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
  • 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
  • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
• • 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
• • 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
  • C10L1/20—Organic compounds containing halogen
  • C10L1/206—Organic compounds containing halogen macromolecular compounds

Definitions

• This invention is directed at the production of a fuel having improved low temperature flow properties. More specifically, the present invention is directed at improving the low temperature flow-properties of a middle distillate fuel having an atmospheric boiling point ranging between about 120°C and about 450°C.
• middle distillate fuels In the production of middle distillate fuels, one of the major problems encountered is the formation of relatively large wax-type crystals which may plug fuel lines and/or fuel filters. While the consumption of gasoline is projected to show little, if any, growth in most industrial countries, the consumption of middle distillate fuels, particularly diesel fuel, is expected to increase significantly. Therefore, it would be advantageous to broaden the range of middle distillates which could be utilized as fuels. However, one significant barrier to broadening the boiling range of middle distillates utilized as fuels has been the poor low temperature flow properties of the middle distillates. At low temperatures paraffinic compounds present in the middle distillates, particularly normal paraffins, tend to precipitate, forming waxy compounds which tend to plug fuel lines and fuel filters. These problems tend to be particularly acute in diesel fuel, where the fuel filters frequently have openings of about 5-50 microns in diameter.
• U. S. Patent No. 2,084,512 is directed at improving the pour point of a lubricating oil.
• This patent discloses the use of bright stocks in combination with a pour inhibitor, such as the low temperature aluminum chloride condensation of halogenated paraffin wax and naphthalene.
• a pour inhibitor such as the low temperature aluminum chloride condensation of halogenated paraffin wax and naphthalene.
• additives which are effective for pour point depression of a lube oil may not be effective for improving the low temperature flow properties of ⁇ - middle distillate fuel. While acceptable pour point depression may be accomplished in a lube oil having relatively large wax crystals present, large wax crystals may plug the small pores of fuel filters.
• U. S. Patent No. 3,660,057 discloses the addition to a middle distillate of an essentially saturated hydrocarbon fraction substantially free of normal paraffinic hydrocarbons having a number average molecular weight range of about 600 to 3,000 in combination with a copolymer of ethylene with an ethylenically unsaturated monomer, such as an unsaturated ester or an alpha-olefin.
• This patent discloses in Table I that the finest screen through which the distillate fuel could be passed was a 40 mesh screen, which has openings of about 420 microns.
• U. S. Patent No. 3,832,150 discloses the use of recycle cat cycle oil in combination with ethylene .and vinyl acetate as a pour depressant for middle distillate fuel oil boiling in the range of about 250°F and about 670 o F. While this combination of additives permits middle distillate fuel oil to flow through openings 2,250 microns in diameter, it is not believed that this combination will improve the cold flow of the distillate fuels by reducing the size of the wax crystals so as to enable them to flow through the fine mesh filters commonly found on diesel engines.
• U. S. Patent No. 3,389,979 discloses the combination of ethylene vinyl acetate and a resin extracted from a hydrocarbon. While this combination is reported to improve the flow rate of hydrocarbon distillate fuels through a copper tubing it is not believed that this combination will improve the cold flow of distillates by reducing the size of the wax crystals formed to permit flow through the fine mesh filters associated with diesel engines.
• U. S. Patent No. 3,640,691 discloses the use of ethylene vinyl acetate and a normal paraffinic hydrocarbon in the C 24 -C 40 range for use as a flow improver in tests utilizing screens having 570 micron diameter openings. While the use of this combination may have enabled middle distillate fuel to pass through coarse screens several hundred microns in diameter, it is not believed that this combination will permit flow through the fine mesh screens of diesel engines.
• the present invention is directed at the addition to a middle distillate fuel of deas p halted residuum in combination with a copolymer to improve the low temperature flow properties of the fuel.
• the present invention is directed at a wax-containing petroleum distillate fuel having a boiling range between about 120°C to about 450°C which has deasphalted residuum and a copolymer added thereto to improve its low temperature flow properties.
• the copolymer preferably is selected from the group of copolymers consisting of ethylene and vinyl acetate, and ethylene and vinyl chloride.
• the present invention also is directed at a method for improving the low temperature flow properties of a middle distillate fuel boiling in the range of about 120°C to about 450 o C, preferably in the range of about 120°C to about 400 o C, more preferably in the range of about 120°C to about 370°C, which comprises adding to the middle distillate fuel oil deasphalted residuum and a copolymer.
• the copolymer preferably is selected from the group of copolymers consisting of copolymers of ethylene and vinyl acetate and ethylene and vinyl chloride.
• the deasphalted residuum added to the distillate fuel comprises below about 5 weight percent of the fuel, and preferably ranges between about 1 weight percent and about 3 weight percent of the middle distillate fuel.
• the copolymer added to the middle distillate fuel preferably comprises below about 0.5 weight percent of the fuel and preferably ranges between about 0.02 and about 0.15 weight percent of the fuel.
• the deasphalted residuum and the copolymer may be added to the distillate fuel at any point which will assure good mixing of the additive with the middle distillate fuel oil.
• the present invention is directed at improvement in the low temperature flow properties of middle distillates by promoting the formation of relatively small wax crystals from the precipitated wax.
• the present invention is directed at improving the cold flow properties of middle distillate fuels by the addition to the fuel of a deasphalted residuum, or deasphalted oil, and a copolymer.
• the copolymer preferably comprises a copolymer of ethylene and vinyl acetate and/or ethylene and vinyl chloride.
• middle distillate fuels refers to fuels having an atmospheric boiling point ranging between about 120°C and about 450 o C, preferably between about 120 0 C and about 400°C, and more preferably between about 120°C and about 370 o C.
• Commonly used middle distillate fuels comprise diesel fuel, Number 2 fuel oil, kerosene, and turbine fuel.
• deasphalted residuum or “deasphalted oil” refers to hydrocarbon bottoms from an atmospheric and/or vacuum pipestill which have had the asphaltenic components at least partially removed. Methods for producing a deasphalted residuum are well-known in the art and do not form a part of this invention.
• Deasphalting commonly is conducted by contacting the residuum with an alkane solvent selected from the group consisting of propane, butane, pentane and hexane. While the deasphalting process normally reduces the Conradson carbon content and the metals content of the deasphalted oil significantly, the actual degree to which these are removed by the deasphalting process will be a function of many factors, including the crude processed, the Conradson carbon content and metals content of the residuum, the solvent utilized, the feed throughput rate and the solvent addition rate.
• an alkane solvent selected from the group consisting of propane, butane, pentane and hexane.
• pour point depressant tests have not been particularly useful in predicting the performance of middle distillate fuels at low temperatures. While the pour point measures the lowest temperature at which a fuel may still flow, it has been found that this measure of a fuel is not a.reliable indication of the degree to which the fuel will flow through the relatively small pores of a fuel filter. Since the openings in an automobile fuel filter - typically may range between about 5 and about 50 microns, and the openings in screens of fuel heating systems may range between about 400 and about 1,000 microns, it is essential that the crystals of wax formed, if any, be relatively small so that they do not plug the openings in the filters.
• a test has been devised which has been found to be a relatively accurate indicator of cold flow performance of fuels in passing through filter media.
• LTFT Low Temperature Filterability Test
• 200 ml of the test fuel is cooled at a rate of 2°F/hour to the desired test temperature and subsequently passed through a screen having openings of 17 microns diameter under a vacuum of 20 kPa.
• the fuel is determined to pass the test only if all of the test fuel that can pass through the screen, passes through the screen in one minute. If any of the of test fuel that should pass through the screen has not passed through the screen in one minute, the test is designated a failure.
• This test procedure is described in more detail at page C-15 in CRC Report No. 528, entitled "CRC Diesel Fuel Low Temperature Operability Field Test", September, 1983, published by Coordinating Research Counsel, Atlanta, Georgia, the disclosure of which is incorporated herein by reference.
• One measure of the effectiveness of an additive in improving the low temperature flow properties of a middle distillate fuel is the degree to which the fuel flows at temperatures below the cloud point, i.e., the lower the temperature below the cloud point at which the fuel passes the LTFT test, the better the additive in improving the low temperature flow properties of the fuel.
• the diesel fuel employed had a boiling range of 171 to 343 0 C.
• the ethylene vinyl acetate copolymer had a number average molecular weight of approximately 1800.
• the ethylene vinyl chloride copolymer had a number average molecular weight of approximately 2500.
• the flow improvers that are employed in this invention are of the type comprising a copolymer of ethylene and at least one second unsaturated monomer.
• the second unsaturated monomer can be another monoolefin, e.g., a C 3 to C 16 alpha-monoolefin, or it can be an unsaturated ester, as for example vinyl acetate, vinyl butyrate, vinyl propionate, lauryl methacrylate, ethyl acrylate or the like. (See Canadian Patent Nos. 676,875 and 695,679).
• Other monomers include N-vinyl pyrrolidone. (See Canadian Patent No. 658,216).
• the second monomer can also be a mixture of unsaturated mono- or diester and a branched or straight chain alpha monoolefin.
• Mixtures of copolymers can also be used, as for example a mixture of a copolymer of ethylene and vinylacetate with an alkylated polystyrene or acylated polystyrene. (See U. S. Patent Nos. 3,037,850 and 3,069,245).
• the copolymer useful in this invention will consist essentially of about 3 to 40, and preferably 3 to 20, molar proportions of ethylene per molar proportion of the ethylenically unsaturated monomer, which latter monomer can be a single monomer or a mixture of such monomers in any proportion, said polymer being oil-soluble and having a number average molecular weight in the range of about 1,000 to 50,000, preferably about 1,500 to about 5,000 molecular weight.
• Molecular weights can be measured by vapor phase osmometry, for example by using a Mechrolab Vapor Phase Osmometer Model 310A.
• the unsaturated monomers, copolymerizable with ethylene include unsaturated acids, acid anhydrides, and mono- and diesters of the general formula: wherein R 1 is hydrogen or methyl; R 2 is a ⁇ OOCR 4 , or ⁇ COOR 4 group wherein R4 is hydrogen or a Cl to C 10 , more usually a C l to C 4 straight or branched chain alkyl group and R 3 is hydrogen or ⁇ COOR 4 .
• the monomer, when R 1 to R 3 are hydrogen and R 2 is ⁇ OOCR 4 includes vinyl alcohol esters of C 2 to. C 17 monocarboxylic acids. Examples of such esters include vinyl acetate, vinyl isobutyrate, vinyl laurate, vinyl myristate, vinyl palmitate, etc.
• esters include C 8 Oxo alcohol acrylate, methyl acrylate, methyl methacrylate, lauryl acrylate, isobutyl methacrylate, palmityl alcohol ester of alpha-methyl-acrylic acid, C 13 Oxo alcohol esters of methacrylic acid, etc.
• monomers wherein R 1 is hydrogen and R 2 and R 3 are ⁇ OOCR 4 groups include mono-C 13 Oxo alcohol fumarate, di-C 13 Oxo alcohol fumarate, diisopropyl maleate, dilauryl fumarate, ethyl methyl fumarate, fumaric acid, maleic acid, etc.
• unsaturated monomers copolymerizable with ethylene to prepare pour point depressants or flow improvers useful in this invention include C 3 to C 16 branched chain or straight-chain alpha monoolefins, as for example propylene, n-octene-1, 2-ethyldecene-l, n-decene-1, etc.
• a copolymer of 3 to 40 moles of ethylene with one mole of a mixture of 30 to 99 mole percent of unsaturated ester and 70 to 1 mole percent of olefin could be used.
• copolymers that are formed are random copolymers consisting primarily of an ethylene polymer backbone along which are distributed side chains of hydrocarbon or oxy-substituted hydrocarbon.
• the concentration of each of the components added to the middle distillate fuel should be sufficiently low that it does not cause a significantly adverse effect on the combustion properties of the fuel oil. Moreover, since the cost of copolymer is substantially higher than the cost of the deasphalted residuum, 'the minimum quantity of copolymer should be utilized which will give the desired cold flow properties.
• the quantity of the deasphalted residuum added to the fuel should be maintained below about 5 weight percent, preferably within the range of about 1 weight percent to about 3 weight percent of the fuel.
• the quantity of the copolymer added to the fuel should generally be maintained below 0.5 weight percent, preferably within the range of about 0.02 to about 0.15 weight percent.
• the point at which the deasphalted residuum and copolymer are added to the fuel is not critical.
• a preferred method would be to pre-mix both components and add this mixture during the final blending of the product, although it would be possible to add the components either singly or in combination at other points in the manufacture or distribution process.
• the preferred method would facilitate the relatively uniform distribution of the small quantity of copolymer in the fuel.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1985
  • 1985-09-27 JP JP60212761A patent/JPS61166885A/ja active Pending
  • 1985-09-27 ZA ZA857496A patent/ZA857496B/xx unknown
  • 1985-09-27 AU AU47971/85A patent/AU4797185A/en not_active Abandoned
  • 1985-09-27 EP EP85306918A patent/EP0177306A3/de not_active Withdrawn

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