EP0011069B1 - Verfahren zur Herstellung öllöslicher hochbasischer Magnesiumsalze - Google Patents

Verfahren zur Herstellung öllöslicher hochbasischer Magnesiumsalze Download PDF

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EP0011069B1
EP0011069B1 EP19780300625 EP78300625A EP0011069B1 EP 0011069 B1 EP0011069 B1 EP 0011069B1 EP 19780300625 EP19780300625 EP 19780300625 EP 78300625 A EP78300625 A EP 78300625A EP 0011069 B1 EP0011069 B1 EP 0011069B1
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equivalents
mixture
process according
sulphonic acid
acid
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EP0011069A1 (de
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Theo Ioannou Eliades
Ronald Johnston Muir
James Donald Horner
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Surpass Chemicals Ltd
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Surpass Chemicals Ltd
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    • 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

  • This invention relates to over-based, oil-soluble magnesium salts of sulphonic acids having metal ratios ranging from 10 up to 40 and processes for preparing such over-based magnesium salts of sulphonic acids.
  • Over-based, oil-soluble magnesium salts of sulphonic acids are used as additives in oil-based compositions, such as lubricants, greases, fuels, and the like. They function as detergents and acid neutralizers, thereby reducing wear and corrosion and extending the engine life.
  • over-based magnesium sulphonates may be prepared in a one-step operation by using a reaction promoter system comprising (1) a carboxylic compound selected from the group of compounds consisting of lower carboxylic acids, lower carboxylic anhydrides, substituted lower carboxylic acids, metals salts and esters of lower carboxylic acids and mixture thereof, all having from 1 to 5 carbon aroms; (2) water and optionally (3) an alcohol selected from the group of compounds consisting of lower alkanols, lower alkoxy alkanols and mixtures thereof, all having from 1 to 5 carbon atoms.
  • a reaction promoter system comprising (1) a carboxylic compound selected from the group of compounds consisting of lower carboxylic acids, lower carboxylic anhydrides, substituted lower carboxylic acids, metals salts and esters of lower carboxylic acids and mixture thereof, all having from 1 to 5 carbon aroms; (2) water and optionally (3) an alcohol selected from the group of compounds consisting of lower alkanols, lower alkoxy alkanol
  • This invention provides a reaction promotor system for use in the manufacture of an over-based, oil-soluble magnesium salt of a sulphonic acid having metal ratios of from 10 up to 40, in a one-step operation of contacting an acidic gas with a mixture containing the sulphonic acid to be over-based.
  • a process for preparing an over-based oil soluble magnesium salt of a sulphonic acid having a metal ratio of equivalents of magnesium to equivalents of sulphonic acid of from 10 to 40; comprising contacting an acidic gas with a mixture comprising:
  • reaction mixture may be filtered either before or after the stripping of the volatile components to give the product in solution or in concentrated form. 4
  • Additional water and/or alcohol may be added continuously or portion-wise to the reaction mixture during the time that the acidic gas is contacted with the mixture.
  • the amount of water used in total should not exceed 30 equivalents per equivalent of sulphonic acid and the total amount of alcohol used should not exceed 35 equivalents per equivalent of sulphonic acid.
  • the essentially oil-insoluble carboxylic compounds is represented by the formula: wherein X is H, - eH 2 0 H, -CH2C" -CH 2 Br, -CH 2 COCH 3 , R or RNH 2 and Y is H, R, or M n where R is an alkyl radical of from 1 to 4 carbon atoms, the sum of all the carbon atoms in the R radicals not exceeding 5, and M " is an alkali or alkaline earth metal atom wherein n is an integer of 1 or 2.
  • Preferred oil-insoluble carboxylic compounds of this invention are acetic acid, propionic acid, butanoic acid, glycine, chloroacetic acid, bromoacetic acid, glycolic acid, ethyl acetoacetate, sodium acetate, calcium acetate, and magnesium acetate. These compounds may be used individually or in combination with one another where the amount of this promoter ranges from .5 up to 5 equivalents per equivalent of oil-soluble sulphonic acid. Preferably, the amount ranges from 0.7 to 1.3 equivalents.
  • the initial reaction mixture should have at least 2 equivalents of water per equivalent of sulphonic acid.
  • the mixture may have up to 15 equivalents of water where the preferred range in the initial mixture is from 2 to 8 equivalents of water per equivalent of sulphonic acid.
  • the total amount of water added to the mixture over the entire reaction time should not exceed 30 equivalents per equivalent of oil-soluble sulphonic acid used.
  • the optimum amount of water to be used is determined by the amount of magnesium oxide used and the metal ratio desired because a larger amount of water results in a product having a higher metal ratio.
  • the alcohols used in this process include lower aliphatic alkanols, alkoxy alkanols, and mixtures thereof, where the number of carbon atoms does not exceed 5.
  • the alcohols include methanol, ethanol, isopropanol, n-propanol, butanol, and pentanol.
  • the preferred alcohol is methanol because of the low cost and ease of removal from the reaction mixture.
  • the alkoxy alkanols include methoxy ethanol and ethoxy ethanol.
  • the sulphonic acids to be used in this process are those which are widely known by those skilled in the art as oil-soluble sulphonic acids. Such compounds may be derived from natural petroleum fractions or various synthetically prepared sulphonated compounds. Typical oil-soluble sulphonic acids which may be used include:
  • mixtures of the sulphonic acids may be used in preparing an over-based magnesium sulphonate.
  • the process according to this invention is operative with low sulphonate concentrations which thereby allows the use of oil-based feed stock compositions containing as little as 10% by weight of magnesium sulphonate without further concentration of the oil-based stock.
  • acidic gases may be used in over-basing magnesium sulphonates.
  • the preferred acidic gases are carbon dioxide, sulphur dioxide, nitrogen dioxide, and hydrogen sulphide. These gases are bubbled through the reaction mixture as it is being mixed to that the selected gas or gases become intimately mixed and in contact with the components of the reaction mixture.
  • the temperatures at which the contacting of the gas with the reaction temperature mixture may vary from 10 to 93.3°C (50 to 200°F), although preferably within the 48.9 to 76.7°C (120 to 170°F) range.
  • magnesium oxide used in a preferred embodiment of the process is the light or active form.
  • Such magnesium oxides are sold under the Trade Marks: MAGNESITE, available from Martin Marietta Chemicals, Hunt Valley, Maryland; MICHIGAN No. 3, MICHIGAN No. 15, MICHIGAN No.
  • the amount of magnesium oxide used is dependent upon the metal ratio desired in the final product.
  • the metal ratio is the ratio of the number of equivalents of magnesium in the over-based compound to the equivalents of sulphonic acid in the over-based compound.
  • the non-volatile diluents are generally mineral or synthetic lubricating oils, such as lubricating oils having a viscosity around 0.2 St (cm2s-1) (100 SUS) at 37.8°C (100°F) or higher.
  • the volatile diluents which are inert to the reaction are preferably hydrocarbons with boiling points ranging from 65.6 to 148.9°C (150 to 300°F). These can be aliphatic, aromatic, or a mixture of both types of solvents. For example, naphtha is a particularly useful diluent.
  • Suitable diluents include Stoddard solvent, cycloaliphatic and aromatic hydrocarbons, and corresponding halogenated hydrocarbons, such as chlorobenzene, and other conventional organic diluents generally employed in the over-basing procedures in this particular art of manufacture.
  • the amount of diluents used is sufficient to lower the viscosity of the reaction mixture to facilitate mixing thereof during the introduction and contacting of the acidic gases with the mixture.
  • the length of time that the acidic gas is contacted with the reaction mixture depends upon the desired level of magnesium in the over-based magnesium sulphonate.
  • the contacting of the gas with the mixture may be continued until no further gas is absorbed to indicate that substantially all of the magnesium oxide originally introduced into the system has been reacted to form an over-based magnesium sulphonate.
  • An oil-soluble magnesium sulphonate was prepared by charging into a 1 litre reactor, equipped with stirrer, dropping funnel, thermometer, cooling and vent, 310 gm of a solvent refined lubricating oil having a viscosity of 0.7 St (330 SUS) at 37.8°C (100°F) and while stirring vigorously, 103 gm of 25 percent by weight oleum was added dropwise over a half hour period. The temperature was maintained at 32.2 to 43.3°C (90 to 110°F).
  • the mixture was stirred for an additional 10 minutes and then quenched with 25 gm water, 310 gm VM&P naphtha (Varnish Makers and Painters Naphtha) was added and the mixture allowed to settle in a separatory funnal for 3 hours; 80 gm spent acid was separated and removed.
  • the organic naphtha layer was washed with 120 gm water and the aqueous lower yellowish layer was separated and discarded.
  • To the upper sulphonic acid/naphtha layer was added 100 gm water, 10 gm methanol and 8 gm magnesium oxide.
  • the mixture was stirred at 60°C (140°F) effecting neutralisation of the sulphonic acid and allowed to stand.
  • the bottom aqueous layer which separated was discarded and the naphtha layer was stripped of solvent and water to give a 30 wt% solution of magnesium sulphonate in oil.
  • the product of carbonation was then filtered with the aid of diatomaceous filter aid. Water, methanol and naphtha were then stripped off by heating to 204.4°C (400°F) leaving a product which was clear and bright with a magnesium content of 9.2% which is equivalent to a metal ratio of 27.0.
  • the mixture was heated near its reflux temperature 65.6°C (150°F) and carbon dioxide was introduced while mixing via the dispersion tube into the mixture at a flow rate of 100 ml/min. Carbonation was continued for 2-1/2 hours, during which 8 gm water and 8 gm methanol were added after 40 minutes of carbonation and further 4 gm of water and 8 gm methanol were added after 80 minutes of carbonation.
  • the product of the carbonation was filtered with the aid of diatomaceous filter aid.
  • the volatile components of solvent, water, methanol and naphtha were stripped off by heating to 204.4°C (400°F).
  • a stream of C0 2 was introduced to the heated mixture to remove the last traces of solvents.
  • the final product thus obtained was a clear and bright oil soluble solution which contained 9.4% by weight magnesium, 26.5% by weight magnesium sulphonate and had a viscosity of 1.2 St (525 SUS) at 98.9°C) (210°F).
  • the metal ratio of the product was 14.8.
  • Example 2 illustrates the effect of temperature during carbonation.
  • the exact procedure of Example 2 was followed except that the mixture was maintained at 32.2 to 43.3°C (90 to 110°F) during carbonation.
  • the final product was a clear and bright oil soluble solution which contained 6.9% by weight magnesium, 26.9% by weight magnesium sulphonate.
  • the metal ratio of the product was 10.7.
  • Table 1 illustrates the effect on the metal ratio in varying the amounts of methanol and water used during the carbonation step.
  • the procedure is as for Example 2 with water/methanol addition made at 0, 40 and 80 minutes during the carbonation step.
  • Table 2 summarises results of a series of experiments which illustrate the effect of adding the water/methanol at different time intervals. The procedure used in each experiment is similar to that used in Example 2.
  • Table 4 summarises the results of a series of experiments which illustrate the use of different promoters. All conditions of the procedure in each experiment are similar to that used in Example 2 except for using an equivalent amount of the different promoters as listed.
  • over-based magnesium salts of sulphonic acids may be manufactured and used as additives in lubricating oils, greases and other types of oil-based products, such as fuel oils, bunker oils, etc., where the metal ratio of the additives are in the range of 5 to 40.
  • the products are permanently soluble in many organic environments and therefore find application as additives in the field of lubricants and fuels.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Claims (16)

1. Verfahren zur Herstellung eines überbasischen öllöslichen Magnesiumsalzes einer Sulfonsäure mit einem Metallverhältnis von Magnesiumäquivalenten zu Sulfonsäureäquivalenten von 10-40, dadurch gekennzeichnet, dass man ein saures Gas in Berührung bringt mit einer Mischung enthaltend:
(a) ein öllösliches Magnesiumsalz einer Sulfonsäure;
(b) von 10 bis zu 40 Äquivalenten eines leichten Magnesiumoxids pro Äquivalent Sulfonsäure;
(c) ein Promotorsystem aus:
(1) von 0,5 bis 5 Äquivalenten einer im wesentlichen ölunlöslichen Karbonsäureverbindung pro Äquivalent der Sulfonsäure, wobei die Verbindung ausgewählt ist aus der Gruppe der Verbindungen, bestehend aus Niedrigkarbonsäuren, Niedrigkarbonsäureanhydriden, substituierten Niedrigkarbonsäuren, Metallsalzen und Estern von Niedrigkarbonsäuren und Mischungen davon, alle mit 1 bis 5 Kohlenstoffatomen,
(2) von 2 bis 30 Äquivalenten Wasser pro Äquivalent Sulfonsäure, und
(3) von 0 bis 35 Äquivalenten eines Alkohols pro Äquivalent Sulfonsäure, wobei der Alkohol ausgewählt ist aus der Gruppe bestehend aus aus Niedrigalkanolen, Niedrigalkoxyalkanolen und Mischungen davon, alle mit 1 bis 5 Kohlenstoffatomen; und
(d) ein inertes Lösungsmittel zur Erniedrigung der Viskosität der Mischung zum Erleichtern des Mischens;
wobei das Inberührungbringen durchgeführt wird bei einer Temperatur im Bereich von 10°C (50°F) bis zur Rückflusstemperatur der Mischung und die flüchtigen Komponenten aus dem Reaktionsgemisch nach Absorption des sauren Gases durch die Reaktionsmischung auf ein gewünschtes Niveau abgestreift werden, unter Erhalt eines überbasischen öllöslichen Magnesiumsalzes einer Sulfonsäure.
2. Verfahren gemäss Anspruch 1, dadruch gekennzeichnet, dass das Inberührungbringen durchgeführt wird bei einer Temperatur von 10 bis 93,3°C (50 bis 200°F).
3. Verfahren gemäss Anspruch 2, dadurch gekennzeichnet, dass das Inberührungbringen durchgeführt wird bei einer Temperatur von 48,9 bis 76,7°C (120 bis 170°F).
4. Verfahren gemäss Ansprüchen 1, 2 oder 3, dadurch gekennzeichnet, dass das saure Gas mit . der Mischung in Berührung gebracht wird, bis die Absorption des Gases in der Mischung im wesentlichen vollständig ist.
5. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Promotorsystem 0,5 bis 3 Äquivalente der im wesentlichen ölunlöslichen Karbonsäuresäure pro Äquivalent der Sulfonsäure einschliesst.
6. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass 0,7 bis 1,3 Äquivalente der Karbonsäureverbindung verwendet werden.
7. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Anfangsmenge Wasser weniger als 30 Äquivalente beträgt und dass zusätzliches Wasser su der Mischung während der Zeit, während der das saure Gas mit der Mischung in Berührung gebracht wird, zugegeben wird, um die Gesamtmenge des Verwendeten Wassers auf nicht mehr als 30 Äquivalente pro Äquivalent Sulfonsäure zu bringen.
8. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Anfangsmenge des gewählten Alkohols in der Mischung ausreicht für die Anfangsabsorption des sauren Gases, und dass man eine zusätzliche Menge an Alkohol zu der Mischung während der Zeit, während der das saure Gas in Berührung mit der Mischung ist, zugibt, um die Gesamtmenge des Verwendeten Alkohols auf nicht mehr als 35 Äquivalente pro Äquivalent der Sulfonsäure zu bringen.
9. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das saure Gas ausgewählt ist aus der Gruppe bestehend aus Kohlendioxid, Schwefeldioxid, Schwefelwasserstoff und Stickstoffdioxid.
10. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das saure Gas Kohlendioxid ist.
11. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Menge des in der Mischung vor dem Inberührungbringen der Mischung mit dem sauren Gas vorhandenen Wassers im Bereich von 2 bis 15 Äquivalenten liegt.
12. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Menge des in der Mischung vor dem Inberührungbringen der Mischung mit dem Kohlendioxidgas vorhandenen Wassers im Bereich von 2 bis 8 Aquivalenten liegt.
13. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Gesamtmenge des Verwendeten Alkohols im Bereich von 4 bis ungefähr 20 Äquivalenten liegt.
14. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Alkohol ausgewählt ist aus der Gruppe bestehend aus Methanol, Ethanol, Isopropanol, n-Propanol, Butanol, Pentanol, Methoxyethanol und Ethoxyethanol.
15. Verfahren gemäss einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Karbonsäure die allgemeine Formel
Figure imgb0011
hat, worin X H, -CH2OH, -CH2C1, -CH2Br, -CHZCOCH3, R oder NRH2 und Y H, R oder M" bedeutet, wobei R ein Alkylrest mit 1 bis 4 Kohlenstoffatomen ist und die Summe aller Kohlenstoffatome in den R-Resten 5 nicht übersteigt und M" ein Alkali- oder Erdalkalimetallatom ist, worin n eine ganze Zahl von 1 bis 2 bedeutet.
16. Verfahren gemäss Anspruch 15, dadurch gekennzeichnet, dass die Karbonsäure ausgewählt ist aus der Gruppe bestehend aus Essigsäure, Propionsäure. Buttersäure, Glyzin, Chloressigsäure, Bromessigsäure, Glykolsäure, Ethylacetoacetat, Natriumacetat, Kalziumacetat, Magnesiumacetat und Mischungen davon.
EP19780300625 1978-11-14 1978-11-14 Verfahren zur Herstellung öllöslicher hochbasischer Magnesiumsalze Expired EP0011069B1 (de)

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DE7878300625T DE2862080D1 (en) 1978-11-14 1978-11-14 Process for preparing overbased oil soluble magnesium salts
EP19780300625 EP0011069B1 (de) 1978-11-14 1978-11-14 Verfahren zur Herstellung öllöslicher hochbasischer Magnesiumsalze

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CA1224803A (en) * 1983-09-09 1987-07-28 Witco Corporation One-step process for preparation of overbased calcium sulfonate greases and thickened compositions
US4647387A (en) * 1985-04-11 1987-03-03 Witco Chemical Corp. Succinic anhydride promoter overbased magnesium sulfonates and oils containing same
CN112697892B (zh) * 2020-11-19 2023-04-25 中国石油天然气股份有限公司 定量检测石油采出液中环烷基磺酸盐组分和渣油磺酸盐组分的方法

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US3027325A (en) * 1955-11-07 1962-03-27 Lubrizol Corp Oil-soluble calcium carbonate dispersions and method of preparation
NL85761C (de) * 1957-02-06
GB1100985A (en) * 1966-11-30 1968-01-31 Mobil Oil Corp Metal formate-overbased metal sulphonate complexes
US3446736A (en) * 1968-02-08 1969-05-27 Mobil Oil Corp Mixed carboxylate derivatives of basic alkaline earth metal sulfonates
US3609076A (en) * 1968-10-15 1971-09-28 Standard Oil Co Method of preparing over-based alkaline earth sulfonates
SU502930A1 (ru) * 1974-07-25 1976-02-15 Предприятие П/Я Р-6711 Способ получени высокощелочной сульфонатной присадки

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