 燃料油の流動性改良剤
DE2156425C2 (de) † 1970-11-16 1987-03-26 Exxon Research and Engineering Co., Linden, N.J. Heiz- oder Treibölmischung, bzw. Konzentrat zur Verbesserung der Fließeigenschaften dieser
JPS63245488A (ja) † 1987-04-01 1988-10-12 Kao Corp 燃料油用流動性改良剤
EP0356256A2 (fr) † 1988-08-26 1990-02-28 Exxon Chemical Patents Inc. Compositions chimiques et leur utilisation comme additifs pour combustibles

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3233986A (en) * 1962-06-07 1966-02-08 Union Carbide Corp Siloxane-polyoxyalkylene copolymers as anti-foam agents
FR1405551A (fr) * 1963-07-16 1965-07-09 Exxon Research Engineering Co Additifs anti-usure destinés à améliorer l'onctuosité d'hydrocarbures liquides
US3287273A (en) * 1965-09-09 1966-11-22 Exxon Research Engineering Co Lubricity additive-hydrogenated dicarboxylic acid and a glycol
GB1413323A (en) * 1972-07-06 1975-11-12 United Lubricants Ltd Diesel fuel additives
CA1017568A (en) * 1972-08-24 1977-09-20 Nicholas Feldman Additive combination for cold flow improvement of distillate fuel oil
US3966428A (en) * 1973-10-31 1976-06-29 Exxon Research And Engineering Company Ethylene backbone polymers in combination with ester polymers having long alkyl side chains are low viscosity distillate fuel cold flow improvers
FR2313440A1 (fr) * 1975-06-06 1976-12-31 Rhone Poulenc Ind Dispersions homogenes de compositions diorganopolysiloxaniques dans des huiles minerales
FR2448130A1 (fr) * 1979-02-05 1980-08-29 Octel Sa Procede et dispositif de controle d'un debit de liquide
ATE7151T1 (de) * 1979-11-23 1984-05-15 Exxon Research And Engineering Company Kombinationen von zusaetzen und sie enthaltende brennstoffe.
US4365973A (en) * 1980-12-18 1982-12-28 Union Oil Company Of California Middle distillate fuel additive
DE3049553A1 (de) * 1980-12-31 1982-07-29 Basf Ag, 6700 Ludwigshafen Erdoeldestillate mit verbessertem kaelteverhalten
US4464182A (en) * 1981-03-31 1984-08-07 Exxon Research & Engineering Co. Glycol ester flow improver additive for distillate fuels
BR8206717A (pt) * 1982-05-06 1984-01-03 Xpcl Corp Aditivo lubrificante, mistura de combustivel de alcool aditivo lubrificante e processos para preparar uma mistura de combustivel de etanol / e combustivel de metanol/ aditivo lubrificante
US4460380A (en) * 1982-12-27 1984-07-17 Exxon Research & Engineering Co. Water shedding agents in distillate fuel oils
NO168054C (no) * 1985-03-29 1992-01-08 Dow Corning Polysiloksan-polyoksyalkylen-kopolymer som antiskummiddeltil diesel og flybensin.
US5018645A (en) * 1990-01-30 1991-05-28 Zinsmeyer Herbert G Automotive fluids dispensing and blending system
DK0518966T3 (da) * 1990-03-05 1996-01-29 Polar Molecular Corp Motorbrændstofadditiv og fremgangsmåde til fremstilling deraf
CA2042855A1 (fr) * 1990-06-28 1991-12-29 Nicholas Feldman Composition servant a ameliorer les proprietes d'ecoulement de distillats moyens au froid
EP0476196B1 (fr) * 1990-09-20 1993-11-18 Ethyl Petroleum Additives Limited Compositions combustibles hydrocarburées et additifs pour celles-ci
GB9219962D0 (en) * 1992-09-22 1992-11-04 Exxon Chemical Patents Inc Additives for organic liquids
GB9316021D0 (en) * 1993-08-03 1993-09-15 Exxon Chemical Patents Inc Additive for hydrocarbon oils
GB9410820D0 (en) * 1994-05-31 1994-07-20 Exxon Chemical Patents Inc Oil additives and compositions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2156425C2 (de) † 1970-11-16 1987-03-26 Exxon Research and Engineering Co., Linden, N.J. Heiz- oder Treibölmischung, bzw. Konzentrat zur Verbesserung der Fließeigenschaften dieser
DE3031344A1 (de) † 1980-08-20 1982-04-08 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von polymerisat-sekundaerdispersionen und die verwendung der sekundaerdispersionen als stockpunktserniedriger fuer mineraloele
EP0085803A1 (fr) † 1982-02-10 1983-08-17 Nippon Oil And Fats Company, Limited Méthode pour améliorer l'écoulement à froid d'huiles combustibles
JPS5953594A (ja) † 1982-09-22 1984-03-28 Dai Ichi Kogyo Seiyaku Co Ltd 燃料油用流動性向上剤
DD215803A5 (de) † 1982-12-22 1984-11-21 Voest Alpine Ag Verfahren zur durchfuehrung von metallurgischen oder chemischen prozessen und niederschachtofen
EP0183447A1 (fr) † 1984-11-15 1986-06-04 Exxon Research And Engineering Company Polyesters comme agents améliorateurs de l'écoulement pour hydrocarbures
JPS61213292A (ja) † 1985-03-19 1986-09-22 Kao Corp 燃料油の流動性改良剤
JPS63245488A (ja) † 1987-04-01 1988-10-12 Kao Corp 燃料油用流動性改良剤
EP0356256A2 (fr) † 1988-08-26 1990-02-28 Exxon Chemical Patents Inc. Compositions chimiques et leur utilisation comme additifs pour combustibles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023247973A1 (fr) * 2022-06-24 2023-12-28 Innospec Limited Compositions de carburant comprenant un additif, et procédés et utilisations associés

Also Published As

Publication number Publication date
EP0721492B1 (fr) 1999-09-15
NO960254L (no) 1996-03-15
EP0885948A3 (fr) 1999-01-27
EP0908507A1 (fr) 1999-04-14
DE69420736T3 (de) 2002-11-07
DE69420736D1 (de) 1999-10-21
CA2167672A1 (fr) 1995-02-02
CA2167672C (fr) 2005-06-21
EP0885948A2 (fr) 1998-12-23
WO1995003377A1 (fr) 1995-02-02
DE69420736T2 (de) 2000-03-09
EP0721492A1 (fr) 1996-07-17
EP0885948B1 (fr) 2004-12-29
JPH09503530A (ja) 1997-04-08
DE69434213T2 (de) 2006-01-26
KR100325574B1 (ko) 2002-07-03
NO960254D0 (no) 1996-01-22
GB9315205D0 (en) 1993-09-08
KR960704015A (ko) 1996-08-31
NO321605B1 (no) 2006-06-12
DE69434213D1 (de) 2005-02-03

Similar Documents

Publication Publication Date Title
EP0721492B2 (fr) Additifs et compositons de combustibles
EP0629231B1 (fr) Additifs pour huiles
EP0665873B1 (fr) Compositions et additifs pour combustibles
EP0663000B1 (fr) Additifs pour liquides organiques
EP0743974B1 (fr) Compositions d'huile combustible comprenant des huiles combustibles a base de petrole, des copolymers ethylene-esters non satures et des esters des alcools polyhydriques avec des acides carboxyliques
US6306186B1 (en) Oil additives compositions and polymers for use therein
US20070161519A1 (en) Pour point depressant additives for oil compositions
US6554876B1 (en) Oil compositions
US20050183326A1 (en) Oil compositions
EP0713519B1 (fr) Composition de combustible de distillat moyen
EP0746598B1 (fr) Compositions pour huiles
US6251146B1 (en) Fuel oil composition containing mixture of wax additives
EP1007606B2 (fr) Additifs pour compositions petroliferes
EP0778874B1 (fr) Additifs et compositions pour huiles et polymeres utilises dans ceux-ci
EP1491614B1 (fr) Compositions d'huile
US6187065B1 (en) Additives and oil compositions
CA2286916C (fr) Compositions d'huiles ameliorees
CA2499890C (fr) Additifs pour compositions de carburant
WO1998027184A1 (fr) Combustible distilles renfermant des derives de diacide polyalkylene glycol utilises comme agents ameliorant la fluidite
EP0804523A1 (fr) Compositions de mazout

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960222

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

17Q First examination report despatched

Effective date: 19970708

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INFINEUM USA L.P.

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

ITF It: translation for a ep patent filed
AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT

REF Corresponds to:

Ref document number: 69420736

Country of ref document: DE

Date of ref document: 19991021

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: CLARIANT GMBH

Effective date: 20000609

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20020619

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): DE FR GB IT

ET3 Fr: translation filed ** decision concerning opposition
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20130624

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130731

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20130712

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20130715

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69420736

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20140721

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20140723

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20140721