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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
  • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/12—Inorganic 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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
  • C10L10/16—Pour-point depressants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
  • C10L2200/0446—Diesel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
  • C10L2250/04—Additive or component is a polymer
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

• the invention relates to the use, in hydrocarbon distillates whose initial crystallization temperature of paraffins is greater than or equal to -5 ° C., of a developer of the effectiveness of conventional hydrocarbon filterability additives with respect to the filterability limit temperature of these distillates and their flow temperature at low temperatures.
• the invention also provides an additive composition comprising a conventional hydrocarbon filterability additive in combination with an efficiency developer as well as fuels, fuel and fuel comprising these additive combinations.
• TLF Filtration Limit
• the prior art describes the use of other products having a synergistic effect with the known filterability additives, in particular the ethylene and vinyl acetate and / or vinyl propionate polymers, vis-à-vis improvement of the filterability limit temperature and the low temperature flow temperature of conventional hydrocarbon distillates.
• the patent US 3 275427 discloses a distillate distillation distillate of between 177 and 400 ° C containing an additive consisting of 90 to 10% by weight of an ethylene copolymer comprising from 10 to 30% of vinyl acetate units of molecular weight between 1000 and and 3000 and from 10 to 90% by weight of a lauryl polyacrylate and / or lauryl polymethacrylate of molecular weight by weight ranging from 760 to 100,000. It is noted that these polyacrylates improve the filterability temperature determined according to the NF EN116 standard without damaging the pour point temperature determined by the NF 60105 standard while the ethylene-vinyl acetate copolymer improves the flow.
• a copolymer of ethylene and vinyl acetate comprising from 1 to 40, preferably from 14 to 24 vinyl acetate units of average molecular weight from 20,000 to 60,000, the molar ratio of olefinic ester polymer to copolymer of ethylene and vinyl acetate ranging from 0.1 to 10: 1.
• the distillates used are generally derived from more complex refining operations than those resulting from the direct distillation of hydrocarbons and can come from cracking, hydrocracking and catalytic cracking processes and visbreaking processes.
• the refiner tends to want to introduce cuts that are more difficult to use in these fuels, such as the heaviest cuts resulting from cracking and visbreaking processes which are loaded with heavy paraffins, ie that is, comprising more than 18 carbon atoms.
• the synthetic distillates resulting from the transformation of the gas such as those resulting from the Fischer Tropsch process, but also those resulting from the treatment of biomass of plant or animal origin, such as NexBTL and distillates comprising esters of vegetable or animal oils, have appeared on the market and constitute a new range of products that can be used as fuel and base bases.
• domestic fuel oil also comprising paraffinic chains close to or greater than 18 carbon atoms.
• this invention applies not only to distillates resulting from the direct distillation of hydrocarbons derived from crude oils which are heavily loaded with paraffins, but also and especially from hydrocarbons obtained from the heaviest cuts of refining operations, that is to say from cracking, hydrocracking and catalytic cracking processes and visbreaking processes or synthetic distillates resulting from gas transformation such as those derived from the Fischer Tropsch process, but also those resulting from the treatment of plant or animal biomass, such as in particular the NexBTL and distillates containing esters of vegetable and / or animal oils, alone or in admixture.
• One of the routes chosen by the applicant is that of improving the activity of conventional filterability additives with respect to the temperature limit of filterability of the middle distillates by the addition of another polymer as an agent to reveal the effectiveness of conventional filterability additives present in the middle distillate by producing a synergistic effect.
• the present invention provides the use in a hydrocarbon distillate of boiling point between 150 and 450 ° C and starting crystallization temperature measured by differential scanning calorimetry greater than or equal to -5 ° C preferably -5 ° C to + 10 ° C, a homopolymer obtained from an olefinic carboxylic acid ester of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of more than 16 carbon atoms and optionally a olefinic double bond, as a compound for revealing the effectiveness of filterability additives based on copolymer and / or terpolymer of ethylene and vinyl ester of a carboxylic acid of 3 to 5 carbon atoms and a monohydric alcohol comprising from 1 to 10 carbon atoms.
• the hydrocarbon distillate comprises a content by weight of n-paraffins containing more than 18 carbon atoms greater than 4%.
• the hydrocarbon distillate comprises a content by weight greater than or equal to 0.7% of n-paraffins whose carbon number is greater than 24, preferably a mixture of 0.7 to 2% by weight of n-paraffins. having a carbon number ranging from C24 to C40.
• the filterability additives are copolymers of ethylene containing more than 20% of ester units.
• the filterability additives are chosen from copolymers of ethylene and vinyl acetate, ethylene and vinyl propionate of ethylene and of vinyl, ethylene and (alkyl) acrylate versatate.
• ethylene- and (alkyl) methacrylates taken alone or as a mixture, comprising from 20 to 40% by weight of ester units.
• the said esters are of the vinyl acetate, vinyl propionate, vinyl versatate, (alkyl) acrylate and (alkyl) methacrylate type, the alkyl group containing from 1 to 7 carbon atoms.
• the homopolymer is obtained by polymerization of an olefinic ester of acrylic acid optionally substituted with an alkyl group having from 1 to 7 carbon atoms, and an alcohol comprising more than 16 carbon atoms, preferably from 18 to 50 carbon atoms, the homopolymer having a weight average molecular weight Mw of between 5,000 and 20,000, preferably between 10,000 and 19,000.
• the homopolymer is a polyacrylate comprising hydrocarbon side chains of 18 to 40 carbon atoms.
• the distillate is chosen from boiling point distillates of between 150 and 450 ° C., comprising straight-run distillation distillates, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or or the hydrocracking of vacuum distillates, the distillates resulting from conversion processes of the ARDS type (by atmospheric residue desulphurization) and / or visbreaking, the distillates from the recovery of Fischer Tropsch cuts, and the distillates resulting from the conversion BTL of plant and / or animal biomass, and distillates containing alkyl esters of vegetable or animal oils, alone or as a mixture.
• a and B being in a ratio producing a synergistic effect with respect to the TLF filterability temperature measured according to the NF EN116 standard, hydrocarbon distillates having a boiling point of between 150 and 450 ° C. and a measured starting crystallization temperature.
• Differential Calorimetric Analysis greater than or equal to -5 ° C preferably -5 to + 10 ° C.
• the invention relates to a composition
• a composition comprising (A) from 85 to 99% by weight of at least one filterability additive based on a copolymer and / or terpolymer of ethylene and a vinyl ester of a carboxylic acid of 3 to 5 carbon atoms and a monohydric alcohol having 1 to 10 carbon atoms; and (B) 1 to 15% by weight of a homopolymer of an olefinic carboxylic acid ester of 3 to 12 carbon atoms and a fatty alcohol comprising more than 16 carbon atoms.
• the homopolymer has a weight average molecular weight Mw of between 5,000 and 20,000, preferably between 10,000 and 19,000.
• the homopolymer is an olefinic ester of acrylic acid with an alcohol comprising from 18 to 50 carbon atoms.
• the homopolymer is a polyacrylate comprising side hydrocarbon chains of 18 to 40 carbon atoms.
• the filterability additive is chosen from ethylene copolymers and terpolymers containing more than 20% of ester units, these ester units being themselves chosen from acetate-type esters.
• vinyl, vinylpropionate, alkylacrylates and alkylmethacrylates taken alone or in a mixture, the alkyl group containing from 1 to 7 carbon atoms.
• the filterability additives are chosen from copolymers or terpolymers of ethylene and vinyl acetate, and / or vinyl propionate, and / or vinyl versatate, ethylene and / or (alkyl) acrylates, and / or (alkyl) methacrylates, alone or as a mixture, comprising from 20 to 40% by weight of ester units.
• the filterability additives are chosen from copolymers or terpolymers of ethylene and vinyl acetate, and / or vinyl propionate, and / or vinyl versatate, ethylene and / or (alkyl) acrylates, and / or (alkyl) methacrylates having a weight average molecular weight of from 3,000 to 20,000.
• the composition according to the invention comprises from 85 to 98% by weight of copolymers of ethylene and of vinyl acetate comprising from 25 to 30% by weight of vinyl acetate units and from 2 to 15% by weight. % by weight of polyacrylate comprising side hydrocarbon chains of 18 to 40 carbon atoms and average molecular weight ranging from 10,000 to 19,000.
• the invention relates to a hydrocarbon distillate comprising from 0 to 5000 ppm of sulfur, and containing from 10 to 5000 ppm of said composition according to the invention, optionally mixed with other detergent dispersant additives, demulsifiers, antifoams, biocides, deodorants, cetane improvers, anti-corrosions, friction modifiers, lubricant, combustion, cloud point, pour point, antisedimentation and conductivity improvers.
• the distillate comprises at least one hydrocarbon fraction derived from the group consisting of distillates with a boiling temperature of between 150 ° and 450 ° C. and an initial crystallization temperature Tcc greater than or equal to -5 ° C., preferably between 5 ° C and + 10 ° C, including straight-run distillates, vacuum distillates, hydrotreated distillates, distillates from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from conversion processes type ARDS and / or visbreaking, distillates from the recovery of Fischer Tropsch cuts, distillates resulting from the BTL conversion of plant and / or animal biomass, taken alone or in combination, and esters of vegetable and animal oils or their mixtures.
• Tcc initial crystallization temperature
• the distillate comprises an n-paraffin content containing more than 18 carbon atoms greater than 4% by weight.
• the distillate comprises a content greater than or equal to 0.7% by weight of n-paraffins whose carbon number is greater than 24.
• the distillate comprises from 0.7 to 2% of n-paraffins having a carbon number varying from C24 to C40.
• the invention relates to a diesel fuel comprising from 0 to 500 ppm of sulfur comprising at least one distillate according to the invention.
• the invention relates to a heating oil comprising 0 to 5000 ppm of sulfur comprising at least one distillate according to the invention.
• the invention relates to a heavy fuel oil comprising at least one distillate according to the invention.
• the invention applies to distillates that can be used as diesel fuel or heating fuel still referred to as domestic fuel oil. These distillates have a starting crystallization temperature or Tcc greater than or equal to -5 ° C, preferably between -5 ° C and + 10 ° C. This temperature Tcc is measured by ACD, this technique making it possible to determine the temperature at which the first paraffin crystals are formed, these generally corresponding to normal paraffins of chain length greater than or equal to 18 carbon atoms, the paraffins being over of 24 carbon atoms being the first to crystallize when the temperature decreases.
• the advantage of the present invention lies in the synergistic effect of the use of compounds according to the invention known as "developers" of the effectiveness of conventional filterability additives or TLF with respect to the reduction of the temperature of the filterability of these hydrocarbon distillates refractory to the action of conventional filterability additives used alone.
• the invention is particularly directed to the use of a homopolymer-type developer compound in a hydrocarbon distillate comprising a content by weight of n-paraffins containing more than 18 carbon atoms greater than 4%.
• the hydrocarbon distillate comprises a content by weight greater than or equal to 0.7% of n-paraffins whose carbon number is greater than 24.
• the distillate is a fraction of a boiling point between 150 and 450 ° C, and comprises a mixture of 0.7 to 2% by weight of n-paraffins having a carbon number ranging from C24 to C40.
• the filterability additives of the invention are copolymers or terpolymers of ethylene containing more than 20% of ester units. These esters are of the vinyl acetate, vinyl propionate, vinyl versatate, (alkyl) acrylate and (alkyl) methacrylate type, the alkyl group containing from 1 to 7 carbon atoms.
• the preferred filterability additives are selected from copolymers of ethylene and vinyl acetate, and / or vinyl propionate, and / or vinyl versatate, and / or (alkyl) acrylates, and / or (alkyl) methacrylates, alone or in admixture, comprising from 20 to 40% by weight of ester units.
• the filterability additives used in the invention are copolymers or terpolymers of between 5,000 and 20,000. These copolymers or terpolymers have ester levels of between 20% and 40%.
• the additives revealing the effectiveness of the filterability additives according to the invention are homopolymers obtained by polymerization of an olefinic ester of acrylic acid optionally substituted with an alkyl group having from 1 to 7 carbon atoms, and an alcohol comprising more than 16 carbon atoms, preferably from 18 to 50 carbon atoms.
• the homopolymer has a weight average molecular weight M w of between 5,000 and 20,000 and preferably between 10,000 and 19,000.
• the homopolymer is a polyacrylate comprising side hydrocarbon chains of 18 to 40 carbon atoms.
• the effectiveness of the developer varies with its weight-average molecular weight, the chain length of the alcohol, and the nature of the carboxylic acid used to synthesize the ester.
• the homopolymers according to the invention for revealing the effectiveness of conventional TLF filterability additives are selected from a set of polyacrylates useful for improving the pour point of easy-to-treat distillates. However, not all are effective at revealing a synergistic effect with conventional TLF additives.
• the distillates targeted by the invention are chosen from distillates having a boiling point of between 150 and 450 ° C. and starting crystallization temperature Tcc of greater than or equal to -5 ° C., preferably of between -5 ° C. and + 10 ° C, including straight-run distillates, vacuum distillates, hydrotreated distillates, distillates from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS and / or visbreaking, distillates derived from the recovery of Fischer Tropsch slices, and distillates resulting from the BTL conversion of plant and / or animal biomass, and distillates containing alkyl esters of vegetable or animal oils and / or their mixture.
• Another subject of the invention is a synergistic composition of additives dedicated to distillates with a boiling point of between 150 ° C. and 450 ° C., with an initial crystallization temperature close to zero, in particular between -5 and + 10 ° C. vs.
• This synergistic composition comprises a mixture consisting of a filterability additive and a homopolymer according to the invention in a ratio producing a synergistic effect with respect to the TLF filterability temperature of the distillates according to the invention, TLF measured according to the standard NF EN116.
• this composition comprises from 85 to 99% by weight of at least one filterability additive based on ethylene copolymer or terpolymer and a vinyl ester of a carboxylic acid of 3 to 5 carbon atoms and a monohydric alcohol having 1 to 10 carbon atoms, and 1 to 15% by weight of a homopolymer of an olefinic ester of carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol comprising more than 16 carbon atoms.
• the homopolymer has a weight average molecular weight Mw of between 5,000 and 20,000, preferably between 10,000 and 19,000. It is an olefinic ester of acrylic acid with an alcohol comprising from 18 to 50 carbon atoms.
• the homopolymer is a polyacrylate comprising side hydrocarbon chains of 18 to 40 carbon atoms.
• the filterability additives adapted to the said composition according to the invention are chosen from ethylene copolymers and terpolymers containing more than 20% of ester units, these ester units being themselves chosen from vinyl acetate type propionate esters.
• vinyl, (alkyl) acrylates and (alkyl) methacrylates the alkyl group containing from 1 to 7 carbon atoms.
• these filterability additives are chosen from copolymers or terpolymers of ethylene of vinyl acetate, and / or of vinyl propionate, and / or of vinyl, ethylene and / or (alkyl) versatate.
• acrylates, and / or (alkyl) methacrylates comprising from 20 to 40% by weight of ester units.
• These polymers or terpolymers have a weight-average molecular weight of between 3,000 and 20,000.
• the composition will comprise from 85% to 98% by weight of copolymers of ethylene and vinyl acetate comprising from 25 to 30% by weight vinyl acetate units, and from 2 to 15% by weight. % by weight of polyacrylate comprising side hydrocarbon chains of 18 to 40 carbon atoms and average molecular weight ranging from 10,000 to 19,000.
• Another subject of the invention concerns the hydrocarbon distillate whose sulfur content is between 0 and 5000 ppm and which comprises from 10 to 5000 ppm of said composition, optionally mixed with other detergent, dispersant and demulsifier additives, biocides, antifoams, resorbers, cetane improvers, anti-corrosions, friction modifiers, lubricity, combustion, cloud point, pour point, antisedimentation and conductivity improvers.
• This distillate according to the invention comprises a major portion of at least one hydrocarbon fraction having a starting crystallization temperature Tcc of greater than or equal to -5 ° C., preferably of between -5 ° C. and + 10 ° C., resulting from the group. consisting of boiling point distillates of between 150 ° C and 450 ° C including straight-run distillates, vacuum distillates, hydrotreated distillates, distillates from catalytic cracking and / or distillate hydrocracking under empty, distillates resulting from conversion processes ARDS and / or visbreaking type, distillates derived from the recovery of Fischer Tropsch slices, distillates resulting from the BTL conversion of plant and / or animal biomass, taken alone or in combination, and esters of vegetable and animal oils or their mixtures.
• These distillates comprise an n-paraffin content containing more than 18 carbon atoms greater than 4% by weight, and preferably a content greater than or equal to 0.7% by weight of n-paraffins whose carbon number is greater than 24%.
• the distillates which are particularly reactive with the said composition comprise in their chemical composition from 0.7 to 2% of n-paraffins having a carbon number varying from 24 to 40, the n-paraffin distribution being continuous or discontinuous; that is, all n-paraffin families are present or some are absent, thus constituting discontinuities, especially when distillate mixtures are made.
• the invention also relates to a fuel, a fuel comprising from 0 to 500 ppm of sulfur and / or a heating oil comprising from 0 to 5000 ppm of sulfur or a heavy fuel oil used as fuel in marine engines and industrial boilers, these products containing a major portion of hydrocarbon base consisting of at least one distillate according to the invention and a corresponding minor portion of 50 to 5000 ppm of a synergistic composition of additives using a developer compound according to the invention.
• This additive composition may be present in the fuel or fuel with at least one additive of the group consisting of detergent additives, dispersants, demulsifiers, biocides, antifoams, deodorants, cetane improvers, anticorrosions, friction modifiers, lubricant, combustion, cloud point, pour point, antisedimentation and conductivity improvers.
• detergent additives dispersants, demulsifiers, biocides, antifoams, deodorants, cetane improvers, anticorrosions, friction modifiers, lubricant, combustion, cloud point, pour point, antisedimentation and conductivity improvers.
• This example describes the nature of the components of the invention and comparative compounds.
• TLF filterability temperature
• PT cloud point temperature measured by ASTM D2500 or EN 23015.
• Tcc starting crystallization temperature measured by Differential Scanning Calorimetry (DSC or DSC) or according to IP389-93
• the TEP or pour point measured for distillates used as fuels is the lowest temperature at which the hydrocarbon can still flow.
• PT or cloud point is a visual appreciation of sprouting and crystallization of paraffins, this measurement is less accurate than that of the starting crystallization temperature Tcc.
• TLF the filterability limit temperature of paraffin crystals precipitating in hydrocarbons at low temperature
• TLF, PTE and Tcc are not necessarily related to each other and are most often dependent on the chemical composition of the products.
• Examples of the F1, F2 and F3 distillates according to the invention have an n-paraffin content greater than or equal to 0.7% and a Tcc of -5 ° C., whereas the distillates G1, G2 have a n paraffins less than 0.7% and Tcc ⁇ -5 ° C.
• the distribution of paraffins is determined by liquid / gas chromatography. This method makes it possible to determine the n-paraffin concentration of C9 to C30 in the middle distillates.
• liquid chromatography makes it possible to separate the middle distillate according to the chemical families (saturated, mono, di and aromatic tri).
• saturated, mono, di and aromatic tri saturated, mono, di and aromatic tri.
• the n-paraffins being in the saturated fraction, the latter is recovered and injected onto a column in gas chromatography where the paraffins are separated according to their boiling point and therefore their carbon number.
• paraffins are quantified by calibration.
• the filterability additives used are copolymers of ethylene and vinyl acetate, hereinafter referred to as EVAi in Table II below. ⁇ u> TABLE II ⁇ / u> Viscosity at 100 ° C (Pa.S-1) Vinyl acetate level (% by weight) Molecular weight Mw EVA 1 0.3 28 9500 EVA 2 0.4 31 15000 EVA 3 0.4 36 18000 EVA 4 0.3 24 10000
• the developers used are bi-labeled polyacrylates whose characteristics are given at 30% of active ingredients in a solvarex-type aromatic solvent (aromatic hydrocarbon fraction of 8 to 20 carbons and boiling point ranging from 140 to 320 ° C.) in Table III below.
• a solvarex-type aromatic solvent aromatic hydrocarbon fraction of 8 to 20 carbons and boiling point ranging from 140 to 320 ° C.
• these polyacrylates are obtained by polymerization under an inert nitrogen atmosphere of the monomer as follows.
• the present example aims to demonstrate the interest of the developers Bi according to the invention and their influence on the effectiveness of TLF additives on the distillates Fi of the invention and the distillates Gi.
• distillates Fi of Tcc greater than -5 ° C are little or not reactive to EVAi alone but are reactive to synergistic mixtures EVAi / Bi while distillates out of the invention Gi whose Tcc is less than -5 ° C are only reactive to EVA alone.
• the present example describes the influence of the relative concentration of Bi developers and TLF EVAi additives on the reduction of TLF temperatures of the typical F 2 distillates.
• Table V collates the filterability temperatures of F1 and F2 distillates when the concentration of Bi developer is varied for varying concentrations of EVAi / Bi composition.
• ⁇ u> TABLE V ⁇ / u> F 0 ppm 100 ppm 200 ppm F1 EVA1 1 -7 -11 F1 EVA1 / B1: 97.8 / 2.2 1 -13 -11 F1 EVA1 / B1: 95.5 / 4.5 1 -11 -10 F1 EVA1 / B1: 90/10 1 -11 -11 G1 EVA1 -4 -15 -17 G1 EVA1 / B1: 96/4 -4 -15 -17 G1 EVA1 / B1: 92/8 -4 -12 -14 G1 EVA1 / B1: 82/18 -4 -8 -11
• the present example describes the preferred polymers of the invention selected from olefinic ester polymers of carboxylic acids and alcohol.
• the content of homopolymers of olefinic ester of carboxylic acids and alcohol is 4.5% for an EVA content of 95.5%.
• the content of the composition in the distillates ranges from 0 to 300 ppm in the present example.
• the effectiveness of the developer compound varies depending on the chain length of the alcohol and the nature of the carboxylic acid used to synthesize the polyester.
• carboxylic acid is also an important parameter, the above-described assays performed substituting B1 with homopolymers of C12 methacrylic acid esters; C16 or C18-C24 show that they are not as effective than their counterparts obtained by homopolymerization of acrylic acid esters.

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