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
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
• • 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
  • C10L1/146—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 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
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
• • 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
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 present invention relates to the use of particular cationic polymers as cold-keeping additives in fuel and combustible compositions, for example to improve their cold-keeping properties during their storage and/or use at low temperatures.
• the present invention also relates to fuel and combustible compositions additive with such polymers.
• the present invention finally relates to additive compositions (or "additive packages”) containing these polymers, in combination with at least one cold flow additive (CFI), as well as a method for lowering the filterability limit temperature of a fuel or combustible composition using such a polymer.
• CFI cold flow additive
• 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 have deteriorated flow properties at low temperatures, typically below 0°C.
• middle distillates obtained by distillation from crude oils of petroleum origin such as diesel or heating oil are known to contain different quantities of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperatures, blocking pipes, conduits, pumps and filters, for example in the fuel circuits of motor vehicles.
• CFIs Common cold flow improvers
• FLT Filterability Limit Temperature
• FP pour point
• FLT additives polymers of ethylene and vinyl acetate and/or vinyl propionate
• This type of additive very widely known to those skilled in the art, is systematically added to conventional middle distillates at the refinery outlet. These additivated distillates are used as diesel engine fuels or as heating fuels. Additional quantities of these additives can be added to fuels sold at service stations, in particular to meet the so-called Extreme Cold specifications.
• the document EP0857776 proposes to use alkylphenol-aldehyde resins resulting from the condensation of alkylphenol and aldehyde in association with ethylene/vinyl ester copolymers or terpolymers, to improve the fluidity of mineral oils.
• the patent application WO 2008/006965 describes the use of a combination of a homopolymer obtained from an olefinic ester of a carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of more than 16 carbon atoms and optionally an olefinic double bond and a cold flow additive (CFI) of the EVA or EVP type, to increase the effectiveness of CFI additives by amplifying their effect on the TLF.
• CFI cold flow additive
• This additive is particularly useful as a TLF booster in association with a cold flow additive (CFI).
• CFI cold flow additive
• Another purpose of cold-holding additives is to ensure the dispersion of paraffin crystals, so as to delay or prevent the sedimentation of such crystals and to avoid the formation of a paraffin-rich layer at the bottom of containers, tanks or storage reservoirs; these paraffin dispersing additives are called anti-sedimentation additives or WASA (acronym for the English term "Wax Anti-Settling Additive").
• WASA anti-sedimentation additives
• Modified alkylphenol-aldehyde resins have been described in the document FR2969620 as an anti-sedimentation additive in combination with a TLF additive.
• the document CN 104 193 892 A discloses a copolymer of methacryloyloxyethyl trimethylammonium chloride and dimethyl diallyl ammonium chloride and its use as an antistatic additive in a fuel oil composition.
• the patent applications WO 2017/046526 A And WO 2018/125666 A disclose copolymers conforming to the definition of the present claim 1, as well as the use of said copolymers as a detergent additive for fuel or combustible.
• This need is particularly important for fuels or combustibles 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.
• distillates used in fuels and combustibles are increasingly derived from more complex refining operations than those from direct distillation of petroleum, and can come in particular from cracking, hydrocracking, catalytic cracking and visbreaking processes.
• the refiner tends to introduce into these fuels more difficult to exploit cuts, such as the heavier cuts 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 from the direct distillation of crude oils, but also to bases from other sources, such as those described above.
• the aim of the present invention is to propose new additives and concentrates containing them, which can be used as additives in fuel and combustible compositions, among others, to improve their cold holding properties, in particular their cold flow properties at low temperatures, typically below 0°C, and better still below -5°C.
• the aim of the present invention is further to propose new additives for fuels and combustibles, and concentrates containing such additives, acting on the Filterability Limit Temperature (FLT), the pour point (FP), and delaying and/or preventing the sedimentation of crystals of hydrocarbon compounds, in particular paraffins.
• FLT Filterability Limit Temperature
• FP pour point
• these polymers possess unexpected properties for improving the cold resistance of fuel and combustible compositions, including those which are particularly difficult to process.
• the polymer defined above is used as a so-called “TLF booster” additive, i.e. in combination with a flow improvement additive or cold flow improver (CFI) whose performance it improves.
• TEZ booster flow improvement additive or cold flow improver
• the invention also relates to an additive composition (or "additive package”) comprising such a polymer in association with at least one cold resistance additive different from the polymers according to the invention, as well as an additive concentrate containing such a composition.
• the cold resistance additive is chosen from copolymers and terpolymers of ethylene and vinyl ester(s), alone or as a mixture.
• the weight ratio between the content of polymer(s) as defined above on the one hand, and the content of copolymer(s) of ethylene and vinyl ester(s) on the other hand, is in the range from 0.1:100 to 10:100.
• C N compound or group denotes a compound or group containing N carbon atoms in its chemical structure.
• the group E is preferably the group -O-CO-.
• the group E of formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group E is linked to the vinyl carbon by the carbon atom.
• the group E is preferably the group -CO-O-.
• the group E is a -CO-O- group, E being linked to the vinyl carbon by the carbon atom.
• the group G of formula (I) contains a hydrocarbon chain R 2 chosen from C 1 to C 34 hydrocarbon chains, cyclic or acyclic, linear or branched.
• R 2 denotes a linear or branched C 1 to C 18 hydrocarbon chain, more preferably C 1 to C 8 , even more preferably a linear C 2 to C 4 hydrocarbon chain.
• the quaternary ammonium function(s) of the group Q may be chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium, isoxazolium, trialkylammonium, iminium, amidinium, formamidinium, guanidinium and biguanidinium, and preferably trialkylammonium.
• X - corresponds to the formula R-COO - with R a linear or branched alkyl group, preferably linear, in C 1 to C 24 , more preferably in C 2 to C 18 , even more preferably in C 2 to C 8 .
• the polymer according to the invention comprises at least 70 mol% of units of formula (I), preferably at least 80 mol%, and better still at least 90 mol%.
• the polymer according to the invention is formed from units of formula (I), that is to say that it does not contain units different from the units of formula (I) above.
• the polymer according to the invention is a homopolymer, that is to say that it is formed from a single repeating unit of formula (I).
• the polymer used in the present invention can be obtained by homopolymerization or copolymerization of one or more monomer(s) corresponding to the following formula (IV): in which R 1 , E and G are as defined above, the preferred variants of R 1 , E and G according to formula (I) described above also being preferred variants of formula (IV).
• the polymer used in the invention is obtained by homopolymerization of a single monomer of formula (IV).
• the polymer according to the invention is obtained by polymerization of intermediate monomers corresponding to the following formula (V): in which R 1 and E are as defined above according to formula (I) and G' represents a group of formula -R 2 -P in which R 2 denotes a C 1 to C 34 hydrocarbon chain optionally substituted by one or more hydroxyl group(s), as defined above, and P denotes a group comprising a tertiary amine function capable of leading to the group Q as defined above, by reaction with a quaternization agent.
• the quaternizing agent is preferably an epoxide, and preferably an epoxide in combination with a monocarboxylic acid which is preferably a monocarboxylic acid containing from 2 to 12 carbon atoms as described above, preferably 4 to 8 carbon atoms.
• the polymerization is advantageously a block polymerization.
• the block polymerization may be of the group transfer polymerization (GTP) type or controlled radical polymerization; for example, atom transfer radical polymerization (ATRP); nitroxide-mediated radical polymerization (NMP); degenerative transfer processes such as degenerative iodine transfer polymerization (ITRP-iodine transfer radical polymerization) or reversible addition-fragmentation chain transfer radical polymerization (RAFT); ATRP-derived polymerizations such as polymerizations using initiators for continuous activator regeneration (ICAR) or using activators regenerated by electron transfer (ARGET).
• GTP group transfer polymerization
• ATRP atom transfer radical polymerization
• NMP nitroxide-mediated radical polymerization
• degenerative transfer processes such as degenerative iodine transfer polymerization (ITRP-iodine transfer radical polymerization) or reversible addition-fragmentation chain transfer radical polymerization (RAFT)
• RAFT radical polymerization descriptions include the following documents: WO1998/01478 , WO1999/31144 , WO2001/77198 , WO2005/00319 , WO2005/000924 .
• the polymer according to the invention advantageously has a number-average molar mass (Mn) of between 500 and 5,000 g.mol -1 , more preferably between 1,200 and 3,000 g.mol -1 .
• Mn number-average molar mass
• the number-average molar masses of a polymer are, in a manner known per se, measured by nuclear magnetic resonance (NMR).
• the polymer described above is used to improve the cold resistance properties of a fuel or combustible composition, in particular, of a composition chosen from diesel oils, biodiesels, type B x diesel oils and fuel oils such as in particular domestic fuel oils (DFO).
• a fuel or combustible composition in particular, of a composition chosen from diesel oils, biodiesels, type B x diesel oils and fuel oils such as in particular domestic fuel oils (DFO).
• DFO domestic fuel oils
• the fuel or combustible composition is as described below and advantageously comprises at least one hydrocarbon cut from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic sources.
• the polymer according to the invention is used to improve the low temperature flow properties of the fuel or combustible during its storage and/or its use at low temperature, by lowering its filterability limit temperature (or TLF, measured according to standard NF EN 116) and/or its pour point (or PE, measured according to standard ASTM D 7346) and/or by delaying or preventing the sedimentation of crystals, and preferably by lowering its filterability limit temperature (TLF, measured according to standard NF EN 116).
• TLF filterability limit temperature
• PE pour point
• TLF filterability limit temperature
• the polymer according to the invention can be used to delay or prevent the sedimentation of paraffin crystals and more particularly of n-alkanes, preferably n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms, even more preferably at least 24.
• the polymer according to the invention is used as a TLF booster additive, i.e. in combination with at least one flow improvement additive or cold flow improver (CFI).
• CFI cold flow improver
• the cold flow additive is preferably chosen from copolymers and terpolymers of ethylene and vinyl ester(s) and/or acrylic ester(s), alone or as a mixture, preferably from ethylene/vinyl acetate (EVA) copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and a other vinyl ester.
• CFI cold flow additive
• the polymer according to the invention is used to amplify the fluidizing effect of the cold fluidizing additive, in particular by lowering the filterability limit temperature (FLT) and/or the pour point, and/or by delaying or preventing the sedimentation of crystals, such as those containing paraffins.
• FLT filterability limit temperature
• TLF booster This effect is usually referred to as the "TLF booster" effect since the presence of the polymer according to the invention improves the fluidizing character of the CFI additive.
• This improvement results, in particular, in a significant reduction in the TLF of the fuel composition or combustible additive with this combination compared to the same fuel composition or combustible additive only with the CFI additive, at the same treatment rate.
• a significant reduction in the TLF results in a decrease of at least 3°C in the TLF according to standard NF EN 116.
• the polymer is used to amplify the fluidizing (flow) effect of the cold flow additive (CFI) by improving the Filterability Limit Temperature (FLT) of the fuel, the FLT being measured according to standard NF EN 116.
• CFI cold flow additive
• FLT Filterability Limit Temperature
• the polymer can be added to fuels or combustibles within the refinery, and/or be incorporated downstream of the refinery, possibly in a mixture with other additives, in the form of a concentrated composition of additives, also called according to usage "additive package”.
• the polymer is advantageously used at a content of at least 0.0001% by weight, relative to the total weight of the fuel or combustible composition.
• the content of said polymer ranges from 0.0001 to 0.01% by weight, preferably from 0.0002 to 0.005% by weight, and more preferably from 0.0003 to 0.002% by weight, relative to the total weight of the fuel or combustible composition.
• composition of additives is a composition of additives:
• the invention also relates to an additive composition
• an additive composition comprising a polymer as described above, and at least one cold flow additive (CFI) chosen from copolymers of ethylene and vinyl ester(s), the weight ratio between the content of polymer(s) formed from units of formula (I) on the one hand, and the content of copolymer(s) of ethylene and vinyl ester(s) on the other hand, being in the range from 0.1:100 to 10:100.
• CFI cold flow additive
• Said copolymers of ethylene and vinyl ester(s) are different from the polymers formed from units of formula (I).
• Copolymers and terpolymers of ethylene and vinyl and/or acrylic ester(s) may be used alone or as a mixture.
• examples include copolymers of ethylene and unsaturated ester, such as ethylene/vinyl acetate (EVA), ethylene/vinyl propionate (EVP), ethylene/vinyl ethanoate (EVE), ethylene/methyl methacrylate (EMMA), and ethylene/alkyl fumarate copolymers described, for example, in documents US3048479 , US3627838 , US3790359 , US3961961 And EP261957 . Mention may also be made of terpolymers of ethylene, vinyl acetate and another vinyl ester, for example vinyl neodecanoate.
• the copolymers of ethylene and vinyl ester(s) are chosen from ethylene/vinyl acetate copolymers (EVA), ethylene/vinyl propionate copolymers (EVP) and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably from ethylene/vinyl acetate copolymers (EVA) and their blends with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
• EVA ethylene/vinyl acetate copolymers
• EVP ethylene/vinyl propionate copolymers
• terpolymers of ethylene, vinyl acetate and another vinyl ester such as in particular vinyl neodecanoate.
• the weight ratio between the content of polymer(s) according to the invention on the one hand, and the content of copolymer(s) of ethylene and vinyl ester(s) on the other hand, is in the range from 0.1:100 to 10:100, preferably from 0.5:100 to 5:100.
• a particularly preferred weight ratio is 1:100 ⁇ 10%.
• the additive composition may also include one or several anti-sedimentation additives and/or paraffin dispersants (WASA), different from the polymer according to the invention and the cold-thinning additives described above.
• WASA paraffin dispersants
• These additives may be, in particular, but not limited to, chosen from the group consisting of (meth)acrylic acid/alkyl (meth)acrylate copolymers amidated with a polyamine, polyamine alkenylsuccinimides, phthalamic acid and double-chain fatty amine derivatives; optionally grafted alkylphenol resins.
• WASA anti-settling and/or paraffin dispersant additives
• the additive composition may also comprise one or more other additives commonly used in fuels or combustibles, different from the polymer according to the invention and the cold resistance additives described previously.
• the additive composition may typically comprise one or more other additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or smoothness additives, combustion aids (catalytic combustion and soot promoters), anti-wear agents and/or conductivity modifying agents.
• additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or smoothness additives, combustion aids (catalytic combustion and soot promoters), anti-wear agents and/or conductivity modifying agents.
• the additive composition may advantageously comprise from 0.1 to 50% by weight of polymer as described above, preferably from 0.2 to 20% by weight, and more preferably from 0.5 to 10% by weight, relative to the total weight of the additives present in said additive composition.
• the present invention also relates to an additive concentrate comprising an additive composition as described above, mixed 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 derived from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic.
• the organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent marketed under the name name “SOLVESSO”, alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or in mixture.
• Mineral sources are preferably petroleum.
• the fuel or combustible composition according to the invention advantageously comprises said polymer(s) formed from units of formula (I) in a content ranging from 0.0002 to 0.005% by weight, and better still from 0.0003 to 0.002% by weight, relative to the total weight of the fuel or combustible composition.
• CFI cold flow additives
• the fuel composition advantageously contains between 50 and 1,000 ppm (between 0.005% and 0.1% by weight) in total of cold-thinning additive(s) chosen from copolymers of ethylene and vinyl ester(s).
• composition may further contain one or more anti-sedimentation additives and/or paraffin dispersants (WASA), different from the polymers according to the invention formed from units of formula (I) and copolymers of ethylene and vinyl ester(s).
• WASA paraffin dispersants
• Such additives are advantageously chosen from those described above.
• the fuels or combustibles may be chosen from liquid hydrocarbon fuels or combustibles, alone or in a mixture.
• the liquid hydrocarbon fuels or combustibles include in particular middle distillates with a boiling point between 100 and 500°C.
• distillates may 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 (atmospheric residue desulfurization) and/or visbreaking conversion processes, distillates resulting from the valorization of Fischer Tropsch cuts, distillates resulting from BTL (biomass to liquid) conversion of plant and/or animal biomass, taken alone or in combination, and/or biodiesels of animal and/or plant origin and/or vegetable and/or animal oils and/or esters.
• ARDS atmospheric residue desulfurization
• BTL biomass to liquid
• the sulfur content of the fuels or combustibles is preferably less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm, and advantageously sulfur-free.
• the fuel or combustible is preferably chosen from diesels, biodiesels, type B x diesels and fuel oils, preferably domestic fuel oils (DFO).
• diesels preferably chosen from diesels, biodiesels, type B x diesels and fuel oils, preferably domestic fuel oils (DFO).
• DFO domestic fuel oils
• Type B diesel fuel x for diesel engines means a diesel fuel containing x% (v/v) of esters of vegetable or animal oils (including used cooking oils) transformed by a chemical process called transesterification, which reacts this oil with an alcohol to obtain fatty acid esters (FAEs). With methanol and ethanol, fatty acid methyl esters (FAMEs) and ethyl esters are obtained respectively. fatty acid esters (FEA). The letter “B” followed by a number x ranging from 0 to 100, which indicates the percentage of FEA contained in the diesel. Thus, a B99 contains 99% FEA and 1% middle distillates of fossil origin, B20, 20% FEA and 80% middle distillates of fossil origin etc...
• B100 B 0 type diesel fuels which do not contain oxygenated compounds
• Bx type diesel fuels which contain x% (v/v) of vegetable or animal oil esters or fatty acids, most often methyl esters (EMHV or EMAG).
• EMHV methyl esters
• the fuel or combustible may also contain hydrogenated vegetable oils, known to those skilled in the art as HVO (from the English “hydrotreated vegetable oil”) or HDRD (from the English “hydrogenation-derived renewable diesel”).
• HVO from the English “hydrotreated vegetable oil”
• HDRD from the English “hydrogenation-derived renewable diesel”.
• a method for improving the cold resistance properties of a fuel composition comprises a step of adding to said composition a polymer formed from units of formula (I) as defined above.
• the method of improving cold holding properties is typically intended for a fuel or combustible composition as described above.
• Step (a) is carried out according to any known method and is common practice in the field of fuel additives. This step involves defining a characteristic representative of the cold holding properties of the fuel, for example the low temperature flow characteristics, setting the target value (including a given specification for the cold holding properties), and then determining the improvement required to achieve such a target value.
• a characteristic representative of the cold holding properties of the fuel for example the low temperature flow characteristics
• setting the target value including a given specification for the cold holding properties
• a specification relating to cold resistance may be a European Extreme Cold specification defining, in particular, a maximum TLF according to standard NF EN 116.
• the determination of the quantity of additive composition(s) to be added to the fuel or combustible composition to achieve the specification will typically be carried out by comparison with the fuel or combustible composition without said additive composition(s).
• the amount of additive composition required to treat the fuel or combustible composition may vary depending on the nature and origin of the fuel or combustible, in particular depending on the rate and nature of the paraffinic compounds that it contains. contains. The nature and origin of the fuel or combustible can therefore also be a factor to take into account for step a).
• the method for improving the cold holding properties may also comprise an additional step after step b) of verifying the target achieved and/or adjusting the treatment rate with the additive composition(s).
• amine monomer 10.0 g (69.84 mmol) of amine monomer are introduced into a 50 mL single-necked flask, then 3.02 g (8.7 mmol) of RAFT agent and 11.2 g of 1,4-dioxane are added. The flask is then degassed for 30 minutes under nitrogen and magnetic stirring, then sealed. In parallel, 0.179 g (1.09 mmol) of AIBN are introduced into a second 25 mL flask, along with 2.0 g of 1,4-dioxane as a dissolution solvent. The second flask is in turn degassed for 30 minutes under nitrogen. The AIBN solution is then transferred using a nitrogen-purged syringe into the 50 mL flask, previously heated to 80°C, to start the polymerization. The reaction is left 24 hours.
• the intermediate polymer thus obtained has a number average molar mass Mn of 1500 G.mol -1 which corresponds to an average of 8 units of formula (I) per polymer chain.
• the conversion rate is 99% by weight (i.e. 1% by weight of residual monomer).
• the latter is characterized by NMR in order to determine the quaternization rate.
• the quaternization rate of the polymer P1 thus obtained is 100% (in molar percentage).
• the latter is characterized by NMR in order to determine the quaternization rate.
• the quaternization rate of the P2 polymer thus obtained is 100% (in molar percentage).
• Additive A was incorporated into diesel composition G at a content of 300 ppm by weight of active material relative to the total weight of the diesel composition.
• composition G1 Each polymer was added at a content of 3 ppm by weight (0.0003% by weight) to composition G1, to give diesel G2, the TLF of which was then measured, in accordance with standard EN 116.

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