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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • 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
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
  • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
• • 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
• • 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
  • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds 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 an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
• • 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
• • 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
  • C10L1/1963—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
• • 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

Definitions

• the present invention relates to improving the cold flow of distillate fuels, and more particularly relates in one non-limiting embodiment to improving the cold filter plugging point of middle distillate fuels by chemical treatment.
• middle distillate fuels include jet fuel, kerosene, heating oil and diesel fuel. More particularly, the fluidity problems involve paraffins in the fuel agglomerate at low temperatures to form a waxy semi-solid or gel-like material that plugs pipes and filters, inhibiting transmission of the fuel to, for example, an engine.
• a chemical composition called a low temperature fluidity modifier can co-crystallize with or adsorb the paraffins in the fuel oil to precipitate the paraffin before agglomeration occurs or alternatively to modify paraffin crystal growth so that the resulting irregularity in size and shape of the crystals inhibits agglomeration or efficient packing of the crystals, thereby reducing the tendency toward plug formation.
• pour point depressants are directed simply to viscosity reduction of fluids at low temperatures. Pour point reduction still involves some crystal modification but may not need to be as efficient or keep the crystals as small.
• low temperature modifiers operate by affecting the crystal growth of the paraffins in the fuel being treated
• the selection and composition of a low temperature fluidity modifier for a particular fuel is based on the nature of the paraffins in that fuel.
• low temperature modifiers typically are coordinated with the paraffins in the fuel so that the solubility characteristics of the modifier added to the fuel match the solubility characteristics of the paraffins in the fuel.
• the modifier is typically designed to crystallize at about 10° F. ( ⁇ 12° C.) as well, thereby to interfere with the crystallization of the paraffins.
• esterified olefin/maleic anhydride copolymers for use in low temperature fluidity modifier additive compositions by esterifying certain olefin/maleic anhydride copolymers with an array of aliphatic alcohols having chain lengths in the range of from about four to about forty carbon atoms, and to select the distribution of aliphatic chain lengths in that range in coordination with the paraffins in the fuel as discussed above.
• U.S. Pat. No. 5,857,287 discloses adding to a fuel oil a composition of from about 1 to about 40 parts by weight ethylene/vinyl acetate copolymer having a vinyl acetate content of from about 10% by weight to about 50% by weight and a weight average molecular weight of from about 2,000 to about 10,000, and 1 part by weight esterified copolymer of at least one generally linear alpha-olefin of from about 18 to about 50 carbon atoms and maleic anhydride in an alpha-olefin to maleic anhydride molar ratio of from about 4:1 to about 1:2, the copolymer having a weight average molecular weight of from about 2,000 to about 20,000, the esterified copolymer having been esterified with a plurality of aliphatic alcohols having from about four to about forty carbon atoms, imparts to the fuel oil surprisingly improved low temperature fluidity, provided that the alcohols include an eight carbon alcohol making up from about 50 to about 85 molar percent of the alcohol
• low temperature fluidity modifiers Despite the existence of a variety of low temperature fluidity modifiers, none provides completely satisfactory performance in all fuels. In fact, because of the disparities in the characteristics of fuel oils, particular low temperature fluidity modifiers meet with varying success from fuel to fuel. Thus, there is a continual search for ever more effective low temperature fluidity modifiers, particularly for use in a variety of fuels.
• the additive may include, but is not necessarily limited to (a) polymerized alpha-olefins per se, (b) alphaolefins copolymerized or reacted with a second component selected from the group consisting of maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl methacrylates, and combinations thereof to give a reaction product, (c) alpha-olefins copolymerized or reacted with a second component selected from the group consisting of maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl methacrylates, and combinations thereof to give a reaction product, where the reaction product is in turn blended with alkylphenol-formaldehyde resins, and/or (d
• a distillate fuel composition that includes a distillate fuel and an additive, where the additive may be selected from (a), (b), (c) and/or (d) noted above, in an amount effective to improve the cold flow of the distillate fuel, particularly the cold filter plugging point (CFPP) of a middle distillate fuel.
• the additive may be selected from (a), (b), (c) and/or (d) noted above, in an amount effective to improve the cold flow of the distillate fuel, particularly the cold filter plugging point (CFPP) of a middle distillate fuel.
• the components (a), (b), (c) and/or (d) are not esterified. In another non-limiting embodiment, the components (a), (b), (c) and/or (d) do not include esterified copolymers of alpha-olefins and maleic anhydride.
• compositions which include polymerized alpha-olefins used alone or alpha-olefins copolymerized with, grafted with, otherwise reacted with or even simply blended with additional components will give a synergistic improvement in a cold flow property of a distillate fuel as compared the expected sum of the additive effect of the components when used separately.
• unexpected improvement is seen when the improved cold flow property is compared with an otherwise identical distillate fuel composition absent the alpha-olefin component.
• CFPP cold filter plugging point
• the alpha-olefin suitable for use in the various compositions herein include those having carbon numbers ranging from 6 independently to 30, and even higher, in a non-limiting embodiment.
• the alpha-olefins may have a carbon number ranging from 10 independently to 28; alternatively from 12 independently to 16.
• any lower threshold may be combined with any upper threshold to give a suitable alternative range.
• these may have a weight average molecular weight of from about 1000 independently to about 20,000; alternatively from about 2000 independently to about 10,000.
• composition herein includes functionalized alphaolefins (a first component) copolymerized with or otherwise reacted with (for instance grafted with) a second component including, but not necessarily limited to, maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl methacrylates, and combinations thereof.
• a second component including, but not necessarily limited to, maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl methacrylates, and combinations thereof.
• the “alkyl” in alkyl acrylates and alkyl methacrylates is defined as a straight or branched alkyl group having carbon numbers ranging from 1 to 8, alternatively from 1 to 4.
• Alpha-olefins copolymerized/grafted with maleic anhydride may have a weight ratio ranging from 1% maleic anhydride to 50% maleic anhydride of the alpha-olefin, alternatively from 5 wt % to 25 wt % of alpha-olefin.
• the mole ratio of maleic anhydride to alpha-olefin may range from 0.03/1 independently to 3/1; alternatively from 0.15/1 independently to 2/1.
• Alpha-olefins copolymerized/grafted with acrylic acid may have a weight ratio ranging from 1% acrylic acid to 20% acrylic acid to the alpha-olefin, alternatively from 3 wt % to 10 wt % of alpha-olefin. Expressed as mole ratio, the mole ratio of acrylic acid to alpha-olefin may range from 0.04/1 independently to 0.9/1; alternatively from 0.1/1 independently to 0.4/1.
• Alpha-olefins copolymerized/grafted with vinyl acetate may have a weight ratio ranging from 1% vinyl acetate to 40% vinyl acetate of the alphaolefin, alternatively from 10 wt % to 25 wt % of alpha-olefin. Expressed as mole ratio, the mole ratio of vinyl acetate to alpha-olefin may range from 0.04/1 independently to 2/1; alternatively from 0.4/1 independently to 1/1.
• graft polymers or other reaction products with the alpha-olefins may have a weight average molecular weight of from about 1000 independently to about 20,000; alternatively from about 2000 independently to about 10,000.
• alkylphenol-formaldehyde resin components they may range in weight average molecular weight from about 2000 independently to about 20,000; alternatively from about 5000 independently to about 12,000.
• EVA copolymer components they may range in weight average molecular weight from about 1000 independently to about 10,000; alternatively from about 2000 independently to about 4000.
• the alpha-olefins may be homopolymerized using methods well known in the art, and further, the alpha-olefins may be reacted with the second components using methods well known in the art. These polymerization and other reactions may be carried out at a temperature between about 60 and about 180° C., and a pressure between about 0 and about 200 psig. The reactions may be carried out in the absence or presence of a catalyst. If a catalyst is used, suitable catalysts include, but are not necessarily limited to, peroxide catalysts, such as di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, and t-butyl hydroperoxide and the like.
• peroxide catalysts such as di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, and t-butyl hydroperoxide and the like.
• the functionalized alpha-olefins may be blended with alkylphenol-formaldehyde resins.
• the weight ratio of the functionalized alpha-olefins with alkylphenol-formaldehyde resins ranges from about 5/1 independently to about 100/1; alternatively from about 1/1 independently to about 20/1.
• the functionalized alpha-olefins noted above may be blended with alkylphenol-formaldehyde resins, and further blended with ethylene-vinyl acetate copolymers (EVA).
• EVA ethylene-vinyl acetate copolymers
• the amount of EVA may range from about 99% independently to about 1 wt %; alternatively from about 98% independently to about 2 wt %, based on the amount of functionalized alpha-olefins and alkylphenol-formaldehyde resin.
• the effective amount of the additive useful to obtain the best results in the distillate fuel e.g. middle distillate fuel
• one good suitable procedure is simply empirical testing, since as previously noted, the cold flow improver may need to be matched to the paraffins in the fuel.
• the alpha-olefin portion that is blended or reacted with the second component or EVA ranges between about 1 independently to about 50 vol %, alternatively between about 5 independently to about 20 vol %
• the dosage range in middle distillate fuels of the final product blend or reaction product would be about 10 ppm-vol independently to about 10,000 ppm-vol; alternatively from about 50 ppm-vol independently to about 500 ppm-vol.
• the dosage of the alpha-olefin portion would range between about 1 ppm-vol independently to about 5,000 ppm-vol; alternatively from about 2.5 ppm-vol independently to about 100 ppm-vol.
• middle distillate fuels in which the methods and compositions described herein are expected to be effective include, but are not necessarily limited to, jet fuel, kerosene, heating oil and diesel fuel, whether or not they include fatty acid methyl esters (FAME).
• FAME fatty acid methyl esters
• the now common practice of introducing FAME into middle distillate fuels may lead to additional wax crystal formation from saturated FAME.
• some fuel companies are considering adding hydrogenated vegetable oils as biofuel components, which may introduce further paraffinic waxes into the middle distillate fuels.
• the additives and methods described herein are expected to be effective in these fuels as well.
• the distillate fuels as described herein do not encompass polymerized alpha-olefins (PAO) as a major component thereof, that is, a synthetic fuel where PAO is a major (more than 50 volume percent) component thereof.
• PAO polymerized alpha-olefins
• EVA polymer 50% active* T3005 EVA polymer, 50% active C1608 C30+ alpha-olefin-maleic anhydride polymer, 25% active 1787-123 C20-24 alpha-olefin-acrylic acid polymer, 50% active 1787-125 C20-24 alpha-olefin-acrylic acid polymer, 80% active 1787-189 C20-24/C24-28 alpha-olefin polymer, 25% active 1789-001 C20-24 alpha-olefin-vinyl acetate, (polymer) 25% active 1789-097 C20-24 + C24-28 alpha-olefin-vinyl acetate (19%), (polymer) 25% active 1789-155 C20-24 + C24-28 alpha-olefin-vinyl acetate (9.5%), (polymer) 25% active *Active refers to actual polymer; the balance is aromatic solvent.
• Table II presents the CFPP test results for four different fuels using a total of 200 ppm (includes solvent) dosage for each Example, except the blank.
• the comparative Examples are 2 and 4 where no alpha-olefin component is present. It may be seen that the other Examples, which had an alpha-olefin component, gave noticeable and unexpected improvements as compared to Examples 2 and 4. More specifically, compare Examples 3 and 6-9 with Example 2, and compare Example 5 with Example 4.
• the present invention may also suitably comprise, consist of or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
• the method for improving cold flow of a distillate fuel may consist of or consist essentially of adding to the distillate fuel an effective amount of an additive to improve a cold flow property, where the additive is (a) polymerized alpha-olefins, (b) alpha-olefins copolymerized or reacted with a second component selected from the group consisting of maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates, methacrylic acid, alkyl methacrylates, and combinations thereof to give a reaction product, (c) alpha-olefins copolymerized or reacted with a second component selected from the group consisting of maleic anhydride, acrylic acid, vinyl acetate, alkyl acrylates and combinations thereof to give a reaction product, where the reaction product is in turn blended with alkylphenol-formaldehyde resin
• a distillate fuel composition having improved cold flow that consists of or consists essentially of a distillate fuel and an effective amount to improve a cold flow property of the distillate fuel of an additive, where the additive is either (a), (b), (c) and/or (d) as described above.

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• 2013
  • 2013-03-06 US US13/786,674 patent/US20130239465A1/en not_active Abandoned
  • 2013-03-07 CA CA2866931A patent/CA2866931A1/en not_active Abandoned
  • 2013-03-07 IN IN7207DEN2014 patent/IN2014DN07207A/en unknown
  • 2013-03-07 CN CN201380014485.3A patent/CN104185674A/zh active Pending
  • 2013-03-07 SG SG11201405427TA patent/SG11201405427TA/en unknown
  • 2013-03-07 WO PCT/US2013/029586 patent/WO2013138154A1/en not_active Ceased
  • 2013-03-07 EP EP13761651.2A patent/EP2825620A4/en not_active Withdrawn

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