NO135252B - - Google Patents

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Publication number
NO135252B
NO135252B NO2999/73A NO299973A NO135252B NO 135252 B NO135252 B NO 135252B NO 2999/73 A NO2999/73 A NO 2999/73A NO 299973 A NO299973 A NO 299973A NO 135252 B NO135252 B NO 135252B
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Norway
Prior art keywords
lubricant
weight
lubricants
ssu
hydrogenated
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NO2999/73A
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Norwegian (no)
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NO135252C (en
Inventor
G Souillard
F Van Quaethoven
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Labofina Sa
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Publication of NO135252B publication Critical patent/NO135252B/no
Publication of NO135252C publication Critical patent/NO135252C/no

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/104Aromatic fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/106Naphthenic fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026Butene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028Overbased salts thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046Overbasedsulfonic acid salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/252Diesel engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/25Internal-combustion engines
    • C10N2040/252Diesel engines
    • C10N2040/253Small diesel engines
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00Engines characterised by air compression and subsequent fuel addition
    • F02B3/06Engines characterised by air compression and subsequent fuel addition with compression ignition

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Description

Foreliggende oppfinnelse angår smoremidler spesielt for anvendelse i marine dieselmotorer. The present invention relates to lubricants in particular for use in marine diesel engines.

Nåværende marine dieselmotorer er som oftest motorer med lav hastighet (120 omdreininger maksimalt) og med stor styrke som kan opp-gå til ^4-000 héstekrefter pr. sylinder. Disse motorer har to separate smbresystemer: et system for den lavere del av motoren (lågere, krysshode, veivhoder) og det andre system for sylindrene. Current marine diesel engines are most often engines with low speed (120 revolutions maximum) and with great power which can amount to ^4-000 horsepower per cylinder. These engines have two separate lubrication systems: one system for the lower part of the engine (bearings, crosshead, cranks) and the other system for the cylinders.

Den separate smoring av sylindrene skjer ved at smoremidlet injiseres direkte inn i hver sylinder under hver cyklus. Smoremidlet injiseres radialt ved hjelp av dyser rundt sylinderen. Antall smore-innlop er begrenset av praktiske grunner, f.eks. er avstanden mellom to innlop ca. 35 cm i store motorer med sylindere med en diameter opp til 100 cm. The separate lubrication of the cylinders takes place by injecting the lubricant directly into each cylinder during each cycle. The lubricant is injected radially using nozzles around the cylinder. The number of smore inlets is limited for practical reasons, e.g. the distance between two inlets is approx. 35 cm in large engines with cylinders with a diameter of up to 100 cm.

I disse motorer foreligger okende trykk mellom sylinderveggene og stempelringene og også storre avstand mellom smoreinnlopene bevirker at det innsprøytede smøremiddel spres utover med større vanskelig-het. Dette hindrer ens og fullstendig smøring og fører derfor til unormal slitasje av motoren. In these engines, there is increasing pressure between the cylinder walls and the piston rings and also a greater distance between the lubricant inlets causes the injected lubricant to spread outwards with greater difficulty. This prevents even and complete lubrication and therefore leads to abnormal wear of the engine.

Ennvidere er det vanlig å drive marine dieselmotorer med billig brennstoff, nærmere bestemt tunge brennstoff som inneholder betydelige mengder svovel og askedannende urenheter. Disse brennstoff bevirker direkte eller indirekte en hurtig slitasje av sylindrene ved korrosjon og avslipning. Det -er vel kjent at disse brennstoff forbrenner i disse motorer under dannelse av svoveloxy-der som ved kondensering på sylinderveggene føfer til dannelse av korrosiv svovelsyrling og svovelsyrer. Disse syrer nedsetter motorens levetid ikke bare på grunn av deres korrosive virkning, men også fordi disse syrer aktiverer dannelsen av avleiringer (nemlig sulfater) som øker slitasjen av stempelringer og sylindervegger. Furthermore, it is common to run marine diesel engines with cheap fuel, specifically heavy fuel that contains significant amounts of sulfur and ash-forming impurities. These fuels directly or indirectly cause rapid wear of the cylinders through corrosion and grinding. It is well known that these fuels burn in these engines with the formation of sulfur oxides which, by condensation on the cylinder walls, lead to the formation of corrosive sulfuric acid and sulfuric acids. These acids reduce engine life not only because of their corrosive effect, but also because these acids activate the formation of deposits (namely sulphates) which increase the wear of piston rings and cylinder walls.

Et mål med foreliggende oppfinnelse er å tilveiebringe smøremidler for marine dieselmotorer. Det er ennvidere et mål ved oppfinnelsen å tilveiebringe smøremidler som oppfyller spesifikke An aim of the present invention is to provide lubricants for marine diesel engines. It is a further object of the invention to provide lubricants which meet specific

krav og utviser spesielle egenskaper for marine dieselmotorer. Et annet mål er å tilveiebringe smøremidler for dieselmotorer, hvilke danner en kontinuerlig og homogen film, selv mellom smøremiddelinn-løpene, og som beskytter de metalliske overflater overfor korrosjon og'errosjon og som nedsetter slitasjen. requirements and exhibits special properties for marine diesel engines. Another object is to provide lubricants for diesel engines which form a continuous and homogeneous film, even between the lubricant inlets, and which protect the metallic surfaces against corrosion and erosion and which reduce wear.

Oppfinnelsen angår følgelig et smøremiddel for marine dieselmotorer omfattende 59 - 90 v-ekt% mineralolje, 50 - 10 vekt% av en hydrogenert eller ikke-hydrogenert polymer av butylen eller isobutylen og et superbasisk tilsetningsstoff, hvilket smøremid-del er kjennetegnet ved at den hydrogenerte eller ikke-hydrogenerte polymer av butylen eller isobutylen har en molekylvekt mindre enn 1500 og er en blanding omfattende en polymer med en Saybolt viskositet ved 98,9°C på mellom 150 og 3000 SSU og en polymer med en Saybolt viskositet ved 98,9°C på mellom 40 og 100 SSU, og at det superbasiske tilsetningsstoff foreligger i en mengde av fra 15 til 30 %,basert på smøremidlets vekt, tilstrekkelig til å gi smøremid-let en alkalinitetsindeks på 60 - 70. The invention therefore relates to a lubricant for marine diesel engines comprising 59 - 90% by weight of mineral oil, 50 - 10% by weight of a hydrogenated or non-hydrogenated polymer of butylene or isobutylene and a super basic additive, which lubricant part is characterized by the fact that the hydrogenated or non-hydrogenated polymer of butylene or isobutylene has a molecular weight of less than 1500 and is a mixture comprising a polymer having a Saybolt viscosity at 98.9°C of between 150 and 3000 SSU and a polymer having a Saybolt viscosity at 98.9° C of between 40 and 100 SSU, and that the super basic additive is present in an amount of from 15 to 30%, based on the weight of the lubricant, sufficient to give the lubricant an alkalinity index of 60 - 70.

Den mineralolje som anvendes i smøremidlene ifølge oppfinnelsen har en Saybolt viskositet som vanligvis er mellom 50 og 1000 SSU ved 37,8°C. Mineraloljer som gir spaltningsprodukter som ikke virker som bindende midler for de faste partikler som resulterer fra stofforbrenningen foretrekkes. Mineralolje av nafthen-typen anvendes fortrinsvis. Additivets kjemiske natur er imidlertid av større viktighet enn den kjemiske natur av smøreoljen, og paraffiniske oljer kan også anvendes. The mineral oil used in the lubricants according to the invention has a Saybolt viscosity which is usually between 50 and 1000 SSU at 37.8°C. Mineral oils which give decomposition products which do not act as binding agents for the solid particles resulting from the combustion of the substance are preferred. Mineral oil of the naphthene type is preferably used. However, the chemical nature of the additive is of greater importance than the chemical nature of the lubricating oil, and paraffinic oils can also be used.

For å nedsette sylinderslitasjen med hensyn til korrosjon innarbeides basiske additiver vanligvis i de smørende komposisjoner. Disse tilsetningsstoffer virker som nøytraliserende midler for de korrosive syrer som dannes ved forbrenning av brenn-stoffet. Smøremidlets effektivitet med hensyn til anti-korrosive egenskaper avhenger av smøremidlets alkalinitetsindeks. In order to reduce cylinder wear with respect to corrosion, basic additives are usually incorporated into the lubricating compositions. These additives act as neutralizing agents for the corrosive acids that are formed when the fuel is burned. The lubricant's effectiveness with regard to anti-corrosive properties depends on the lubricant's alkalinity index.

Alkalinitetsindeksen (som også kalles totalt basetall, TBN) er ekvivalenten i mg KOH pr. gram smøremiddel.- Følgelig bør smøremidlet ha så høyt TBN som mulig for å nøytralisere de viktige mengder sure forbrenningsprodukter. Sammenlignende forsøk har imidlertid vist at en bestemt grense foreligger for dette TBN, og at et TBN høyere enn denne grense ikke resulterer i en forbedring av smøremidlets anti-korrosive egenskap. En økende mengde basisk tilsetningsstoff er ofte skadelig, idet mengden av avleiringer The alkalinity index (which is also called total base number, TBN) is the equivalent in mg KOH per grams of lubricant.- Consequently, the lubricant should have as high a TBN as possible to neutralize the important amounts of acidic combustion products. However, comparative experiments have shown that a certain limit exists for this TBN, and that a TBN higher than this limit does not result in an improvement in the lubricant's anti-corrosive properties. An increasing amount of basic additive is often harmful, as the amount of deposits

økes. Smøremidler med en alkalinitetsindeks som ikke overskrider 70, og som vanligvis er mellom 60 og 70, foretrekkes derfor. is increased. Lubricants with an alkalinity index that does not exceed 70, and which is usually between 60 and 70, are therefore preferred.

De basiske additiver er valgt fra gruppen bestående av superbaiskse sulfonater eller fenater av magnesium eller jordal-kalimetaller, spesielt superbasiske petroleumsulfonater av kalsium eller barium. Et superbasisk sulfonat av barium fremstilles f.eks. ved å omsette en petroleumsulfonsyre med bariummethylat og derefter boble CO2 gjennom blandingen. Disse superbasiske sulfonater er således forskjellige fra petroleumsulfonatene av kalsium, som vanligvis anvendes som dispergeringsmidler i smøremidler for The basic additives are selected from the group consisting of superbasic sulfonates or phenates of magnesium or alkaline earth metals, especially superbasic petroleum sulfonates of calcium or barium. A superbasic sulfonate of barium is prepared, e.g. by reacting a petroleum sulphonic acid with barium methylate and then bubbling CO2 through the mixture. These superbasic sulfonates are thus different from the petroleum sulfonates of calcium, which are usually used as dispersants in lubricants for

2- og 4-takts motorer. 2- and 4-stroke engines.

De superbasiske sulfonater eller fenater har en visko-sitetsindeks på ca. 250 til 400. Smøremidlene ifølge oppfinnelsen omfatter vanligvis 15 - 30 vekt% (basert på smøremidlets vekt) superbasisk tilsetningsstoff. The superbasic sulphonates or phenates have a viscosity index of approx. 250 to 400. The lubricants according to the invention usually comprise 15 - 30% by weight (based on the weight of the lubricant) super basic additive.

Slitasje grunnet korrosjon reduseres med smøremidler bestående av en mineralolje og et superbasisk tilsetningss toff. For også å redusere slitasjen som skyldes at avsetninger og smøre-filmer som ikke er homogene, har der allerede vært foreslått å bruke smøremidler inneholdende polymerer av butylen eller isobutylen med en viskositet mellom 30 og 600 SSU ved 98,9°C og med en molekylvekt som ikke overskrider 1000. Slitasje av marine dieselmotorer og dannelse av avsetninger som er skadelige for motorenes levetid og effektivitet nedsettes med disse smørende komposisjoner. Wear due to corrosion is reduced with lubricants consisting of a mineral oil and a super basic additive. In order to also reduce the wear caused by deposits and lubricating films that are not homogeneous, it has already been proposed to use lubricants containing polymers of butylene or isobutylene with a viscosity between 30 and 600 SSU at 98.9°C and with a molecular weight which does not exceed 1000. Wear of marine diesel engines and the formation of deposits that are harmful to the engines' lifetime and efficiency are reduced with these lubricating compositions.

Ytterligere forsøk er blitt utført for å oppfylle de nye krav som er oppstått på grunn av bruk av motorer med høy styrke og på grunn av den større størrelse på disse motorer. Det er funnet at den mekaniske slitasje er viktigere enn slitasjen som skyldes forbrenningsprodukter. På det nuværende tidspunkt må smø-remidler oppfylle stringente krav med hensyn til homogenitet og stabilitet av den smørende film ved de høye trykk og temperaturer som motorene arbeider ved. Further attempts have been made to meet the new requirements that have arisen due to the use of high power motors and due to the larger size of these motors. It has been found that the mechanical wear is more important than the wear caused by combustion products. At the present time, lubricants must meet stringent requirements with regard to the homogeneity and stability of the lubricating film at the high pressures and temperatures at which the engines work.

Det er ganske uventet blitt funnet at motorslitasjen ble betydelig nedsatt når en blanding av polybutylener og/eller polyisobutylener innarbeides i mineraloljen. Quite unexpectedly, it has been found that engine wear is significantly reduced when a mixture of polybutylenes and/or polyisobutylenes is incorporated into the mineral oil.

Sammenlignende forsøk har vist at: Comparative trials have shown that:

- en av polymerene må ha en Saybolt viskositet ved 98,9°C på ikke høyere enn 100 SSU, og vanligvis mellom 40 og 95 SSU, - den annen polymer må ha en Saybolt viskositet ved 98,9°C på mellom 150 og 3000 SSU. - one of the polymers must have a Saybolt viscosity at 98.9°C of no higher than 100 SSU, and usually between 40 and 95 SSU, - the other polymer must have a Saybolt viscosity at 98.9°C of between 150 and 3000 SSU.

Disse polymerer har derfor en relativt lav molekylvekt som ikke overskrider 1500. These polymers therefore have a relatively low molecular weight that does not exceed 1500.

Disse polymerer er polybutylener eller polyisobutylener som fremstilles ved polymerisering av hydrocarbonfraksjoner inneholdende hovedsakelig olefiner med i nærvær av Friedel-Crafts katalysatorer. Isobutylen er den mest reaktive monomer, These polymers are polybutylenes or polyisobutylenes which are produced by polymerization of hydrocarbon fractions containing mainly olefins in the presence of Friedel-Crafts catalysts. Isobutylene is the most reactive monomer,

og en førstepolymerisasjon gir et produkt bestående hovedsakelig av polyisobutylen. Restfraksjonen polymeriseres derefter under dannelse av en polymer bestående hovedsakelig av polybutylen med en liten prosent polyisobutylen. Ifølge oppfinnelsen inneholder smøremidlene såvel polyisobutylener som polybutylener, og disse polymerer kan på forhånd være hydrogenerte eller ikke-hydrogenerte. Den viktigste faktor er polymerenes viskositet. For enkelhets skyld vil disse polymerer herefter bli angitt som poly-C^. and a first polymerization gives a product consisting mainly of polyisobutylene. The residual fraction is then polymerized to form a polymer consisting mainly of polybutylene with a small percentage of polyisobutylene. According to the invention, the lubricants contain both polyisobutylenes and polybutylenes, and these polymers can be hydrogenated or non-hydrogenated in advance. The most important factor is the viscosity of the polymers. For simplicity, these polymers will hereafter be referred to as poly-C 2 .

Smøremidlene ifølge oppfinnelsen omfatter generelt The lubricants according to the invention generally include

50 - 90 vekt% mineralolje slik som ovenfor angitt, og respektivt 50 - 10 vekt% av en blanding av poly-C^. Ifølge en foretrukken utførelsesform inneholder smøremidlene 80 — 65 vekt% av en mineralolje og 20 - 35 % av en blanding av poly-C^. 50 - 90% by weight of mineral oil as indicated above, and respectively 50 - 10% by weight of a mixture of poly-C^. According to a preferred embodiment, the lubricants contain 80-65% by weight of a mineral oil and 20-35% of a mixture of poly-C^.

Sammenlignende forsøk har vist at ved å tilsette en blanding av poly-C4 til en mineralolje, er de resulterende komposisjoner spesielt egnede smøremidler for marine dieselmotorer, selvom disse poly-C^ er polymerer med en relativt lav molekylvekt. Ifølge teknikkens stand inneholder smøreoljer vanligvis mineraloljer og poly-C^ med en høyere molekylvekt enn 5000, eller blandinger av poly-C^ og olefincopolymerer. Ennvidere har der for smøring ved høye temperaturer med kontinuerlig innføring av smø-remidlet, som f.eks. i dieselmotorer, vært foreslått å bruke komposisjoner inneholdende en basisolje og en blanding inneholdende en hoveddel av.poly-C^ med en midlere molekylvekt på ca. 5000 og en mindre mentgde poly-C^ med en midlere molekylvekt på ca. 150.000. Hovedformålet med disse komposisjoner inneholdende polymerer med en høy molekylvekt er å forhindre viktige variasjoner i viskositet som funksjon av temperaturen og for å nedsette dannelsen av carbonavleiringer ved høye temperaturer. Comparative tests have shown that by adding a mixture of poly-C4 to a mineral oil, the resulting compositions are particularly suitable lubricants for marine diesel engines, even though these poly-C4 are polymers with a relatively low molecular weight. According to the state of the art, lubricating oils usually contain mineral oils and poly-C^ with a higher molecular weight than 5000, or mixtures of poly-C^ and olefin copolymers. Furthermore, for lubrication at high temperatures with continuous introduction of the lubricant, such as e.g. in diesel engines, it has been proposed to use compositions containing a base oil and a mixture containing a major part of poly-C^ with an average molecular weight of approx. 5000 and a smaller amount of poly-C^ with an average molecular weight of approx. 150,000. The main purpose of these compositions containing polymers with a high molecular weight is to prevent important variations in viscosity as a function of temperature and to reduce the formation of carbon deposits at high temperatures.

I moderne dieselmotorer er effektiviteten ved høye temperaturer bare et av de krav som stilles, og de ovenfor angitte smøreoljer er ikke tilfredsstillende. Smøremidlet må danne en kontinuerlig og homogen film; evnen til å spres, oljebeskaffenhet, mekanisk stabilitet og fordampningshastighet er også viktige kri-terier. In modern diesel engines, efficiency at high temperatures is only one of the requirements, and the above-mentioned lubricating oils are not satisfactory. The lubricant must form a continuous and homogeneous film; the ability to spread, oil quality, mechanical stability and evaporation rate are also important criteria.

Ved bruk av blandinger av poly-C^ som her angitt, og med relativt lav molekylvekt oppfylles disse krav. When using mixtures of poly-C^ as indicated here, and with a relatively low molecular weight, these requirements are met.

De følgende eksempler illustrerer oppfinnelsen ytter-liggere. The following examples further illustrate the invention.

Ydeevnen til de smøremidler som beskrives i disse eksempler er blitt bestemt ved bruk av smøremidlene ved smøring av The performance of the lubricants described in these examples has been determined by using the lubricants in the lubrication of

en marin dieselmotor BOLNES 3DNL. Denne motor er en 2-takts motor med 3 sylindre. Sylinderdiameteren er 190 mm, og stempelslaget er 350 mm. En slik motor med overladning har en styrke på 350 heste-krefter ved 500 omdreininger pr. minutt. a marine diesel engine BOLNES 3DNL. This engine is a 2-stroke engine with 3 cylinders. The cylinder diameter is 190 mm, and the piston stroke is 350 mm. Such a supercharged engine has a strength of 350 horsepower at 500 rpm. minute.

Smøring av stemplene og lagrene utføres ved en separat føding for hver sylinder ved individuelle pumper og oljekar, slik at oljene for de tre sylindre kan sammenlignes under forsøkene. Hver sylinder har to motsatt anordnede innløp for smøring. Lubrication of the pistons and bearings is carried out by a separate feeding for each cylinder by individual pumps and oil pans, so that the oils for the three cylinders can be compared during the tests. Each cylinder has two oppositely arranged inlets for lubrication.

F6ringene og andre hjelpeanordninger smøres av oljen The bearings and other auxiliary devices are lubricated by the oil

i veivkassen, og denne olje anvendes også for å kjøle stemplenes indre. in the crankcase, and this oil is also used to cool the inside of the pistons.

For å bedømme smøremidlenes ydeevne kontrolleres vekttapet på hver ring ved veining av ringene før og efter hver test. Ennvidere kontrolleres motorens renhet efter hver test ifølge CECM-02-T-70 (European Coordination Council for the development of performance tests for engines lubricants and fuels). Ifølge denne fremgangsmåte undersøkes motoren med hensyn til mekaniske og kjemiske nedbrytninger og avleiringer. Kvalitetskriteriene erholdes ved hjelp av en skala hvor 100 angir en absolutt ren overflate. To assess the performance of the lubricants, the weight loss on each ring is checked by weighing the rings before and after each test. Furthermore, the engine's cleanliness is checked after each test according to CECM-02-T-70 (European Coordination Council for the development of performance tests for engines lubricants and fuels). According to this procedure, the engine is examined with regard to mechanical and chemical breakdowns and deposits. The quality criteria are obtained using a scale where 100 indicates an absolutely clean surface.

Eksempel 1 Example 1

Et smøremiddel ble fremstillet ved å blande: A lubricant was made by mixing:

70 vektdeler av en nafthenisk baseolje med viskositet på 185 centistoke ved 37,8°C, 24 " polybutylen med midlere molekylvekt på 610 (Saybolt viskositet: 259 SSU ved 98,9°C). 6 " polybutylen med midlere molekylvekt på 420 (Saybolt viskositet: 64 SSU ved 98,9°C). 70 parts by weight of a naphthenic base oil with a viscosity of 185 centistokes at 37.8°C, 24 " polybutylene with an average molecular weight of 610 (Saybolt viscosity: 259 SSU at 98.9°C). 6 " polybutylene with an average molecular weight of 420 (Saybolt viscosity: 64 SSU at 98.9°C).

Til denne blanding ble tilsatt 25 vektdeler superbasisk kalsiumsulfonat (LUBRIZOL 56) med en alkalinitetsindeks på 285. To this mixture was added 25 parts by weight of superbasic calcium sulphonate (LUBRIZOL 56) with an alkalinity index of 285.

Smøremidlet hadde en alkalinitetsindeks eller TBN på 62. The lubricant had an alkalinity index or TBN of 62.

Dette smøremiddel som kalles "Smøremiddel A", ble testet i den tidligere beskrevne dieselmotor. This lubricant, called "Lubricant A", was tested in the previously described diesel engine.

For sammenligning ble et lignende smøremiddel fremstillet, men ved bruk av 30 deler polybutylen med en molekylvekt på 400 i stedet for blandingen av polybutylener. Dette smøremiddel kalles "Smøremiddel B". For comparison, a similar lubricant was prepared, but using 30 parts polybutylene with a molecular weight of 400 instead of the mixture of polybutylenes. This lubricant is called "Lubricant B".

Disse smøremidlers ydeevne ble sammenlignet med ydeevnen til en kommersiell smøreolje eller referanseolje. The performance of these lubricants was compared to that of a commercial lubricating oil or reference oil.

Denne oljes vekttap ble fastsatt til 100, og vekttapet med smøremidlene A og B er gitt som relative tap sammenlignet med denne indeks 100. This oil's weight loss was set at 100, and the weight loss with lubricants A and B are given as relative losses compared to this index 100.

Det fremgår at ved bruk av smøremiddel A ifølge oppfinnelsen er vekttapet ved slitasje.betydelig nedsatt, og kvaliteten er høy. En høy kvalitet angir en meget lav korrosjon eller dannelse av avleiringer. It appears that when using lubricant A according to the invention, the weight loss due to wear is significantly reduced, and the quality is high. A high quality indicates a very low corrosion or formation of deposits.

Smøremiddel B inneholdende bare en poly-C^ type, er og-så meget verdifullt med hensyn til vekttap, men dette smøremiddel er imidlertid mindre fordelaktig, idet kvaliteten er lavere. Lubricant B containing only one poly-C^ type is also very valuable with regard to weight loss, but this lubricant is however less advantageous, as the quality is lower.

Eksempel 2 Example 2

Et smøremiddel lik smøremiddel A i eksempel 1 ble fremstillet, men ved bruk av A lubricant similar to lubricant A in example 1 was prepared, but using

15 vektdeler av like deler polybutylen og polyisobutylen med midlere molekylvekt på 1290 (Saybolt viskositet: 3000 ved 98,9°C), og 15 " polybutylen med midlere molekylvekt på 420 (Saybolt viskositet: 64 ved 98,9°C). 15 parts by weight of equal parts polybutylene and polyisobutylene with an average molecular weight of 1290 (Saybolt viscosity: 3000 at 98.9°C), and 15 "polybutylene with an average molecular weight of 420 (Saybolt viscosity: 64 at 98.9°C).

Eksempel 3 Example 3

Et smøremiddel ble fremstillet fra: A lubricant was made from:

65 vektdeler av en mineralolje med viskositet på 192 centistoke ved 37,8°C, 20 " hydrogenert polybutylen med midlere molekylvekt på 925 og en Saybolt viskositet på 1008 SSU ved 98,9°C, 15 " hydrogenert polybutylen med midlere molekylvekt på 635 og en Saybolt viskositet på 255 SSU ved 98,9°C. 65 parts by weight of a mineral oil having a viscosity of 192 centistokes at 37.8°C, 20" hydrogenated polybutylene having an average molecular weight of 925 and a Saybolt viscosity of 1008 SSU at 98.9°C, 15" hydrogenated polybutylene having an average molecular weight of 635 and a Saybolt viscosity of 255 SSU at 98.9°C.

Dette smøremiddel ble oppdelt i tre deler, og superbasisk magnesiumsulfonat ble tilsatt til hver del til alkalini-tetsindekser på 50, 65 og 85. This lubricant was divided into three portions, and superbasic magnesium sulfonate was added to each portion to alkalinity indices of 50, 65, and 85.

Claims (3)

1. Smøremiddel for marine dieselmotorer omfattende 50 - 90 vekt% mineralolje, 50 - 10 vekt% av en hydrogenert eller ikke-hydrogenert polymer av butylen eller isobutylen og et superbasisk tilsetningsstoff, karakterisert ved at den hydrogenerte eller ikke-hydrogenerte polymer av butylen eller isobutylen har en molekylvekt mindre enn 1500 og er en blanding omfattende en polymer med en Saybolt viskositet ved 98,9°C på mellom 150 og 3000 SSU og en polymer med en Saybolt viskositet ved 98,9°C på mellom 40 og 100 SSU, og at det superbasiske tilsetningsstoff foreligger i en mengde av fra 15 til 30 % basert på smøremidlets vekt, tilstrekkelig til å gi smøremidlet en alkalinitetsindeks på 60 - 70.1. Lubricant for marine diesel engines comprising 50 - 90% by weight of mineral oil, 50 - 10% by weight of a hydrogenated or non-hydrogenated polymer of butylene or isobutylene and a super basic additive, characterized in that the hydrogenated or non-hydrogenated polymer of butylene or isobutylene has a molecular weight of less than 1500 and is a mixture comprising a polymer with a Saybolt viscosity at 98.9°C of between 150 and 3000 SSU and a polymer with a Saybolt viscosity at 98.9°C of between 40 and 100 SSU, and that the super basic additive is present in an amount of from 15 to 30% based on the weight of the lubricant, sufficient to give the lubricant an alkalinity index of 60 - 70. 2. Smøremiddel ifølge krav 1, karakterisert ved at mineraloljen er en nafthenisk olje med en Saybolt viskositet ved 37,8°C på mellom 50 og 1000 SSU.2. Lubricant according to claim 1, characterized in that the mineral oil is a naphthenic oil with a Saybolt viscosity at 37.8°C of between 50 and 1000 SSU. 3. Smøremiddel ifølge krav 1, karakterisert ved at det omfatter 65 - 80 vekt% mineralolje og 35 - 20 vekt% av blandingen av polymerer.3. Lubricant according to claim 1, characterized in that it comprises 65 - 80% by weight of mineral oil and 35 - 20% by weight of the mixture of polymers.
NO2999/73A 1972-12-19 1973-07-25 NO135252C (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE125511A BE792976A (en) 1972-12-19 1972-12-19 LUBRICANTS FOR MARINE DIESEL ENGINES.

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FR (1) FR2210659B1 (en)
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US3878115A (en) 1975-04-15
CH578613A5 (en) 1976-08-13
ZA737795B (en) 1974-08-28
SE383641B (en) 1976-03-22
JPS532442B2 (en) 1978-01-28
NL7313036A (en) 1974-06-21
FR2210659B1 (en) 1978-03-03
FR2210659A1 (en) 1974-07-12
IT992752B (en) 1975-09-30
NO135252C (en) 1977-03-09
DE2342563C2 (en) 1986-04-03
BE792976A (en) 1973-04-16
DK142060C (en) 1981-01-12
DE2342563A1 (en) 1974-06-20
GB1408369A (en) 1975-10-01
JPS49102703A (en) 1974-09-27
DK142060B (en) 1980-08-18

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