EP2497818B1 - Utilisation d' un additif composite d'huile lubrifiante marine - Google Patents
Utilisation d' un additif composite d'huile lubrifiante marine Download PDFInfo
- Publication number
- EP2497818B1 EP2497818B1 EP12158753.9A EP12158753A EP2497818B1 EP 2497818 B1 EP2497818 B1 EP 2497818B1 EP 12158753 A EP12158753 A EP 12158753A EP 2497818 B1 EP2497818 B1 EP 2497818B1
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- EP
- European Patent Office
- Prior art keywords
- base number
- oil
- alkyl
- superhigh
- detergent
- Prior art date
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- 239000000654 additive Substances 0.000 title claims description 48
- 239000002131 composite material Substances 0.000 title claims description 45
- 230000000996 additive effect Effects 0.000 title claims description 43
- 239000010687 lubricating oil Substances 0.000 title description 10
- 239000010727 cylinder oil Substances 0.000 claims description 39
- 239000003599 detergent Substances 0.000 claims description 38
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 239000002199 base oil Substances 0.000 claims description 27
- 239000011575 calcium Substances 0.000 claims description 20
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 20
- 229920002367 Polyisobutene Polymers 0.000 claims description 18
- 229960002317 succinimide Drugs 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl calcium naphthenate Chemical compound 0.000 claims description 16
- 229940031826 phenolate Drugs 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 125000005609 naphthenate group Chemical group 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 13
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims description 10
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 8
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 32
- 239000003921 oil Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 14
- 239000010729 system oil Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 6
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 6
- 238000004939 coking Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
Images
Classifications
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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 use of a marine cylinder oil composite additive formulation for cylinder oils , 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 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 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:
- 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.
- EP 1 640 442 A1 discloses a method (and a corresponding system) of creating a cylinder oil, the method comprising modification of at least one initial fluid by determining a desired TBN(s) of the at least one initial fluid, determining a desired TBN of cylinder oil and adjusting the TBN(s) of the at least one initial fluid accordingly by blending the at least one initial fluid with suited additive(s).
- the suited additive(s) comprise at least on base, wherein the at least one base comprise basic salts of alkaline or earth alkaline elements, and/or detergents and/or dispersants.
- EP 1126010 A1 disclosed a lubricating oil composition
- a lubricating oil composition comprising a major amount of a base oil of lubricating viscosity, an overbased sulfurized alkylphenate detergent, an overbased alkylsulfonate detergent, an ashless dispersant, and a zinc dialkyldithiophosphate or of a zinc diaryldithiophosphate, wherein the weight ratio between the overbased sulfurized alkylphenate detergent and the overbased alkylsulfonate detergent is in the range of 55:45 to 95:5.
- 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 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, wherein Ri, R 2 , R 3 and R 4 are long-chain primary alkyl groups each comprising 12-18 carbon atoms, or R i , 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.
- 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.
- 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. Components Contents (%) Linear alkyl (C22) calcium sulfonate with superhigh base number 15 Sulfurized calcium alkyl (C25) phenolate with superhigh base number 45 Alkyl (C20) calcium naphthenate with superhigh base 20 number Zinc primary alkyl (C12) thiophosphate 2 Mono-polyisobutylene succinimide 8 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 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 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 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. Components Contents (%) Linear alkyl (C26) calcium sulfonate with superhigh base number 20 Sulfurized calcium alkyl (C22) phenolate with superhigh base number 42 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
- 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. Components Contents (%) Linear alkyl (C20) calcium sulfonate with superhigh base number 16 Sulfurized calcium alkyl (C24) phenolate with superhigh base number 40 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
- 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. Components Contents (%) Linear alkyl (C20) calcium sulfonate with superhigh base number 19 Sulfurized calcium alkyl (C24) phenolate with superhigh base number 40 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 uses 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.
- Example 1 Comparison of the physical and chemical properties of the tri-detergent cylinder oil composite additives designed for the BOB system Item Sample Technical requirement Method
- Example 2 Example 3
- Example 4 Example 5
- the composite additive designed for the BOB system using triple detergents used 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 composite additive designed for the BOB system using triple detergents used 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 .
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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)
Claims (2)
- Utilisation d'un additif pour huile de cylindre marine pour huile de cylindre composite dans un système mélangeur-bord à bord, caractérisé en ce que, par rapport au poid total de l'additif, il comprend: 15 à 25% de détergent sulfonate avec un indice de base très élevée, 35-45 % de détergent phénolate avec un indice de base très élevée, 20-30% de détergent naphtalénate avec un indice de base très élevée, 0-8% de dispersant, 0-4% d'agents anti-usure, et 10-20% d'huile de base groupe I avec un indice de viscosité élevé, qui est choisi parmi les suivants: 400SN, 500SN et 650SN;
dans laquelle le détergent avec l'indice de base très élevée, est un sulfonate d'alkylbenzène linéaire de calcium en C22-C30 et le nombre de base est 395 à 430 mg de KOH / g;
dans laquelle le détergent phénolate avec un indice très élevé de base est un alkyle sulfurée phénolate de calcium en C18-C24, dans lequel l'indice de base est de 290-310 mg de KOH / g;
ledit détergent naphtalénate avec un indice de base très élevée est une longue chaîne alkyle naphtalénate de calcium en C20-C30, dans lequel l'indice de de base est 390-420 mg KOH / g;
dans lequel l'agent de dispersion est choisi parmi les suivants: mono-polyisobutylène, bis-polyisobutylène et multi-polyisobutylène;
dans lequel l'agent anti-usure est un alkyle en zinc thiophosphate à longue chaîne ayant
la structure selon la formule suivante, - Utilisation d'un additif pour huile de cylindre marine pour huile de cylindre composite dans un système mélangeur-bord à bord selon la revendication 1, caractérisé en ce que la viscosité cinématique de l'huile de base est de 8,0 à 11,0 cSt à 100 ° C
Applications Claiming Priority (1)
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CN201110058054XA CN102676273B (zh) | 2011-03-10 | 2011-03-10 | 一种船用气缸油复合剂 |
Publications (2)
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EP2497818A1 EP2497818A1 (fr) | 2012-09-12 |
EP2497818B1 true EP2497818B1 (fr) | 2016-10-19 |
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EP12158753.9A Active EP2497818B1 (fr) | 2011-03-10 | 2012-03-09 | Utilisation d' un additif composite d'huile lubrifiante marine |
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US (2) | US20120231985A1 (fr) |
EP (1) | EP2497818B1 (fr) |
CN (1) | CN102676273B (fr) |
WO (1) | WO2012119273A1 (fr) |
Families Citing this family (10)
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CN104232247A (zh) * | 2013-06-07 | 2014-12-24 | 天津市百年润滑油工贸有限公司 | 一种复合纳米粒子润滑油及其制备方法 |
CN103555400B (zh) * | 2013-10-24 | 2015-08-26 | 大连海事大学 | 一种矿油型蒸汽气缸油组合物,其制备方法及应用 |
CN104450091A (zh) * | 2014-12-02 | 2015-03-25 | 中国石油天然气股份有限公司 | 一种船用气缸油组合物及其制备方法与应用 |
KR20170137709A (ko) * | 2015-01-26 | 2017-12-13 | 셰브런 오로나이트 테크놀로지 비.브이. | 선박용 디젤 엔진 윤활유 조성물 |
DK179212B1 (en) * | 2015-10-20 | 2018-02-05 | A P Møller Mærsk As | Method and apparatus for preparing an oil to be supplied to the cylinders of a two-stroke crosshead engine |
EP3374610B1 (fr) * | 2015-11-11 | 2023-09-27 | A.P. Møller - Mærsk A/S | Mélangeur et procédé de préparation d'une huile destinée à être fournie aux cylindres d'un moteur à crosse à deux temps |
CN108165353A (zh) * | 2018-02-01 | 2018-06-15 | 山东莱恩国立生物科技有限公司 | 一种生物润滑油添加剂及其制备方法 |
CN112239697A (zh) * | 2019-07-17 | 2021-01-19 | 中国石油化工股份有限公司 | 船用气缸油组合物及其用途 |
CN112646646A (zh) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | 铁路机车油组合物、制备方法及其用途 |
CN116064188A (zh) * | 2021-11-04 | 2023-05-05 | 中国石油化工股份有限公司 | 润滑油组合物及其制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1640442A1 (fr) * | 2004-09-24 | 2006-03-29 | A.P. Moller - Maersk A/S | Méthode et système permettant la modification d'un liquide hydrocarboné usé afin de créer une huile pour cylindre |
Family Cites Families (14)
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GB8723909D0 (en) * | 1987-10-12 | 1987-11-18 | Exxon Chemical Patents Inc | Lubricant oil additive |
GB8804171D0 (en) * | 1988-02-23 | 1988-03-23 | Exxon Chemical Patents Inc | Dispersant for marine diesel cylinder lubricant |
GB9611317D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
DE69917902T2 (de) * | 1998-03-12 | 2005-05-25 | Crompton Corp., Greenwich | Hochviskose detergentien enthaltende marinezylinderöle |
US6339051B1 (en) * | 1998-06-11 | 2002-01-15 | Mobil Oil Corporation | Diesel engine cylinder oils |
US6551965B2 (en) * | 2000-02-14 | 2003-04-22 | Chevron Oronite Company Llc | Marine diesel engine lubricating oil composition having improved high temperature performance |
JP4011815B2 (ja) * | 2000-02-14 | 2007-11-21 | シェブロンジャパン株式会社 | 二サイクルクロスヘッドディーゼル内燃機関用潤滑油組成物および該潤滑油組成物用添加剤組成物 |
EP1233053B1 (fr) * | 2001-02-16 | 2008-07-30 | Infineum International Limited | Additifs détergents surbasiques |
EP1728849B1 (fr) * | 2005-05-27 | 2019-12-18 | Infineum International Limited | Procédé de lubrification des chemises de cylindre et des carters dans des moteurs marins Diesel de type à crosse |
EP1963469B1 (fr) * | 2005-10-14 | 2015-04-22 | The Lubrizol Corporation | Procede de graissage d un moteur diesel marin |
ES2655116T3 (es) * | 2006-09-19 | 2018-02-16 | Infineum International Limited | Una composición de aceite lubricante |
US20080153726A1 (en) * | 2006-12-11 | 2008-06-26 | Klaus-Werner Damm | Method and system for operating two-and four-stroke engines using low sulfur fuels |
CN101161798B (zh) * | 2007-09-25 | 2012-12-26 | 无锡惠源高级润滑油有限公司 | 船用气缸油及其加工方法 |
CN101570712B (zh) * | 2008-04-30 | 2012-05-09 | 中国石油天然气股份有限公司 | 一种高碱值船用气缸润滑油 |
-
2011
- 2011-03-10 CN CN201110058054XA patent/CN102676273B/zh active Active
- 2011-04-22 WO PCT/CN2011/000707 patent/WO2012119273A1/fr active Application Filing
-
2012
- 2012-03-09 US US13/416,079 patent/US20120231985A1/en not_active Abandoned
- 2012-03-09 EP EP12158753.9A patent/EP2497818B1/fr active Active
-
2014
- 2014-11-21 US US14/550,626 patent/US20150144430A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1640442A1 (fr) * | 2004-09-24 | 2006-03-29 | A.P. Moller - Maersk A/S | Méthode et système permettant la modification d'un liquide hydrocarboné usé afin de créer une huile pour cylindre |
Also Published As
Publication number | Publication date |
---|---|
EP2497818A1 (fr) | 2012-09-12 |
CN102676273B (zh) | 2013-10-16 |
US20120231985A1 (en) | 2012-09-13 |
CN102676273A (zh) | 2012-09-19 |
US20150144430A1 (en) | 2015-05-28 |
WO2012119273A1 (fr) | 2012-09-13 |
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