EP0025328B1 - Production de sulfonate de calcium superbasique, produit ainsi obtenu et huile lubrifiante le contenant - Google Patents

Production de sulfonate de calcium superbasique, produit ainsi obtenu et huile lubrifiante le contenant Download PDF

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Publication number
EP0025328B1
EP0025328B1 EP19800303029 EP80303029A EP0025328B1 EP 0025328 B1 EP0025328 B1 EP 0025328B1 EP 19800303029 EP19800303029 EP 19800303029 EP 80303029 A EP80303029 A EP 80303029A EP 0025328 B1 EP0025328 B1 EP 0025328B1
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EP
European Patent Office
Prior art keywords
weight
oil
process according
mixture
sulphonic acid
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Expired
Application number
EP19800303029
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German (de)
English (en)
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EP0025328A1 (fr
Inventor
Alan Michael Dominey
Dennis John Simpkin
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Publication of EP0025328A1 publication Critical patent/EP0025328A1/fr
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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

Definitions

  • the present invention relates to the production of overbased calcium sulphonates and to the overbased calcium sulphonates thereby produced.
  • Overbased calcium sulphonates which consist of colloidal calcium carbonate dispersed in calcium sulphonate have been known as lubricant additives for some time. They act as dispersants and their basicity neutralises acids formed in the lubricant thus reducing corrosion.
  • lubricant additives For some time, they act as dispersants and their basicity neutralises acids formed in the lubricant thus reducing corrosion.
  • overbased calcium sulphonates in lubricating oils has been that the colloidal calcium carbonate has tended to form haze and sediment in the oil. In addition the materials can be difficult to filter after manufacture.
  • Overbased calcium sulphonates are generally produced by carbonating mixtures of an oil soluble sulphonic acid or an alkaline earth metal sulphonate, an alcohol, often methanol, calcium oxide and oil. In some processes second solvents, promoters and alkaline earth metal halides are used. Processes for the production of overbased calcium sulphonates are described in United Kingdom patent specifications 1,299,253 and 1,309,172. European patent publication no. A 0-000264 describes the production of improved basic calcium sulphonate by carbonation of certain reaction mixtures containing excess calcium hydroxide at a temperature in the range 20 to 35°C in the presence of from 4 wt.% to 35 wt.% of water based on the weight of calcium hydroxide.
  • the calcium carbonate present generally contains both crystalline and amorphous material and it appears that the greater the amount of crystalline material present in the final product the more difficult it is to filter and the greater the tendency for haze and sediment formation.
  • the present invention therefore provides a process for the production of highly basic calcium sulphonates comprising the following steps.
  • Component (a) of the reaction mixture includes oil-soluble sulphonic acids and these may be natural or synthetic sulphonic acids, e.g. a mahogany or petroleum alkyl sulphonic acid; an alkyl sulphonic acid; or an alkaryl sulphonic acid.
  • the alkyl sulphonic acid should preferably have at least 18 carbon atoms in the alkyl chain. Most suitable are sulphonic acids of molecular weight from 300 to 700, preferably from 400 to 500, suitable sulphonates are the salts of such sulphonic acids.
  • an alkaline earth metal sulphonate can be used, for example, a calcium sulphonate.
  • Component (a) can be conveniently used as a mineral oil solution, e.g. one consisting of 70% by weight by sulphonic acid or sulphonate and 30% by weight of oil.
  • Component (b) of the reaction mixture is an aromatic or aliphatic hydrocarbon solvent.
  • Aromatic hydrocarbons are preferred, and examples of these are toluene, xylene and ethyl benzene.
  • Suitable aliphatic hydrocarbons include paraffinic hydrocarbons such as n-hexane, n-heptane, n-decane, n-dodecane, white spirit, naphtha or iso-paraffins.
  • Component (c) is preferably methanol although other C, to C 5 alcohols such as ethanol can be used.
  • Additional reaction promoters may be used and these may be the ammonium carboxylates such as those described in United Kingdom patent 1,307,172 where the preferred ammonium carboxylates are those derived from C, to C 3 saturated monocarboxylic acids, e.g. formic acid, acetic acid or propionic acid.
  • the preferred ammonium carboxylate is ammonium formate.
  • alkali metal salts of a C, to C 3 carboxylic acid may be used, the preferred being those of C, to C 3 saturated monocarboxylic acids.
  • the preferred alkali metals are sodium and potassium.
  • a metal halide or sulphide may be used as an alternative promoter.
  • the preferred metals are alkali metals or alkaline earth metals, e.g. sodium, potassium, lithium, calcium, barium, and strontium. Salts of aluminium, copper, iron, cobalt and nickel may also be used.
  • the water content of the initial reaction mixture is critical to obtaining the desired product and should not be more than 4 wt % and not less than 0.50 wt % based on weight of the excess calcium oxide, we prefer to use from 1 wt % to 3 wt % based on the weight of the excess calcium oxide.
  • the reactants which are used are therefore preferably anhydrous, including the carbon dioxide and any calcium oxide which is added later to the reaction mixture.
  • the water level must be adjusted after formation of the reaction mixture to allow for water in the components and the water formed by neutralisation of the sulphonic acid, here we prefer that the C, to C 5 alcohol is not added until the formation of the mixture of (a), (b), (d) and (e) since the presence of the alcohol at this stage could interfere with the removal of water.
  • the reaction mixture is an oil solution of components (a), (b), (c) and (e) and suitable oils include hydrocarbon oils, particularly those of mineral origin. Oils which have viscosities of 15 to 30 cS at 100°F are very suitable. Alternatively other oils which may be used are the lubricating oils which are described later in the specification.
  • the volume ratio of components (b) and (c) should preferably be between 30:70 and 80:20, otherwise if there is too much of component (b) the resulting product will be greasy, whereas with too much of component (c) the reaction mixture will be too viscous during addition of carbon dioxide and any calcium oxide.
  • Preferred volume ratios of (b) and (c) are between 50:50 and 70:30.
  • a promoter we prefer to use less than 10%, e.g. between 3.0% and 7.0% by weight based on the total weight of calcium oxide in the reaction mixture, (i.e. including any calcium oxide which is added at a later stage in the reaction).
  • the relative quantities of the other components of the reaction mixture are not so critical, but it is preferred that the weight of component (a) is 40% to 220% of the total weight of oil in the reaction mixture; and that the amounts by weight of components (b) and (c) are each between 30% and 160% of the total weight of oil, in the reaction mixture.
  • the calcium oxide may be added in several batches but we prefer that the weight of each charge is preferably between 20 and 30% by weight based on the total weight of oil plus component (a).
  • the carbon dioxide is introduced into the mixture while it is at a temperature below the boiling point of the lowest boiling component of the mixture, generally the alcohol, until the pH of the reaction mixture is in the range 6.0 to 7.5, preferably 6.5 to 7.0, as is indicated by monitoring with narrow-range pH paper.
  • the Infra-Red Spectrum of the reaction mixture may be monitored and stopped on appearance of the 872 cm-' peak in the Spectrum which corresponds to the crystalline calcium carbonate. If carbonation is continued without removal of methanol at this point the peak at 872 - ' grows rapidly whilst the peak at 865 cm-' declines to result in a predominantly crystalline product giving haze and sediment problems.
  • the peak at 872 cm-' tends to appear when the pH of the reaction mixture is in the range 6.5 to 7.0 and we find that if excess methanol is removed at this point and carbonation continued the peak at 865 cm-' is retained giving a final product with peaks at both 865 cm-' and 872 cm-' and does not give haze and sediment problems.
  • the reaction mixture should be heated to an elevated temperature, e.g. above 130°C, to remove volatile materials (components (b), water and any remaining alcohol) and thereafter filtered, a filter aid is generally used.
  • the desired overbased detergent additive usually having a TBN of 300 or more, is obtained as the filtrate.
  • water is added to the reaction mixture after introduction of carbon dioxide is complete and before removal of the volatile materials.
  • the water is generally removed with the other volatiles we have found that this addition of water reduces the tendency of the product to form a skin on storage.
  • the above process can be varied by including in the reaction mixture a sixth component (f) and that is a long-chain monocarboxylic acid, or anhydride, or a long-chain di-carboxylic acid or anhydride.
  • long-chain we mean that the molecular weight of the acid is at least 500.
  • Preferred carboxylic acids are those having a molecular weight of between 600 and 3000, e.g. between 800 and 1800.
  • the quantity of component (f) which is used is preferably from 20 to 55 wt.% of the weight of component (a).
  • the combined weight of components (a) and (f) are then preferably 40% to 220% of the total weight of oil in the reaction mixture.
  • the reaction mixture can include small amounts (e.g. between 4% and 15% by weight of oil) of an alkyl phenol containing at least 7 carbon atoms in the alkyl chain. Suitable examples are n-decyl phenol, cetyl phenol and nonyl phenol. Alkyl phenols act as copromoters and also enhance the speed of rotation.
  • the overbased detergent of this invention is suitable for use in lubricating oils, both mineral and synthetic.
  • the lubricating oil may be an animal, vegetable or mineral oil, for example petroleum oil fractions ranging from naphthas or spindle oil to SAE 30, 40 or 50 lubricating oil grades, castor oil, fish oils or oxidised mineral oil.
  • Suitable synthetic ester lubricating oils include diesters such as di-octyl adipate, dioctyl sebacate, didecyl azelate, tridecyl adipate, didecyl succinate, didecyl glutarate and mixtures thereof.
  • the synthetic ester can be a polyester such as that prepared by reacting polyhydric alcohols such as trimethylolpropane and pentaerythritol with monocarboxylic acids such as butyric acid, caproic acid, caprylic acid and pelargonic acid to give the corresponding tri- and tetra-esters.
  • complex esters may be used as base oils such as those formed by esterification reactions between a dicarboxylic acid, a glycol and an alcohol and/or a monocarboxylic acid.
  • Blends of diesters with minor proportions of one or more thickening agents may also be used as lubricants.
  • the amount of overbased detergent added to the lubricating oil should be a minor proportion, e.g. between 0.01% and 10% by weight, preferably between 0.1% and 5% by weight.
  • the final lubricating oil may contain other additives according to the particular use for the oil.
  • viscosity index improvers such as ethylene propylene copolymers may be present as may succinic acid based dispersants, other metal containing dispersant additives and the well known zinc dialkyldithiophosphate antiwear additives.
  • the reaction mixture was stripped at 150°C liquid temperature to remove the volatiles, 40.1 grams of oil being added during stripping.

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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)

Claims (8)

1. Procédé de production de sulfonates de calcium fortement basiques, caractérisé en ce qu'il comprend les étapes suivantes:
(i) formation d'un mélange contenant
(a) un acide sulfonique ou un sulfonate de métal alcalino-terreux soluble dans l'huile,
(b) un solvant hydrocarboné aromatique ou aliphatique,
(c) un alcool en C, à C5,
(d) une huile,
(e) un excès d'oxyde de calcium par rapport à la quantité nécessaire pour réagir avec l'acide sulfonique,
(ii) réglage de la teneur en eau entre 0,50 et 4% du poids d'oxyde de calcium en excès,
(iii) carbonation du mélange de (i) à une température inférieure au point d'ébullition du composant de plus bas point d'ébullition du mélange jusqu'à ce que le pH de ce dernier se situe dans la plage de 6,0 à 7,5 ou jusqu'à ce que le spectre infrarouge indique pour la première fois la formation de vatérite comme représenté par la présence d'un pic à 872 cm-1,
(iv) élimination des matières volatiles.
2. Procédé suivant la revendication 1, caractérisé en ce que l'acide sulfonique est un acide alkylarylsulfonique de poids moléculaire compris entre 300 et 700.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que le solvant hydrocarboné est le toluène, le xylène ou l'éthylbenzène.
4. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le rapport en volume des composants (b) et (c) va de 30:70 à 80:20.
5. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que le poids du composant (a) va de 40 à 200% en poids par rapport au poids total d'huile dans le mélange.
6. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce que de l'eau est ajoutée au mélange réactionnel lorsque l'introduction d'anhydride carbonique est terminée.
7. Procédé suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'une proportion de 4 à 15% en poids, sur la base du poids d'huile, d'un alkylphénol est ajoutée au mélange réactionnel.
8. Une huile lubrifiante contenant 0,01 à 10% en poids d'un sulfonate de calcium fortement basique, produit par un procédé suivant l'une quelconque des revendications précédentes.
EP19800303029 1979-08-31 1980-08-29 Production de sulfonate de calcium superbasique, produit ainsi obtenu et huile lubrifiante le contenant Expired EP0025328B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7930286 1979-08-31
GB7930286A GB2058118A (en) 1979-08-31 1979-08-31 Overbased calcium sulphonate production

Publications (2)

Publication Number Publication Date
EP0025328A1 EP0025328A1 (fr) 1981-03-18
EP0025328B1 true EP0025328B1 (fr) 1983-03-23

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EP19800303029 Expired EP0025328B1 (fr) 1979-08-31 1980-08-29 Production de sulfonate de calcium superbasique, produit ainsi obtenu et huile lubrifiante le contenant

Country Status (6)

Country Link
EP (1) EP0025328B1 (fr)
JP (1) JPH0243730B2 (fr)
BR (1) BR8005430A (fr)
CA (1) CA1152101A (fr)
DE (1) DE3062445D1 (fr)
GB (1) GB2058118A (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4677074A (en) * 1984-06-21 1987-06-30 The Lubrizol Corporation Process for reducing sulfur-containing contaminants in sulfonated hydrocarbons
GB8819215D0 (en) * 1988-08-12 1988-09-14 Shell Int Research Lubricant additives
JPH0737625B2 (ja) * 1990-08-31 1995-04-26 株式会社松村石油研究所 高塩基性カルシウムスルホネートの製造方法
GB9116382D0 (en) * 1991-07-30 1991-09-11 Shell Int Research Liquid composition
GB9120038D0 (en) * 1991-09-19 1991-11-06 Exxon Chemical Patents Inc Overbased metal-containing detergents
US6015778A (en) * 1998-03-27 2000-01-18 The Lubrizol Corporation Process for making overbased calcium sulfonate detergents using calcium oxide and a less than stoichiometric amount of water
US6977319B2 (en) * 2004-03-12 2005-12-20 Chevron Oronite Company Llc Alkylated aromatic compositions, zeolite catalyst compositions and processes for making the same
US7422999B2 (en) 2005-02-14 2008-09-09 The Lubrizol Corporation Overbased vaterite containing salt composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1053522A (fr) * 1963-08-23
US3429811A (en) * 1966-08-17 1969-02-25 Exxon Research Engineering Co Preparation of overbased sulfonates
DE2861618D1 (en) * 1977-07-04 1982-03-18 Exxon Research Engineering Co The production of highly basic calcium sulphonates.

Also Published As

Publication number Publication date
BR8005430A (pt) 1981-03-10
GB2058118A (en) 1981-04-08
JPS5643258A (en) 1981-04-21
EP0025328A1 (fr) 1981-03-18
JPH0243730B2 (ja) 1990-10-01
CA1152101A (fr) 1983-08-16
DE3062445D1 (en) 1983-04-28

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