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
  • C10L1/146—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
  • 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
  • C10L1/197—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
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
• • 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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • 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
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0461—Fractions defined by their origin
  • C10L2200/0469—Renewables or materials of biological origin
  • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel

Definitions

• Additive composition comprising at least one copolymer, a cold-thinning additive and an anti-sedimentation additive
• the present invention relates to a composition of particular additives and its use for improving the cold-keeping properties of fuels and combustibles during their storage and / or their use at low temperature.
• the present invention also relates to fuel compositions and fuel containing such an additive composition.
• Fuels or combustibles containing paraffinic compounds in particular compounds containing n-alkyl, iso-alkyl or n-alkenyl groups such as paraffinic waxes, are known to exhibit deteriorated flow properties at low temperature, typically below 0 ° C.
• the middle distillates obtained by distillation from crude oils of petroleum origin such as diesel or heating oil, contain different amounts of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperatures, clogging hoses, pipes, pumps and filters, for example in the fuel circuits of motor vehicles.
• cold flow improvers in English “cold flow improvers” or CFI
• CFI cold thinning additives
• TLF Filterability Limit Temperature
• PE pour point
• TLF additives polymers of ethylene and vinyl acetate and / or vinyl propionate
• an additive consisting of 90 to 10% by mass of an ethylene copolymer comprising from 10 to 30% of vinyl acetate units with a molecular weight by weight of between 1000 and 3000 g.mol and from 10 to 90% by weight of a lauryl polyacrylate and / or of a polymethyl lauryl methacrylate of varying weight by weight from 760 to 100,000 g.mol- l.
• Document EP0857776 proposes using alkylphenol-aldehyde resins resulting from the condensation of alkylphenol and aldehyde in combination with ethylene / vinyl ester copolymers or terpolymers, to improve the fluidity of mineral oils.
• Patent application WO 2008/006965 describes the use of a combination of a homopolymer obtained from an olefinic ester of carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of 16 carbon atoms and possibly an olefinic double bond and of a cold fluidizing additive (CFI) of EVA or EVP type, to increase the effectiveness of CFI additives by amplifying their effect on TLF.
• CFI cold fluidizing additive
• Patent application WO 2016/128379 describes the use, as a cold-keeping additive of a fuel or combustible, of a block copolymer comprising:
• a block A consisting of a chain of structural units derived from one or more ⁇ , b-unsaturated acrylate or alkyl methacrylate monomers
• a block B consisting of a chain of structural units derived from one or more a, b-unsaturated monomers containing at least one aromatic nucleus.
• This additive is particularly useful as a TLF booster in combination with a cold thinning additive (CFI).
• CFI cold thinning additive
• Another object of the cold-keeping additives is to ensure the dispersion of the paraffin crystals, so as to delay or prevent the sedimentation of such crystals and of avoid training a layer rich in paraffins at the bottom of containers, tanks or storage tanks; these paraffin dispersant additives are called anti-sedimentation additives or WASA (acronym of the English term "Wax Anti-Settling Additive").
• WASA anti-sedimentation additives
• Modified alkylphenol-aldehyde resins have been described in document FR2969620 as an anti-sedimentation additive in combination with a TLF additive.
• This need is particularly important for fuels or fuels comprising one or more paraffinic compounds, for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
• paraffinic compounds for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
• distillates used in fuels and fuels are increasingly produced from more complex refining operations than those resulting from direct petroleum distillation, and can originate in particular from cracking, hydrocracking, catalytic cracking and visbreaking processes.
• the refiner tends to introduce into these fuels cuts that are more difficult to use, such as the heavier cuts resulting from cracking and visbreaking processes which are rich in long chain paraffins.
• the present invention applies to fuels and combustibles containing not only conventional distillates such as those resulting from the direct distillation of crude oils, but also to bases obtained from other sources, such as those described above.
• the object of the present invention is to propose a new composition of additives which can advantageously be used to improve the cold-keeping properties, in particular the cold-flow properties of these fuels or combustibles, during their storage. and / or their use at low temperature, typically below 0 ° C.
• the aim of the present invention is further to propose a new composition of additives for fuels and combustibles, and concentrates containing such a composition, acting on the Filterability Limit Temperature (TLF), the pour point (PE), and delaying and / or preventing the sedimentation of crystals of hydrocarbon compounds, in particular paraffins.
• TEZ Filterability Limit Temperature
• PE pour point
• Another object of the invention is to provide a fuel or fuel composition having improved cold-holding properties, in particular at temperatures below 0 ° C, preferably below -5 ° C.
• composition of additives comprising:
• Ri represents a hydrogen atom or a methyl group
• X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
• R2 represents a C1 to C24 alkyl group
• R represents a C 2 to C 34 group, comprising at least one nitrogen heterocycle
• At least one cold-thinning additive chosen from copolymers of ethylene and of unsaturated ester (s);
• the invention also relates to the use of the composition of additives according to the invention for improving the cold-keeping properties of a fuel or fuel composition.
• the invention also relates to a concentrate of additives containing such a composition, as well as a fuel or fuel composition.
• CN compound or group denotes a compound or group containing in its chemical structure N carbon atoms.
• composition of additives is a composition of additives:
• the invention uses an additive composition comprising at least one copolymer comprising at least one unit of formula (I) below:
• Ri represents a hydrogen atom or a methyl group
• X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
• R2 represents a C 1 to C 24 alkyl group.
• X -O-CO-, it being understood that X is then linked to the vinyl carbon by the oxygen atom;
• X -CO-O-, it being understood that X is then linked to the vinyl carbon by the carbon atom;
• X -CO-NH-, it being understood that X is then linked to the vinyl carbon by the carbon atom.
• the group X of formula (I) is preferably the group -O- CO-.
• the group X of formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group X is linked to the vinyl carbon by the carbon atom.
• the group X of formula (I) is preferably the group -CO-O-.
• the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom.
• the group R 2 of formula (I) is a C 1 to C 24 alkyl radical.
• This alkyl radical can be linear or branched, cyclic or acyclic.
• This alkyl radical can comprise a linear or branched part and a cyclic part.
• the group R2 of formula (I) is an acyclic linear or branched C8-C24, preferably C10-C22, more preferably C12-C22, alkyl radical.
• the group R2 of formula (I) is a linear or branched C12-C14 acyclic alkyl radical.
• the group R2 of formula (I) is a linear or branched C18-C22 acyclic alkyl radical.
• R2 groups of alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl, isododecyl. , lauryl, stearyl, octadecyl, behenyl, C 14 alkyl groups.
• the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched C8-C24 acyclic alkyl radical, preferably in C10-C22, more preferably in C12-C22.
• the units according to this embodiment correspond to those derived from monomers chosen from acrylates and alkyl methacrylates of C8-C24, preferably of C10-C22, more preferably of C12-C22.
• the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched C12-C14 acyclic alkyl radical.
• the patterns according to this embodiment correspond to those from monomers chosen from acrylates and C12-C14 alkyl methacrylates.
• the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is an alkyl radical linear acyclic or branched C 1 8 - C 22.
• the units according to this embodiment correspond to those derived from monomers chosen from acrylates and C 1 8 -C 22 alkyl methacrylates.
• the copolymer used in the present invention also comprises at least one unit of formula (II) below:
• R represents a group from C 2 to C 34, preferably from C 2 to C 1 2, more preferably from C 2 to Ce, and comprising at least one nitrogen heterocycle.
• nitrogen heterocycle denotes, in a manner known per se, a cyclic group comprising carbon atoms and at least one nitrogen atom in the ring.
• the group R can be saturated or unsaturated, monocyclic or polycyclic, it being possible for the ring or rings to be substituted or unsubstituted.
• the substituent (s) optionally present on the cycle (s) may be saturated or unsaturated, and may in particular be chosen from hydrocarbon, oxygenated, nitrogenous, halogenated substituents, etc.
• the nitrogen heterocycle (s) are chosen from rings formed from 5 to 7 atoms among which 1, 2, 3 or 4 atoms are nitrogen atoms, these cycles being saturated or unsaturated, substituted or unsubstituted.
• nitrogen heterocycles the following cycles may be cited: pyrrolidine, pyrroline, pyrrole, pyrazolidine, imidazolidine, pyrazoline, imidazoline, pyrazole, imidazole, triazole, tetrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, pyrazine, triazine.
• the nitrogen hetero ring (s) may also contain, in addition to carbon and nitrogen atoms, one or more other heteroatoms such as in particular one or more oxygen atoms, which can be part of the cycle or be attached to it.
• one or more other heteroatoms such as in particular one or more oxygen atoms, which can be part of the cycle or be attached to it.
• the group R contains at least one nitrogen heterocycle having from one to three nitrogen atoms, more preferably two nitrogen atoms.
• Preferred R groups are in particular chosen from the following rings: a substituted or unsubstituted imidazole ring, a substituted or unsubstituted triazole ring, a substituted or unsubstituted pyrrolidone ring.
• the group R is a substituted or unsubstituted imidazole ring.
• the units of formula (II) come from one or more vinyl monomers carrying an R group as described above.
• Examples of preferred monomers that may be mentioned include:
• the copolymer used in the present invention may or may not be crosslinked. Preferably, it is not crosslinked.
• the copolymer according to the invention advantageously contains from 50 to 99 mol% of units of formula (I), preferably from 60 to 95 mol%, more preferably from 70 to 90 mol%, and better still from 75 to 85 % in moles.
• the copolymer according to the invention advantageously contains from 1 to 50 mol% of units of formula (II), preferably from 5 to 40 mol%, more preferably from 10 to 30 mol%, and better still from 15 to 25 % in moles.
• the copolymer used in the present invention contains only units of formula (I) and units of formula (II).
• the copolymer used in the present invention is advantageously a random copolymer or a block copolymer. According to a particularly preferred embodiment, it is a random copolymer.
• the copolymer used in the present invention can be obtained by copolymerization of:
• Ri, X and R 2 are as defined above, the preferred variants of Ri, X and R 2 according to formula (I) described above also being preferred variants of formula (IA), and
• the monomer of formula (IA) is preferably chosen from Cs to C 24 , preferably Cio to C 24 , more preferably C 2 to C 22 vinyl alkyl esters.
• the monomer of formula (IA) is chosen from C 1 to C 4 alkyl vinyl esters.
• the monomer of formula (IA) is chosen from C 1 to C 22 alkyl vinyl esters.
• the alkyl radical of the vinyl alkyl ester is linear or branched, cyclic or acyclic, preferably acyclic.
• vinyl ester alkyl monomers that may be mentioned, for example, vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl 2-ethylhexanoate.
• the monomer of formula (IA) is typically chosen from Cs to C 24, preferably Cio to C 24, more preferably C 12 to C 22 alkyl acrylates and methacrylates. According to a particular embodiment, the monomer of formula (IA) is chosen from acrylates and C 1 2 to C 1 4 alkyl methacrylates. According to another particular embodiment, the monomer of formula (IA) is chosen from acrylates and C 1 to C 22 alkyl methacrylates.
• alkyl (meth) acrylates which can be used as monomers in the manufacture of the copolymer used in the invention, mention may be made of C Ce to C 24 alkyl acrylates and of C à to C alkyl methacrylates 24, and in particular, by way of nonlimiting examples: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate , n-dodecyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, stearyl acrylate, octadecyl acrylate,
• the monomers of formula (IIA) are vinyl monomers carrying an R group as described above.
• the group R contains at least one unsaturated nitrogen heterocycle having from one to three nitrogen atoms, more preferably two atoms nitrogen, such as in particular an imidazole ring, substituted or unsubstituted.
• the copolymer used in the invention were obtained from monomers different from those of formula (IA) and (IIA) above, insofar as the final copolymer corresponds to a polymer comprising units of formula (I) and units of formula (II) as defined above.
• the polymer were obtained by polymerization of different monomers, followed by post-functionalization.
• the units of formula (I) can be obtained from acrylic acid, by transesterification reaction.
• the copolymer used in the invention can be prepared by any known method of polymerization.
• the various techniques and conditions of polymerization and crosslinking are widely described in the literature and fall within the general knowledge of a person skilled in the art.
• a polymerization is advantageously chosen from controlled radical polymerization; for example, by atomic transfer radical polymerization (ATRP in English “Atom Transfer Radical Polymerization”); radical polymerization with nitroxide (NMP in English “Nitroxide-mediated polymerization”); degenerative transfer processes (in English “degenerative transfer processes”) such as degenerative iodine transfer polymerization (in English “ITRP- iodine transfer radical polymerization ”) or radical polymerization by reversible chain transfer by addition-fragmentation (RAFT in English“ Reversible Addition-Fragmentation Chain Transfer ”); polymerizations derived from ATRP such as polymerizations using initiators for continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ”).
• ATRP atomic transfer radical polymerization
• NMP radical polymerization with nitroxide
• degenerative transfer processes in English “de
• the copolymer used in the invention advantageously has a weight-average molar mass (M w ) of between 1,000 and 50,000 g. mol 1 , more preferably between 1,000 and 20,000 g. mol 1 , even more preferably between 3,000 and 15,000 g. mol 1 .
• the copolymer according to the invention advantageously has a number-average molar mass (Mn) of between 1,000 and 50,000 g. mol 1 , more preferably between 1,000 and 20,000 g. mol 1 , even more preferably between 2,000 and 10,000 g. mol 1 .
• Mn number-average molar mass
• the number and weight average molar masses are measured by size exclusion chromatography (SEC).
• composition of additives according to the invention may advantageously comprise from 0.1 to 30% by weight of copolymer as described above, preferably from 1 to 20% by weight, more preferably from 2 to 10% by weight, per relative to the total weight of the additive composition.
• the additive composition according to the invention also comprises at least one cold-thinning additive (CEI) chosen from copolymers of ethylene and of unsaturated ester (s).
• CEI cold-thinning additive
• the cold-thinning additive is chosen from copolymers of ethylene and of vinyl ester (s) and / or acrylic (s), such as ethylene / vinyl acetate (EVA), ethylene copolymers. / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in documents US3048479, US3627838, US3790359, US3961961 and EP261957 . We may also cite terpolymers of ethylene, vinyl acetate and another vinyl ester, for example vinyl neodecanoate.
• EVA ethylene / vinyl acetate
• EVE ethylene / vinyl ethanoate
• EMMA ethylene / methyl methacrylate
• alkyl fumarate described, for example, in documents US3048479, US3627838, US3790359, US3961961 and EP261957
• the cold fluidizing additive is chosen from copolymers of ethylene and vinyl ester (s), preferably from ethylene / vinyl acetate (EVA) copolymers, ethylene vinyl propionate copolymers (TEUs) and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably still, ethylene / vinyl acetate copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
• EVA ethylene / vinyl acetate
• TOUs ethylene vinyl propionate copolymers
• terpolymers of ethylene, vinyl acetate and another vinyl ester more preferably still, ethylene / vinyl acetate copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
• composition of additives according to the invention may advantageously comprise from 50 to 90% by weight of cold-thinning additive (CFI) as described above, preferably from 60 to 90% by weight, more preferably from 70 to 90% by weight relative to the total weight of the additive composition.
• CFI cold-thinning additive
• the additive composition according to the invention also comprises at least one paraffin dispersant and / or dispersant additive.
• (WASA) can be in particular, but not limited to, chosen from the group consisting of acid copolymers
• (meth) acrylic / (meth) acrylate amidified by a polyamine the condensation products of one or more carboxylic acids with one or more polyamines, alkenyl succinimides of polyamine, phthalamic acid and fatty amine derivatives double chain; optionally grafted alkylphenol resins, modified alkylphenol-aldehyde resins.
• additives are given in the following documents: EP261959, EP59333 1, EP674689, EP327423, EP5 12889, EP832172; US2005 / 022363 1;
• the particularly preferred anti-sedimentation and / or paraffin dispersant (WASA) additive is chosen from resins alkylphenol and alkylphenol resins grafted, for example, by functional groups such as polyamines.
• the additive composition according to the invention may advantageously comprise from 1 to 50% by weight of anti-sedimentation additive and / or paraffin dispersant as described above, preferably from 2 to 30% by weight, more preferably from 5 to 20% by weight relative to the total weight of the additive composition.
• the additive composition according to the invention may also comprise one or more other additives commonly used in fuels or combustibles, different from the copolymer, the cold-keeping additive, and the anti-sedimentation additive described above.
• the additive composition can typically include one or more other additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
• additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
• procetane additives in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably tert-butyl peroxide;
• anti-foam additives in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590;
• detergent and / or anti-corrosion additives in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenyl succinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, ammonium salts quaternary and triazole derivatives; examples of such additives are given in the following documents: EP0938535,
• the present invention also relates to the use, to improve the cold-keeping properties of a fuel or fuel composition, of the composition of additives according to the invention.
• Said fuel or fuel composition can be a composition chosen from gas oils, biodiesel, gas oils of type B x containing x% (v / v) of vegetable or animal oil esters or fatty acids, oils hydrogenated vegetables, and fuel oils such as domestic fuel oils, x being a number strictly greater than 0 and less than or equal to 100.
• the fuel or fuel composition is as described below and advantageously comprises at least one section of hydrocarbons obtained from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal sources , vegetable and synthetic.
• said additive composition is used to improve the low temperature flow properties of the fuel or fuel during its storage and / or use. at low temperature, by lowering its filterability limit temperature (or TLF, measured according to standard NF EN 1 16) and / or its pour point (or PE, measured according to standard ASTM D 7346) and / or by delaying or by preventing the sedimentation of crystals, and preferably by lowering its limit filterability temperature (TLF, measured according to standard NF EN 1 16).
• TLF filterability limit temperature
• PE pour point
• the additive composition according to the invention can be used to delay or prevent the sedimentation of paraffin crystals and more particularly of n-alkanes, preferably, the n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms.
• the present invention also relates to a concentrate of additives comprising the composition of additives according to the invention, in admixture with an organic liquid.
• the organic liquid is advantageously inert with respect to the constituents of the additive composition, and miscible with fuels or combustibles, in particular those originating from one or more sources chosen from the group consisting of mineral sources, preferably the petroleum, animal, vegetable and synthetic.
• the organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "Solvesso 150", alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
• the invention also relates to a fuel or fuel composition, comprising: (1) at least one cut of hydrocarbons from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and
• the mineral sources are preferably petroleum.
• the fuel or fuel composition according to the invention advantageously comprises the copolymer (s) in a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition.
• the content of copolymer (s) ranges from 0.0001 to 0.01% by weight, more preferably from 0.0002 to 0.005% by weight relative to the total weight of the fuel or fuel composition.
• the fuel or fuel composition according to the invention advantageously comprises the additive or additives cold thinning in a content ranging from 0.0005 to 0.2% by weight, preferably from 0.001 to 0.1% by weight, more preferably from 0.0015 to 0.05% by weight relative to the total weight of the fuel or fuel composition.
• the fuel or fuel composition according to the invention advantageously comprises the anti-sedimentation additive or additives and / or paraffin dispersant (s) in a content ranging from 0.0001 to 0.1% by weight, preferably from 0 .0005 to 0.05% by weight, more preferably from 0.001 to 0.02% by weight, relative to the total weight of the fuel or fuel composition.
• the fuels or fuels can be chosen from liquid hydrocarbon fuels or fuels, alone or as a mixture.
• Fuels or liquid hydrocarbon fuels include in particular distillais with a boiling temperature of between 100 and 500 ° C.
• These distillates can, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates resulting from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion processes (by residue desulfurization atmospheric) and / or visbreaking, the distillates resulting from the valorization of Fischer Tropsch cuts, the distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination, and / or biodiesels of animal and / or vegetable origin and / or oils and / or esters of vegetable and / or animal oils.
• the sulfur content of the fuels or fuels is preferably less than 5000 ppm, more preferably less than 500 ppm, and more preferably still less than 50 ppm, or even even less than 10 ppm, and advantageously without sulfur.
• the fuel or fuel is preferably chosen from gas oils, biodiesel, Bx type gas oils and fuel oils, preferably domestic fuel oils (FOD).
• FOD domestic fuel oils
• type B x diesel for diesel engine is meant a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a process chemical called transesterification reacting this oil with an alcohol in order to obtain fatty acid esters (EAG). With methanol and ethanol, methyl esters of fatty acids (EMAG) and ethyl esters of fatty acids (EEAG) are obtained respectively.
• EMAG methyl esters of fatty acids
• EEAG ethyl esters of fatty acids
• the letter "B” followed by a number indicates the percentage of EAG contained in diesel, x being a number strictly greater than 0 and less than or equal to 100.
• a B 99 contains 99% EAG and 1% distillates means of fossil origin, B 20, 20% EAG and 80% of middle distillates of fossil origin etc ...
• diesel fuels of type Bo which do not contain oxygenated compounds
• diesel fuels of type Bx which contain x% (v / v) of vegetable or animal oil esters or fatty acids, most often methyl esters (EMHV or EMAG).
• EAG methyl esters
• the fuel or combustible can also contain hydrogenated vegetable oils, known to the skilled person under the designation HVO (from the English “hydrogenated vegetable oil”) or HDRD (from the English “hydrogenation-derived renewable diesel”).
• HVO from the English “hydrogenated vegetable oil”
• HDRD from the English “hydrogenation-derived renewable diesel”.
• the fuel or fuel is chosen from gas oils, biodiesel and gas oils of type B x , hydrogenated vegetable oils (HVO), and their mixtures.
• the fuel or combustible composition can also contain one or more additional additives, different from the copolymers, of the cold-thinning additive and of the anti-sedimentation additive described above.
• additional additives can in particular be chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or additives oiliness, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
• Additional additives can generally be present in an amount ranging from 0.005 to 0.1% by weight, relative to the weight of the fuel or fuel composition (each).
• the subject of the invention is also a method of improving the cold-keeping properties of a fuel or fuel composition consisting in adding a composition of additives as described above.
• the various polymers were synthesized by radical polymerization in solution.
• the monomers were dissolved in a solvent chosen from toluene or dioxane, and the transfer agent was added to the mixture.
• the system was degassed under nitrogen flow for 40 minutes and then allowed to heat until reaching 70 ° C. Once at this temperature, the initiator was added to start the polymerization. The reaction was left for 6 h. The system was then opened to air and allowed to cool until it reached room temperature. The polymer formed was recovered by drying under vacuum.
• the recovered polymer was characterized by NMR spectroscopy and gas chromatography (GPC) in order to determine the composition and the molar mass of the copolymer, respectively.
• composition G 1 and G 2 were prepared.
• composition G l includes:
• the G2 composition includes:
• composition G l comprises a comparative additive composition.
• the composition G l is therefore a comparative composition.
• Composition G2 comprises an additive composition according to the invention.
• the composition G2 is therefore a composition according to the invention.
• Two levels of MDFI A additive are tested at 100 and 150 ppm.
• composition G2 170 ppm of WASA 2 additive was added. Two levels of additive MDFI A are tested at 100 and 150 ppm.
• the figure shows the TLF results obtained by adding each of the additives defined above, as a function of the additive rate MDFI A, the additive rate WASA 1, WASA 2 respectively, being constant (170 ppm).
• Curve A corresponds to the results concerning the comparative composition G l.
• Curve B corresponds to the results concerning the composition G2 according to the invention.
• the TLF target to be reached is set at -28 ° C, as shown in the single figure (dotted lines).
• the figure thus shows that the composition of additives according to the invention makes it possible to reach the TLF target of -28 ° C. with an MDFI A additive content of only 100 ppm.
• This same TLF of -28 ° C. is reached with the composition of comparative additives with a higher rate of 50%, i.e. 150 ppm.
• the use of the additive composition according to the invention makes it possible to reduce the treatment rate by 33%, compared with the comparative composition. Furthermore, at an identical treatment rate, the composition of additives according to the invention makes it possible to obtain better cold performance.
• Example 3 Evaluation of the performance of cold resistance
• composition G ’of diesel fuel type which is particularly difficult to process, and the characteristics of which are detailed in Table IV below:
• compositions G’l, G’2 and G’3 were prepared.
• composition G’l includes:
• Composition G’2 includes:
• Composition G’3 includes:
• compositions G’l and G’2 include a comparative additive composition.
• the compositions G’l and G’2 are therefore comparative compositions.
• Composition G’3 comprises a composition of additives according to the invention.
• Composition G’3 is therefore a composition according to the invention.
• two levels of additive MDFI B are tested: 400 and 600 ppm.
• composition G 200 ppm of WASA 1 additive was added.
• composition G For composition G’3, 200 ppm of WASA 2 additive was added.

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• 2018
  • 2018-08-28 FR FR1857717A patent/FR3085383B1/fr active Active
• 2019
  • 2019-08-23 US US17/272,069 patent/US20210340453A1/en not_active Abandoned
  • 2019-08-23 EP EP19758410.5A patent/EP3844251A1/de active Pending
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