EP0133088B1 - Verfahren zur Herstellung von auf Calcium basierten Detergenz-Dispergierzusätzen mit sehr hoher Alkalität und die erhaltenen Produkte - Google Patents

Verfahren zur Herstellung von auf Calcium basierten Detergenz-Dispergierzusätzen mit sehr hoher Alkalität und die erhaltenen Produkte Download PDF

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Publication number
EP0133088B1
EP0133088B1 EP84401440A EP84401440A EP0133088B1 EP 0133088 B1 EP0133088 B1 EP 0133088B1 EP 84401440 A EP84401440 A EP 84401440A EP 84401440 A EP84401440 A EP 84401440A EP 0133088 B1 EP0133088 B1 EP 0133088B1
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EP
European Patent Office
Prior art keywords
ranging
process according
glycol
lime
alkylphenol
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
EP84401440A
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English (en)
French (fr)
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EP0133088A1 (de
Inventor
Jean-Louis Le Coent
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Orogil SA
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Orogil SA
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Filing date
Publication date
Application filed by Orogil SA filed Critical Orogil SA
Priority to AT84401440T priority Critical patent/ATE27298T1/de
Publication of EP0133088A1 publication Critical patent/EP0133088A1/de
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Publication of EP0133088B1 publication Critical patent/EP0133088B1/de
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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 a process for the preparation of detergent-dispersant additives of very high alkalinity for lubricating oils as well as the products obtained.
  • An improved variant of said process consists in carrying out the first step in the presence of an optionally hydroxylated C 1 -C 4 carboxylic acid such as formic acid, acetic acid, glycolic acid or oxalic acid.
  • alkyl benzene sulfonic acids acids obtained by the sulfonation of alkylbenzenes having or alk y radicals contain from 15 to 30 carbon atoms and are derived from linear olefins or olefin oligomers, as well as those obtained by sulfonation of petroleum fractions; their molecular mass expressed as sodium salt generally corresponds to a value of 430 to 560. They are generally used in solution at around 70% in dilution oil.
  • alkylphenols means alkylphenols carrying one or more C 9 -C 15 alkyl substituents and preferably nonyl, decyl, dodecyl or tetradecylphenols.
  • paraffinic oils such as 100 Neutral oil, as well as naphthenic or mixed oils.
  • the amount of oil favorably used is such that the amount of oil contained in the final product (including that coming from the starting alkylbenzene sulfonic acid) represents from 20 to 60% by weight of said product, preferably 25 at 55% and very particularly from 30 to 40% by weight of said product.
  • halide ions mention may preferably be made of CI-; they are used by means of ammonium or metal salts such as ammonium chloride, calcium chloride, zinc chloride ...
  • This first step during which the alkylbenzene sulfonic acid is transformed into neutral alkylbenzene sulfonate, can last from a few minutes to 1 hour and generally of the order of half an hour.
  • the step of removing the water formed is generally carried out at a temperature of 110-150 ° C and preferably 130-140 ° C.
  • C 6 -C 14 alkanols or cycloalkanols such as ethylhexanol , alcohols oxo, decyl alcohol, tridecyl alcohol, trimethylcyclohexanol ...
  • ethers of alkylene glycols such as butoxy-2 ethanol, butoxy-2 propanol, hexyloxy-2 ethanol, methyl ethers of dipropylene glycol
  • alkylene glycols such as propylene glycol, hexylene glycol; butanediols.
  • the glycol and the heavy alcohol can be introduced in full at the start of the third stage or preferably by fraction during the third stage.
  • the sulfur necessary for sulfurization can be introduced at the start of the third stage or else it can already be present in the first stage.
  • the sulfurization operation is carried out at a temperature ranging from 160 ° C. to a temperature below the boiling point of heavy alcohol at normal pressure or under slight depression; it usually lasts 1 to 2 hours.
  • the carbonation operation is favorably carried out at a temperature ranging from 160 ° C. to a temperature lower than that of boiling of the heavy alcohol, for a period which can range from 1 to 4 hours and generally about 2 hours; the amount of C0 2 introduced is between that which can be completely absorbed by the reaction medium and an excess of 30% of this amount.
  • this carbonation operation can be carried out in the presence of an additional quantity of fresh glycol to compensate for the glycol which may be vaporized.
  • the fifth step is preferably carried out under vacuum at a temperature of 160-220 ° C in about one hour.
  • the present invention also relates to detergents-dispersants of high alkalinity based on calcium obtained by the process described above.
  • the amount of TBN 350 detergent-dispersant that can be added to lubricating oils is generally between 1.5 and 2% for a gasoline engine oil, between 3 and 4% for a diesel engine oil and between 7 and 20% for a marine engine oil.
  • the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products.
  • hard coal and synthetic oils for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of liquid acids of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkyl biphenyl ethers, polymers silicon.
  • Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; we can cite for example antioxidant additives, anti-corrosion, ashless dispersant additives ...
  • the mixture is heated at 90 ° C for 30 minutes.
  • glycol and a fraction of butylglycol are added over ten minutes, then the remainder of butylglycol over fifty minutes. It is heated to 160 ° C under slight vacuum for 1 hour.
  • the vacuum is gradually tightened to 66.5 X 10 2 Pa and then heated to 200 ° C for 1 hour.
  • the finished product is added to a SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 25% of additive.
  • the amounts of reagents used are those used in Example 1.
  • the mixture is heated to 90 ° C. and then sulfur and ammonium chloride are added.
  • glycol and a fraction of butylglycol are heated in twenty minutes and then the rest of the butylglycol in 1 hour.
  • the mixture is heated to 165 ° C. and then carbonated for 2 hours at atmospheric pressure.
  • Example 21 The operation described in Example 21 is carried out by replacing the 18 g of acetic acid with 13.8 g of formic acid.
  • Example 1 The operation described in Example 1 is carried out by replacing the (100 + 560 g) of butylglycol with a mixture of (100 + 193 g) of 1,4-butanediol and of (100 + 400 g) of 2-ethylhexanol and decreasing the amount of glycol.
  • the results obtained are shown in Table VI.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (14)

1. Verfahren zur Herstellung von Detergentien-Dispergiermitteln,
dadurch gekennzeichnet, daß man
a) bei einer Temperatur oberhalb 70° C und unterhalb 130° C
eine Alkylbenzolsulfonsäure,
ein Alkylphenol,
Verdünnungsöl,
Halogenidionen,
Kalk und
gegebenenfalls eine - gegebenenfalls hydroxylierte - C1-C4 Carbonsäure zusammenbringt,
b) das entstandene Wasser entfernt,
c) das entstandene Produkt mit Schwefel in Gegenwart von Glykol und einem schweren Alkohol mit Siedepunkt oberhalb 155°C sulfurisiert,
d) das entstandene sulfurisierte Produkt mit Kohlensäure sättigt,
e) das Glykol und den schweren Alkohol mit hohem Siedepunkt entfernt und
f) filtriert, um das entstandene Additiv zu gewinnen; wobei die Mengen der in den Stufen a) und c) eingesetzten Reaktionspartner folgenden Molverhältnissen entsprechen:
Alkylphenol/Alkylbenzolsulfonsäure 0,4 bis 10,
Kalk/(Alkylphenol + Alkylbenzolsulfonsäure) 2,6 bis8,
Halogenidion/Kalk 0,005 bis 0,15,
Säure/Kalk 0 bis 0,2,
Schwefel/Alkylphenol 0,6 bis 2,
Glykol/Kalk 0,03 bis 0,6, schwerer Alkohol/Glykol 0,1 bis 30.
2. Verfahren nach Anspruch 1,
dadurch gekennzeichnet, daß die Halogenidionen Chloridionen sind.
3. Verfahren nach Anspruch 2,
dadurch gekennzeichnet, daß das Chloridion in Form von Ammoniumchtorid oder einem Metallchlorid eingesetzt wird.
4. Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, daß der schwere Alkohol unter den C6 - C14-Alkanolen oder -Cycloalkanolen, den Alkylenglykolethern, Alkylenglykolen und Butandiolen ausgewählt wird.
5. Verfahren nach einem der vorangehenden Ansprüche
dadurch gekennzeichnet, daß die Carbonsäure Ameisensäure, Essigsäure, Glykolsäure oder Oxalsäure ist.
6. Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, daß die Stufe a) in Gegenwart von Mengen an Reaktionspartnern durchgeführt wird, die folgenden Molverhältnissen entsprechen:
Alkylphenol/Alkylbenzolsulfonsäure 0,8 bis 5
Kalk/(Alkylphenol + Alkylbenzolsulfonsäure) 2,8 bis 6
Halogenidion/Kalk 0,015 bis 0,09
Säure/Kalk 0,01 bis 0,2.
7. Verfahren nach einem der vorangehenden Ansprüche
dadurch gekennzeichnet, daß die Stufe c) der Sulfurisation bei einer Temperatur von 160°C bis zu einer Temperatur unterhalb des Siedepunktes des schweren Alkoholes durchgeführt wird.
8. Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, daß der Schwefel in der Stufe c) eingebracht wird.
9. Verfahren nach einem der Ansprüche 1 bis 6,
dadurch gekennzeichnet, daß der Schwefel in der Stufe a) anwesend ist.
10. Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, daß die Menge der zur Durchführung der Stufe c) der Sulfurisation eingesetzten Reaktionspartner folgenden Molverhältnissen entspricht:
Schwefel/Alkylphenol 0,8 bis 1,5
Glykol/Kalk 0,05bis 0,4
schwerer-Alkohol/Glykol 0,5 bis 25.
11. Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, daß die Stufe d) der Sättigung mit Kohlensäure bei einer Temperatur von 160° C bis zu einer Temperatur unterhalb des Siedepunktes des schweren Alkohols durchgeführt wird.
12. Verfahren nach einem der vorangehenden Ansprüche,
dadurch gekennzeichnet, daß die zur Durchführung der Stufe d) eingesetzte Menge CO2 zwischen derjenigen, die vollständig von dem Reaktionsmedium absorbiert werden kann, und einem Überschuß von 30 % über diese Menge liegt.
13. Detergentien-Dispergiermittel, erhalten nach dem Verfahren gemäß einem der vorangehenden Ansprüche.
14. Schmiermittel, enthaltend einen Hauptanteil Schmieröl sowie 1,5 bis 20 Gew.-% eines Detergens-Dispergiermittels gemäß Anspruch 13.
EP84401440A 1983-07-11 1984-07-06 Verfahren zur Herstellung von auf Calcium basierten Detergenz-Dispergierzusätzen mit sehr hoher Alkalität und die erhaltenen Produkte Expired EP0133088B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84401440T ATE27298T1 (de) 1983-07-11 1984-07-06 Verfahren zur herstellung von auf calcium basierten detergenz-dispergierzusaetzen mit sehr hoher alkalitaet und die erhaltenen produkte.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8311494 1983-07-11
FR8311494A FR2549080B1 (fr) 1983-07-11 1983-07-11 Procede de preparation d'additifs detergents-dispersants de tres haute alcalinite a base de calcium et additifs detergents-dispersants pour huiles lubrifiantes ainsi obtenus

Publications (2)

Publication Number Publication Date
EP0133088A1 EP0133088A1 (de) 1985-02-13
EP0133088B1 true EP0133088B1 (de) 1987-05-20

Family

ID=9290698

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84401440A Expired EP0133088B1 (de) 1983-07-11 1984-07-06 Verfahren zur Herstellung von auf Calcium basierten Detergenz-Dispergierzusätzen mit sehr hoher Alkalität und die erhaltenen Produkte

Country Status (18)

Country Link
US (1) US4698170A (de)
EP (1) EP0133088B1 (de)
JP (1) JPS6044595A (de)
AT (1) ATE27298T1 (de)
AU (1) AU574082B2 (de)
BR (1) BR8403428A (de)
CA (1) CA1217480A (de)
DE (1) DE3463785D1 (de)
DK (1) DK163131C (de)
ES (1) ES8504240A1 (de)
FR (1) FR2549080B1 (de)
GB (1) GB2142928B (de)
GR (1) GR81650B (de)
MX (1) MX27008A (de)
PH (1) PH20608A (de)
PT (1) PT78881B (de)
SG (1) SG50187G (de)
ZA (1) ZA845265B (de)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2584414B1 (fr) * 1985-07-08 1987-10-30 Orogil Nouveaux additifs detergents-dispersants sulfones et sulfurises pour huiles lubrifiantes
NZ221128A (en) * 1986-08-08 1989-09-27 Chevron Res Overbased sulphurised alkylphenols as lube oil additives
GB8628609D0 (en) * 1986-11-29 1987-01-07 Bp Chemicals Additives Lubricating oil additives
US5714443A (en) * 1986-11-29 1998-02-03 Bp Chemicals (Additives) Limited Sulphurised alkaline earth metal hydrocarbyl phenates, their production and use thereof
US5716914A (en) * 1986-11-29 1998-02-10 Bp International Limited Alkaline earth metal hydrocarbyl phenates, their sulphurized derivatives, their production and use thereof
US4780224A (en) * 1987-12-07 1988-10-25 Texaco Inc. Method of preparing overbased calcium sulfonates
US4810396A (en) * 1988-04-29 1989-03-07 Texaco Inc. Process for preparing overbased calcium sulfonates
GB8814012D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Chemical process
GB8814009D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Lubricating oil additives
GB8814013D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Additives Chemical process
GB8814010D0 (en) * 1988-06-14 1988-07-20 Bp Chemicals Addivites Ltd Lubricating oil additives
US4879053A (en) * 1988-07-11 1989-11-07 Texaco Inc. Process for preparing overbased calcium sulfonates
AU638705B2 (en) * 1989-04-20 1993-07-08 Lubrizol Corporation, The Methods for reducing friction between relatively slideable components using metal overbased colloidal disperse systems
GB2232665A (en) * 1989-05-31 1990-12-19 Exxon Chemical Patents Inc Sulphonic acid derivatives and their use as emulsifiers
GB8917094D0 (en) * 1989-07-26 1989-09-13 Bp Chemicals Additives Chemical process
US4929373A (en) * 1989-10-10 1990-05-29 Texaco Inc. Process for preparing overbased calcium sulfonates
US5259966A (en) * 1992-11-10 1993-11-09 The Lubrizol Corporation Low chlorine overbased calcium salts
US5401424A (en) * 1993-10-04 1995-03-28 The Lubrizol Corporation Mixed carboxylate overbased gels
GB9400417D0 (en) * 1994-01-11 1994-03-09 Bp Chemicals Additives Lubricating oil composition
GB9611317D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611428D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611424D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
GB9611318D0 (en) 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
US6043209A (en) * 1998-01-06 2000-03-28 Playtex Products, Inc. Stable compositions for removing stains from fabrics and carpets and inhibiting the resoiling of same
CA2543446A1 (en) * 2003-10-30 2005-05-12 The Lubrizol Corporation Process for preparing an overbased detergent
CN103370402B (zh) * 2010-12-21 2016-04-06 路博润公司 含清净剂的润滑组合物

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB194963I5 (de) * 1962-05-15
US3178368A (en) * 1962-05-15 1965-04-13 California Research Corp Process for basic sulfurized metal phenates
FR1382559A (fr) * 1963-02-12 1964-12-18 Lubrizol Corp Compositions métalliques solubles dans les huiles et leur procédé de préparation
US3282835A (en) * 1963-02-12 1966-11-01 Lubrizol Corp Carbonated bright stock sulfonates and lubricants containing them
GB1044148A (en) * 1963-09-16 1966-09-28 Lubrizol Corp Carbonated calcium sulfonate complexes
US3365396A (en) * 1965-12-28 1968-01-23 Texaco Inc Overbased calcium sulfonate
US3493516A (en) * 1966-05-04 1970-02-03 Chevron Res Carboxylate modified phenates
US3544463A (en) * 1968-12-19 1970-12-01 Mobil Oil Corp Overbased oil-soluble metal salts
JPS5272707A (en) * 1975-12-15 1977-06-17 Karonaito Kagaku Kk Preparation of additive for perbasic lubricating oil
FR2416942A1 (fr) * 1978-02-08 1979-09-07 Orogil Procede de preparation de detergents-dispersants de haute alcalinite pour huiles lubrifiantes

Also Published As

Publication number Publication date
DK163131B (da) 1992-01-20
DK338184A (da) 1985-01-12
PT78881B (fr) 1986-06-02
MX27008A (es) 1994-03-31
DK338184D0 (da) 1984-07-10
AU574082B2 (en) 1988-06-30
PH20608A (en) 1987-02-24
ZA845265B (en) 1985-03-27
GB8417478D0 (en) 1984-08-15
GR81650B (de) 1984-12-11
DK163131C (da) 1992-06-09
ATE27298T1 (de) 1987-06-15
JPS6044595A (ja) 1985-03-09
ES534163A0 (es) 1985-04-01
US4698170A (en) 1987-10-06
FR2549080A1 (fr) 1985-01-18
ES8504240A1 (es) 1985-04-01
DE3463785D1 (en) 1987-06-25
JPH0225397B2 (de) 1990-06-01
PT78881A (fr) 1984-08-01
SG50187G (en) 1987-08-28
CA1217480A (fr) 1987-02-03
GB2142928A (en) 1985-01-30
AU3040084A (en) 1985-01-17
FR2549080B1 (fr) 1986-04-04
BR8403428A (pt) 1985-06-25
EP0133088A1 (de) 1985-02-13
GB2142928B (en) 1987-01-07

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