EP0086141B1 - Procédé de préparation de complexes organo-solubles du calcium, les complexes obtenus et leur utilisation, notamment comme additifs pour améliorer la combustion des gazoles et des fuel-oils - Google Patents

Procédé de préparation de complexes organo-solubles du calcium, les complexes obtenus et leur utilisation, notamment comme additifs pour améliorer la combustion des gazoles et des fuel-oils Download PDF

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Publication number
EP0086141B1
EP0086141B1 EP83400194A EP83400194A EP0086141B1 EP 0086141 B1 EP0086141 B1 EP 0086141B1 EP 83400194 A EP83400194 A EP 83400194A EP 83400194 A EP83400194 A EP 83400194A EP 0086141 B1 EP0086141 B1 EP 0086141B1
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EP
European Patent Office
Prior art keywords
calcium
process according
proportion
sulfonic acid
gram
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83400194A
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German (de)
English (en)
French (fr)
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EP0086141A1 (fr
Inventor
Maurice Born
Lucienne Briquet
Guy Parc
Nicole Thevenin
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen

Definitions

  • the invention relates to an improved process for the preparation of organosoluble calcium complexes, which can be used in particular as additives which improve the combustion of liquid fuels. It also relates to the complexes obtained by this process and their use.
  • liquid hydrocarbons such as for example gas oils, fuel oil, light fuels, heavy fuels, or even kerosene
  • unburnt substances solid, liquid or gaseous, such as soot, cracked hydrocarbons, carbon monoxide, as well as nitrogen oxides.
  • the main disadvantages of these unburnt products are that they lower the efficiency of the energy generators (fuel oil burners, diesel engines, etc.), as a result of the loss of combustible material and the formation of deposits (especially soot) on the heat exchangers, which leads to a decrease in the heat transfer coefficients; and lead to the emission of harmful fumes, which should be reduced as much as possible.
  • liquid fuels gas oils or fuel oils, for example
  • organosoluble compounds of iron, calcium or barium for example, having the effect of preventing the emission of fumes, or at least reduce its importance.
  • organosoluble compounds of iron, calcium or barium for example, having the effect of preventing the emission of fumes, or at least reduce its importance.
  • organosoluble calcium complexes which have an increased calcium content compared to the content of organosoluble calcium complexes obtained by the methods described in the prior art.
  • the process thus defined makes it possible, in particular thanks to the simultaneous use of methanol and of the second alcohol in the particular proportions indicated, to obtain sulfonic complexes having a very high calcium content.
  • a particularly important operating advantage lies in the fact that the process takes place within a single liquid phase, the reaction water being kept in solution by the presence of the second alcohol; on the contrary, in the absence of this alcohol, the appearance of a hydroalcoholic phase very significantly disturbs the course of carbonation.
  • a sulfonic acid is first used, which can be aliphatic, alicyclic or aromatic. It will most often be an aromatic sulfonic acid.
  • aromatic sulfonic acids mention may be made of sulfonic alkylbenzene acids which contain from about 10 to 20 carbon atoms. Mention may also be made of industrial alkylbenzene sulfonic acids (so-called “heavy alkylbenzene sulfonic acids”) which contain from about 20 to 35 carbon atoms.
  • the compound with nitrogen functions and with long hydrocarbon chain (s) can consist in particular of a polyalkenylsuccinimide-amine or a bis (polyalkenylsuccinimide) -amine corresponding respectively to the general formulas: and in which R represents a substantially saturated aliphatic hydrocarbon radical containing from 20 to 250 carbon atoms, preferably from 75 to 100, X represents an alkylene radical of 2 to 5 carbon atoms, the two valences of which are located on separate carbon atoms, and m takes a value from 1 to 5, preferably from 1 to 3.
  • the radical R results from the polymerization or copolymerization of one or more light olefins having for example from 2 to 6 carbon atoms, such as for example ethylene, propylene , butenes -1 and -2, isobutene or 2-methyl-pentene-1.
  • the radical R can be, more specifically, a polyisobutenyl radical having a molecular mass of approximately 900 to 1300.
  • the radical X is most often the ethylene radical -CH 2 -CH Z - and m takes for example the value 3 .
  • polyalkenylsuccinimidine-amine or bis (polyalkenylsuccinimide) -amine involves polyisobutenyl succinic anhydride and tetraethylene pentamine at a rate of 1 (or 2) mol of anhydride per mole of tetraethylenepentamine.
  • R 1 represents a monovalent hydrocarbon radical (for example aliphatic) which contains from 6 to 22 carbon atoms
  • n takes an integer value from 0 to 4
  • p zero when n is zero, takes the value 0, 1 or 2 when n is not zero.
  • R 1 is defined as above and can for example be a mixture of alkyl radicals of 12 to 14 carbon atoms.
  • the compound with nitrogen functions and with long hydrocarbon chain (s) is generally introduced into the reaction medium in a proportion of 10 to 30% by mass and preferably of 15 to 25% by mass relative to the sulfonic acid used.
  • the reaction medium advantageously comprises a dilution oil which generally consists of a mineral oil of low viscosity, such as for example a 100 Neutral Solvent oil.
  • a dilution oil which generally consists of a mineral oil of low viscosity, such as for example a 100 Neutral Solvent oil.
  • the mass proportion of this oil with respect to sulfonic acid generally corresponds to a ratio ranging from about 1: 5 to 2: 1.
  • the implementation of the process of the invention requires the use of a hydrocarbon or halo-hydrocarbon solvent, more particularly constituting an aromatic hydrocarbon such as for example benzene, toluene, xylene, mono- or di -ethylbenzene or mono- or di-isopropylbenzene: or in a halogenated aliphatic hydrocarbon such as for example trichlorethylene.
  • a hydrocarbon or halo-hydrocarbon solvent more particularly constituting an aromatic hydrocarbon such as for example benzene, toluene, xylene, mono- or di -ethylbenzene or mono- or di-isopropylbenzene: or in a halogenated aliphatic hydrocarbon such as for example trichlorethylene.
  • Various petroleum fractions can also be used, such as gas oils or domestic fuel oils.
  • the organosoluble calcium complex in the form of a solution, it is advantageous to use a solvent which has a boiling point high enough not to be eliminated. under the operating conditions of the final stage of obtaining the additive as they will be defined below.
  • Solvents of this type are for example diisopropylbenzene, gas oils or domestic fuel oils.
  • hydrocarbon or halo-hydrocarbon solvent thus defined is generally used in a proportion ranging from 1 to 10 kg per kilogram of sulfonic acid.
  • the C 3 or C 4 monoalcohol is preferably isopropanol.
  • Methanol and C 3 or C 4 monoalcohol are generally introduced in a total proportion ranging from 80 to 1000 ml / l of hydrocarbon or halo-hydrocarbon solvent.
  • the volume ratio of C 3 or C 4 alcohol to methanol is generally 1: 100 to 3.5: 1 as previously indicated, but preferred values are in the range of 1: 5 to 3: 1.
  • calcium oxide is introduced into the reaction medium in excess relative to the stoichiometry of basic calcium sulfonate (which corresponds to 1 gram atom of calcium per gram equivalent d 'sulfonic acid).
  • the proportion of calcium oxide or hydroxide used can range from 1 to 30 atoms- grams of calcium per gram equivalent of sulfonic acid.
  • the reaction mixture constituted as described above is heated to a temperature of 20 to 65 ° C (preferably of the order of 55 to 60 ° C), under strong stirring, so as to neutralize the sulfonic acid.
  • the carbonation of a substantial proportion is carried out. tial and preferably as much as possible, of the excess oxide or hydroxide dispersed in the reaction mixture. Carbonation is generally carried out using gaseous carbon dioxide, pure or diluted by an inert gas with respect to the reactants present, in very divided form, the reaction mixture being kept, always with stirring, at a temperature from 20 to 65 ° C, and preferably between 55 to 60 ° C.
  • the liquid obtained contains the unreacted oxide or hydroxide in suspension, the carbonation yield cannot be total.
  • the carbonation yield decreases when an increasing excess of oxide or hydroxide is involved.
  • the volatile constituents of the mixture obtained water, methanol, second alcohol, toluene, benzene, chlorinated solvent, etc.
  • the volatile constituents of the mixture obtained are removed, for example by evaporation under reduced pressure in a rotary thin layer evaporator.
  • Solid particles of unreacted metal oxide or hydroxide are removed, for example by filtration or centrifugation.
  • the additive obtained under the conditions described is in the form of a glassy solid, however, entirely soluble in petroleum hydrocarbons.
  • the organosoluble complexes of the invention are collected in the form of a very fluid clear liquid additionally containing the dilution oil. possibly introduced at the start.
  • Organo-soluble complexes of calcium ob - made by the method of the invention may contain very high calcium content.
  • the proportion of calcium introduced can range from 5 to 20 gram atoms of calcium per gram equivalent of sulfonic acid.
  • organosoluble calcium complexes can be used as additives for improving the combustion of various liquid fuels (gas oils, fuel oils). They are then added to these fuels in a proportion which can range, for example, from 10 to 150 ppm, preferably from 25 to 75 ppm, by mass of calcium relative to the mass of the liquid fuel.
  • the total basic index of the products was determined according to standard ASTM D 664-58. Certain pressures are expressed in bars. The bar is worth 0.1 MPa.
  • the temperature of the mixture is brought to 50 ° C while ensuring vigorous stirring.
  • the pH of the mixture is monitored as a function of the% CO 2 introduced.
  • the brown solution obtained, containing the excess lime, is transferred to a thin layer rotary evaporator where it is freed from its volatile constituents (water, alcohols) by evaporation under reduced pressure (110 ° C, 4 ⁇ 10 3 Pa) .
  • the hot suspension thus obtained is transferred into a single-plate filter of the Gauthier type (filtering surface: 113 cm 2 ), then filtered in approximately 1 h under an effective pressure of 2 bars. 1100 g of clear, very fluid organic solution constituting the additive are thus collected, ie approximately 60% by mass of the theoretical amount.
  • the filter cake is dispersed with twice 500 cm 3 of hexane, the suspension obtained being again filtered under 2 bars.
  • Example 2 The same experiment as in Example 1 is carried out by replacing diisopropylbenzene with the same volume of a light petroleum solvent, toluene.
  • the suspension is transferred to the Gauthier filter, where it is filtered in approximately 1 hour under an effective pressure of 2 bars.
  • the filter cake twice with 500 cm 3 of hexane the filtered hydrocarbon fractions collected are stripped of their volatile constituents in the rotary thin layer evaporator (reaction water, alcohols, toluene). 915 g of an additive are thus recovered which is presented at room temperature in the form of a very viscous translucent liquid, completely soluble in petroleum hydrocarbons and which represents approximately 93.5% by mass of the theoretical amount. additive obtainable.
  • the high value of the measured TBN indicates a content of calcium carbonate in the colloidal state of the order of 48.1% of the total mass of additive, and an amount of calcium sulfonate of approximately 24.6%, which means that the ratio of the number of calcium atoms to the number of acid molecules contained is of the order of 10.7, or that the ratio of the number of calcium atoms, to the carbonate state colloidal, the number of calcium atoms in the sulfonate state, is of the order of 21.3.
  • Example 2 The same experiment as in Example 1 is carried out by replacing methyl alcohol with the same volume of pure isopropyl alcohol, ie a total volume of this alcohol of 240 cm 3 (total absence of methyl alcohol).
  • Example 2 The same experiment as in Example 1 is carried out by replacing isopropyl alcohol with the same volume of methyl alcohol, ie a total volume of this alcohol of 240 cm 3 (total absence of isopropyl alcohol).
  • Example 2 The same experiment as in Example 1 is carried out by replacing diisopropylbenzene with the same volume of engine diesel. Finally recovered, and under these conditions, 1744 g of a solution containing 9.75% by mass of calcium, or approximately 95.4% by mass of the theoretical amount of additive that can be obtained.
  • Example 1 Various experiments are carried out under the conditions of Example 1, using mixtures of methyl and isopropyl alcohols in various proportions.
  • Example 3 the isopropanol used in the same proportion as the mixture of alcohols of Example 1 is unsuitable for the carbonation of lime.
  • Example 4 it is also observed that in Example 4, the replacement of isopropanol by methanol allows the carbonation of lime but that this reaction is not carried out under conditions as satisfactory as that carried out in Example ple 1 in the presence of the mixture of the two alcohols, as evidenced by the excessive duration of the filtration and the low yield obtained.
  • Example 1 It therefore appears in Example 1 that the best carbonation conditions are the fact that the reaction water is kept in solution by the presence of isopropyl alcohol which acts as a compatibilizing agent.
  • Example 3 shows, however, the essential nature of the presence of methanol in the medium, since isopropanol alone does not allow the operation to be carried out successfully.
  • the high value of the measured TBN indicates a content of calcium carbonate in the colloidal state of the order of 58% of the total mass of the additive.
  • the determination of the quantity of sulphonic acid contained in the additive shows that only part of this acid is present in the additive, and that the ratio of the number of calcium atoms to the number of molecules of acid contained is of the order of 17.4, or even that the ratio of the number of calcium atoms in the state of colloidal carbonate to the number of calcium atoms in the state of sulfonate is of the order of 34.4, which constitutes a quite remarkable result.
  • the temperature of the mixture is brought to 40 ° C. and then 177 kg of CO z are admitted into the suspension over 3 hours.
  • This solution is filtered, then directed to a fractionation column to remove the residual methyl alcohol and traces of reaction water.
  • This fraction rich in alcoholic compound is then directed as a mixture with the upper phase to the distillation column for the recovery of the alcohol.
  • the detergent additive thus obtained after elimination of the toluene, is characterized by a calcium content of 12.9% by mass and by a TBN of 340 (ASTM D 664).
  • the single liquid phase containing the additive is filtered and then directed, as before, to a distillation column for the recovery of the solvents.
  • the solvent-free additive is recovered liquid at the bottom of the column, the accumulation of solid organic products no longer occurring.
  • Example 1 An additive prepared according to the operating protocol of Example 1 is used in a series of tests relating to the reduction in the “Bosch” smoke index of a Peugeot Indenor engine.
  • the additive is introduced into the diesel fuel at concentrations between 0.5 and 2 per 1000.
  • the smoke index is determined for each test according to the “Bosch” method.
  • Example 2 An additive prepared according to the operating protocol of Example 1 is used in a series of tests relating to the reduction in the rate of emission of unburnt from a heavy fuel oil No. 2.
  • the additive is introduced into No. 2 heavy fuel oil (having a viscosity of 36.3 cSt at 100 ° C.) at 2 concentrations corresponding to 50 and 100 ppm by mass of calcium.
  • the heavy fuel oil is sprayed mechanically under a pressure of 29 bars; the fuel supply rate is 90 kg / h.
  • the air intake temperature is 25 ° C and the excess air is 25%.
  • the blackening weight index is determined for each test according to standard NF X 43-003. This is the gravimetric content of the solid particles corresponding to 1 thermal release (it is expressed in mg / th).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP83400194A 1982-02-05 1983-01-28 Procédé de préparation de complexes organo-solubles du calcium, les complexes obtenus et leur utilisation, notamment comme additifs pour améliorer la combustion des gazoles et des fuel-oils Expired EP0086141B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8202026 1982-02-05
FR8202026A FR2521158A1 (fr) 1982-02-05 1982-02-05 Procede de preparation de complexes organo-solubles au calcium, les complexes obtenus et leur utilisation, notamment comme additifs pour ameliorer la combustion des gazoles et des fuel-oils

Publications (2)

Publication Number Publication Date
EP0086141A1 EP0086141A1 (fr) 1983-08-17
EP0086141B1 true EP0086141B1 (fr) 1985-07-03

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EP83400194A Expired EP0086141B1 (fr) 1982-02-05 1983-01-28 Procédé de préparation de complexes organo-solubles du calcium, les complexes obtenus et leur utilisation, notamment comme additifs pour améliorer la combustion des gazoles et des fuel-oils

Country Status (4)

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US (1) US4737298A (enrdf_load_stackoverflow)
EP (1) EP0086141B1 (enrdf_load_stackoverflow)
DE (1) DE3360331D1 (enrdf_load_stackoverflow)
FR (1) FR2521158A1 (enrdf_load_stackoverflow)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2588270B1 (fr) * 1985-10-03 1988-02-05 Elf France Procede de preparation d'un additif pour les huiles lubrifiantes, l'additif ainsi obtenu et une composition lubrifiante renfermant ledit additif
GB8917094D0 (en) * 1989-07-26 1989-09-13 Bp Chemicals Additives Chemical process
RU2244734C2 (ru) * 2002-12-27 2005-01-20 Общество с ограниченной ответственностью "ПЛАСТНЕФТЕХИМ" Способ получения высокощелочной модифицированной сульфонатной присадки к смазочным маслам

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3488284A (en) * 1959-12-10 1970-01-06 Lubrizol Corp Organic metal compositions and methods of preparing same
GB1028063A (en) * 1962-04-06 1966-05-04 Lubrizol Corp Grease composition
US3282835A (en) * 1963-02-12 1966-11-01 Lubrizol Corp Carbonated bright stock sulfonates and lubricants containing them
GB1068547A (en) * 1963-12-26 1967-05-10 Exxon Research Engineering Co Metal carbonate overbased lubricant detergent-dispersants
US3377283A (en) * 1967-03-09 1968-04-09 Lubrizol Corp Process for preparing thickened compositions
GB1121578A (en) * 1967-11-06 1968-07-31 Lubrizol Corp Reaction products of high molecular weight hydrocarbon succinic acid compounds, amines and heavy metal compounds
US3539511A (en) * 1967-11-24 1970-11-10 Standard Oil Co Preparation of alkaline earth sulfonates
US3714042A (en) * 1969-03-27 1973-01-30 Lubrizol Corp Treated overbased complexes
US3853774A (en) * 1972-12-20 1974-12-10 Chevron Res Process for preparing oil-soluble basic magnesium salts
FR2236001A1 (en) * 1973-07-03 1975-01-31 Inst Francais Du Petrole Overbased detergent additives for lubricants - prepd from sulphonic acids contg beta-amino acids
FR2265848A1 (en) * 1974-03-29 1975-10-24 Inst Francais Du Petrole Over based detergent additive for lubricants - obtd by carbonating metal hydroxide-oil soluble metal sulphonate-polyalkenyl-succinimide-amine salt
FR2271281B2 (enrdf_load_stackoverflow) * 1974-03-29 1977-01-21 Inst Francais Du Petrole
US4218328A (en) * 1978-12-28 1980-08-19 Chevron Research Company Lubricating oil additive

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Publication number Publication date
FR2521158B1 (enrdf_load_stackoverflow) 1984-03-30
US4737298A (en) 1988-04-12
EP0086141A1 (fr) 1983-08-17
FR2521158A1 (fr) 1983-08-12
DE3360331D1 (en) 1985-08-08

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