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
  • 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
  • C10L1/143—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
• • 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
  • C10L2200/043—Kerosene, jet 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
  • 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
  • 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

• the invention relates to the use of copolymers of ⁇ -olefin, vinyl ester and ⁇ , ⁇ -unsaturated carboxylic acid ester, as additives improving cold resistance of fuels and lubricants as well as fuel oils and packages containing these copolymers.
• compositions of hydrocarbons notably based on middle distillate types containing paraffinic waxes, such as for example diesel fuels and heating oils, exhibit a significant decrease in their flow properties. It is well-known that the crystallization of paraffins is a limiting factor in the use of middle distillates. Also, it is important to prepare diesel fuels adapted to temperatures at which they will be used in motor vehicles, i.e. to the surrounding climate. Generally, cold operability of fuels at ⁇ 10° C. is sufficient in many hot or temperate countries. But in countries with a cold climate such as the Scandinavian countries, Canada and the countries of North Asia, temperatures of use of the fuels much lower than ⁇ 20° C. may be attained.
• paraffins are crystallized at the bottom of the tank, upon starting they may be driven into the fuel circuit and notably block the filters and pre-filters positioned upstream from the injection systems (pump and injectors). Also, when storing domestic oils, paraffins precipitate to the bottom of the tank and may be driven and obstruct the conduits upstream from the pump and from the supply system of the boiler (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents normal circulation of the middle distillate.
• EP 261 957 which are generally copolymers of ethylene and of an 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 propionate
• 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 the ethylene/unsaturated ester type with lubricants (mono- or poly-carboxylic acid esters of mono- or poly-alcohols (see for example EP 721 492), with anti-sedimentation agents (see for example FR 2 490 669), with ethers (see for example U.S. Pat. No. 3,999,960, EP 187 488).
• lubricants mono- or poly-carboxylic acid esters of mono- or poly-alcohols
• anti-sedimentation agents see for example FR 2 490 669
• ethers see for example U.S. Pat. No. 3,999,960, EP 187 488).
• CFI additives which are terpolymers or copolymers derived from more than 3 distinct monomers are also found.
• U.S. Pat. No. 6,509,424 describes a method for preparing terpolymers of ethylene and of at least two compounds containing ethylenic unsaturations, such as vinyl esters, (meth)acrylic esters, alkyl vinyl ethers, in a tubular reactor. These terpolymers may be used as additives improving cold flow of petroleums and petroleum distillates.
• 3,642,459 describes terpolymers comprising 40-89% by weight of ethylene, 10-40% by weight of vinyl ester derived from a short chain (C 2 -C 4 ) carboxylic acid, such as vinyl acetate, and unsaturated monoesters having a C 10 -C 22 alkyl chain; these terpolymers are used as additives for lowering the pour point of petroleum distillates and as anti-wax agents and for improving their filterability.
• U.S. Pat. No. 4,156,434 describes terpolymers of ethylene, vinyl acetate and of acrylic ester deriving from a C 12 -C 24 alcohol which lower the pour point of the fuels into which they are incorporated but nothing is said on the improvement of cold filterability of these additives.
• WO 2005/054314 describes terpolymers of ⁇ -olefin, vinyl ester and ⁇ , ⁇ -unsaturated mono carboxylic acid ester, which may be used.
• Terpolymers are exemplified, particularly preferred by the applicant, which contain more than 80% by moles of ethylene and less than 9% by moles of vinyl acetate.
• these terpolymers containing less than 9% by moles of vinyl acetate although having an effect on the decrease in LFT for middle distillates containing more than 18% of n-paraffins, are not satisfactory as regards solubility on the one hand and tendency to blocking (or room temperature filterability) on the other hand: damageable filter cloggings are reported.
• EP 1 391 498 describes additives improving low temperature fluidity of middle distillates, which are vinyl polymers (A), preferably ethylene-vinyl ester copolymers, for which the amount of hexane-insoluble materials exceeds 60% by weight at ⁇ 20° C. and is less than 30% by weight at 10° C.; the examples of EP 1 391 498 clearly show that the filterability temperature (cold filter plug point (CFPP)) is lowered for copolymers and terpolymers, for which the amount of hexane-insoluble material exceeds 60% by weight at ⁇ 20° C. and is less than 30% by weight at 10° C.
• CFPP cold filter plug point
• the exemplified copolymers are EVA copolymers and ethylene-(vinyl acetate)-(vinyl neodecanoate or 2-ethylhexanoate) terpolymers.
• the present invention relates to the use of copolymers as additives improving cold resistance of fuels (CFI additives); these copolymers contain units derived from at least one ⁇ -olefin, at least one vinyl ester and at least one ⁇ , ⁇ -unsaturated mono-carboxylic ester, and are preferably terpolymers of ethylene, of vinyl acetate and of ethyl-2-hexyl acrylate.
• the copolymers according to the invention which may be used as CFI additives comprise
• the copolymers which may be used as CFI additives are inscribed in a quadrilateral ABCD in which A, B, C and D represent the apices of said quadrilateral and correspond to the molar percentages of at least the vinyl ester and of at least the ⁇ , ⁇ -unsaturated mono-carboxylic acid ester:
• copolymers may be prepared in a known way by any polymerization method, (see for example, Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition, “Waxes”, Vol. A 28, p. 146; U.S. Pat. No. 3,627,838; EP 7 590) notably by radical polymerization, preferably under high pressure, typically of the order of 1,000 to 3,000 bars (100 to 300 MPa), preferably from 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 selected from organic peroxides and/or oxygen- or nitrogen-containing compounds, and of a molecular weight regulator (aliphatic ketone or aldehyde, .
• a radical initiator generally selected from organic peroxides and/or oxygen- or nitrogen-containing compounds
• a molecular weight regulator aliphatic ketone or aldehyde, .
• the copolymers may for example be prepared in a tubular reactor according to the method described in U.S. Pat. No. 6,509,424.
• the compositions based on hydrocarbons into which the copolymers according to the invention are incorporated, are selected from all types of oils or fuels, such as diesel fuels, domestics oils for heating installations (DOF), kerosene, aviation fuels, heavy fuels, etc. . . . .
• the sulfur content of the hydrocarbon compositions is less than 5,000 ppm, preferably less than 500 ppm, and more preferentially less than 50 ppm, or even less than 10 ppm and advantageously without any sulfur.
• the compositions based on hydrocarbons comprise middle distillates with a boiling temperature comprised between 100 and 500° C.; their initial crystallization temperature Tcc is often greater than or equal to ⁇ 20° C., generally comprised between ⁇ 15° C. and +10° C.
• distillates may for example be selected from distillates obtained by direct distillation of crude hydrocarbons, distillates in vacuo, hydrotreated distillates, distillates from catalytic cracking and/or from hydrocracking of distillates in vacuo, distillates resulting from ARDS (atmospheric residue desulfurization) type conversion processes and/or viscoreduction processes, distillates from upgrading of Fischer Tropsch cuts, distillates resulting from BTL (biomass to liquid) conversion of plant and/or animal biomass, taken alone or as a combination, and/or esters of plant and animal oils or mixtures thereof.
• ARDS atmospheric residue desulfurization
• BTL biomass to liquid
• compositions of hydrocarbons may also contain distillates from more complex refining operations than those from direct distillation of hydrocarbons which may for example stem from cracking, hydrocracking and/or catalytic cracking processes and viscoreduction processes. They may also contain novel sources of distillates, among which mention may notably be made of:
• light middle distillates distillates for which the content in n-paraffins having 24 carbon atoms or more ranges from 0 to less than about 0.7% by weight of the total fuel composition; the C 18 -C 23 n-paraffins of which account for about 3 to about 5% of the total weight of the fuel and for which the mass ratio of C 18 -C 23 n-paraffins over the C 24 and higher paraffins generally ranges from 10 to 35.
• copolymers with Mw comprised between 5,000 and 10,000 and with Mn comprised between 1,500 and 8,000, preferably with Mw comprised between 5,000 and 8,000 and with Mn comprised between 1,500 and 5,000, are particularly effective when they are incorporated into heavy middle distillates and/or with a rather high initial crystallization temperature (which may typically range from 0 to 15° C.).
• heavy middle distillates distillates for which the content in n-paraffins with 24 carbon atoms or more ranges from about 0.7 to about 2% by weight of the total fuel composition; the C 18 -C 23 n-paraffins of which account for about 1 to about 10% of the total weight of the fuel and for which the mass ratio of C 18 -C 23 n-paraffins over C 24 + paraffins generally ranges from 1 to 10.
• the copolymers may be added as such in the compositions of hydrocarbons or preferentially as concentrated solutions, in particular solutions containing from 50 to 80%, preferably from 60 to 70% by weight of copolymer(s) in a solvent, such as aliphatic or aromatic hydrocarbons, either alone or as a mixture (naphtha, kerosene, hydrocarbon fractions such as Solvesso solvent, paraffinic hydrocarbons, such as pentane, hexane).
• a solvent such as aliphatic or aromatic hydrocarbons, either alone or as a mixture (naphtha, kerosene, hydrocarbon fractions such as Solvesso solvent, paraffinic hydrocarbons, such as pentane, hexane).
• the compositions of hydrocarbons comprise from 10 to 50,000 ppm by weight of at least one copolymer described above, optionally, preferably from 100 to 1,000 ppm and advantageously from 150 to 500 ppm.
• compositions of hydrocarbons may also contain one or more other additives different from the copolymers according to the invention, selected from detergents, anti-corrosion agents, dispersants, de-emulsifiers, antifoaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or unctuousness additives, combustion aids (combustion and soot catalytic promoters), agents improving the cloud point, the pour point, the limiting filterability temperature, antisedimentation agents, antiwear agents and/or agents modifying conductivity.
• additives mention may particularly be made of:
• EVA and/or EVP copolymers are EVA and/or EVP copolymers.
• the improved cold resistance additives according to the invention may be added into the compositions of hydrocarbons inside the refinery, and/or be incorporated downstream from the refinery, optionally as a mixture with other additives, as a package or packet of additives.
• terpolymers of ethylene, vinyl acetate and ethyl-2 hexyl acrylate are synthesized by radical polymerization under high pressure (1,400 to 2,500 bars (140 to 250 MPa) and at a polymerization temperature from 200 to 280° C.
• the synthesis is carried out by using an aliphatic aldehyde (propanal) in order to control the molecular masses and by using peroxides as polymerization initiators.
• Mn and Mw of the synthesized terpolymers are indicated the Mn and Mw of the synthesized terpolymers as well as their percentages of monomers.
• the cold resistance LFT efficiency of the terpolymers incorporated in GOM 1 and GOM 2 is measured at the concentration of 210 ppm; the results are grouped in Table 4.
• the terpolymer 17 according to the invention is the most efficient on the gasoil GOM 1. Moreover, from the results obtained in Table 3, it is seen that the terpolymer 17 added in an amount of 400 ppm in GOM 1 does not degrade the blocking tendency. This is not the case of the comparative terpolymers 6; 7; 16 and 18 according to WO 2005/054314, which strongly degrade the blocking tendency measured according to IP 387 and are not as LFT-efficient as the additive 17 of the invention.

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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)

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• 2009
  • 2009-07-03 FR FR0903278A patent/FR2947558B1/fr active Active
• 2010
  • 2010-06-25 CN CN2010800296922A patent/CN102549120A/zh active Pending
  • 2010-06-25 ES ES10734559T patent/ES2706903T5/es active Active
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  • 2010-06-25 JP JP2012518141A patent/JP2012532225A/ja active Pending
  • 2010-06-25 CA CA2765245A patent/CA2765245C/fr active Active
  • 2010-06-25 US US13/381,554 patent/US20120102825A1/en not_active Abandoned
  • 2010-06-25 WO PCT/IB2010/052922 patent/WO2011001352A1/fr not_active Ceased
  • 2010-06-25 KR KR1020117031259A patent/KR102002887B1/ko active Active
  • 2010-06-25 EA EA201270129A patent/EA201270129A1/ru unknown
  • 2010-06-25 EP EP10734559.7A patent/EP2449063B2/fr active Active
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  • 2010-06-29 TW TW099121257A patent/TWI496883B/zh not_active IP Right Cessation
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• 2011
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