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
  • C10L1/18—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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
  • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C08L31/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G 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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic 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
  • C10L1/192—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
  • C10L1/20—Organic compounds containing halogen
  • C10L1/206—Organic compounds containing halogen macromolecular compounds
  • C10L1/207—Organic compounds containing halogen macromolecular compounds containing halogen with or without hydrogen
• • 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
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof

Definitions

• the pour point depressant is a copolymer of ethylene and a vinyl or C to C hydrocarbyl substituted vinyl ester of a C to C saturated aliphatic monocarboxylic acid, said copolymer having a number average molecular weight of about 4,000 to 60,000 and containing about 40 to 95 wt. percent ethylene.
• This invention relates to fuel compositions based on residua-containing fuels, and other base oils.
• pour point depressants Although various pour point depressants are known and have been used, they have been reasonably successful only with middle distillate fuels. It has been found difficult to obtain a potent pour point depressant for shale oils, residua or residua-containing fuels. We have now discovered certain polymers which are potent as pour point depressants in certain hydrocarbons, e.g, residua-containing fuels or crude oils.
• hydrocarbon-containing compositions comprise a major proportion by weight of a residua-containing fuel, shale oil or a crude oil and a minor proportion by weight of a copolymer of ethylene and vinyl (or hydrocarbyl substituted vinyl) ester of a carboxylic acid, said copolymer having a number average molecular weight of above 3,000 and preferably above 3,500.
• the residua-containing fuel is defined as a fuel comprising residua from the distillation of crude oil or shale oil or mixtures thereof.
• the residua-containing fuel (hereinafter referred to simply as the fuel) will contain from about 35% to 100% by weight of residua, and will usually have kinematic viscosities ranging from 10 to 3,500 cs. at 100 F.
• the viscosity of some particularly waxy fuels may be difficult to measure accurately at 100 F., and it is well known in the art that the viscosity of such fuels is measured by the viscosity at a higher temperature. The viscosity at 100 F.
• R.E.F.U.T.A.S. viscosity temperature chart The extrapolated kinematic viscosity will then fall in the desired range at 100 F.
• the R.E.F.U.T.A.S temperature viscosity chart was designed by C. I. Kelly, M.S.C. Tech., F.I.C., M. Inst., P.T., A.M.I.A.E. Copyright reserved in Great Britain and U.S.A. by Paird & Tatlock (London) Ltd., 14-17 Cross Street, Hatton Garden, London, E.C.1. Fuels having kinematic viscosities of between 15 and 1500 cs. at 100 F. are preferred, and also fuels wherein at least 60% by weight of the fuel boils above 500 F. at atmospheric pressure are particularly suitable.
• the fuels to which this invention applies include therefore, light, medium, heavy and bunker or furnace fuels, the viscosities ranging from about 152000 cs. at 100 F., but usually, however, the maximum viscosity will be about 900 cs. at 100 F. Examples of suitable fuels are described in PB Industrial and Marine Fuels of BS2689: 1957.
• the preferred ethylene comonomers are vinyl (or bydrocarbyl, e.g. C to C hydrocarbyl, substituted vinyl) esters of C to C carboxylic acids.
• the carboxylic acid is preferably aliphatic, and saturated and preferably monocarboxylic.
• the particularly preferred ester is vinyl acetate.
• the resulting polymer should contain from to 40 weight percent, preferabl 90 to 60 weight percent, of ethylene.
• One method of preparing the copolymers involves feeding the monomers into a tubular reactor which has been previously purged with nitrogen. A small amount of oxygen, usually 0.005 to 0.05 wt. percent based on the weight of ethylene is also introduced into the reactor. Alternatively a peroxide initiator, e.g. di-t-butyl peroxide, or a mixture of peroxide initiator and oxygen may be introduced into the reactor in place of oxygen alone. A solvent (e.g. benzene, water, saturated hydrocarbons, methanol) may also be employed in the reaction.
• a solvent e.g. benzene, water, saturated hydrocarbons, methanol
• the pressure is maintained between 60 and 2700 atmospheres (900 and 40,000 p.s.i.g.), preferably between and 2000 atmospheres (2,000 and 30,000 p.s.i.g.).
• the temperature should be maintained between 40 C. and 300 C., preferably between 70 C. and 250 C.
• Another method of preparing the copolymers is via a batch process.
• a solvent for the reactants the solvent being for example toluene or hexane.
• the preferred solvent however is benzene.
• the reaction initiator may be any peroxy compound, preferably di-tbutyl peroxide.
• the temperature of the polymerisation reaction is dependent upon the particular peroxide initiator employed and should be high enough for suflicient decomposition of the initiator to occur. This temperature will usually be between 40 C. and 300 C.
• the most suitable temperature is between 130 C. and C.
• the pressure should be between 60 and 1000 atmospheres (900 and 15,000 p.s.i.g.), and preferably being between 75 and 470 atmospheres (1100 and 7000 p.s.i.g.).
• the autoclave or similar equipment containing the solvent, initiator and vinyl or hydrocarbyl substituted vinyl ester is purged with nitrogen and then with ethylene before charging with a sufficient amount of ethylene to yield the desired pressure when heated to the reaction tempertaure. During the polymerization addition ethylene is added to maintain the pressure at the desired level. Further amounts of initiator and/ or solvent, and/ or vinyl and hydrocarbyl substituted vinyl ester may also be added during the reaction. On completion of the reaction free solvent and unreacted monomers are removed by stripping or some other suitable process yielding the desired polymer.
• the copolymers useful in the invention preferably have a number average molecular weight from 3,000 to 60,000 as measured by Vapour Phase Osmometry (using a Mechrolab Vapour Phase Osmometer model 301A) and/or Membrane Osmometry (using a Mechrolab 1 Membrane Osmometer model 501).
• the number average Heehrolab Inc. 1062 Linda Vista Avenue, Mountain View, Calif.
• the copolymer can also be applied down oil wells to crude oil to inhibit the formation of paraffin deposits, or to dissolve existing deposits on the sides of the well casing.
• the copolymer can also be added to crude oils or residua above ground to facilitate their movement through pipe lines.
• the copolymer can be added to any North African crude, to lower the pour points so that they can be more readily pumped.
• copolymer concentrates in suitable hydrocarbon blend stocks.
• suitable solvents are those containing a high proportion of aromatic hydrocarbons, e.g. toluene, xylene, kerosene extract, this extract being the highly aromatic fraction separated from a crude kerosene by a liquid sulphur dioxide extraction process.
• suitable solvents are slack waxes, which are the waxes obtained without purification or refining from lubricating oil dewaxing processes. Such suitable slack waxes will usually have melting points between 20 C. and 62 C. and oil contents of to 50 wt. percent.
• a suitable composition of such copolymer/solvent blends is 5 to 50% by weight of copolymer, and 95 to 50% by weight of solvent.
• particularly suitable blends have been found to be a blend of to 30 e.g. by Weight of an ethylene/vinyl acetate copolymer and 90 to 70% e.g. 75% of a slack wax or a kerosene extract.
• These compositions can be readily blended into fuels to the required concentrations, e.g. up to 1% by weight, at temperatures of about 40 C. and above.
• copolymers may also be used in the fuels, crude oils, etc. in conjunction with other additives commonly used in fuels, e.g. rust-inhibitors, demulsifying agents, corrosion inhibitors, anti-oxidants or dispersants, or other flow improvers or pour depressants.
• additives commonly used in fuels, e.g. rust-inhibitors, demulsifying agents, corrosion inhibitors, anti-oxidants or dispersants, or other flow improvers or pour depressants.
• EXAMPLE 1 In this example, two copolymers were used, and added in different concentrations to two different fuels.
• Copolymer A was a random copolymer of ethylene (67 weight percent and vinyl acetate (33 weight percent) having a number average molecular weight of 13,000 as measured by Vapour Phase Osmometry using chloroform as solvent at 37 C.
• Copolymer B was a random copolymer of ethylene (82 weight percent) and vinyl acetate (18 weight percent) having a number average molecular weight of 12,000 as measured by Vapour Phase Osmometry using benzene as solvent at 37 C. Both A and B were separately blended with a slack wax so that the blends contained 25% by Weight of A and 25% by weight of B respectively. The slack wax had a melting point of 40 C. and contained 29 wt. percent of oil.
• the copolymer/slack wax blends were separately blended into two different residual-containing fuel oils C and D having the following characteristics.
• Fuel oil C contained 32% by weight of distillate fraction boiling between 350 and 680 F., and 68% by weight of residuum with a boiling point of 680+ F., and it had a kinematic viscosity of 43.2 cs. at 100 F.
• Fuel oil D had an initial boiling point Copolymer eoneen- Upper pour tration, Flow point, F. point, F.
• the polymers prepared in Examples 2 and 3 have the following properties:
• POLYMER PROPERTIES 1 Number average molecular Weight measured in toluene solution at 37 C. using a Mechrolab Vapour Phase Osmometer, Model 301A.
• composition according to claim 1 wherein said oil is crude oil and said ester is a vinyl ester.
• composition according to claim 2 wherein said molecular weight is in the range of 4,000 to 20,000.
• composition according to claim 3 wherein said ester is vinyl acetate.
• composition according to claim 1 wherein said oil is fuel oil having at least 60 wt. percent boiling above 500 F. at atmospheric pressure and having a viscosity between 15 and 3,500 cs. at F., and said ester is vinyl ester.
• composition according to claim 5 wherein said molecular weight is in the range of 4,000 to 20,000.

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

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Cited By (28)

Families Citing this family (5)

• 0
  • NL NL134313D patent/NL134313C/xx active
• 1966
  • 1966-06-01 GB GB24368/66A patent/GB1147904A/en not_active Expired
• 1967
  • 1967-05-08 US US636597A patent/US3567639A/en not_active Expired - Lifetime
  • 1967-05-29 DE DE19671645873 patent/DE1645873A1/de active Pending
  • 1967-05-30 NO NO168373A patent/NO118198B/no unknown
  • 1967-05-30 NL NL6707475A patent/NL6707475A/xx unknown
  • 1967-05-31 SE SE7649/67*A patent/SE320542B/xx unknown
  • 1967-05-31 ES ES341195A patent/ES341195A1/es not_active Expired
  • 1967-06-01 BE BE699350D patent/BE699350A/xx not_active IP Right Cessation

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