EP1944353B1 - Composition of water-soluble metal working fluid using distillation residue generated in production of biodiesel - Google Patents
Composition of water-soluble metal working fluid using distillation residue generated in production of biodiesel Download PDFInfo
- Publication number
- EP1944353B1 EP1944353B1 EP07118301A EP07118301A EP1944353B1 EP 1944353 B1 EP1944353 B1 EP 1944353B1 EP 07118301 A EP07118301 A EP 07118301A EP 07118301 A EP07118301 A EP 07118301A EP 1944353 B1 EP1944353 B1 EP 1944353B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oil
- biodiesel
- water
- group
- acid
- 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.)
- Not-in-force
Links
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
- C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
-
- 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
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/04—Fatty oil fractions
-
- 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
- C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
-
- 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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- 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
- C10M173/00—Lubricating compositions containing more than 10% water
-
- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- 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
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
-
- 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
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
- C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids 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
- C10M2207/40—Fatty vegetable or animal oils
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- 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
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives 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
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- 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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
-
- 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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/081—Biodegradable compounds
-
- 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
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- 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
- C10N2030/64—Environmental friendly compositions
-
- 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
- C10N2040/20—Metal working
-
- 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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
-
- 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
Definitions
- the present invention relates to a water-soluble metalworking fluid used in metal machining, and more particularly, to a composition of a water-soluble metalworking fluid produced by adding 5 to 70wt% of additives to 20 to 95wt% of distillation residues that is generated in production of biodiesel and used as lubricating base oil, and 0 to 40wt% of ion exchange water.
- Metalworking fluids are fluids which are used to assist metal machining operations. Traditional metal machining requires a machine tool, a cutting tool, a worked metal, and a machining fluid. Metalworking fluids were first used to increase the lifespan of an instrument for metal processing in the early 1900s.
- the original metalworking fluids were mainly formed of base oil refined from crude oil, and contained a large amount of polyaromatic hydrocarbons (PAHs) that are now known to be carcinogens due to non-development of refinement techniques. Workers can be exposed to these metalworking fluids via many forms and paths while in use, and the fluids may be a cause of cancer, non-malignant respiratory disease, dermatosis, microbial disease, etc. for the workers. Problems caused by oil mists and metalworking fluids were so significant for industrial health that they were even one of the priorities chosen by the U.S. Occupational Safety and Health Administration (OSHA) in 1996.
- PHAs polyaromatic hydrocarbons
- the metalworking fluids reduce friction and abrasion between a cutting tool and a worked metal, improve machining surface characteristics, reduce adhesion or melting of the surface, remove generated heat, prevent deformation caused by heat, and wash cut pieces, fine powder and residues.
- the metalworking fluids also prevent corrosion of machined surfaces, and cool the heated machined surfaces down so as to be more easily handled.
- the water-soluble metalworking fluids include cooling, prevention of welding between the cutting tool and the machined surfaces, prevention of abrasion at high temperature, and prevention of distortion caused by remaining heat.
- the water-soluble metalworking fluids are diluted with a water of about 60 to 85% just before using base oil that is more highly refined than cycloparaffin or paraffin-based oils used in a non-water-soluble environment. Since an available concentration of the water-soluble fluid ranges from 1 to 10%, characteristics of water that is used as a base material are important to performance of the fluid. Water is the best cooling agent due to high specific heat, good thermal conductivity and high latent heat. However, water rusts metal, and thus has less wettability and lubrication than oil.
- the water-soluble metalworking fluids include a rust inhibitor or a surfactant, thereby increasing lubrication.
- a recently developed additive can prevent corrosion for approximately several days to a week, which thus overcomes the poor rust inhibition and poor metal corrosion inhibition of the water-soluble metalworking fluids.
- the water-soluble metalworking fluids are nonflammable like water and non-sticky, so it is preferred by workers due to a clean work environment, but it is corruptible.
- the advantages of the water-soluble metalworking fluids are as follows. It can be used for fast cutting due to good cooling properties, and cleansing, thereby providing safe conditions for workers. Also, it is economical because of the use of water.
- the water-soluble metalworking fluids are classified into two types, which are an emulsion type which is translucent to an emulsion like a milky liquid when diluted with water, and a semi-synthetic and synthetic type.
- the milky white residue of the dilution indicates that an emulsion particle has a sufficient size to reflect transmitted light, and the clear dilution indicates that the particle is so small that the transmitted light mostly penetrates between the particles.
- Components and ratios of the conventional water-soluble metalworking fluids are listed below.
- the present invention is directed to developing a composition of a water-soluble metalworking fluid using a distillation residue generated in production of biodiesel as environmentally-friendly lubricating base oil.
- Biodiesel refers to an alternative energy processed from elemental lipid in vegetables and animals to have similar properties to gasoline, which can be used as a diesel equivalent or for diesel engines by being mixed with the gasoline.
- biodiesel refers to fatty acid methyl esters having a purity of 95% made from the transesterification between alcohols (generally, methanol) and vegetable oil (rice bran, waste cooking oil, soybean oil, rape oil, etc.). (Ministry of Commerce, Industry and Economy (MOCIE) Announcement No. 2000-57)
- the vegetable oil described above that is, a compound including a hydrophobic group insoluble in water, is generally composed of triglycerides represented as the following chemical structural formula.
- the vegetable oil is commonly characterized by the content of the fatty acid, and the length, content and saturation degree of the fatty acid become critical factors in determining physical and chemical characteristics of the oil.
- Animal oil is less useful than the vegetable oil, and only that made from a pig, a cow and a sheep among land animals, and herring and menhaden among fishes are considered as being commercially important.
- the animal oils are composed of saturated and unsaturated triglycerides like the vegetable oils, but include a wide distribution of fatty acids and some odd-numbered chain fatty acids, unlike the vegetable oils.
- the methyl ester from vegetable oil is mainly made of methyl oleate and methyl linoleate as main components, and exhibits excellent performance in machinability or detergency due to low viscosity (40 °C, 1.9 to 6.0 cSt.) and good lubrication when used instead of petroleum-based hydrocarbon lubricating base oil.
- the methyl ester from vegetable oil is made by the following processes.
- R, R' and R" are saturated or unsaturated hydrocarbons with alkyl groups.
- the methyl ester made from vegetable oil has various components and composition ratios depending on components of fatty acid in the vegetable oil and its ratio. Each of the methyl esters of the fatty acids listed in the following table is a component of the methyl ester made from vegetable oil.
- Vegetable oils capable of synthesizing the methyl esters from vegetable oil which may be used in the present invention are listed in the following table.
- Biodiesel may be mixed with gasoline and then used, or 100% pure biodiesel may be used.
- BD5 refers to a mixture of 95% gasoline and 5% biodiesel
- BD20 refers to a mixture including 20% biodiesel.
- Biodiesel attracts attention around the world as a future energy source in the aspects of recycling of waste resources, reduction of greenhouse gas (CO 2 ), and low emission of air pollutants.
- CO 2 greenhouse gas
- biodiesel is in exemplary use or is expanding its supply through model projects all over the world. Europe, which is very positive towards the use of alternative energy, first established a system for biodiesel.
- biodiesel can be used within a range satisfying the standard of general gasoline, and according to European Fuel Standard (EN590) taken effect in January, 2004, gasoline including 5% biodiesel or less (BD5) is recognized as general gasoline (satisfying the requirements of the EN14214 standard).
- EN590 European Fuel Standard
- BD5 gasoline including 5% biodiesel or less
- BD5 European Fuel Standard
- U.S. after National Biodiesel Board was founded in 1992, the Congress and EPA approved BD20 as a fuel for diesel engine vehicles in 1998, and President Bush declared the expansion of new recycled energy including biodiesel in 2001.
- the supply of biodiesel is increasing every year, and biodiesel is used in official vehicles of state governments and buses in addition to the U.S. Army, the U.S. Air Force, the Department of Energy and NASA.
- biodiesel In Korea, based on the announcement regarding a model supply project for biodiesel by MOCCC in May, 2002, the government performed the project for two years, and now is investigating market reaction to and problems with biodiesel.
- the major advantage of biodiesel is a reduction of smoke emitted from vehicles.
- biodiesel also emits the greenhouse gas CO 2 , when viewed from an overall cycle of the process (from production to consumption) it yields very low amounts of CO 2 , and emits relatively low amounts of sulfur oxide (Sox) and particulate matters (PMs).
- Biodiesel made from vegetable resources may be self-produced domestically, which is an advantage for energy security, and may reduce environmental pollution by recycling waste resources, such as waste cooking oil.
- biodiesel has several problems in substituting for conventional gasoline and volatile oils. Although biodiesel has to be mixed in a high ratio to reduce toxic chemicals in exhaust gases from vehicles, it may break down engines due to corrosion, and become denatured in long-term storage.
- methyl esters made from vegetable oil are required for methyl esters made from vegetable oil to be used as fuel oils for vehicles, and thus a separate vacuum distillation process is performed after the reaction of methyl esters.
- the vacuum distillation is performed at 2 to 3 torrs and a maximum temperature of 240 °C. After the vacuum distillation process, the distilled result is used as biodiesel fuel oil, and a distillation residue of about 10% is scrapped.
- Such a distillation residue generated in the production of biodiesel is a reactant of the vegetable oil with a structure of ester, and may be used as environmentally friendly lubricating base oil.
- An embodiment of the invention provides a composition of a water-soluble metalworking fluid which uses a distillation residue generated in production of biodiesel as lubricating oil, and is mixed with other additives.
- the additives include a surfactant, a lubricating additive, a metal corrosion inhibitor, a rust inhibitor, a pH booster, a defoamer, a preservative, a pigment, etc., of which all are less harmful to the environment, and do not include any one of components which have use restrictions, such as nitrite, formaldehyde, boron and derivatives thereof, and an extreme pressure agent.
- the present invention is directed to a composition of a water-soluble metalworking fluid produced by adding 5 to 70wt% of additives to 20 to 95wt% of distillation residues that is generated in production of biodiesel and used as lubricating base oil, and 0 to 40wt% of ion exchange water.
- the distillation residue of the biodiesel is generated from canola oil, soybean oil, palm oil or jatropha oil.
- the additive used in the present invention is at least one selected from the group consisting of a surfactant, a lubricating additive, a metal corrosion inhibitor, a rust inhibitor, a pH booster, a defoamer and a preservative.
- the surfactant used in the present invention is selected from ethoxide of lauryl alcohol or oleyl alcohol, ethoxide of castor oil, ethoxide of laurylamine or oleylamine, amine salt of oleic acid, amine salt of tall oil, amine salt of erucic acid, sulfonate, succinic acid derivatives, amine salt of succinic acid and PEG-fatty acid ester.
- the lubricating base oil used in the present invention is at least one selected from the group consisting of petroleum-based hydrocarbon, vegetable oil and synthetic ester.
- the petroleum-based hydrocarbon is a distilled mineral oil and has a kinematic viscosity of about 5 to 1000 cSt at 40
- the vegetable oil and the synthetic ester are soybean oil, canola oil, sunflower oil, jatropha oil, palm oil, neopentyl glycol dioleate, trimethylolpropane trioleate, pentaerythritol tetraoleate, propylene glycol dioleate, ricinoleic acid condensate, or methyl ester of soybean oil, canola oil, jatropha oil or palm oil.
- the pH booster used in the present invention includes monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, aminomethyl propanol or diglycolamine.
- the metal corrosion inhibitor used in the present invention includes benzotriazol, tolytriazol or derivatives thereof.
- the rust inhibitor used in the present invention includes sebacic acid, dicarboxylic acid, triazine tridicarboxylic acid or derivatives thereof.
- the defoamer used in the present invention includes polydimethyl siloxane, denatured polydimethyl siloxane, organic silicon derivatives or a silicon-based defoamer of silica.
- the preservative used in the present invention includes thiazoline, pyridine, morpholine, phenol, a nitro- or IPBC-based preservative.
- Water-soluble metalworking fluids were manufactured from a distillation residue generated in production of biodiesel, ion exchange water, a lubricating additive 1 (soybean oil, canola oil, palm oil, trimethylolpropane trioleate, pentaerythritol tetraoleate, or ricinoleic acid condensate), a surfactant, a metal corrosion inhibitor, a rust inhibitor, a pH booster, a defoamer and a preservative.
- Water-soluble metalworking fluids were produced from a distillation residue generated in production of biodiesel, a lubricating additive 2 (petroleum-based hydrocarbon, methyl ester of soybean oil or canola oil, soybean oil, canola oil, or palm oil), a surfactant, a metal corrosion inhibitor, a rust inhibitor, a pH booster, a defoamer and a preservative.
- a lubricating additive 2 petroleum-based hydrocarbon, methyl ester of soybean oil or canola oil, soybean oil, canola oil, or palm oil
- surfactant eum-based hydrocarbon, methyl ester of soybean oil or canola oil, soybean oil, canola oil, or palm oil
- metal corrosion inhibitor e.g., a metal corrosion inhibitor
- rust inhibitor e.g., a rust inhibitor
- pH booster e.g., a pH booster
- defoamer a preservative
- Water-soluble metalworking fluids were produced from a distillation residue generated in production of biodiesel, a lubricating additive 3 (petroleum-based hydrocarbon, methyl ester of soybean oil, canola oil or palm oil, trimethylolpropane trioleate, pentaerythritol tetraoleate or ricinoleic acid condensate), a surfactant, a metal corrosion inhibitor, a rust inhibitor, a pH booster, a defoamer and a preservative.
- a lubricating additive 3 mineral oil-based hydrocarbon, methyl ester of soybean oil, canola oil or palm oil, trimethylolpropane trioleate, pentaerythritol tetraoleate or ricinoleic acid condensate
- surfactant a metal corrosion inhibitor
- rust inhibitor a rust inhibitor
- pH booster a defoamer
- defoamer a preservative
- Water-soluble metalworking fluids were produced from a distillation residue generated in production of biodiesel, a lubricating additive 4 (methyl ester of soybean oil, canola oil, jatropha oil or palm oil, soybean oil, canola oil, palm oil, jatropha oil or sunflower oil), a surfactant, a metal corrosion inhibitor, a rust inhibitor, a pH booster, a defoamer and a preservative.
- a lubricating additive 4 methyl ester of soybean oil, canola oil, jatropha oil or palm oil, soybean oil, canola oil, palm oil, jatropha oil or sunflower oil
- a surfactant methyl ester of soybean oil, canola oil, jatropha oil or palm oil, soybean oil, canola oil, palm oil, jatropha oil or sunflower oil
- a surfactant methyl ester of soybean oil, canola oil, jatropha oil or palm oil, soybean oil, canola oil, palm oil, jatropha oil or sunflower oil
- a composition of a water-soluble metalworking fluid, using a biodiesel distillation residue that can be used as environmentally acceptable lubricating base oil, has good biodegradation, excellent lubrication and less toxicity bionomically.
- the water-soluble metalworking fluid may be very useful in business and recycling resources.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020070003692A KR100750394B1 (ko) | 2007-01-12 | 2007-01-12 | 바이오 디젤 생산 시 생성되는 증류 잔류물을 이용한수용성 금속가공유 조성물 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1944353A1 EP1944353A1 (en) | 2008-07-16 |
EP1944353B1 true EP1944353B1 (en) | 2010-03-10 |
Family
ID=38614850
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07118301A Not-in-force EP1944353B1 (en) | 2007-01-12 | 2007-10-11 | Composition of water-soluble metal working fluid using distillation residue generated in production of biodiesel |
Country Status (7)
Country | Link |
---|---|
US (1) | US20080171680A1 (ja) |
EP (1) | EP1944353B1 (ja) |
JP (1) | JP2008169371A (ja) |
KR (1) | KR100750394B1 (ja) |
AT (1) | ATE460469T1 (ja) |
DE (1) | DE602007005212D1 (ja) |
ES (1) | ES2341376T3 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102024103809B3 (de) | 2024-02-12 | 2024-08-14 | Christoph Fuchs | Wassermischbarer Kühlschmierstoff und anwendungsfertige Emulsion |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG155077A1 (en) * | 2008-02-21 | 2009-09-30 | Cheng Kit Yew | Composition and method of manufacture of biodiesel metalworking fluid |
WO2010118891A1 (de) * | 2009-04-17 | 2010-10-21 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Schmierflüssigkeit sowie verfahren zur herstellung derselben |
CA2760898C (en) * | 2009-05-08 | 2017-09-19 | Quaker Chemical Corporation | Small particle size oil in water lubricant fluid |
DE102009026396A1 (de) * | 2009-08-18 | 2011-04-07 | Green Finance Ag | Flux-Additiv für Bitumenmassen |
KR101340007B1 (ko) | 2010-11-17 | 2013-12-10 | (주) 토탈방재 | 바이오디젤 부산물을 이용한 유화제 합성방법 |
JP5890152B2 (ja) * | 2011-11-17 | 2016-03-22 | 出光興産株式会社 | 水溶性金属加工油剤、金属加工液、及び金属加工方法 |
CN104185675A (zh) * | 2011-12-09 | 2014-12-03 | 罗伯特·D·埃文斯 | 金属加工流体组合物及其用于加工致密石墨铸铁的方法 |
US20130237464A1 (en) * | 2012-03-07 | 2013-09-12 | Quaker Chemical Corporation | Cutting oil with vegetal oil |
WO2014011838A1 (en) * | 2012-07-11 | 2014-01-16 | Lacerenza D Matthew | Lubricating oil |
KR101750909B1 (ko) * | 2016-02-01 | 2017-07-11 | ㈜ 바이오 루브 | 광합성 세균 배양액을 포함하는 수용성 절삭유 |
CN106479623A (zh) * | 2016-08-30 | 2017-03-08 | 宝捷润滑油镇江有限公司 | 以植物基合成油为基础的润滑油的制备方法 |
US11396708B2 (en) * | 2018-10-11 | 2022-07-26 | Master Chemical Corporation | Water soluble metalworking concentrate |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1093959A (en) * | 1966-06-20 | 1967-12-06 | Henry W Peabody Ind Ltd | Cold rolling lubrication |
US3923702A (en) * | 1974-08-08 | 1975-12-02 | Emery Industries Inc | Conversion of distillation residues to useful metal working lubricants |
CH654020A5 (en) * | 1982-07-19 | 1986-01-31 | Sp K Byuro Analit Priborostr | Lubricant for cold-forming of metals |
DE3622826A1 (de) * | 1986-07-08 | 1988-01-21 | Henkel Kgaa | Pulverfoermige schmiermittel-additive fuer bohrspuelungen auf wasserbasis |
AU626014B2 (en) * | 1988-10-21 | 1992-07-23 | Malaysian Palm Oil Board | Production of alkyl esters from oils and fats |
JP2955894B2 (ja) * | 1991-07-05 | 1999-10-04 | ミヨシ油脂株式会社 | 金属加工油 |
US6051538A (en) * | 1999-01-26 | 2000-04-18 | The Procter & Gamble Company | Pour point depression of heavy cut methyl esters via alkyl methacrylate copolymer |
KR20010045991A (ko) * | 1999-11-09 | 2001-06-05 | 이태구 | 폐식용유를 이용한 연료유 조성물 |
JP2002265986A (ja) * | 2001-03-15 | 2002-09-18 | Akio Kobayashi | 脂肪酸アルキルエステル及びグリセリンの製造方法 |
WO2003080771A2 (en) * | 2001-08-14 | 2003-10-02 | United Soy Bean Board | Soy-based methyl ester high performance metal working fluids |
US7806945B2 (en) * | 2003-01-27 | 2010-10-05 | Seneca Landlord, Llc | Production of biodiesel and glycerin from high free fatty acid feedstocks |
US20060042158A1 (en) * | 2004-08-26 | 2006-03-02 | Lee John H | Fuel products from plant or animal lipids |
US7700526B2 (en) * | 2005-02-02 | 2010-04-20 | Osamu Yamamoto | Process for machining metal and high performance aqueous lubricant therefor |
US7867958B2 (en) * | 2006-04-28 | 2011-01-11 | Afton Chemical Corporation | Diblock monopolymers as lubricant additives and lubricant formulations containing same |
US9534189B2 (en) * | 2006-05-24 | 2017-01-03 | Nalco Company | Hydraulic fluids and fire-resistant fluids comprising glycerin containing by-products |
-
2007
- 2007-01-12 KR KR1020070003692A patent/KR100750394B1/ko active IP Right Grant
- 2007-09-19 JP JP2007242147A patent/JP2008169371A/ja active Pending
- 2007-10-11 EP EP07118301A patent/EP1944353B1/en not_active Not-in-force
- 2007-10-11 AT AT07118301T patent/ATE460469T1/de not_active IP Right Cessation
- 2007-10-11 DE DE602007005212T patent/DE602007005212D1/de active Active
- 2007-10-11 ES ES07118301T patent/ES2341376T3/es active Active
- 2007-10-16 US US11/974,591 patent/US20080171680A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102024103809B3 (de) | 2024-02-12 | 2024-08-14 | Christoph Fuchs | Wassermischbarer Kühlschmierstoff und anwendungsfertige Emulsion |
Also Published As
Publication number | Publication date |
---|---|
ATE460469T1 (de) | 2010-03-15 |
ES2341376T3 (es) | 2010-06-18 |
EP1944353A1 (en) | 2008-07-16 |
JP2008169371A (ja) | 2008-07-24 |
US20080171680A1 (en) | 2008-07-17 |
KR100750394B1 (ko) | 2007-08-17 |
DE602007005212D1 (de) | 2010-04-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1944353B1 (en) | Composition of water-soluble metal working fluid using distillation residue generated in production of biodiesel | |
CN101870909B (zh) | 一种镁合金切削液 | |
JP3159679B2 (ja) | 燃料潤滑性改良用のジエタノールアミン誘導体とバイオデイーゼル燃料のブレンド | |
CN103819370B (zh) | 脂肪酸单乙醇酰胺琥珀酸酯磺酸盐及其制备方法及应用 | |
CN102660360B (zh) | 高润滑、高水分离性轴承磨削加工用超精油 | |
CN106800963B (zh) | 一种水溶油金属切削液原料及金属切削液 | |
CN103351932B (zh) | 一种透明水溶性切削液及其制备方法 | |
CN105861133A (zh) | 一种金属加工液及其循环使用方法 | |
CN107418673A (zh) | 一种基于聚异丁烯基琥珀酸酐的新型乳化体系的切削液及其制备方法和应用 | |
EP1944352B1 (en) | Biodegradable grease composition using distillation residue generated in production of biodiesel | |
CN103833613B (zh) | 脂肪酸聚氧乙烯琥珀酸酯磺酸盐及其制备方法和用途 | |
CN111117754A (zh) | 一种高润滑稳定型切削液及其制备方法 | |
CN112940833A (zh) | 一种长寿环保切削液及其制备方法 | |
KR100611735B1 (ko) | 식물성 오일, 합성 에스테르, 식물유 메틸에스테르를이용하고 아민류를 사용하지 않은 수용성 절삭유 조성물 | |
TW201602334A (zh) | 水溶性金屬加工油及金屬加工用冷卻劑 | |
KR20090132375A (ko) | 바이오디젤 생산시 생성되는 잔류물로부터 얻어지는 지방산메틸에스테르와 부산물을 이용한 수용성 금속가공유조성물 | |
KR100721602B1 (ko) | 바이오디젤 생산시 생성되는 증류 잔유물을 이용한 수용성절삭유 조성물 | |
CN101649230A (zh) | 一种甲醇汽油金属缓蚀剂 | |
KR20090062462A (ko) | 광물유를 사용하지 않는 수용성 절삭유의 조성물 | |
US8481466B2 (en) | Biodegradable grease composition using distillation residue generated in production of biodiesel | |
JP2007231119A (ja) | 重油組成物 | |
JP2010202789A (ja) | 水系潤滑液組成物 | |
EP0349787B1 (en) | An additive to metal cold rolling oil | |
KR20100003503A (ko) | 바이오디젤 생산시 생성되는 잔류물과 잔류물부터 얻어지는메틸에스테르와 부산물을 이용한 비수용성 금속가공유조성물 | |
RU2329296C1 (ru) | Технологическая смазка для пластической обработки металлов и сплавов |
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): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL BA HR MK RS |
|
17P | Request for examination filed |
Effective date: 20081120 |
|
17Q | First examination report despatched |
Effective date: 20081218 |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAC | Information related to communication of intention to grant a patent modified |
Free format text: ORIGINAL CODE: EPIDOSCIGR1 |
|
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): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK 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: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602007005212 Country of ref document: DE Date of ref document: 20100422 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2341376 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20100310 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20100310 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20100310 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20100310 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: 20100310 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: 20100310 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: 20100310 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: 20100310 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20100310 Ref country code: CY 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: 20100310 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: 20100310 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: 20100310 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: 20100310 Ref country code: NL 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: 20100310 Ref country code: GR 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: 20100611 |
|
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: 20100310 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: 20100710 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: 20100610 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: 20100310 |
|
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: 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: 20100712 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: 20100310 |
|
26N | No opposition filed |
Effective date: 20101213 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20101031 |
|
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: 20101011 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20101011 Ref country code: MT 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: 20100310 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111031 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111031 |
|
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: 20101011 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 Effective date: 20100911 |
|
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: 20100310 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 10 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20210128 Year of fee payment: 14 Ref country code: IT Payment date: 20210128 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20210127 Year of fee payment: 14 Ref country code: ES Payment date: 20210201 Year of fee payment: 14 Ref country code: GB Payment date: 20210222 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602007005212 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20211011 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211011 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220503 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211031 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20211011 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20230203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20211012 |