EP2497818A1 - Additif composite d'huile de cylindre marine - Google Patents

Additif composite d'huile de cylindre marine Download PDF

Info

Publication number
EP2497818A1
EP2497818A1 EP12158753A EP12158753A EP2497818A1 EP 2497818 A1 EP2497818 A1 EP 2497818A1 EP 12158753 A EP12158753 A EP 12158753A EP 12158753 A EP12158753 A EP 12158753A EP 2497818 A1 EP2497818 A1 EP 2497818A1
Authority
EP
European Patent Office
Prior art keywords
base number
oil
composite additive
superhigh
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP12158753A
Other languages
German (de)
English (en)
Other versions
EP2497818B1 (fr
Inventor
Yueki Zhai
Jie Zhang
Gonde Liu
Yuli Ma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Publication of EP2497818A1 publication Critical patent/EP2497818A1/fr
Application granted granted Critical
Publication of EP2497818B1 publication Critical patent/EP2497818B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

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

Definitions

  • the present invention relates to a 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 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.
  • 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, wherein R 1 , R 2 , R 3 and R 4 are long-chain primary alkyl groups each comprising 12-18 carbon atoms, or R 1 , R 2 , R 3 and R 4 are long-chain secondary alkyl groups each comprising 12-16 carbon atoms.
  • Said base oil is Group I base oil with high viscosity index which is selected from the group consisting of 400SN, 500SN and 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).
  • 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 number 20 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 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 number 15 Sulfurized calcium alkyl (C20) phenolate with superhigh base number 35 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
  • 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. Components Contents (%) Linear alkyl (C26) calcium sulfonate with superhigh base number 25 Sulfurized calcium alkyl (C22) phenolate with superhigh base number 35 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
  • 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 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.
  • 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 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 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 Figure 2 .
  • the base number of the cylinder oil formulated from the composite additive decreased from 70 mgKOH/g at the beginning, through 60 mgKOH/g and 50 mgKOH/g, to 40 mgKOH/g at the end.
  • the entire sailing test could be divided into four stages according to the base number of the cylinder oil, and each stage lasted about 1000 hours.
  • 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.

Landscapes

  • 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)
EP12158753.9A 2011-03-10 2012-03-09 Utilisation d' un additif composite d'huile lubrifiante marine Active EP2497818B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110058054XA CN102676273B (zh) 2011-03-10 2011-03-10 一种船用气缸油复合剂

Publications (2)

Publication Number Publication Date
EP2497818A1 true EP2497818A1 (fr) 2012-09-12
EP2497818B1 EP2497818B1 (fr) 2016-10-19

Family

ID=45887914

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12158753.9A Active EP2497818B1 (fr) 2011-03-10 2012-03-09 Utilisation d' un additif composite d'huile lubrifiante marine

Country Status (4)

Country Link
US (2) US20120231985A1 (fr)
EP (1) EP2497818B1 (fr)
CN (1) CN102676273B (fr)
WO (1) WO2012119273A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017067561A1 (fr) * 2015-10-20 2017-04-27 A.P. Møller - Mærsk A/S Procédé et appareil permettant de préparer une huile qui doit être fournie aux cylindres d'un moteur deux temps à crosse
WO2017080563A1 (fr) * 2015-11-11 2017-05-18 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
CN107406784A (zh) * 2015-01-26 2017-11-28 雪佛龙奥伦耐技术有限责任公司 船用柴油机润滑油组合物
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

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0331359A1 (fr) * 1988-02-23 1989-09-06 Exxon Chemical Patents Inc. Dispersant pour lubrifiant de cylindre de moteur diesel marin
EP1126010A1 (fr) * 2000-02-14 2001-08-22 Chevron Oronite Japan Limited Composition lubrifiante avec des performances ameliorees a temperature haute pour la lubrification d'un moteur diesel marin
CN101161798A (zh) * 2007-09-25 2008-04-16 无锡惠源高级润滑油有限公司 船用气缸油及其加工方法
US20080287327A1 (en) * 2005-10-14 2008-11-20 The Lubrizol Corporation Method of Lubricating a Marine Diesel Engine

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8723909D0 (en) * 1987-10-12 1987-11-18 Exxon Chemical Patents Inc Lubricant oil additive
GB9611317D0 (en) * 1996-05-31 1996-08-07 Exxon Chemical Patents Inc Overbased metal-containing detergents
DK1086195T3 (da) * 1998-03-12 2004-10-04 Crompton Corp Skibscylinderolier, der indeholder höjviskositetsdetergenter
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
EP1233053B1 (fr) * 2001-02-16 2008-07-30 Infineum International Limited Additifs détergents surbasiques
ATE440933T1 (de) * 2004-09-24 2009-09-15 Ap Moeller Maersk As Methode und system für die modifizierung eines gebrauchten kohlenwasserstoff-fluids zur herstellung eines zylinderíls
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
ES2655116T3 (es) * 2006-09-19 2018-02-16 Infineum International Limited Una composición de aceite lubricante
WO2008073405A1 (fr) * 2006-12-11 2008-06-19 A.P. Moller-Maersk A/S Procédé et système pour actionner des moteurs à deux et quatre temps en utilisant des carburants à faible teneur en soufre.
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0331359A1 (fr) * 1988-02-23 1989-09-06 Exxon Chemical Patents Inc. Dispersant pour lubrifiant de cylindre de moteur diesel marin
EP1126010A1 (fr) * 2000-02-14 2001-08-22 Chevron Oronite Japan Limited Composition lubrifiante avec des performances ameliorees a temperature haute pour la lubrification d'un moteur diesel marin
US20080287327A1 (en) * 2005-10-14 2008-11-20 The Lubrizol Corporation Method of Lubricating a Marine Diesel Engine
CN101161798A (zh) * 2007-09-25 2008-04-16 无锡惠源高级润滑油有限公司 船用气缸油及其加工方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406784A (zh) * 2015-01-26 2017-11-28 雪佛龙奥伦耐技术有限责任公司 船用柴油机润滑油组合物
EP3250663A4 (fr) * 2015-01-26 2018-06-27 Chevron Oronite Technology B.V. Compositions d'huile lubrifiante pour moteur diesel marin
WO2017067561A1 (fr) * 2015-10-20 2017-04-27 A.P. Møller - Mærsk A/S Procédé et appareil permettant de préparer une huile qui doit être fournie aux cylindres d'un moteur deux temps à crosse
DK201500647A1 (en) * 2015-10-20 2017-05-08 A P Møller - Mærsk As Method and apparatus for preparing an oil to be supplied to the cylinders of a two-stroke crosshead engine
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
WO2017080563A1 (fr) * 2015-11-11 2017-05-18 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
EP4075108A1 (fr) * 2015-11-11 2022-10-19 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
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

Also Published As

Publication number Publication date
US20150144430A1 (en) 2015-05-28
CN102676273A (zh) 2012-09-19
CN102676273B (zh) 2013-10-16
WO2012119273A1 (fr) 2012-09-13
US20120231985A1 (en) 2012-09-13
EP2497818B1 (fr) 2016-10-19

Similar Documents

Publication Publication Date Title
EP2497818A1 (fr) Additif composite d'huile de cylindre marine
EP2497817A1 (fr) Additif composite d'huile lubrifiante marine
EP2055761B1 (fr) Utilisation de Ca-phénate dans des compositions d'huile lubrifiante comportant un carburant biodiesel
RU2015106989A (ru) Композиция смазочного масла для двигателей внутреннего сгорания
JP4778200B2 (ja) 高荷重ディーゼルエンジンの摩耗低減のための方法及び組成物
JP2009108317A (ja) バイオディーゼル燃料と酸化防止剤とを含む潤滑油組成物
WO2016086858A1 (fr) Composition d'huile pour cylindre de moteur marin, son procédé de préparation et son utilisation
JP2010523733A (ja) 潤滑方法
BR102013019316A2 (pt) Composição de óleo lubrificante, método de lubrificação de um motor de combustão interna de ignição por compressão ou de ignição por centelha, e, uso de um componente aditivo
JP2007146161A (ja) 船舶又は定置ディーゼルエンジンを作動させる方法
EP3549999A1 (fr) Composition de mazout lourd c
JP2009523862A (ja) 潤滑油および潤滑油添加剤濃厚液組成物
JP2009024123A (ja) バイオ燃料対応ディーゼルエンジン用潤滑油組成物。
JP4431281B2 (ja) 燐酸エステル基油および該基油を含む航空機用油圧作動油
JP5349088B2 (ja) ガスエンジン用エンジン油組成物
JP5349223B2 (ja) エンジン油組成物
CN104087372B (zh) 一种乙二醇二甲基醚燃料发动机油组合物
JP2011132404A (ja) 内燃機関用潤滑油組成物
JP7064490B2 (ja) バイオディーゼル燃料及びマンニッヒ凝縮生成物を含む潤滑油組成物
US20200263102A1 (en) Marine fuel compositions and methods of making the same
US20210238494A1 (en) Reciprocating-type compressor oil
CN106256887B (zh) 润滑剂组合物
RU2598031C2 (ru) Композиция смазочного масла для газовых турбин
JPH1150070A (ja) ２サイクルエンジン用燃料組成物
EP3423552A1 (fr) Composition lubrifiante

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: ZHANG, JIE

Inventor name: YUEKI, ZHAI

Inventor name: MA, YULI

Inventor name: LIU, GONDE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MA, YULI

Inventor name: LIU, GONDE

Inventor name: ZHANG, JIE

Inventor name: YUEKUI, ZHAI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LIU, GONDE

Inventor name: YUEKUI, ZHAI

Inventor name: MA, YULI

Inventor name: ZHANG, JIE

17P Request for examination filed

Effective date: 20130312

17Q First examination report despatched

Effective date: 20130624

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: PETROCHINA COMPANY LIMITED

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160729

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 838351

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012024238

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 838351

Country of ref document: AT

Kind code of ref document: T

Effective date: 20161019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170119

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170219

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170220

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012024238

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170119

26N No opposition filed

Effective date: 20170720

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20171130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170309

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170309

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170331

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170309

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20120309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20161019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161019

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240108

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20240213

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231229

Year of fee payment: 13