EP0261002B1 - Verwendung von Gemischen aus seltenen Erden, um Kraftstoffe für Dieselmotoren zu stabilisieren - Google Patents

Verwendung von Gemischen aus seltenen Erden, um Kraftstoffe für Dieselmotoren zu stabilisieren Download PDF

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Publication number
EP0261002B1
EP0261002B1 EP87401481A EP87401481A EP0261002B1 EP 0261002 B1 EP0261002 B1 EP 0261002B1 EP 87401481 A EP87401481 A EP 87401481A EP 87401481 A EP87401481 A EP 87401481A EP 0261002 B1 EP0261002 B1 EP 0261002B1
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EP
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Prior art keywords
rare earth
radical
use according
carbon atoms
diesel
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EP87401481A
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English (en)
French (fr)
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EP0261002A1 (de
Inventor
Peter S. Gradeff
John F. Davison
Nicholas A. Sullo
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Rhodia Chimie SAS
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Rhone Poulenc Chimie SA
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    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the subject of the present invention is a composition making it possible to improve the stability of fuels for diesel engines by adding certain organic rare earth compounds to fuels for diesel engines.
  • the invention also relates to its method of implementation.
  • diesel fuel used in the description and the claims designates the fraction of hydrocarbons resulting from the distillation of kerosene.
  • diesel fuel is a mixture of hydrocarbons with a melting point between about 177 ° C and about 371 ° C.
  • the approximate ranges given below correspond to the specifications required for diesel fuels defined in "Federal Specification VV-F-800" from 1967.
  • DF-A arctic
  • DF-1 winter
  • DF- 2 normal
  • DF-4 unheavy.
  • the "arctic” quality is used in high-speed automotive-type diesel engines and burner burner heaters used in environments where the ambient temperature is below -30 ° C.
  • Diesel fuels have a large number of components. In addition to the petroleum fractions used as fuel, they contain many chemical compounds used for several purposes. These chemical additives are used for example to prevent oxidation and prevent the formation of sludge, prevent corrosion, produce a detergent and dispersing action, emulsify, deactivate metals, obtain an antistatic effect and as biocides.
  • diesel fuels pose a significant problem. Indeed, certain components such as, for example, unsaturated hydrocarbons tend to react and precipitate during storage, causing various inconveniences including fouling of tanks and engines. In addition, some of these additives selectively combine with the precipitate, are therefore no longer present in the composition of the fuel and no longer play the role which was assigned to them.
  • Antioxidants are one of the most important classes among diesel fuel additives. Since diesel fuel is a mixture of hydrocarbons, it is very prone to radical oxidation and the formation of acids, ketones, aldehydes and esters. Oxidation forms gums which pass into the colloidal state, agglomerate and precipitate in the form of mud. Mud can clog the burner lines, filters and nozzles.
  • oxidation inhibitors work by eliminating peroxy radicals present in the reaction chain, thus stopping the reaction. This is how the oxidation inhibitors of phenolic type such as dimethyl-2,4-tert-butyl-6-phenol and di-tert-butyl-2,6-methyl-4-phenol.
  • Other oxidation inhibitors include amines such as N, N′-di-sec-butyl p-phenylene diamine and phosphorus and sulfur compounds such as esters of dithiphosphoric acid, barium salts and zinc of said acids.
  • metal deactivators Another important class of additives in diesel fuel is metal deactivators. Generally, these compounds act by chelating the metals found in diesel fuels, the metals being surrounded and isolated in complexes which, instead of precipitating, remain soluble in the fuel.
  • US Patent 4,222,746 describes another group of compounds for reducing the black smoke and visible particles contained in the exhaust gas of diesel internal combustion engines. According to this patent, it is possible to reduce the emissions of smoke black and visible particles by adding wax to the diesel fuel which oxidizes at the same time as an organometallic compound, soluble in the fuel, such as tricarbonylalkylcyclopentadienymanganese.
  • combustion promoters have been developed to improve the combustion efficiency of the hydrocarbons contained in diesel fuel.
  • Combustion promoters promote the combustion of hydrocarbons during the operation of the diesel engine.
  • Cerium octoates tend, however, to contribute to the formation of precipitate and mud in fuels.
  • One of the objectives of the present invention is to provide a means for stabilizing the diesel fuel and effectively preventing fouling of the diesel engine by reducing the accumulation of mud in the diesel fuel.
  • Another object of the present invention is to provide a method for reducing the precipitation of particles in diesel fuel during storage for a relatively long period of time.
  • the present invention also aims to provide a method for maintaining various additives of the diesel fuel in solution during storage so that they fulfill their function during storage and combustion.
  • Another object of the present invention is to provide a method making it possible to significantly reduce the precipitation in diesel fuels using certain rare earth compounds.
  • the present invention relates to the use of a diesel fuel stabilization additive making it possible to significantly reduce precipitation and the formation of mud during storage and transport, characterized in that it consists of an organometallic compound of rare earth corresponding to the following formula: in which M represents one or more rare earth elements chosen from the group comprising yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, promethium thulium, ytterbium and lutetium and R a hydrocarbon group having 3 to 25 carbon atoms.
  • M represents one or more rare earth elements chosen from the group comprising yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, promethium thul
  • said compounds contain carboxyl groups linked to the rare earth element by an oxygen atom.
  • cerium The most abundant lanthanide, cerium, is not in this group. Indeed, it is remarkable and surprising to note that the cerium compounds do not work in the context of the process according to the present invention. It is likely that the cerium compounds behave differently due to the ease with which the cerium enters the tetravalent state which seems responsible for its reactivity towards certain fuel components.
  • the preferred compounds of the present invention correspond to formula (I) in which M represents yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium or their mixtures, which may contain traces of the traces other trivalent lanthanides such as terbium, dysprosium, holmium, erbium, promethium, thulium, ytterbium and lutetium.
  • R is a hydrocarbon group containing approximately from 3 to 25 carbon atoms.
  • R can represent a linear or branched, cycloaliphatic, saturated or unsaturated aliphatic hydrocarbon radical; a monocyclic or polycyclic aromatic radical, these radicals being able to form between them orthocondensed or ortho and pericondensed systems; a heterocyclic, saturated, unsaturated or aromatic, monocyclic or polycyclic radical comprising at least one of the heteroatoms O, N and S.
  • the radical R more specifically represents a linear or branched alkyl radical having from 3 to 25 carbon atoms, an alicyclic radical having from 5 to 8 carbon atoms in the ring, an aryl radical such as phenyl, an alkylaryl radical comprising from 1 to 4 carbon atoms in the substituent such as tolyls, xylyls, a polycyclic aromatic radical having from 10 to 14 carbon atoms, such as the naphthyl radical, a heterocyclic radical comprising at least one of the heteroatoms O, N and S and containing from 5 to 10 atoms in the ring such as, for example, a furanyl, furomethyl, pyridyl, picolyl, indolinyl, etc. radical.
  • the radical R can carry substituent groups such as, for example, hydroxyl groups, alkyloxy radicals preferably having from 1 to 3 carbon atoms or halogen atoms, in particular chlorine.
  • Typical carboxylic groups which make the rare earth element soluble in diesel fuel are, for example, 2-ethyl hexoate (called octoate), naphthenate, neodecanoate, butyrate, hydroxystearate and the like.
  • One embodiment of the additive of the invention consists in adding it to diesel fuels, preferably in the form of a concentrate soluble in said diesel fuel. However, it can be added according to any method known to those skilled in the art.
  • the amount of rare earth element contained in diesel fuel can vary between 5 and 500 ppm.
  • the amount of rare earth element is preferably between 5 and 150 ppm.
  • each sample is filtered on a Millipore filter, the bottle is washed four times with hexane and the filtrate is dried. The weight of the dried precipitate is noted. Then, the bottle is washed three times with a "mixture of three solvents" (toluene, methanol and acetone) to dissolve the gums and the washing liquids are evaporated. Separately, the weight of the gums retained by the mixture of three solvents is noted.
  • Table (I) under the heading "mg of sediment / 100 cm3 of fuel” represents the total weight of precipitate and gums per 100 cm3 of diesel fuel.
  • the tests were carried out with diesel fuel samples from four different sources. Three of these samples were specially selected for their low storage stability, due to their compositions which tend to precipitate during storage. The fourth sample is a commercial diesel fuel.
  • TR represents a mixture of rare earth elements, cerium, praseodymium and neodymium.
  • cerium derivatives have a high reactivity and form deposits which are clearly superior to those of the control test. It is surprising to note that the use of lanthanum, praseodymium, neodymium and other organometallic complexes of the aforementioned rare earths reduces the deposit and apparently changes the nature of the deposit as shown by the color of the deposit.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Claims (10)

1. Verwendung eines Additivs für die Stabilisierung von Dieselkraftstoffen während ihrer Lagerung, dadurch gekennzeichnet, daß das Additiv aus einer metallorganischen SE-Verbindung besteht, die der folgenden Formel
Figure imgb0007
 entspricht, in der M ein oder mehrere SE-Element(e), ausgewählt aus der Gruppe, die Yttrium, Lanthan, Praseodym, Neodym, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Promethium, Thulium, Ytterbium und Lutetium umfaßt, bedeutet und R für eine Kohlenwasserstoffgruppe mit 3 bis 25 Kohlenstoffatomen steht.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß M ein oder mehrere SE-Element(e), ausgewählt aus der Gruppe, die Yttrium, Lanthan, Praseodym, Neodym, Samarium, Europium und Gadolinium umfaßt, bedeutet.
3. Verwendung nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, daß R für einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest, einen gesättigten oder ungesättigten cycloaliphatischen Kohlenwasserstoffrest, einen monocyclischen oder polycyclischen aromatischen Rest, wobei diese Reste untereinander orthokondensierte oder ortho- und perikondensierte Systeme bilden können, einen heterocyclischen Rest, gesättigt, ungesättigt oder aromatisch, monocyclisch oder polycyclisch, der mindestens eines der Heteroatome O, N und S enthält, steht.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß R für einen linearen oder verzweigten Alkylrest mit 3 bis 25 Kohlenstoffatomen, einen alicyclischen Rest mit 5 bis 8 Kohlenstoffatomen im Ring, einen Arylrest, einen Alkylarylrest mit 1 bis 4 Kohlenstoffatomen im Substituenten, einen polycyclischen aromatischen Rest mit 10 bis 14 Kohlenstoffatomen, einen heterocyclischen Rest, der mindestens eines der Heteroatome O, N und S sowie 5 bis 10 Atome im Ring enthält, steht.
5. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß R durch eine Hydroxylgruppe, eine Alkyloxygruppe mit 1 bis 3 Kohlenstoffatomen oder ein Halogenatom substituiert ist.
6. Verwendung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die metallorganische SE-Verbindung, die der Formel (I) entspricht, ein Octoat, Naphtenat, Neodecanoat, Butyrat oder Hydroxystearat ist.
7. Verwendung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Verbindung der Formel (I) eine Verbindung der Formel
Figure imgb0008
 ist.
8. Verwendung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die metallorganische SE-Verbindung dem Dieselkraftstoff in einer solchen Menge zugesetzt wird, daß die Konzentration des SE-Elementes in dem Dieselkraftstoff 5 bis 500 ppm beträgt.
9. Verwendung nach Anspruch 8, dadurch gekennzeichnet, daß die Konzentration 5 bis 150 ppm beträgt.
10. Verwendung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die metallorganische SE-Verbindung dem Dieselkraftstoff in Form eines löslichen Konzentrats zugesetzt wird.
EP87401481A 1986-09-19 1987-06-26 Verwendung von Gemischen aus seltenen Erden, um Kraftstoffe für Dieselmotoren zu stabilisieren Expired - Lifetime EP0261002B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87401481T ATE66957T1 (de) 1986-09-19 1987-06-26 Verwendung von gemischen aus seltenen erden, um kraftstoffe fuer dieselmotoren zu stabilisieren.

Applications Claiming Priority (2)

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US90978286A 1986-09-19 1986-09-19
US909782 1986-09-19

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EP0261002A1 EP0261002A1 (de) 1988-03-23
EP0261002B1 true EP0261002B1 (de) 1991-09-04

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US (1) US4836830A (de)
EP (1) EP0261002B1 (de)
JP (1) JP2552150B2 (de)
AT (1) ATE66957T1 (de)
AU (1) AU604750B2 (de)
BR (1) BR8704825A (de)
DE (1) DE3772685D1 (de)

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US5360459A (en) 1991-05-13 1994-11-01 The Lubrizol Corporation Copper-containing organometallic complexes and concentrates and diesel fuels containing same
US5376154A (en) 1991-05-13 1994-12-27 The Lubrizol Corporation Low-sulfur diesel fuels containing organometallic complexes
US5344467A (en) 1991-05-13 1994-09-06 The Lubrizol Corporation Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same
IL100669A0 (en) 1991-05-13 1992-09-06 Lubrizol Corp Low-sulfur diesel fuel containing organometallic complexes
TW230781B (de) 1991-05-13 1994-09-21 Lubysu Co
IT1256134B (it) * 1992-09-09 1995-11-29 Luigi Boltri Sali lipofili contenenti isotopi neutron attivabili e composizioni che li contengono
FR2698346B1 (fr) * 1992-11-25 1995-01-27 Rhone Poulenc Chimie Agrégat de cristallites d'oxyde cérique, procédé d'obtention et son utilisation pour réduire les résidus de combustion.
US5637118A (en) * 1994-06-30 1997-06-10 United Technologies Corporation Vanadium corrosion inhibitor
RU2472847C1 (ru) * 2011-09-23 2013-01-20 Федеральное государственное учреждение "Всероссийский научно-исследовательский институт охраны и экономики труда" Министерства здравоохранения и социального развития Российской Федерации Антидымная присадка
RU2472844C1 (ru) * 2011-09-23 2013-01-20 Федеральное государственное учреждение "Всероссийский научно-исследовательский институт охраны и экономики труда" Министерства здравоохранения и социального развития Российской Федерации Антидымная присадка
US10077615B2 (en) 2015-07-31 2018-09-18 ASDR Canada Inc. Sound absorber for a drilling apparatus

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Also Published As

Publication number Publication date
US4836830A (en) 1989-06-06
EP0261002A1 (de) 1988-03-23
ATE66957T1 (de) 1991-09-15
AU604750B2 (en) 1991-01-03
AU7849687A (en) 1988-04-28
DE3772685D1 (de) 1991-10-10
JPS6386797A (ja) 1988-04-18
JP2552150B2 (ja) 1996-11-06
BR8704825A (pt) 1988-05-17

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