Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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

Definitions

• the invention relates to the use of copolymers of alpha-olefin, vinyl ester, and alpha, beta-unsaturated carboxylic acid ester as additives improving the resistance to cold of motor fuels and lubricants as well as fuel-oils and the packages containing these copolymers.
• hydrocarbon compositions in particular those with a medium distillate type base containing paraffin waxes, such as for example diesel fuels and heating fuel oils exhibit a significant reduction in their rheological properties. It is well known that the crystallization of paraffins is a factor limiting the use of the middle distillates. It is thus important to prepare diesel fuels which are suitable for the temperatures at which they are used in motor vehicles, i.e. for the ambient climate. Generally, cold operability of motor fuels at ⁇ 10° C. is sufficient in numerous hot or temperate countries. However, in countries with a cold climate, such as the Scandinavian countries, Canada and the countries of Northern Asia, motor fuel use temperatures well below ⁇ 20° C. can be reached.
• paraffins are crystallized at the bottom of the tank, they may be carried along in the fuel system during starting and block in particular the filters and pre-filters arranged upstream of the injection systems (pump and injecters).
• the paraffins precipitate at the bottom of the tank and can be carried along and obstruct the pipes upstream of the pump and the boiler fuel system (nozzle and filter). It is evident that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.
• 3,961,961, EP 261957 which are generally 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.
• EVA ethylene/vinyl acetate
• EVE ethylene/vinyl ethanoate
• EMMA ethylene/methyl methacrylate
• alkyl fumarate copolymers such as ethylene/alkyl fumarate copolymers.
• the prior art also proposes mixtures of conventional CFI additives of ethylene/unsaturated ester type with lubricants (mono- or polycarboxylic acid and mono- or polyalcohol esters (see for example EP 721492), with anti-sedimentation agents (see for example FR 2490669), or with ethers (see for example U.S. Pat. No. 3,999,960, EP 187488).
• lubricants mono- or polycarboxylic acid and mono- or polyalcohol esters
• anti-sedimentation agents see for example FR 2490669
• ethers see for example U.S. Pat. No. 3,999,960, EP 187488.
• CFI additives are also found which are terpolymers or copolymers deriving from more than 3 separate monomers.
• U.S. Pat. No. 6,509,424 describes a process for the preparation of terpolymers of ethylene and at least two compounds containing ethylene unsaturations, such as vinyl esters, (meth)acrylic esters, vinyl alkyl ethers in a tubular reactor. These terpolymers can be used as additives improving the cold flow of petroleums and petroleum distillates.
• U.S. Pat. No. 3,642,459 describes terpolymers comprising 40 to 89% by weight of ethylene, 10 to 40% by weight of vinyl ester derived from short-chain carboxylic acid (C2-C4), such as vinyl acetate, and unsaturated monoesters having a C10-C22 alkyl chain); these terpolymers are used as additives to lower the pour point of petroleum distillates and as anti-wax agents and to improve their filterability.
• C2-C4 short-chain carboxylic acid
• U.S. Pat. No. 4,156,434 describes terpolymers of ethylene, vinyl acetate and acrylic ester deriving from C12-C24 alcohol which lower the pour point of the motor fuels in which they are incorporated but says nothing about the improvement of the cold filterability of these additives.
• WO 2005/054314 describes useable terpolymers of alpha olefin, vinyl ester and alpha-beta unsaturated mono carboxylic acid ester. Examples are given of terpolymers, particularly preferred by the applicant, which contain more than 80% in moles of ethylene and less than 9% in moles of vinyl acetate. Although these terpolymers containing less than 9% in moles of vinyl acetate have an effect on the reduction of the CFPP for middle distillates containing more than 18% n-paraffins, they are not satisfactory as regards solubility on the one hand and blocking tendency (or filterability at ambient temperature) on the other hand: harmful filter blocking is noted.
• EP 1391498 describes additives improving the low temperature fluidity of middle distillates, namely vinyl polymers (A), preferably ethylene-vinyl ester copolymers, in which the quantity of materials which are insoluble in hexane exceeds 60% by weight at ⁇ 20° C. and is less than 30% by weight at 10° C.; the examples of EP 1391498 clearly show that the filterability temperature (CFPP) is lowered for copolymers and terpolymers in which the quantity of material which is insoluble in hexane exceeds 60% by weight at ⁇ 20° C. and is less than 30% by weight at 10° C.
• CFPP filterability temperature
• copolymers and terpolymers having the same repetition units present in the same proportions but in which the quantity of materials which are insoluble in hexane is outside the claimed range;
• copolymers given as examples are EVA copolymers and ethylene-vinyl acetate-neodecanoate or vinyl 2-ethylhexanoate terpolymers.
• the present invention relates to the use of copolymers as additives improving the resistance to cold of motor fuels (CFI additives); these copolymers contain units derived from at least one alpha-olefin, at least one vinyl ester and at least one alpha-beta unsaturated mono carboxylic acid ester, and are preferably terpolymers of ethylene, vinyl acetate and ethyl-2,hexyl acrylate.
• the copolymers according to the invention which can be used as CFI additives comprise:
• copolymers which can be used as CFI additives comprise:
• copolymers according to the invention which are random copolymers have a numerical molecular weight (Mw) measured by GPC generally comprised between 3,000 and 30,000, and an average numerical molecular weight (Mn) measured by GPC generally comprised between 1,000 and 15,000.
• Mw numerical molecular weight measured by GPC generally comprised between 3,000 and 30,000
• Mn average numerical molecular weight measured by GPC generally comprised between 1,000 and 15,000.
• radical polymerization in particular by radical polymerization, preferably under high pressure, typically of the order of 1,000 to 3,000 bars (100 to 300 MPa), preferably 1,500 to 2,000 bars (150 to 200 MPa), the reaction temperatures generally ranging from 160 to 320° C., preferably from 200 to 280° C., and in the presence of at least one radical initiator generally chosen from the organic peroxides and/or the oxygenated or nitrogenated compounds, and a molecular weight regulator (ketone or aliphatic aldehyde etc.).
• the copolymers can for example be prepared in a tubular reactor according to the process described in U.S. Pat. No. 6,509,424.
• hydrocarbon-based compositions in which the copolymers according to the invention are incorporated are chosen from all types of fuel oils or motor fuels, such as diesel fuels, domestic fuel oils for heating installations (DF), kerosene, aviation fuels, heavy fuel oils, etc.
• the sulphur content of the hydrocarbon compositions is less than 5,000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm and advantageously sulphur-free.
• the hydrocarbon-based compositions comprise middle distillates with a boiling temperature comprised between 100 and 500° C.; their initial crystallization temperature ICT is often greater than or equal to ⁇ 20° C., generally comprised between ⁇ 15° C. and +10° C.
• distillates can for example be chosen from distillates obtained by direct distillation of crude hydrocarbons, distillates from vacuum distillation, hydrotreated distillates, distillates originating from catalytic cracking and/or hydrocracking of distillates under vacuum, distillates resulting from conversion processes of ARDS (atmospheric residue desulphuration) type and/or visbreaking, distillates originating from upgrading of the Fischer-Tropsch cuts, distillates resulting from BTL (biomass to liquid) conversion of vegetable and/or animal biomass, taken alone or in combination and/or the esters of vegetable and animal oils or their mixtures.
• ARDS atmospheric residue desulphuration
• BTL biomass to liquid
• the hydrocarbon compositions can also contain distillates originating from refining operations, which are more complex than those originating from the direct distillation of the hydrocarbons which can for example originate from cracking, hydrocracking and/or catalytic cracking processes and visbreaking processes. They can also contain novel sources of distillates, among which there can in particular be mentioned:
• oils and/or esters of vegetable and/or animal oils are oils and/or esters of vegetable and/or animal oils,
• biodiesels of animal and/or vegetable origin are also biodiesels of animal and/or vegetable origin.
• novel motor fuel bases can be used alone or in a mixture with standard petroleum middle distillates as a motor fuel base and/or domestic fuel oil base; they generally comprise long paraffin chains greater than or equal to 10 carbon atoms and preferably C14 to C30.
• copolymers as defined previously with an Mw comprised between 5,000 and 27,000 and an Mn comprised between 1,500 and 22,000, preferably with an Mw comprised between 5,000 and 25,000 and an Mn comprised between 1,500 and 20,000 are particularly effective when they are incorporated into the light middle distillates and/or distillates with a low sulphur content (typically less than 50 ppm) and/or at a low initial crystallization temperature (which may typically be as low as ⁇ 20° C.).
• a low sulphur content typically less than 50 ppm
• initial crystallization temperature which may typically be as low as ⁇ 20° C.
• light middle distillates distillates in which the content of n-paraffins having 24 carbon atoms or more ranges from 0 to approximately less than 0.7% by weight of the total motor fuel composition; wherein the C18-C23 n-paraffins represent approximately 3 to approximately 5% of the total weight of the motor fuel and wherein the mass ratio of the C18-C23 n-paraffins to the C24+ paraffins generally ranges from 10 to 35.
• copolymers with an Mw comprised between 5,000 and 10,000 and an Mn comprised between 1,500 and 8,000, preferably with an Mw comprised between 5,000 and 8,000 and an Mn comprised between 1,500 and 5,000 are particularly effective when they are incorporated into heavy middle distillates and/or at a rather high initial crystallization temperature (typically being able to range from 0 to 15° C.).
• heavy middle distillates distillates in which the content of n-paraffins having 24 carbon atoms or more ranges from approximately 0.7 to approximately 2% by weight of the total motor fuel composition; wherein the C18-C23 n-paraffins represent approximately 1 to approximately 10% of the total weight of the motor fuel and wherein the mass ratio of the C18-C23 n-paraffins to the C24+ paraffins generally ranges from 1 to 10.
• the copolymers can be added to the hydrocarbon compositions as such or preferably in the form of concentrated solutions, in particular solutions containing 50 to 80%, preferably 60 to 70% by weight of copolymer(s) in a solvent, such as the aliphatic or aromatic hydrocarbons, alone or in a mixture (naphtha, kerosene, hydrocarbon fractions such as Solvesso solvent, paraffinic hydrocarbons, such as pentane, hexane.)
• the hydrocarbon compositions comprise 10 to 5,000 ppm by weight of at least one copolymer described above optionally, preferably 100 to 1000 ppm, and advantageously 150 to 500 ppm.
• the hydrocarbon compositions can also contain one or more other additives different from the copolymers according to the invention, chosen from detergents, anti-corrosive agents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or anti-friction additives, combustion-promoting agents (catalytic combustion and soot promoters), cloud point, pour point, cold filter plugging point improvers, anti-sedimentation agents, anti-wear agents and/or conductivity modifying agents.
• additives there can particularly be mentioned:
• procetane additives in particular (but not limitatively) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aroyl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
• anti-foam additives in particular (but not limitatively) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides from vegetable or animal oils. Examples of such additives are given in EP 861182, EP 663000, EP 736590;
• detergent and/or anti-corrosion additives in particular (but not limitatively) chosen from the group constituted by amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines. Examples of such additives are given in EP 938535.
• lubricity additive or anti-wear agent in particular (but not limitatively) chosen from the group constituted by fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and polycyclic carboxylic acid derivatives.
• lubricity additive or anti-wear agent in particular (but not limitatively) chosen from the group constituted by fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and polycyclic carboxylic acid derivatives. Examples of such additives are given in the following documents: EP 680506, EP 860494, WO 98/04656, EP 915944, FR 2772783, FR 2772784.
• cloud point additives in particular (but not limitatively) chosen from the group constituted by long-chain olefin/(meth)acrylic ester/maleimide terpolymers, and fumaric/maleic acid ester polymers.
• examples of such additives are given in EP 71513, EP 100248, FR 2528051, FR 2528051, FR 2528423, EP 112195, EP 172758, EP 271385, EP 291367;
• anti-sedimentation additives and/or paraffin dispersants in particular (but not limitatively) chosen from the group constituted by (meth)acrylic acid/polyamine-amidified alkyl(meth)acrylate copolymers, polyamine alkenylsuccinimides, derivatives of phthalamic acid and of double-chain fatty amine; alkyl phenol resins.
• examples of such additives are given in EP 261959, EP 593331, EP 674689, EP 327423, EP 512889, EP 832172; US 2005/0223631; U.S. Pat. No. 5,998,530; WO 93/14178.
• the improved cold-resistance additives according to the invention can be added to the hydrocarbon compositions within the refinery, and/or be incorporated downstream of the refinery, optionally in a mixture with other additives, in the form of a package of additives.
• Terpolymers of ethylene, vinyl acetate and ethyl-2,hexyl acrylate were synthesized in a tubular reactor by radical polymerization under high pressure (1,400 to 2,500 bars (140 to 250 MPa)) and at a polymerization temperature of 200 to 280° C.
• the synthesis was carried out using an aliphatic aldehyde (propanal) to control the molecular weights and using peroxides as polymerization initiators.
• Table 1 below shows the Mn and Mw of the synthesized terpolymers as well as their percentages of monomers.
• the terpolymers according to the invention make it possible not to degrade the filter blocking tendency of GOM 1 i.e. that GOM 1 with 400 ppm of terpolymer added has an FBT of less than 1.41.
• the results are shown in Table 3 below.
• IP387 TABLE 3 Filter blocking tendency (IP387) of the GOM 1 with 400 ppm of the different terpolymers added.
• Additive added FBT index (IP 387) 1 1.01 2 1 3 1.3 4 1.14 5 1.06 6 (comparative) 6.08 7 (comparative) 6.08 8 (comparative) 1.53 9 (comparative) 1.8 10 (comparative) 1.02 11 (comparative) 2.69 12 (comparative) 1.01 13 (comparative) 1.03 14 1.01 15 1.01 16 (comparative) 5.1
• the cold resistance effectiveness CFPP of the terpolymers incorporated into GOM 2 to GOM 6 was measured at a concentration of 140, 210 or 280 ppm; the results are compiled in Table 4.
• the terpolymers 1; 2; 3; 4 according to the invention are the most effective in the different gas oils GOM 2 to GOM 6. Moreover, from the results in Table 3, it is noted that these terpolymers 1; 2; 3 and 4 added at a level of 400 ppm to the GOM 1 do not degrade the filter blocking tendency. This is not the case with the comparative terpolymers 6; 7; 8; 9; 11 and 16 according to WO 2005/054314, which greatly degrade the filter blocking tendency measured according to IP 387 and are also not as effective as regards CFPP as the additives of the invention such as for example the additives 1; 2; 4 and 5.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Combustion & Propulsion (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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