EP2497817A1 - A marine lubricating oil composite additive - Google Patents

A marine lubricating oil composite additive Download PDF

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Publication number
EP2497817A1
EP2497817A1 EP12158752A EP12158752A EP2497817A1 EP 2497817 A1 EP2497817 A1 EP 2497817A1 EP 12158752 A EP12158752 A EP 12158752A EP 12158752 A EP12158752 A EP 12158752A EP 2497817 A1 EP2497817 A1 EP 2497817A1
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Prior art keywords
base number
composite additive
oil
base
long
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German (de)
French (fr)
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EP2497817B1 (en
Inventor
Jie Zhang
Gongde Liu
Yueki Zhai
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Petrochina Co Ltd
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Petrochina Co 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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01M—LUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M9/00—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
    • F01M9/02—Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00 having means for introducing additives to lubricant
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02—Well-defined aliphatic compounds
    • C10M2203/0206—Well-defined aliphatic compounds used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086—Imides
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04—Detergent property or dispersant property
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26—Waterproofing or water resistance
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the present invention relates to a composite additive used for marine lubricating oils, and more particularly to a composite additive designed for cylinder lubricating oils which is applied in shipborne BOB systems.
  • the current BOB (Blender-on-Board) online blending system equipped on ocean vessels is an automatic control system that blends the marine system oil with a composite additive which is designed for the marine lubricating oils in the BOB system so as to provide a cylinder lubricating oil that have an optional target base number, and such cylinder lubricating oil can be rapidly transferred to the engine in order to meet the different requirements for the base number of the cylinder lubricating oil in cases of using fuels with different sulfur contents.
  • a schematic diagram for the operating principle of BOB online blending system is shown in Figure 1 .
  • the operating procedure of the BOB system is as follows: the system oil is pumped from the main oil tank to each lubrication point of the engine so as to provide lubrication and thereafter recycled back to the main oil tank, wherein part of the system oil is side-drawn and then blended with a composite additive in the BOB blending device to form a cylinder oil with required base numbers, which is burned off after fulfilling lubrication, and the residue thereof flows into a waste oil tank.
  • the composite additives designed for the BOB system are remarkably different from the traditional marine lubricating oils.
  • the later are lubricating oil products with fixed base numbers, which are produced in blending plants and may be directly used by adding into the oil tank of vessels, whereas the former are additives produced by blending plants and blended with the system oil before adding into a tank of vessels so as to provide marine cylinder lubricating oils with different base numbers in order to meet the requirement of the use in engines.
  • the composite additives designed for the BOB system have several features in terms of the technical requirement:
  • the purpose of the present invention is to provide a marine lubricating oil composite additive that can not only satisfy the requirement of the marine BOB online blending system but also have wide adaptability.
  • the marine lubricating oil composite additive is characterized in that based on the total weight of the composite additive, it comprises: 25-45% sulfonate detergent with superhigh base number, 40-60% phenolate detergent with low base number, 0-8% dispersing agent, 0-4% antiwear agent, and 10-20% Group I base oil with high viscosity index.
  • Said sulfonate detergent with superhigh base number is C 22 -C 30 linear alkyl benzene calcium sulphonate, wherein the base number thereof is 395-430 mgKOH/g.
  • Said phenolate detergent with low base number is C 20 -C 25 alkyl sulfurized calcium phenolate, wherein the base number thereof is 240-265 mgKOH/g.
  • Said dispersing agent is selected from the group consisting of mono-polyisobutylene succinimide, bis-polyisobutylene succinimide and multi-polyisobutylene succinimide.
  • Said antiwear agent is zinc long-chain alkyl thiophosphate with the structure corresponding to the following formula, wherein R 1 , R 2 , R 3 and R 4 are long-chain primary alkyl groups each comprising 12-18 carbon atoms, or R 1 , R 2 , R 3 and R 4 are long-chain secondary alkyl groups each comprising 12-16 carbon atoms.
  • Said base oil is Group I base oil with high viscosity index which is selected from the group consisting of 400SN, 500SN and 600SN, the kinematic viscosity of which is 8.5-11.5 cst at 100°C.
  • the appropriate base oils are commercially available from PetroChina Company.
  • the marine lubricating oil composite additive according to the present invention employs two composed detergents supplemented by antiwear agent and dispersing agent, and takes advantage of not only the excellent detergency and dispersion performance of the sulfonate detergent with superhigh base number but also the excellent antiwear and antioxidization performance of the phenolate detergent with low base number.
  • the formulation of composite additive is optimized so as to satisfy the requirement of the BOB online blending system.
  • the technical features of the present invention are as follows: the requirement of BOB system process for the viscosity and base number can be satisfied; the composite additive according to the present invention is compatible with many system oils under typical foreign brands, and the formulated cylinder lubricating oils with different base numbers have excellent performances in terms of antiwear, antioxidization and high temperature detergency.
  • the present composite additive has been tested by sailing over 4000 hours, and has been technically certified by MAN B&W, the engine OEM (original equipment manufacturer).
  • the composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • the blending process is as follows: the base oil is firstly added into a blending barrel/tank, and then the temperature is raised to 65 ⁇ 5°C, wherein the base oil should have a kinematic viscosity of 7.0-12.0 mm 2 /s at 100°C; the antiwear agent, the dispersing agent and the detergents are subsequently introduced into said blending barrel/tank, and stirring is carried out at 65 ⁇ 5°C for 2 hours until completely homogeneous.
  • the above process is implemented in every example hereafter.
  • the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g.
  • the sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 240 mgKOH/g.
  • the antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 12 carbon atoms.
  • the dispersing agent is bis-polyisobutylene succinimide.
  • the base oil is group I base oil 600SN available from PetroChina Daqing Petrochemical Company. Components Contents (%) Linear alkyl (C22) calcium sulfonate with superhigh base number 25 Sulfurized calcium alkyl (C25) phenolate with low base number 55 Zinc primary alkyl (C12) thiophosphate 2 Bis-polyisobutylene succinimide 8 Group I base oil of 600SN 10
  • the composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 30 carbon atoms, and the base number thereof is 395 mgKOH/g.
  • the sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 20 carbon atoms, and the base number thereof is 265 mgKOH/g.
  • the antiwear agent is zinc long-chain secondary alkyl thiophosphate wherein the long-chain secondary alkyl group comprises 16 carbon atoms.
  • the dispersing agent is multi-polyisobutylene succinimide.
  • the base oil is group I base oil 500SN available from PetroChina Daqing Petrochemical Company. Components Contents (%) Linear alkyl (C30) calcium sulfonate with superhigh base number 45 Sulfurized calcium alkyl (C20) phenolate with low base number 41 Zinc secondary alkyl (C16) thiophosphate 4 Multi-polyisobutylene succinimide 0 Group I base oil of 500SN 10
  • the composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g.
  • the sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 250 mgKOH/g.
  • the antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 18 carbon atoms.
  • the dispersing agent is bis-polyisobutylene succinimide.
  • the base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company. Components Contents (%) Linear alkyl (C22) calcium sulfonate with superhigh base number 32 Sulfurized calcium alkyl (C25) phenolate with low base number 40 Zinc primary alkyl (C18) thiophosphate 0 Bis-polyisobutylene succinimide 8 Group I base oil of 400SN 20
  • the composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g.
  • the sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 240 mgKOH/g.
  • the antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 12 carbon atoms.
  • the dispersing agent is bis-polyisobutylene succinimide.
  • the base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company. Components Contents (%) Linear alkyl (C22) calcium sulfonate with superhigh base number 28 Sulfurized calcium alkyl (C25) phenolate with low base number 60 Zinc primary alkyl (C12) thiophosphate 2 Bis-polyisobutylene succinimide 0 Group I base oil of 400SN 10
  • the composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 30 carbon atoms, and the base number thereof is 410 mgKOH/g.
  • the sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 265 mgKOH/g.
  • the antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 18 carbon atoms.
  • the dispersing agent is multi-polyisobutylene succinimide.
  • the base oil is group I base oil 600SN available from PetroChina Daqing Petrochemical Company. Components Contents (%) Linear alkyl (C30) calcium sulfonate with superhigh base number 30 Sulfurized calcium alkyl (C25) phenolate with low base number 45 Zinc primary alkyl (C18) thiophosphate 4 Multi-polyisobutylene succinimide 6 Group I base oil of 600SN 15
  • the composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 410 mgKOH/g.
  • the sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 20 carbon atoms, and the base number thereof is 300 mgKOH/g.
  • the antiwear agent is zinc long-chain secondary alkyl thiophosphate wherein the long-chain secondary alkyl group comprises 12 carbon atoms.
  • the dispersing agent is mono-polyisobutylene succinimide.
  • the base oil is Group I base oil 500SN available from PetroChina Daqing Petrochemical Company. Components Contents (%) Linear alkyl (C22) calcium sulfonate with superhigh base number 40 Sulfurized calcium alkyl (C20) phenolate with low base number 40 Zinc secondary alkyl (C12) thiophosphate 1 Mono-polyisobutylene succinimide 4 Group I base oil of 500SN 15
  • the composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g.
  • the sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 240 mgKOH/g.
  • the antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 18 carbon atoms.
  • the dispersing agent is bis-polyisobutylene succinimide.
  • the base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company. Components Contents (%) Linear alkyl (C22) calcium sulfonate with superhigh base number 32 Sulfurized calcium alkyl (C25) phenolate with low base number 58 Zinc primary alkyl (C18) thiophosphate 0 Bis-polyisobutylene succinimide 0 Group I base oil of 400SN 10
  • the present invention provides a bis-detergent composite additive designed for the BOB system, and the physical and chemical properties of such composite additive are able to satisfy the requirement of Maersk Fluid Co. about the composite additive designed for the BOB system.
  • the physical and chemical properties of the composite additives obtained by the above examples are listed in Table 1.
  • Example 1 Comparison of the physical and chemical properties of the bis-detergent cylinder oil composite additives designed for the BOB system Item Sample Technical requirement Method
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Example 7 Kinematic viscosity (100°C), mm 2 /s 81.68 90.46 85.38 86.72 92.36 86.46 88.69 ⁇ 95 according to OEM GB/T 265 Base number, mgKOH/g 305 295 310 290 292 302 298 ⁇ 285 according to OEM SH/T 0251 Density (20°C), kg/m 3 1097.6 1085.5 1072.0 1095.0 1079.6 1105.4 1092.6 Report SH/T 0604 Flash point (closed), °C 185 186 192 178 184 198 186 ⁇ 150 GB/T 261 Moisture, % 0.18 0.03 0.06 0.08 0.03 0.06 0.03 ⁇ 0.2 GB/T 260 Mechanical impurity, % 0.032 0.0
  • the composite additive designed for the BOB system using double detergents provided by the present invention is well compatible with system oil products under typical domestic and foreign brands, for example Exxon-Mobile Company, BP Company and PetroChina.
  • the performances of the formulated cylinder oils with different base numbers are individually studied by simulated experiments, and the results demonstrate that the cylinder oils with different base numbers maintain good combination property as for lubricating oil, for example the antioxidization, antiwear, detergency and water resisting performances and etc.
  • the antioxidization performance of the cylinder oil is evaluated according to the oxidative induction time which is measured by differential scanning calorimetry (PDSC).
  • the antiwear performance is evaluated by the Pb value and the long wear extent which are obtained by four-ball test.
  • the coking tests are carried out in order to test the detergency performance of the cylinder oil, while the gel tests are carried out so as to test the storage stability.
  • the bis-detergent composite additive designed for the BOB system formulated according to the formulation of Example 6 is blended with Exxon-Mobile system oil Mobilgard M300, BP system oil Energol OE-HT30 and Kunlun system oil DCC3008, respectively, so as to provide cylinder oils with the base numbers of 70 mgKOH/g, 60 mgKOH/g, 50 mgKOH/g and 40 mgKOH/g as shown in Tables 2, 3, 4 and 5.
  • Table 2 Physical and chemical properties of the cylinder oil with the base number of 70 mgKOH/g and the simulated performance thereof Item Unit Mobilgard M300 Energol OE-HT30 KUNLUN DCC3008 Method Dosage of the composite additive, % 22 22 21.2 Viscosity, 100°C mm 2 /s 13.77 14.23 13.37 GB/T 265 Viscosity coefficient - 103 105 100 ISO2909 Base number mgKOH /g 69.7 69.4 69.4 SH/T 0251 Flash point °C 258 252 250 GB/T 261 Sulfated ash, % w% 7.49 7.85 7.38 GB/T 2433 Oxidative induction time by PDSC min 15.13 15.06 13.24 SH/T 0719, the test condition is: 200°C, 3.0MPa, O 2 Pb value by four-ball test N 1254 1186 1186 GB/T 3142 Long wear extent by four-ball test mm 0.33 0.34 0.33 SH/T 01
  • the composite additive designed for the BOB system using double detergents provided by the present invention can be blended with system oils so as to provide cylinder oils that can satisfy the requirement of the engine.
  • Such composite additive has been tested by sailing over 4000 hours wherein BP Energol OE-HT30 is used as the system oil by the vessel, and has been technically certified by MAN B&W. Samples of the fresh/waste cylinder oils using such composite additive during the sailing were monitored, and the data are illustrated in Figure 2 .
  • the base number of the cylinder oil formulated from the composite additive decreased from 70 mgKOH/g at the beginning, through 60 mgKOH/g and 50 mgKOH/g, to 40 mgKOH/g at the end.
  • the entire sailing test could be divided into four stages according to the base number of the cylinder oil, and each stage lasted about 1000 hours. It can be clearly seen from Figure 2 that the residual base number in the waste oil was not notably decreased, and the Fe content resulted from the wear was not notably increased, either, that is, the both important index fluctuated within normal ranges.
  • the cylinder lubricating oil maintained steady combination performance in case that the variation of the dosage of the composite additive reached the extent close to 50%, especially in terms of the antiwear performance under extreme pressure and the ability to preserve the base number.
  • the test results sufficiently satisfied the requirement of the engine about the lubricating oil performance and were technically certified by the engine OEM.

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

The present invention relates to a marine lubricating oil composite additive. Based on the total weight of the composite additive, said marine lubricating oil composite additive comprises: 25-45% sulfonate detergent with superhigh base number, 40-60% phenolate detergent with low base number, 0-8% dispersing agent, 0-4% antiwear agent, and 10-20% Group I base oil with high viscosity index which is selected from the group consisting of 400SN, 500SN and 600SN. The composite additive according to the present invention can satisfy the requirement of BOB system about the viscosity and base number, and can be blended with many system oils under a number of domestic and foreign brands so as to provide cylinder lubricating oils with different base numbers. The composite additive according to the present invention has good adaptability and excellent performances in terms of antiwear, antioxidization and high temperature detergency, which meet the requirement of marine engines about the performance of cylinder lubricating oils. Moreover, the composite additive according to the present invention is able to maintain good stability in the base oil of the system oil as well as good compatibility, and thus the lubricating performance of the cylinder lubricating oil will not be adversely affected.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a composite additive used for marine lubricating oils, and more particularly to a composite additive designed for cylinder lubricating oils which is applied in shipborne BOB systems.
    • BACKGROUND OF THE INVENTION
  • The current BOB (Blender-on-Board) online blending system equipped on ocean vessels is an automatic control system that blends the marine system oil with a composite additive which is designed for the marine lubricating oils in the BOB system so as to provide a cylinder lubricating oil that have an optional target base number, and such cylinder lubricating oil can be rapidly transferred to the engine in order to meet the different requirements for the base number of the cylinder lubricating oil in cases of using fuels with different sulfur contents. A schematic diagram for the operating principle of BOB online blending system is shown in Figure 1.
  • The operating procedure of the BOB system is as follows: the system oil is pumped from the main oil tank to each lubrication point of the engine so as to provide lubrication and thereafter recycled back to the main oil tank, wherein part of the system oil is side-drawn and then blended with a composite additive in the BOB blending device to form a cylinder oil with required base numbers, which is burned off after fulfilling lubrication, and the residue thereof flows into a waste oil tank. The composite additives designed for the BOB system are remarkably different from the traditional marine lubricating oils. The later are lubricating oil products with fixed base numbers, which are produced in blending plants and may be directly used by adding into the oil tank of vessels, whereas the former are additives produced by blending plants and blended with the system oil before adding into a tank of vessels so as to provide marine cylinder lubricating oils with different base numbers in order to meet the requirement of the use in engines.
  • Therefore, the composite additives designed for the BOB system have several features in terms of the technical requirement:
    1. 1. Sufficient antiwear and antioxidization properties should be preserved when relatively low dosage is used;
    2. 2. Good compatibility to system oils under different brands;
    3. 3. The composite additive should satisfy the requirement of being pumped within the BOB system and fit with the blending system.
  • According to the novelty search within Chinese and worldwide patents, no related reference documents are found in the field of both shipborne BOB online blending system and the composite additive designed the BOB system.
  • In the light of the disclosure reported by related Chinese and worldwide patents, it is known that the binary detergent system composed by a sulfonate detergent and a phenolate detergent is widely used in the formulation of the cylinder oil at present. Meanwhile, the above two primary additives of sulfonate and phenolate detergents are both easy to purchase and cheap in price in the international market. With an aim to the world market of the marine lubricating oil, the establishment of an international blending and supplying network can, on one hand, expand the oil supplying network of PetroChina and improve the sale and service level, and can benefit to reducing the production cost so as to sharpen the competitive edge of self-owned brand products of PetroChina.
    • SUMMARY OF THE INVENTION
  • The purpose of the present invention is to provide a marine lubricating oil composite additive that can not only satisfy the requirement of the marine BOB online blending system but also have wide adaptability.
  • The marine lubricating oil composite additive is characterized in that based on the total weight of the composite additive, it comprises: 25-45% sulfonate detergent with superhigh base number, 40-60% phenolate detergent with low base number, 0-8% dispersing agent, 0-4% antiwear agent, and 10-20% Group I base oil with high viscosity index.
  • Said sulfonate detergent with superhigh base number is C22-C30 linear alkyl benzene calcium sulphonate, wherein the base number thereof is 395-430 mgKOH/g.
  • Said phenolate detergent with low base number is C20-C25 alkyl sulfurized calcium phenolate, wherein the base number thereof is 240-265 mgKOH/g.
  • Said dispersing agent is selected from the group consisting of mono-polyisobutylene succinimide, bis-polyisobutylene succinimide and multi-polyisobutylene succinimide.
  • Said antiwear agent is zinc long-chain alkyl thiophosphate with the structure corresponding to the following formula,
    Figure imgb0001
     wherein R1, R2, R3 and R4 are long-chain primary alkyl groups each comprising 12-18 carbon atoms, or R1, R2, R3 and R4 are long-chain secondary alkyl groups each comprising 12-16 carbon atoms.
  • Said base oil is Group I base oil with high viscosity index which is selected from the group consisting of 400SN, 500SN and 600SN, the kinematic viscosity of which is 8.5-11.5 cst at 100°C. The appropriate base oils are commercially available from PetroChina Company.
  • The marine lubricating oil composite additive according to the present invention employs two composed detergents supplemented by antiwear agent and dispersing agent, and takes advantage of not only the excellent detergency and dispersion performance of the sulfonate detergent with superhigh base number but also the excellent antiwear and antioxidization performance of the phenolate detergent with low base number. The formulation of composite additive is optimized so as to satisfy the requirement of the BOB online blending system. The technical features of the present invention are as follows: the requirement of BOB system process for the viscosity and base number can be satisfied; the composite additive according to the present invention is compatible with many system oils under typical foreign brands, and the formulated cylinder lubricating oils with different base numbers have excellent performances in terms of antiwear, antioxidization and high temperature detergency. The present composite additive has been tested by sailing over 4000 hours, and has been technically certified by MAN B&W, the engine OEM (original equipment manufacturer).
    • DESCRIPTION OF DRAWINGS
    • Figure 1 shows a schematic diagram for the operating principle of BOB online blending system.
    • Figure 2 shows the monitoring data for samples of the fresh/waste cylinder oils using the composite additive of the present application during the sailing.
    DETAILED DESCRIPTION OF THE INVENTION Example 1:
  • The composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process. The blending process is as follows: the base oil is firstly added into a blending barrel/tank, and then the temperature is raised to 65±5°C, wherein the base oil should have a kinematic viscosity of 7.0-12.0 mm2/s at 100°C; the antiwear agent, the dispersing agent and the detergents are subsequently introduced into said blending barrel/tank, and stirring is carried out at 65±5°C for 2 hours until completely homogeneous. The above process is implemented in every example hereafter.
  • In this example, the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g. The sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 240 mgKOH/g. The antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 12 carbon atoms. The dispersing agent is bis-polyisobutylene succinimide. The base oil is group I base oil 600SN available from PetroChina Daqing Petrochemical Company.
    Components Contents (%)
    Linear alkyl (C22) calcium sulfonate with superhigh base number 25
    Sulfurized calcium alkyl (C25) phenolate with low base number 55
    Zinc primary alkyl (C12) thiophosphate 2
    Bis-polyisobutylene succinimide 8
    Group I base oil of 600SN 10
    • Example 2:
  • The composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • In this example, the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 30 carbon atoms, and the base number thereof is 395 mgKOH/g. The sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 20 carbon atoms, and the base number thereof is 265 mgKOH/g. The antiwear agent is zinc long-chain secondary alkyl thiophosphate wherein the long-chain secondary alkyl group comprises 16 carbon atoms. The dispersing agent is multi-polyisobutylene succinimide. The base oil is group I base oil 500SN available from PetroChina Daqing Petrochemical Company.
    Components Contents (%)
    Linear alkyl (C30) calcium sulfonate with superhigh base number 45
    Sulfurized calcium alkyl (C20) phenolate with low base number 41
    Zinc secondary alkyl (C16) thiophosphate 4
    Multi-polyisobutylene succinimide 0
    Group I base oil of 500SN 10
    • Example 3:
  • The composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • In this example, the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g. The sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 250 mgKOH/g. The antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 18 carbon atoms. The dispersing agent is bis-polyisobutylene succinimide. The base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company.
    Components Contents (%)
    Linear alkyl (C22) calcium sulfonate with superhigh base number 32
    Sulfurized calcium alkyl (C25) phenolate with low base number 40
    Zinc primary alkyl (C18) thiophosphate 0
    Bis-polyisobutylene succinimide 8
    Group I base oil of 400SN 20
    • Example 4:
  • The composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • In this example, the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g. The sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 240 mgKOH/g. The antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 12 carbon atoms. The dispersing agent is bis-polyisobutylene succinimide. The base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company.
    Components Contents (%)
    Linear alkyl (C22) calcium sulfonate with superhigh base number 28
    Sulfurized calcium alkyl (C25) phenolate with low base number 60
    Zinc primary alkyl (C12) thiophosphate 2
    Bis-polyisobutylene succinimide 0
    Group I base oil of 400SN 10
    • Example 5:
  • The composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • In this example, the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 30 carbon atoms, and the base number thereof is 410 mgKOH/g. The sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 265 mgKOH/g. The antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 18 carbon atoms. The dispersing agent is multi-polyisobutylene succinimide. The base oil is group I base oil 600SN available from PetroChina Daqing Petrochemical Company.
    Components Contents (%)
    Linear alkyl (C30) calcium sulfonate with superhigh base number 30
    Sulfurized calcium alkyl (C25) phenolate with low base number 45
    Zinc primary alkyl (C18) thiophosphate 4
    Multi-polyisobutylene succinimide 6
    Group I base oil of 600SN 15
    • Example 6:
  • The composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • In this example, the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 410 mgKOH/g. The sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 20 carbon atoms, and the base number thereof is 300 mgKOH/g. The antiwear agent is zinc long-chain secondary alkyl thiophosphate wherein the long-chain secondary alkyl group comprises 12 carbon atoms. The dispersing agent is mono-polyisobutylene succinimide. The base oil is Group I base oil 500SN available from PetroChina Daqing Petrochemical Company.
    Components Contents (%)
    Linear alkyl (C22) calcium sulfonate with superhigh base number 40
    Sulfurized calcium alkyl (C20) phenolate with low base number 40
    Zinc secondary alkyl (C12) thiophosphate 1
    Mono-polyisobutylene succinimide 4
    Group I base oil of 500SN 15
    • Example 7:
  • The composite additive used in BOB system may be prepared from the components mentioned below (their contents in weight percentage are also given in detail) by means of normal process.
  • In this example, the sulfonate with superhigh base number is calcium long-chain linear alkyl benzene sulphonate with superhigh base number wherein the long-chain linear alkyl group comprises 22 carbon atoms, and the base number thereof is 430 mgKOH/g. The sulfurized alkyl phenolate with low base number is sulfurized calcium long-chain alkyl phenolate wherein the alkyl group comprises 25 carbon atoms, and the base number thereof is 240 mgKOH/g. The antiwear agent is zinc long-chain primary alkyl thiophosphate wherein the long-chain primary alkyl group comprises 18 carbon atoms. The dispersing agent is bis-polyisobutylene succinimide. The base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company.
    Components Contents (%)
    Linear alkyl (C22) calcium sulfonate with superhigh base number 32
    Sulfurized calcium alkyl (C25) phenolate with low base number 58
    Zinc primary alkyl (C18) thiophosphate 0
    Bis-polyisobutylene succinimide 0
    Group I base oil of 400SN 10
  • The present invention provides a bis-detergent composite additive designed for the BOB system, and the physical and chemical properties of such composite additive are able to satisfy the requirement of Maersk Fluid Co. about the composite additive designed for the BOB system. The physical and chemical properties of the composite additives obtained by the above examples are listed in Table 1. Table 1 Comparison of the physical and chemical properties of the bis-detergent cylinder oil composite additives designed for the BOB system
    Item Sample Technical requirement Method
    Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7
    Kinematic viscosity (100°C), mm2/s 81.68 90.46 85.38 86.72 92.36 86.46 88.69 ≤95 according to OEM GB/T 265
    Base number, mgKOH/g 305 295 310 290 292 302 298 ≥285 according to OEM SH/T 0251
    Density (20°C), kg/m3 1097.6 1085.5 1072.0 1095.0 1079.6 1105.4 1092.6 Report SH/T 0604
    Flash point (closed), °C 185 186 192 178 184 198 186 ≥150 GB/T 261
    Moisture, % 0.18 0.03 0.06 0.08 0.03 0.06 0.03 ≤0.2 GB/T 260
    Mechanical impurity, % 0.032 0.012 0.020 0.030 0.018 0.028 0.032 ≤0.1 GB/T 511
    Sulfated ash, % 32.96 36.68 38.42 37.61 34.98 35.29 30.64 Report GB/T 2433
  • The composite additive designed for the BOB system using double detergents provided by the present invention is well compatible with system oil products under typical domestic and foreign brands, for example Exxon-Mobile Company, BP Company and PetroChina. The performances of the formulated cylinder oils with different base numbers are individually studied by simulated experiments, and the results demonstrate that the cylinder oils with different base numbers maintain good combination property as for lubricating oil, for example the antioxidization, antiwear, detergency and water resisting performances and etc.
  • Herein, the antioxidization performance of the cylinder oil is evaluated according to the oxidative induction time which is measured by differential scanning calorimetry (PDSC). The antiwear performance is evaluated by the Pb value and the long wear extent which are obtained by four-ball test. The coking tests are carried out in order to test the detergency performance of the cylinder oil, while the gel tests are carried out so as to test the storage stability.
  • The bis-detergent composite additive designed for the BOB system formulated according to the formulation of Example 6 is blended with Exxon-Mobile system oil Mobilgard M300, BP system oil Energol OE-HT30 and Kunlun system oil DCC3008, respectively, so as to provide cylinder oils with the base numbers of 70 mgKOH/g, 60 mgKOH/g, 50 mgKOH/g and 40 mgKOH/g as shown in Tables 2, 3, 4 and 5. Table 2 Physical and chemical properties of the cylinder oil with the base number of 70 mgKOH/g and the simulated performance thereof
    Item Unit Mobilgard M300 Energol OE-HT30 KUNLUN DCC3008 Method
    Dosage of the composite additive, % 22 22 21.2
    Viscosity, 100°C mm2/s 13.77 14.23 13.37 GB/T 265
    Viscosity coefficient - 103 105 100 ISO2909
    Base number mgKOH /g 69.7 69.4 69.4 SH/T 0251
    Flash point °C 258 252 250 GB/T 261
    Sulfated ash, % w% 7.49 7.85 7.38 GB/T 2433
    Oxidative induction time by PDSC min 15.13 15.06 13.24 SH/T 0719, the test condition is: 200°C, 3.0MPa, O2
    Pb value by four-ball test N 1254 1186 1186 GB/T 3142
    Long wear extent by four-ball test mm 0.33 0.34 0.33 SH/T 0189
    Coking test mg 12 18 16 SH/T 0300
    Gel test ml 0.5 0.25 0.1 1 % of water and 99% of oil are blended in the test tube, stirred by an agitator blade (2000 rpm) for 60 sec and stored at 70°C for 96 h. The precipitation amount at tube bottom is observed.
    Table 3 Physical and chemical properties of the cylinder oil with the base number of 60 mgKOH/g and the simulated performance thereof
    Item Unit Mobilgard M300 Energol OE-HT30 KUNLUN DCC3008 Method
    Dosage of the composite additive, % 18.64 18.64 17.8
    Viscosity, 100°C mm2/ s 13.26 13.70 12.82 GB/T 265
    Viscosity coefficient - 103 105 102 ISO2909
    Base number mgK OH/g 69.6 69.7 60.5 SH/T 0251
    Flash point °C 254 254 258 GB/T 261
    Sulfated ash, % w% 7.10 7.28 7.05 GB/T 2433
    PDSC min 13.20 14.22 12.83 SH/T 0719, the test condition is: 200°C, 3.0MPa, O2
    Pb value by four-ball test N 1186 1117 1186 GB/T 3142
    Long wear extent by four-ball test mm 0.34 0.35 0.34 SH/T 0189
    Coking test mg 16 22 9 SH/T 0300
    Gel test ml 0.3 0.3 0.2 1 % of water and 99% of oil are blended in the test tube, stirred by an agitator blade (2000 rpm) for 60 sec and stored at 70°C for 96 h. The precipitation amount at tube bottom is observed.
    Table 4 Physical and chemical properties of the cylinder oil with the base number of 50 mgKOH/g and the simulated performance thereof
    Item Unit Mobilgard M300 Energol OE-HT30 KUNLUN DCC3008 Method
    Dosage of the composite additive, % 15.25 15.25 14.38
    Viscosity, 100°C mm2/ s 12.89 13.36 12.36 GB/T 265
    Viscosity coefficient - 101 105 101 ISO2909
    Base number mgK OH/g 49.5 49.4 49.3 SH/T 0251
    Flash point °C 252 260 252 GB/T 261
    Sulfated ash, % w% 6.83 6.78 6.62 GB/T 2433
    PDSC min 12.98 13.68 12.22 SH/T 0719, the test condition is: 200°C, 3.0MPa, O2
    Pb value by four-ball test N 1117 1049 1117 GB/T 3142
    Long wear extent by four-ball test mm 0.34 0.35 0.35 SH/T 0189
    Coking test mg 19 26 12 SH/T 0300
    Gel test ml 0.5 0.45 0.35 1 % of water and 99% of oil
    are blended in the test tube, stirred by an agitator blade (2000 rpm) for 60 sec and stored at 70°C for 96 h. The precipitation amount at tube bottom is observed.
    Table 5 Physical and chemical properties of the cylinder oil with the base number of 40 mgKOH/g and the simulated performance thereof
    Item Unit Mobilgard M300 Energol OE-HT30 KUNLUN DCC3008 Method
    Dosage of the composite additive, % 11.86 11.86 10.96
    Viscosity, 100°C mm2/ s 12.56 12.89 11.98 GB/T 265
    Viscosity coefficient - 102 104 100 ISO2909
    Base number mgK OH/g 39.8 39.2 40.2 SH/T 0251
    Flash point °C 250 254 249 GB/T 261
    Sulfated ash, % w% 6.53 6.39 6.31 GB/T 2433
    PDSC min 12.74 13.34 11.96 SH/T 0719, the test condition is: 200°C, 3.0MPa, O2
    Pb value by four-ball test N 1117 1117 1186 GB/T 3142
    Long wear extent by four-ball test mm 0.34 0.35 0.34 SH/T 0189
    Coking test mg 21 24 18 SH/T 0300
    Gel test ml 0.4 0.25 0.5 1 % of water and 99% of oil are blended in the test tube, stirred by an agitator blade (2000 rpm) for 60 sec and stored at 70°C for 96 h. The precipitation amount at tube bottom is observed.
  • The composite additive designed for the BOB system using double detergents provided by the present invention can be blended with system oils so as to provide cylinder oils that can satisfy the requirement of the engine. Such composite additive has been tested by sailing over 4000 hours wherein BP Energol OE-HT30 is used as the system oil by the vessel, and has been technically certified by MAN B&W. Samples of the fresh/waste cylinder oils using such composite additive during the sailing were monitored, and the data are illustrated in Figure 2.
  • Throughout the test of 4000 hours, the base number of the cylinder oil formulated from the composite additive decreased from 70 mgKOH/g at the beginning, through 60 mgKOH/g and 50 mgKOH/g, to 40 mgKOH/g at the end. The entire sailing test could be divided into four stages according to the base number of the cylinder oil, and each stage lasted about 1000 hours. It can be clearly seen from Figure 2 that the residual base number in the waste oil was not notably decreased, and the Fe content resulted from the wear was not notably increased, either, that is, the both important index fluctuated within normal ranges.
    1. 1. The Fe content in the waste oil was never abnormally high, and the Fe content of all the samples was always less than 200 ppm, which satisfied the requirement of the engine OEM about the performance of cylinder oils;
    2. 2. The residue base number of the waste oil from the four different stages tended to decrease due to the decrease of the base number of fresh oils. Furthermore, even if the cylinder oil with a base number of 40 mgKOH/g was used, the residue base number in the waste oil was still above 12 mgKOH/g. It is shown that the composite additive has strong ability to "store" the base number, and thus effectively prevent the wear of engine parts to occur.
  • In conclusion, the cylinder lubricating oil maintained steady combination performance in case that the variation of the dosage of the composite additive reached the extent close to 50%, especially in terms of the antiwear performance under extreme pressure and the ability to preserve the base number. The test results sufficiently satisfied the requirement of the engine about the lubricating oil performance and were technically certified by the engine OEM.

Claims (2)

  1. A marine lubricating oil composite additive, characterized in that, based on the total weight of the composite additive, it comprises: 25-45% sulfonate detergent with superhigh base number, 40-60% phenolate detergent with low base number, 0-8% dispersing agent, 0-4% antiwear agent, and 10-20% Group I base oil with high viscosity index which is selected from the group consisting of 400SN, 500SN and 600SN;
    said sulfonate detergent with superhigh base number is C22-C30 linear alkyl benzene calcium sulphonate, wherein the base number thereof is 395-430 mgKOH/g;
    said phenolate detergent with low base number is C20-C25 alkyl sulfurized calcium phenolate, wherein the base number thereof is 240-265 mgKOH/g;
    said dispersing agent is selected from the group consisting of mono-polyisobutylene succinimide, bis-polyisobutylene succinimide and multi-polyisobutylene succinimide;
    said antiwear agent is zinc long-chain alkyl thiophosphate with the structure corresponding to the following formula,
    Figure imgb0002
     wherein R1, R2, R3 and R4 are long-chain primary alkyl groups each comprising 12-18 carbon atoms, or R1, R2, R3 and R4 are long-chain secondary alkyl groups each comprising 12-16 carbon atoms.
  2. The marine lubricating oil composite additive according to claim 1, characterized in that, the kinematic viscosity of said base oil is 8.5-11.5 cst at 100°C.
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US20080287327A1 (en) * 2005-10-14 2008-11-20 The Lubrizol Corporation Method of Lubricating a Marine Diesel Engine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2767578B1 (en) 2013-02-19 2016-02-03 LUKOIL Marine Lubricants Germany GmbH Process and apparatus for the preparation of a cylinder oil
US10240497B2 (en) 2013-02-19 2019-03-26 Lukoil Marine Lubricants Germany Gmbh Process and apparatus for the preparation of a cylinder oil
US10975739B2 (en) 2013-02-19 2021-04-13 Lukoil Marine Lubricants Germany Gmbh Process and apparatus for the preparation of a cylinder oil

Also Published As

Publication number Publication date
WO2012119272A1 (en) 2012-09-13
US20120231984A1 (en) 2012-09-13
US20150144429A1 (en) 2015-05-28
CN102676272A (en) 2012-09-19
CN102676272B (en) 2014-07-16
EP2497817B1 (en) 2016-12-21

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