US20150144430A1 - Marine cylinder oil composite additive - Google Patents

Marine cylinder oil composite additive Download PDF

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Publication number
US20150144430A1
US20150144430A1 US14/550,626 US201414550626A US2015144430A1 US 20150144430 A1 US20150144430 A1 US 20150144430A1 US 201414550626 A US201414550626 A US 201414550626A US 2015144430 A1 US2015144430 A1 US 2015144430A1
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base number
oil
composite additive
superhigh
detergent
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US14/550,626
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Yuekui Zhai
Jie Zhang
Gongde Liu
Yuli Ma
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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to US14/550,626 priority Critical patent/US20150144430A1/en
Assigned to PETROCHINA COMPANY LIMITED reassignment PETROCHINA COMPANY LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Liu, Gongde, Ma, Yuli, ZHAI, Yuekui, ZHANG, JIE
Publication of US20150144430A1 publication Critical patent/US20150144430A1/en
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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
    • C10M161/00Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M163/00Lubricating 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
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01MLUBRICATING OF MACHINES OR ENGINES IN GENERAL; LUBRICATING INTERNAL COMBUSTION ENGINES; CRANKCASE VENTILATING
    • F01M9/00Lubrication means having pertinent characteristics not provided for in, or of interest apart from, groups F01M1/00 - F01M7/00
    • F01M9/02Lubrication 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
    • 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
    • C10M2203/02Well-defined aliphatic compounds
    • 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
    • C10M2203/02Well-defined aliphatic compounds
    • C10M2203/0206Well-defined aliphatic compounds used as base material
    • 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/086Imides
    • 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
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/04Detergent property or dispersant property
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/26Waterproofing or water resistance
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52Base number [TBN]
    • 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
    • C10N2070/00Specific manufacturing methods for lubricant compositions
    • C10N2070/02Concentrating of additives

Definitions

  • the present invention relates to a marine cylinder oil composite additive formulation, and more particularly to a composite additive designed for cylinder 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 oil that have an optional target base number, and such cylinder oil can be rapidly transferred to the engine in order to meet the different requirements for the base number of the cylinder 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 FIG. 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 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 composite additive should satisfy the requirement of being pumped within the BOB system and fit with the blending system.
  • the sulfonate detergent with superhigh base number has excellent detergency and dispersion performances and the sulfurized calcium phenolate has excellent antiwear and antioxidization performances
  • the cylinder oil formulation is commonly composed by the sulfonate detergent and the sulfurized calcium phenolate; the naphthenate has good oil film diffusibility, and the burned residue thereof is relatively soft and readily cleaned by the lubricating oil.
  • Such combustion behavior of the naphthenate is particularly important for the “disposable” cylinder oil, and its relatively fast diffusion rate on the cylinder wall could just compensate for the lacking of oil film strength at low injection rate.
  • the application of the cylinder oil composite additive formulation comprising three detergents of the sulfonate detergent, sulfurized calcium phenolate detergent and naphthenate detergent can not only enhance the performance of the cylinder oil but also utilize the abundant naphthenate resource of PetroChina so as to build significant superiority in the technology of marine oil self-owned by PetroChina.
  • the purpose of the present invention is to provide a marine cylinder 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: 15-25% sulfonate detergent with superhigh base number, 35-45% phenolate detergent with superhigh base number, 20-30% naphthenate detergent with superhigh 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 650SN.
  • 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 superhigh base number is C 18 -C 24 alkyl sulfurized calcium phenolate, wherein the base number thereof is 290-310 mgKOH/g.
  • Said naphthenate detergent with superhigh base number is C 20 -C 30 long chain alkyl calcium naphthenate, wherein the base number thereof is 390-420 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,
  • 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 650SN, the kinematic viscosity of which is 8.0-11.0 cst at 100° C.
  • the appropriate base oils are commercially available from PetroChina Company.
  • the marine cylinder oil composite additive provided by the present invention employs three composed detergents, wherein the sulfonate detergent with superhigh base number has excellent detergency and dispersion performances but relatively poor antiwear and antioxidization performances; the sulfurized calcium phenolate has excellent antiwear and antioxidization performances but relatively poor detergency and dispersion performances; the naphthenate has good oil film diffusibility but relatively poor detergency and antiwear performances.
  • the above three detergents are composed so as to allow full play to their advantages and compensate for their shortages.
  • the technical features of the present invention are as follows: the requirement of the BOB system process for the viscosity and base number can be satisfied by the composite additive, which can be online blended and widely applied.
  • the cylinder oils with different base numbers can be formulated based on system oils under a number of domestic and foreign brands.
  • 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.
  • the composite additive according to the present invention can remain good stability in solution as well as good compatibility, and thus the lubricating performance of the cylinder oil would not be adversely affected.
  • Such 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).
  • FIG. 1 shows a schematic diagram for the operating principle of BOB online blending system.
  • FIG. 2 shows the monitoring data for samples of the fresh/waste cylinder oils using the composite additive of the present application during the sailing.
  • 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 blending 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 long-chain linear C 22 -alkyl benzene calcium sulphonate with superhigh base number and its base number is 430 mgKOH/g
  • the sulfurized alkyl phenolate with superhigh base number is long-chain C 25 -alkyl sulfurized calcium phenolate and the base number thereof is 290 mgKOH/g
  • the naphthenate detergent with superhigh base number is C 20 -alkyl calcium naphthenate with superhigh base number and the base number thereof is 390 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 mono-polyisobutylene succinimide.
  • the base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company.
  • 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 long-chain linear C 30 -alkyl benzene calcium sulphonate with superhigh base number and its base number is 395 mgKOH/g
  • the sulfurized alkyl phenolate with superhigh base number is long-chain C 18 -alkyl sulfurized calcium phenolate and the base number thereof is 310 mgKOH/g
  • the naphthenate detergent with superhigh base number is C 30 -alkyl calcium naphthenate with superhigh base number and the base number thereof is 420 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 bis-polyisobutylene succinimide.
  • the base oil is group I base oil 500SN available from PetroChina Daqing Petrochemical Company.
  • 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 long-chain linear C 26 -alkyl benzene calcium sulphonate with superhigh base number and its base number is 410 mgKOH/g
  • the sulfurized alkyl phenolate with superhigh base number is long-chain C 22 -alkyl sulfurized calcium phenolate and the base number thereof is 300 mgKOH/g
  • the naphthenate detergent with superhigh base number is C 26 -alkyl calcium naphthenate with superhigh base number and the base number thereof is 405 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 500SN available from PetroChina Daqing Petrochemical Company.
  • 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 long-chain linear C 22 -alkyl benzene calcium sulphonate with superhigh base number and its base number is 430 mgKOH/g
  • the sulfurized alkyl phenolate with superhigh base number is long-chain C 24 -alkyl sulfurized calcium phenolate and the base number thereof is 290 mgKOH/g
  • the naphthenate detergent with superhigh base number is C 20 -alkyl calcium naphthenate with superhigh base number and the base number thereof is 390 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 bis-polyisobutylene succinimide.
  • the base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company.
  • 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 long-chain linear C 20 -alkyl benzene calcium sulphonate with superhigh base number and its base number is 410 mgKOH/g
  • the sulfurized alkyl phenolate with superhigh base number is long-chain C 24 -alkyl sulfurized calcium phenolate and the base number thereof is 300 mgKOH/g
  • the naphthenate detergent with superhigh base number is C 26 -alkyl calcium naphthenate with superhigh base number and the base number thereof is 405 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 650SN available from PetroChina Daqing Petrochemical Company.
  • 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 long-chain linear C 20 -alkyl benzene calcium sulphonate with superhigh base number and its base number is 410 mgKOH/g
  • the sulfurized alkyl phenolate with superhigh base number is long-chain C 24 -alkyl sulfurized calcium phenolate and the base number thereof is 300 mgKOH/g
  • the naphthenate detergent with superhigh base number is C 26 -alkyl calcium naphthenate with superhigh base number and the base number thereof is 405 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 650SN available from PetroChina Daqing Petrochemical Company.
  • the present invention provides a tri-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.
  • the composite additive designed for the BOB system using triple 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 tri-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.
  • the test condition induction time by is: 200° C., 3.0 MPa, O 2 PDSC Pb value by N 1254 1186 1186 GB/T 3142 four-ball test Long wear extent mm 0.34 0.33 0.34 SH/T 0189 by four-ball test Coking test mg 21 20 18 SH/T 0300 Gel test ml 0.3 0.5 0.25 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 triple 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 FIG. 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.
  • the Fe content in the waste oil was never abnormally high, and the Fe content of all the samples was always less than 150 ppm, which satisfied the requirement of the engine OEM about the performance of cylinder oils;
  • the cylinder 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)
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  • General Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

The present invention relates to a marine cylinder oil composite additive. Based on the total weight of the composite additive, said marine cylinder oil composite additive comprises: 15-25% sulfonate detergent with superhigh base number, 35-45% phenolate detergent with superhigh base number, 20-30% naphthenate detergent with superhigh 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 650SN. The benefit of the present invention lies in the fact that the composite additive 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 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 oil will not be adversely affected.

Description

    CLAIM OF PRIORITY
  • This application is a divisional of and claims the benefit of priority to U.S. patent application Ser. No. 13/416,079, filed Mar. 9, 2012, which claims the benefit of priority of Chinese Patent Application 201110058054.X, filed on Mar. 10, 2011, which applications are incorporated by reference as if reproduced herein and made a part hereof in their entirety, and the benefit of priority of each of which is claimed herein.
  • FIELD OF THE INVENTION
  • The present invention relates to a marine cylinder oil composite additive formulation, and more particularly to a composite additive designed for cylinder 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 oil that have an optional target base number, and such cylinder oil can be rapidly transferred to the engine in order to meet the different requirements for the base number of the cylinder 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 FIG. 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 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. Sufficient antiwear and antioxidization properties should be preserved when relatively low dosage is used;
  • 2. Good compatibility to system oils under different brands;
  • 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.
  • It can be known from the corresponding Chinese and worldwide patents that the sulfonate detergent with superhigh base number has excellent detergency and dispersion performances and the sulfurized calcium phenolate has excellent antiwear and antioxidization performances, and thus the cylinder oil formulation is commonly composed by the sulfonate detergent and the sulfurized calcium phenolate; the naphthenate has good oil film diffusibility, and the burned residue thereof is relatively soft and readily cleaned by the lubricating oil. Such combustion behavior of the naphthenate is particularly important for the “disposable” cylinder oil, and its relatively fast diffusion rate on the cylinder wall could just compensate for the lacking of oil film strength at low injection rate.
  • The application of the cylinder oil composite additive formulation comprising three detergents of the sulfonate detergent, sulfurized calcium phenolate detergent and naphthenate detergent can not only enhance the performance of the cylinder oil but also utilize the abundant naphthenate resource of PetroChina so as to build significant superiority in the technology of marine oil self-owned by PetroChina.
  • SUMMARY OF THE INVENTION
  • The purpose of the present invention is to provide a marine cylinder 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: 15-25% sulfonate detergent with superhigh base number, 35-45% phenolate detergent with superhigh base number, 20-30% naphthenate detergent with superhigh 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 650SN.
  • 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 superhigh base number is C18-C24 alkyl sulfurized calcium phenolate, wherein the base number thereof is 290-310 mgKOH/g.
  • Said naphthenate detergent with superhigh base number is C20-C30 long chain alkyl calcium naphthenate, wherein the base number thereof is 390-420 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 US20150144430A1-20150528-C00001
  • 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 650SN, the kinematic viscosity of which is 8.0-11.0 cst at 100° C. The appropriate base oils are commercially available from PetroChina Company.
  • The marine cylinder oil composite additive provided by the present invention employs three composed detergents, wherein the sulfonate detergent with superhigh base number has excellent detergency and dispersion performances but relatively poor antiwear and antioxidization performances; the sulfurized calcium phenolate has excellent antiwear and antioxidization performances but relatively poor detergency and dispersion performances; the naphthenate has good oil film diffusibility but relatively poor detergency and antiwear performances. The above three detergents are composed so as to allow full play to their advantages and compensate for their shortages.
  • The technical features of the present invention are as follows: the requirement of the BOB system process for the viscosity and base number can be satisfied by the composite additive, which can be online blended and widely applied. The cylinder oils with different base numbers can be formulated based on system oils under a number of domestic and foreign brands. 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. Moreover, the composite additive according to the present invention can remain good stability in solution as well as good compatibility, and thus the lubricating performance of the cylinder oil would not be adversely affected. Such 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
  • FIG. 1 shows a schematic diagram for the operating principle of BOB online blending system.
  • FIG. 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 blending 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 long-chain linear C22-alkyl benzene calcium sulphonate with superhigh base number and its base number is 430 mgKOH/g, the sulfurized alkyl phenolate with superhigh base number is long-chain C25-alkyl sulfurized calcium phenolate and the base number thereof is 290 mgKOH/g, and the naphthenate detergent with superhigh base number is C20-alkyl calcium naphthenate with superhigh base number and the base number thereof is 390 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 mono-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 15
    number
    Sulfurized calcium alkyl (C25) phenolate with superhigh base 45
    number
    Alkyl (C20) calcium naphthenate with superhigh base number 20
    Zinc primary alkyl (C12) thiophosphate 2
    Mono-polyisobutylene succinimide 8
    Group I base oil of 400SN 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 long-chain linear C30-alkyl benzene calcium sulphonate with superhigh base number and its base number is 395 mgKOH/g, the sulfurized alkyl phenolate with superhigh base number is long-chain C18-alkyl sulfurized calcium phenolate and the base number thereof is 310 mgKOH/g, and the naphthenate detergent with superhigh base number is C30-alkyl calcium naphthenate with superhigh base number and the base number thereof is 420 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 bis-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 15
    number
    Sulfurized calcium alkyl (C20) phenolate with superhigh base 35
    number
    Alkyl (C30) calcium naphthenate with superhigh base number 27
    Zinc secondary alkyl (C16) thiophosphate 4
    Bis-polyisobutylene succinimide 4
    Group I base oil of 500SN 15
  • 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 long-chain linear C26-alkyl benzene calcium sulphonate with superhigh base number and its base number is 410 mgKOH/g, the sulfurized alkyl phenolate with superhigh base number is long-chain C22-alkyl sulfurized calcium phenolate and the base number thereof is 300 mgKOH/g, and the naphthenate detergent with superhigh base number is C26-alkyl calcium naphthenate with superhigh base number and the base number thereof is 405 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 500SN available from PetroChina Daqing Petrochemical Company.
  • Components Contents (%)
    Linear alkyl (C26) calcium sulfonate with superhigh base 25
    number
    Sulfurized calcium alkyl (C22) phenolate with superhigh base 35
    number
    Alkyl (C26) calcium naphthenate with superhigh base number 20
    Zinc primary alkyl (C18) thiophosphate 2
    Multi-polyisobutylene succinimide 6
    Group I base oil of 500SN 12
  • 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 long-chain linear C22-alkyl benzene calcium sulphonate with superhigh base number and its base number is 430 mgKOH/g, the sulfurized alkyl phenolate with superhigh base number is long-chain C24-alkyl sulfurized calcium phenolate and the base number thereof is 290 mgKOH/g, and the naphthenate detergent with superhigh base number is C20-alkyl calcium naphthenate with superhigh base number and the base number thereof is 390 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 bis-polyisobutylene succinimide. The base oil is group I base oil 400SN available from PetroChina Daqing Petrochemical Company.
  • Components Contents (%)
    Linear alkyl (C26) calcium sulfonate with superhigh base 20
    number
    Sulfurized calcium alkyl (C22) phenolate with superhigh base 42
    number
    Alkyl (C26) calcium naphthenate with superhigh base number 20
    Zinc secondary alkyl (C12) thiophosphate 0
    Bis-polyisobutylene succinimide 8
    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 long-chain linear C20-alkyl benzene calcium sulphonate with superhigh base number and its base number is 410 mgKOH/g, the sulfurized alkyl phenolate with superhigh base number is long-chain C24-alkyl sulfurized calcium phenolate and the base number thereof is 300 mgKOH/g, and the naphthenate detergent with superhigh base number is C26-alkyl calcium naphthenate with superhigh base number and the base number thereof is 405 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 650SN available from PetroChina Daqing Petrochemical Company.
  • Components Contents (%)
    Linear alkyl (C20) calcium sulfonate with superhigh base 16
    number
    Sulfurized calcium alkyl (C24) phenolate with superhigh base 40
    number
    Alkyl (C26) calcium naphthenate with superhigh base number 20
    Zinc secondary alkyl (C16) thiophosphate 4
    Multi-polyisobutylene succinimide 0
    Group I base oil of 650SN 20
  • 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 long-chain linear C20-alkyl benzene calcium sulphonate with superhigh base number and its base number is 410 mgKOH/g, the sulfurized alkyl phenolate with superhigh base number is long-chain C24-alkyl sulfurized calcium phenolate and the base number thereof is 300 mgKOH/g, and the naphthenate detergent with superhigh base number is C26-alkyl calcium naphthenate with superhigh base number and the base number thereof is 405 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 650SN available from PetroChina Daqing Petrochemical Company.
  • Components Contents (%)
    Linear alkyl (C20) calcium sulfonate with superhigh base 19
    number
    Sulfurized calcium alkyl (C24) phenolate with superhigh base 40
    number
    Alkyl (C26) calcium naphthenate with superhigh base number 25
    Zinc secondary alkyl (C16) thiophosphate 2
    Multi-polyisobutylene succinimide 4
    Group I base oil of 650SN 10
  • The present invention provides a tri-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 tri-detergent
    cylinder oil composite additives designed for the BOB system
    Sample
    Example Example Example Example Example Example Technical
    Item 1 2 3 4 5 6 requirement Method
    Kinematic 93.68 89.64 90.52 88.78 91.38 92.80 ≦95 GB/T 265
    viscosity according
    (100° C.), to OEM
    mm2/s
    Base number, 308 298 302 295 298 306 ≧285 SH/T 0251
    mgKOH/g according
    to OEM
    Density (20° C.), 1095.2 1082.5 1090.6 1080.8 1092.6 1098.7 Report SH/T 0604
    kg/m3
    Flash point 188 192 186 191 188 195 ≧150 GB/T 261
    (closed), ° C.
    Moisture, % 0.10 0.06 0.03 0.06 0.05 0.08 ≦0.2 GB/T 260
    Mechanical 0.030 0.020 0.018 0.028 0.015 0.020 ≦0.1 GB/T 511
    impurity, %
    Sulfated 38.62 33.54 35.86 34.62 37.54 36.91 Report GB/T 2433
    ash, %
  • The composite additive designed for the BOB system using triple 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 tri-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
    Mobilgard Energol KUNLUN
    Item Unit M300 OE-HT30 DCC3008 Method
    Dosage of the 22 22 21.2
    composite
    additive, %
    Viscosity, 100° C. mm2/s 14.12 14.72 13.81 GB/T 265
    Viscosity 105 102 104 ISO2909
    coefficient
    Base number mgKOH/ 69.2 70.2 69.8 SH/T 0251
    g
    Flash point ° C. 252 250 258 GB/T 261
    Sulfated ash, % w % 7.82 7.72 7.68 GB/T 2433
    Oxidative min 14.72 13.98 13.20 SH/T 0719, the test condition
    induction time by is: 200° C., 3.0 MPa, O2
    PDSC
    Pb value by N 1254 1186 1186 GB/T 3142
    four-ball test
    Long wear extent mm 0.34 0.33 0.34 SH/T 0189
    by four-ball test
    Coking test mg 21 20 18 SH/T 0300
    Gel test ml 0.3 0.5 0.25 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
    Mobilgard Energol KUNLUN
    Item Unit M300 OE-HT30 DCC3008 Method
    Dosage of the 18.64 18.64 17.8
    composite
    additive, %
    Viscosity, 100° C. mm2/s 13.86 14.35 13.47 GB/T 265
    Viscosity 102 100 108 ISO2909
    coefficient
    Base number mgKOH/g 59.2 59.8 60.2 SH/T 0251
    Flash point ° C. 250 258 252 GB/T 261
    Sulfated ash, % w % 7.36 7.40 7.35 GB/T 2433
    PDSC min 14.14 13.08 12.89 SH/T 0719, the test condition
    is: 200° C., 3.0 MPa, O2
    Pb value by N 1186 1117 1186 GB/T 3142
    four-ball test
    Long wear extent mm 0.34 0.34 0.33 SH/T 0189
    by four-ball test
    Coking test mg 19 20 16 SH/T 0300
    Gel test ml 0.5 0.2 0.25 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
    Mobilgard Energol KUNLUN
    Item Unit M300 OE-HT30 DCC3008 Method
    Dosage of the 15.25 15.25 14.38
    composite
    additive, %
    Viscosity, 100° C. mm2/s 13.46 13.98 13.06 GB/T 265
    Viscosity coefficient 105 100 102 ISO2909
    Base number mgK 49.8 49.2 49.7 SH/T 0251
    OH/g
    Flash point ° C. 246 258 250 GB/T 261
    Sulfated ash, % w % 6.97 6.86 6.94 GB/T 2433
    PDSC min 13.86 13.04 11.95 SH/T 0719, the test condition
    is: 200° C., 3.0 MPa, O2
    Pb value by four-ball N 1049 1117 1117 GB/T 3142
    test
    Long wear extent by mm 0.35 0.34 0.34 SH/T 0189
    four-ball test
    Coking test mg 26 18 20 SH/T 0300
    Gel test ml 0.45 0.32 0.50 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
    Mobilgard Energol KUNLUN
    Item Unit M300 OE-HT30 DCC3008 Method
    Dosage of the 11.86 11.86 10.96
    composite
    additive, %
    Viscosity, 100° C. mm2/s 12.92 13.62 12.67 GB/T 265
    Viscosity coefficient 100 108 102 ISO2909
    Base number mgK 39.6 40.1 39.8 SH/T 0251
    OH/g
    Flash point ° C. 246 250 258 GB/T 261
    Sulfated ash, % w% 6.50 6.36 6.58 GB/T 2433
    PDSC min 12.82 13.41 11.98 SH/T 0719, the test condition
    is: 200° C., 3.0 MPa, O2
    Pb value by four-ball N 1117 1117 1186 GB/T 3142
    test
    Long wear extent by mm 0.35 0.34 0.35 SH/T 0189
    four-ball test
    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 triple 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 FIG. 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 FIG. 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. The Fe content in the waste oil was never abnormally high, and the Fe content of all the samples was always less than 150 ppm, which satisfied the requirement of the engine OEM about the performance of cylinder oils;
  • 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 15 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 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 (7)

1. (canceled)
2. An engine system, comprising:
a system oil storage tank having a system oil outlet stream for providing a system oil;
an additive tank having an additive outlet stream for providing a composite additive comprising 15-25% sulfonate detergent with superhigh base number, 35-45% phenolate detergent with superhigh base number, 20-30% naphthenate detergent with superhigh 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 650SN;
a blend on board device operably connected to the system oil outlet stream and the composite additive outlet stream and having a cylinder oil outlet stream, the blend on board device being operable to combine the system oil with the composite additive to form a cylinder oil having a predetermined base number;
a cylinder oil storage tank operably having an ejector outlet stream, the cylinder oil storage tank connected to the cylinder oil outlet stream and configured to retain receive the cylinder oil for a predetermined period of time; and
a main engine operably connected to a fuel oil inlet stream and the ejector outlet stream to receive the retained cylinder oil and intermix the fuel oil with the cylinder oil.
3. The engine system of claim 2, wherein:
the sulfonate detergent with superhigh base number is C22-C30 linear alkyl benzene calcium sulphonate, wherein the base number thereof is 395-430 mgKOH/g.
the phenolate detergent with superhigh base number is C18-C24 alkyl sulfurized calcium phenolate, wherein the base number thereof is 290-310 mgKOH/g;
the naphthenate detergent with superhigh base number is C20-C30 long chain alkyl calcium naphthenate, wherein the base number thereof is 390-420 mgKOH/g;
the dispersing agent is selected from the group consisting of mono-polyisobutylene succinimide, bis-polyisobutylene succinimide and multi-polyisobutylene succinimide;
the antiwear agent is zinc long-chain alkyl thiophosphate with the structure corresponding to the following formula,
Figure US20150144430A1-20150528-C00002
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.
4. The engine system of claim 2, wherein the kinematic viscosity of the base oil is 8.0-11.0 cSt at 100° C.
5. The engine system of claim 2, wherein the cylinder oil resulting from the combination of the system oil with the composite additive has a base number greater than or equal to 285 mgKOH/g.
6. The engine system of claim 2, wherein the cylinder oil resulting from the combination of the system oil with the composite additive has a kinematic viscosity at 100° C. less than or equal to 95 mm2/s.
7. A method for treating a marine cylinder oil comprising:
blending a marine cylinder oil, in a shipborne Blender-on-Board system; with a composite additive comprising, based on the total weight of the composite additive:
15-25% sulfonate detergent with superhigh base number, 35-45% phenolate detergent with superhigh base number, 20-30% naphthenate detergent with superhigh 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 650SN;
wherein:
the sulfonate detergent with superhigh base number is C22-C30 linear alkyl benzene calcium sulphonate, wherein the base number thereof is 395-430 mgKOH/g.
the phenolate detergent with superhigh base number is C18-C24 alkyl sulfurized calcium phenolate, wherein the base number thereof is 290-310 mgKOH/g;
the naphthenate detergent with superhigh base number is C20-C30 long chain alkyl calcium naphthenate, wherein the base number thereof is 390-420 mgKOH/g;
the dispersing agent is selected from the group consisting of mono-polyisobutylene succinimide, bis-polyisobutylene succinimide and multi-polyisobutylene succinimide;
the antiwear agent is zinc long-chain alkyl thiophosphate with the structure corresponding to the following formula,
Figure US20150144430A1-20150528-C00003
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.
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