EP2238225B1 - Terpolymere ethylene/acetate de vinyle /esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides - Google Patents

Terpolymere ethylene/acetate de vinyle /esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides Download PDF

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Publication number
EP2238225B1
EP2238225B1 EP08872789.6A EP08872789A EP2238225B1 EP 2238225 B1 EP2238225 B1 EP 2238225B1 EP 08872789 A EP08872789 A EP 08872789A EP 2238225 B1 EP2238225 B1 EP 2238225B1
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EP
European Patent Office
Prior art keywords
moles
copolymer
ppm
ethylene
additives
Prior art date
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EP08872789.6A
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German (de)
English (en)
French (fr)
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EP2238225A2 (fr
Inventor
Erwan Chevrot
Laurent Dalix
Frédéric Tort
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TotalEnergies Marketing Services SA
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Total Marketing Services SA
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Priority to PL08872789T priority Critical patent/PL2238225T3/pl
Priority to SI200831747A priority patent/SI2238225T1/sl
Publication of EP2238225A2 publication Critical patent/EP2238225A2/fr
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Publication of EP2238225B1 publication Critical patent/EP2238225B1/fr
Priority to HRP20170032TT priority patent/HRP20170032T1/hr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C10L1/143—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, 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

Definitions

  • the invention relates to the use of alpha-olefin, vinyl ester and alpha, beta-unsaturated carboxylic acid ester copolymers as additives for improving the cold-running performance of fuels and lubricants, as well as fuel oils and lubricants. packages containing these copolymers.
  • the hydrocarbon compositions especially those based on middle distillate type containing paraffin waxes, such as for example diesel fuels and heating fuel oils have a significant decrease in their flow properties. It is well known that the crystallization of paraffins is a limiting factor for the use of middle distillates. Also, it is important to prepare diesel fuels adapted to the temperatures at which they will be used in motorized vehicles, that is to say to the surrounding climate. Generally, cold operability of fuels at -10 ° C is sufficient in many hot or temperate countries. But in cold climate countries, such as the Scandinavian countries, Canada, and Northeast Asian countries, fuel usage temperatures well below -20 ° C can be achieved. It is the same for domestic fuel stored outside buildings (houses, buildings, ).
  • paraffins are crystallized at the bottom of the tank, they can be driven to start in the fuel system and particularly clog filters and prefilters arranged upstream of the injection systems (pump and injectors). Similarly for the storage of domestic fuel oils, paraffins precipitate at the bottom of the tank and can be driven and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter). It is obvious that the presence of solids, such as paraffin crystals, prevents the normal circulation of the middle distillate.
  • CFI cold flow improvers
  • CFI additives see for example US 3,048,479 , US 3,627,838 , US 3,790,359 , US 3,961,961 , EP 261 957 ) which are generally copolymers of ethylene and unsaturated ester, such as ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methacrylate methyl (EMMA), and ethylene / alkyl fumarate.
  • EVA ethylene / vinyl acetate copolymers
  • EVE ethylene / vinyl propionate
  • EMMA ethylene / vinyl ethanoate
  • EMMA ethylene / methacrylate methyl
  • the prior art also provides conventional CFI ethylene / unsaturated ester additive mixtures with lubricating agents (mono- or polycarboxylic acid esters and mono- or polyalcohols (see, for example EP 721 492 ), with anti-sedimentation agents (see for example FR 2,490,669 ), with ethers (see for example US 3,999,960 , EP187488 )
  • lubricating agents mono- or polycarboxylic acid esters and mono- or polyalcohols
  • anti-sedimentation agents see for example FR 2,490,669
  • ethers see for example US 3,999,960 , EP187488
  • CFI additives which are terpolymers or copolymers derived from more than 3 different monomers.
  • US 6,509,424 discloses a process for preparing terpolymers of ethylene and at least two compounds containing ethylenic unsaturations, such as vinyl esters, (meth) acrylic esters, alkyl vinyl ethers in a tubular reactor. These terpolymers can be used as additives improving the cold flow of oils and petroleum distillates.
  • US 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 (C2-C4) carboxylic acid, 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-waxing agents and to improve their filterability.
  • C2-C459 long chain (C2-C4) carboxylic acid, such as vinyl acetate, and unsaturated monoesters having a C10-C22 alkyl chain
  • WO 2005/054314 discloses terpolymers of alpha olefin, vinyl ester and alpha-beta unsaturated mono carboxylic acid ester useful.
  • terpolymers particularly preferred by the applicant, which contain more than 80 mol% of ethylene and less than 9 mol% of vinyl acetate.
  • these terpolymers containing less than 9 mol% of vinyl acetate although having an effect on the reduction of TLF for middle distillates containing more than 18% of n-paraffins, are not satisfactory for on the one hand solubility and secondly the tendency to clogging (or filterability at room temperature): there is harmful filter clogging.
  • EP 1.391.498 discloses additives improving the low temperature fluidity of middle distillates which are vinyl polymers (A), preferably ethylene-vinyl ester copolymers, the amount of hexane-insoluble matter exceeds 60% by weight at -20 ° C and is less than 30% by weight at 10 ° C; examples of EP 1.391.498 clearly show that the filterability temperature (CFPP) is lowered for copolymers and terpolymers whose amount of hexane insoluble matter exceeds 60% by weight at -20 ° C and is less than 30% by weight at 10 ° C by copolymers and terpolymers having the same units of recurrence present in the same proportions but the amount of hexane insoluble material is outside the claimed range; the copolymers exemplified are EVA copolymers and ethylene-vinyl acetate-neodecanoate or 2-ethylhexanoate vinyl terpolymers.
  • A vinyl polymers
  • CFPP
  • the present invention relates to the use of copolymers as described in the first claim and a hydrocarbon composition comprising these copolymers according to claim 6; 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-acrylate, hexyl.
  • the copolymers according to the invention which are random copolymers have a number-average molecular weight (Mw) measured by GPC in general of between 3,000 and 30,000, and a number-average molecular weight (Mn) measured by GPC in general between 1,000 and 15,000.
  • copolymers can be prepared in a known manner by any polymerization process (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, "Waxes", Vol. A 28, p.146 ; US 3,627,838 ; EP 7,590 ) in particular by radical polymerization, preferably under high pressure, typically of the order of 1000 to 3000 bar (100 to 300 MPa), preferably from 1500 to 2000 bar (150 to 200 MPa), the temperatures of reaction generally ranging from 160 to 320 ° C, preferably from 200 to 280 ° C, and in the presence of at least one radical initiator chosen in general from organic peroxides and / or oxygenated or nitrogen compounds, and from molecular weight regulator (ketone or aliphatic aldehyde, ).
  • the copolymers may for example be prepared in a tubular reactor according to the process described in US 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 fuels, such as diesel fuels, heating oil for heating installations (FOD), kerosene, aviation fuel oil, fuel oil. heavy, etc.
  • fuel oils or fuels such as diesel fuels, heating oil for heating installations (FOD), kerosene, aviation fuel oil, fuel oil. heavy, etc.
  • the sulfur content of the hydrocarbon compositions is less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm and advantageous without sulfur.
  • the hydrocarbon-based compositions comprise middle distillates having a boiling point of between 100 and 500 ° C .; their starting crystallization temperature Tcc is often greater than or equal to -20 ° C, generally between -15 ° C and + 10 ° C.
  • These distillates may for example be chosen from distillates obtained by the direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion processes (by residue desulfurization atmospheric) and / or visbreaking, distillates derived from the recovery of Fischer Tropsch slices, distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination and / or the esters vegetable and animal oils or mixtures thereof.
  • BTL biomass to liquid
  • the hydrocarbon compositions may also contain distillates resulting from more complex refining operations than those resulting from the direct distillation of hydrocarbons which may for example be derived from cracking, hydrocracking and / or catalytic cracking processes and visbreaking processes.
  • copolymers as defined previously of Mw between 5,000 and 27,000 and Mn between 1,500 and 22,000, preferably Mw between 5,000 and 25,000 and Mn between 1,500 and 20,000 are particularly effective. when they are incorporated in light middle distillates and / or low sulfur (typically less than 50 ppm) and / or low initial crystallization temperature (typically up to -20 ° C).
  • copolymers may be added as such in the hydrocarbon compositions or, preferably, in the form of concentrated solutions, in particular solutions containing from 50 to 80%, preferably from 60 to 70% by weight of copolymer (s) in a mixture.
  • solvent such as aliphatic or aromatic hydrocarbons, alone or as a mixture (naphtha, kerosene, hydrocarbon fractions, such as solvent Solvesso, paraffinic hydrocarbons, such as pentane, hexane.
  • the hydrocarbon compositions comprise from 10 to 5000 ppm by weight of at least one copolymer described above, preferably from 100 to 1000 ppm, and advantageously from 150 to 500. ppm.
  • the hydrocarbon compositions may also contain one or more other additives different from the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot) , cloud point improvers, pour point, filterability limit temperature, anti-settling agents, anti-wear agents and / or conductivity modifiers.
  • additives different from the copolymers according to the invention, chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot) , cloud point improvers, pour point, filterability limit temperature, anti-settling agents, anti-wear agents and
  • additives are generally added in an amount ranging from 100 to 1000 ppm (each).
  • the improved cold-strength additives according to the invention may be added to the hydrocarbon compositions within the refinery, and / or may be incorporated downstream of the refinery, optionally mixed with other additives, in the form of a package. additives.
  • high-pressure radical polymerization (1400 to 2500 bar (140 to 250 MPa)) and a polymerization temperature of 200 to 280 ° C. are synthesized of terpolymers of ethylene and vinyl acetate. and 2-ethylhexyl acrylate.
  • the synthesis is carried out using an aliphatic aldehyde (propanal) to control molecular weights and using peroxides as polymerization initiators.
  • Table 1 below, the Mn and Mw of the synthesized terpolymers and their percentages of the monomers are indicated.
  • GOM 1 to GOM 6 The ability to improve the cold strength of these terpolymers is evaluated by incorporating them into 6 diesel engine type distillates called GOM 1 to GOM 6, the characteristics of which are shown in Table 2 below.
  • Table 2 Fuel Characteristics GOM 1 GOM 2 GOM 3 GOM 4 GOM 5 GOM 6 ASTM D86 Distillation T90-T20 (° C) 112.7 100.4 96.9 112.2 100.5 112 PF-T90 (° C) 18.6 24.9 26.1 26.2 17 23 T95 (° C) 353.9 362.4 351.1 350.5 350 356 Cloud point (° C) NF EN 23015 -4 -4 -5 -5 -9 -7 TLF (° C) EN 116 -5 -7 -6 -5 -9 -6 Pour point (° C) NF T 60105 -12 -10 -12 -12 -15 -9 Paraffin content (% mass) Chromatography 19.27 14.68 17.5 18.95 16.1 15.64 TCC (° C) IP 389 -6 -6.3 -6.2 -
  • GOM 1 400 ppm by weight of each copolymer 1 to 16 below is incorporated in the diesel engine type distillate called GOM 1, and then the Filter Blocking Tendency (FBT) is measured according to the IP 387 standard.
  • GOM 1 without additive has an FBT clogging index of 1.01.
  • the terpolymers according to the invention make it possible not to degrade the tendency to clog the GOM 1, ie that the GOM 1 additive with 400 ppm of terpolymer has an FBT of less than 1.41.
  • the results are shown in Table 3 below Table 3 Clogging tendency (IP387) of the GOM 1 additive at 400 ppm of the different terpolymers.
  • the terpolymers 1; 2; 3; 4 according to the invention are the most effective on the different gas oils GOM 2 to GOM 6. Furthermore, from the results of Table 3, it is found that these terpolymers 1; 2; 3 and 4 added at 400 ppm in GOM 1 do not degrade the clogging tendency. This is not the case of comparative terpolymers 6; 7; 8; 9; 11 and 16 according to WO 2005/054314 which greatly degrade the clogging tendency measured according to IP 387 and are not as effective in TLF as the additives of the invention, for example 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP08872789.6A 2007-12-28 2008-12-23 Terpolymere ethylene/acetate de vinyle /esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides Active EP2238225B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PL08872789T PL2238225T3 (pl) 2007-12-28 2008-12-23 Terpolimer etylen/octan winylu/nienasycone estry jako dodatek poprawiający właściwości niskotemperaturowe ciekłych węglowodorów
SI200831747A SI2238225T1 (sl) 2007-12-28 2008-12-23 Terpolimer etilena, vinilacetata, nenasičenih estrov kot aditiv, ki poveča odpornost ogljikovodikov na mraz
HRP20170032TT HRP20170032T1 (hr) 2007-12-28 2017-01-10 Terpolimer etilen/vinil acetat/nezasićeni esteri kao aditiv koji poboljšava otpornost tekućih ugljikovodika na niske temperature

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0709168A FR2925916B1 (fr) 2007-12-28 2007-12-28 Terpolymere ethylene/acetate de vinyle/esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles
PCT/FR2008/001817 WO2009106744A2 (fr) 2007-12-28 2008-12-23 Terpolymere ethylene/acetate de vinyle /esters insatures comme additif ameliorant la tenue a froid des hydrocarbures liquides comme les distillats moyens et les carburants ou combustibles

Publications (2)

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EP2238225A2 EP2238225A2 (fr) 2010-10-13
EP2238225B1 true EP2238225B1 (fr) 2016-12-14

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US (1) US20100281762A1 (pt)
EP (1) EP2238225B1 (pt)
JP (1) JP2011508042A (pt)
KR (1) KR20100135221A (pt)
CN (1) CN101925667A (pt)
AR (1) AR069986A1 (pt)
AU (1) AU2008351922B2 (pt)
BR (1) BRPI0820066B1 (pt)
CA (1) CA2710839C (pt)
CL (1) CL2008003911A1 (pt)
DK (1) DK2238225T3 (pt)
EA (1) EA201070807A1 (pt)
ES (1) ES2612739T3 (pt)
FR (1) FR2925916B1 (pt)
HR (1) HRP20170032T1 (pt)
HU (1) HUE032911T2 (pt)
LT (1) LT2238225T (pt)
MA (1) MA32023B1 (pt)
MX (1) MX2010007225A (pt)
MY (1) MY162899A (pt)
PL (1) PL2238225T3 (pt)
PT (1) PT2238225T (pt)
SG (1) SG162529A1 (pt)
SI (1) SI2238225T1 (pt)
TW (1) TW200932893A (pt)
UA (1) UA104854C2 (pt)
WO (1) WO2009106744A2 (pt)
ZA (1) ZA201005265B (pt)

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CN104371773B (zh) * 2013-08-13 2016-09-28 西安艾姆高分子材料有限公司 一种提高生物柴油低温流动性的方法
AR100387A1 (es) 2014-02-18 2016-10-05 Basf Se Copolímeros que comprenden etileno, ésteres de vinilo y ésteres de ácido (met)acrílico, sus formulaciones y usos como depresor del punto de fluidez, inhibidor de cera y potenciador de flujo para petróleos crudos
FR3034778B1 (fr) 2015-04-10 2017-04-28 Total Marketing Services Additif dispersant des asphaltenes et ses utilisations
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FR3137915B1 (fr) 2022-07-13 2024-07-19 Totalenergies Onetech Composition d’additifs et son utilisation pour ameliorer la pompabilite des melanges d’eau et de petrole brut
WO2024079049A1 (en) 2022-10-11 2024-04-18 Totalenergies Onetech Additive composition and use thereof as asphaltene dispersant in petroleum products
FR3141186B1 (fr) 2022-10-20 2024-10-25 Totalenergies Onetech Composition de carburant marin à basse teneur en soufre

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UA104854C2 (uk) 2014-03-25
FR2925916A1 (fr) 2009-07-03
US20100281762A1 (en) 2010-11-11
HUE032911T2 (hu) 2017-11-28
BRPI0820066A8 (pt) 2018-05-29
EP2238225A2 (fr) 2010-10-13
DK2238225T3 (en) 2017-02-06
EA201070807A1 (ru) 2011-02-28
PL2238225T3 (pl) 2017-05-31
ZA201005265B (en) 2011-04-28
MA32023B1 (fr) 2011-01-03
WO2009106744A2 (fr) 2009-09-03
TW200932893A (en) 2009-08-01
ES2612739T3 (es) 2017-05-18
BRPI0820066A2 (pt) 2015-09-01
MY162899A (en) 2017-07-31
JP2011508042A (ja) 2011-03-10
AU2008351922B2 (en) 2012-12-13
CN101925667A (zh) 2010-12-22
AU2008351922A1 (en) 2009-09-03
BRPI0820066B1 (pt) 2018-06-05
WO2009106744A3 (fr) 2009-10-22
AR069986A1 (es) 2010-03-03
KR20100135221A (ko) 2010-12-24
CA2710839A1 (fr) 2009-09-03
SG162529A1 (en) 2010-07-29
MX2010007225A (es) 2010-09-30
SI2238225T1 (sl) 2017-05-31
HRP20170032T1 (hr) 2017-03-24
FR2925916B1 (fr) 2010-11-12
CL2008003911A1 (es) 2009-07-03
PT2238225T (pt) 2017-02-06
LT2238225T (lt) 2017-02-10
CA2710839C (fr) 2016-06-21

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