EP1944352B1 - Biodegradable grease composition using distillation residue generated in production of biodiesel - Google Patents

Biodegradable grease composition using distillation residue generated in production of biodiesel Download PDF

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Publication number
EP1944352B1
EP1944352B1 EP07118302A EP07118302A EP1944352B1 EP 1944352 B1 EP1944352 B1 EP 1944352B1 EP 07118302 A EP07118302 A EP 07118302A EP 07118302 A EP07118302 A EP 07118302A EP 1944352 B1 EP1944352 B1 EP 1944352B1
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EP
European Patent Office
Prior art keywords
oil
thickener
biodiesel
grease
composition according
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
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EP07118302A
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German (de)
French (fr)
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EP1944352A1 (en
Inventor
Kwang Soon Kim
Sik Lee Moon
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Korea Houghton Corp
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Korea Houghton Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • C10M113/00—Lubricating compositions characterised by the thickening agent being an inorganic material
    • C10M113/08—Metal 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
    • 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
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/102—Silicates
    • C10M2201/103—Clays; Mica; Zeolites
    • C10M2201/1036—Clays; Mica; Zeolites used as thickening agents
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10—Compounds containing silicon
    • C10M2201/105—Silica
    • C10M2201/1056—Silica used as thickening agents
    • 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
    • C10M2207/126—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 monocarboxylic
    • C10M2207/1265—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 monocarboxylic used as thickening agent
    • 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
    • C10M2207/127—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 polycarboxylic
    • C10M2207/1276—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 polycarboxylic used as thickening agent
    • 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
    • C10M2207/128—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 containing hydroxy groups; Ethers thereof
    • C10M2207/1285—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 containing hydroxy groups; Ethers thereof used as thickening agents
    • 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • C10M2207/2895—Partial esters containing free hydroxy groups 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/0406—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds used as thickening agents
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/06—Groups 3 or 13
    • 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
    • C10N2030/64—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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • 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 grease for lubricating machinery, equipment or instruments used in general industry, and more particularly, to a grease composition produced using, as base oil, 10 to 95wt% of final residues which is generated in production of biodiesel using deodorized distillates of soybean oil and canola oil.
  • Component Content Subject 1 Subject 2 Subject 3 C Base Oil 50-95% Petroleum Petroleum Distilled For central refueling O Hydrocarbon Mineral Oil For multi-purposes M -Paraffin-based, For high-weight P Naphthene-based, etc. S I Synthetic Oil PAO-based, Ester-based, Synthetic Oil Grease, T Poly Glycol-based, Low Temperature I Silicone-based, Fluorine- Grease (Dewax) O based, etc. N Thickener 3-30% Soap Formation of soap by Lithium and Lithium reaction between metal Complex Grease, O hydroxide such as Ca, Li, Aluminum Complex F Al, etc.
  • the lubricating grease is classified into a metal soap grease such as Ca, Na, Li, Al, Ba or its complex grease and a non-soap grease such as bentone, silica, urea, graphite or PTFE according to the kind of the thickener, and classified into a mineral oil grease and a synthetic oil grease according to the kind of a base oil.
  • a metal soap grease such as Ca, Na, Li, Al, Ba or its complex grease
  • a non-soap grease such as bentone, silica, urea, graphite or PTFE according to the kind of the thickener
  • a mineral oil grease and a synthetic oil grease according to the kind of a base oil.
  • the greases preserve performance and lifespan of lubricating units and equipment by reducing a friction between units in a lubricating region, reducing wear in metals, enhancing characteristics of a lubricating surface, reducing adhesion to a metal surface and melting, preventing deformation due to heat by removing the heat, and maximizing prevention of impurity injection and sealing effect.
  • the petroleum hydrocarbon lubricating base oil which is produced in the final step of the common crude oil refining process, is generally used as base oil for grease.
  • grease using the petroleum hydrocarbon may cause environmental damage, and may threaten the health of a human who uses the grease.
  • the present invention is directed to developing a grease composition using a distillation residue generated in the 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.
  • Components and ratios of vegetable oil methyl ester depend on components and composition ratios of fatty acid of the vegetable oil.
  • the methyl ester of the fatty acid listed in Table 1 is a component of the vegetable oil methyl ester.
  • 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.
  • 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 grease composition produced by adding additives to distillation residues, which are generated in production of biodiesel by distillation of a reaction mixture obtained by transesterification of vegetable or animal oil with an alcohol, and thickeners.
  • the thickener includes lithium soap, urea, aluminum complex soap or bentonite, and the additive includes a pour point depressant, a lubricating additive, a structure stabilizer, an oxidation inhibitor, or a corrosion inhibitor.
  • the additives are those having less effect the environment and not including any of components with restrictions in use such as nitrite, formaldehyde and derivatives thereof, and petroleum hydrocarbon.
  • the present invention is directed to an industrial lubricating grease for machinery and equipment, and more particularly, to a grease composition produced by adding 3 to 30wt% additives to 10 to 95wt% distillation residues, which is generated in production of biodiesel 10a and 3 to 30wt% thickeners.
  • the distillation residue of biodiesel of the present invention is generated from soybean oil or rapeseed oil.
  • the thickener used in the present invention includes at least one selected from the group consisting of lithium soap, aluminum soap, diurea, bentone and silica gel.
  • the lithium and aluminum soaps include lithium and aluminum metals, and soaps formed by soponification between 12-hydroxy stearic acid, stearic acid, boric acid or benzoic acid and H 2 O.
  • the urea thickener includes a diurea product, formed by a reaction between one selected from the group consisting of a tolylene diisocyanate compound, diisocyanate compounds such as diphenylmethane diisocyanate and naphthalene diisocyanate, and one selected from the group consisting of monoamines such as benzylamine, toluidine and chloroaniline, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonyldecylamine and eicosylamine.
  • a tolylene diisocyanate compound diisocyanate compounds such as diphenylmethane diisocyanate and naphthalene diisocyanate
  • monoamines such as benzylamine, toluidine and chloroaniline, tetradecylamine, pentadecylamine
  • the bentone thickener includes bentonite and a self-activator such as alcohol or by distillation of a reaction mixture obtained by transesterification of vegetable or animal oil with an alcohol water.
  • a self-activator such as alcohol or by distillation of a reaction mixture obtained by transesterification of vegetable or animal oil with an alcohol water.
  • the silica gel thickener is fumed silica which includes hydrophobic and hydrophilic silicas.
  • the additive used in the present invention includes at least one selected from the group consisting of a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor, a structure stabilizer and a thickener.
  • the pour point depressant used in the present invention includes polymethacrylate, aromatic synthetic base oil or derivatives thereof.
  • the lubricating additive includes metal salts of dithiocarbamate, aryl phosphate and phosphoric ester, sulfide or derivatives thereof.
  • the corrosion inhibitor includes benzotriazole, tolyltriazole, mercaptobenzothiazole or derivatives thereof.
  • the oxidation inhibitor includes tetrabutylmethylphenol, a quinoline compound or derivatives thereof.
  • the structure stabilizer includes a copolymer such as ethylene propylene or derivatives thereof.
  • the thickener includes derivatives of polybutene or polyisobutylene.
  • Greases were formed using a distillation residue of biodiesel as lubricating base oil by four thickeners, and then their properties and performances were measured.
  • a lithium soap grease was produced using a distillation residue generated in production of biodiesel, lithium soap (a soponification product of lithium hydroxide and fatty acid such as 12-hydroxy stearic acid, stearic acid, azelaic acid or boric acid), a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor, a structure stabilizer and a thickener.
  • lithium soap a soponification product of lithium hydroxide and fatty acid such as 12-hydroxy stearic acid, stearic acid, azelaic acid or boric acid
  • a pour point depressant such as 12-hydroxy stearic acid, stearic acid, azelaic acid or boric acid
  • a pour point depressant such as 12-hydroxy stearic acid, stearic acid, azelaic acid or boric acid
  • a pour point depressant a lubricating additive
  • corrosion inhibitor an oxidation inhibitor
  • a structure stabilizer a thick
  • Lithium Soap Grease Amount (%) Name 1 2 3 Fatty Acid 6.0 4.0 2.0 Lithium Hydroxide 0.9 0.6 0.3 Biodiesel distillation residue 82.0 83.0 85.0 Pour Point depressant 1.0 1.0 1.0 Lubricating Additive 1.0 1.0 1.0 1.0 Thickener 8.0 9.0 9.0 Etc. Proper quantity Proper quantity Proper quantity Proper quantity Property Categories Worked Penetration 330 367 421 Dropping Point (°C) 170 162 159 4-ball Test (Shell Method), mm 0.6 or less 0.6 or less 0.6 or less Oil Separation % (100°C, 24h) 4.5 6.5 9.0 Copper Corrosion (100°C, 24h) No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change No color change
  • a urea grease was produced using a distillation residue generated in production of biodiesel, a urea thickener (diurea, a tolylene diisocyanate compound, a diisocyanate compound of diphenylmethane diisocyanate or naphthalene diisocyanate, monoamine of benzylamine, toluidine or chloroaniline, or an aromaticamine such as tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonyldecylamine or eicosylamine), a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer.
  • a urea thickener diurea, a tolylene diisocyanate compound, a diisocyanate compound of diphenylmethane diisocyanate or
  • An aluminum complex grease was produced using a distillation residue generated in production of biodiesel, an aluminum complex thickener (an aluminum metal compound, and a fatty acid such as benzoic, palmitic, palmitoleic, stearic, oleic or linoleic acid), a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer.
  • an aluminum complex thickener an aluminum metal compound, and a fatty acid such as benzoic, palmitic, palmitoleic, stearic, oleic or linoleic acid
  • a pour point depressant such as benzoic, palmitic, palmitoleic, stearic, oleic or linoleic acid
  • a pour point depressant such as benzoic, palmitic, palmitoleic, stearic, oleic or linoleic acid
  • a pour point depressant such as be
  • a bentone grease was produced using a distillation residue generated in production of biodiesel, a bentone thickener, a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer.
  • Table 4 Composition and Properties of Bentone Grease Amount (%) Name 1 2 3 Bentonite 10.0 8.0 6.0 Methanol 0.1 0.1 0.1 Biodiesel Distillation Residue 78.0 79.0 81.0 Pour Point Depressant 1.0 1.0 1.0 1.0 Lubricating Additive 1.0 1.0 1.0 Water-Resistance Additive 1.0 1.0 1.0 Thickener 8.0 9.0 9.0 Etc.
  • a silica grease was produced using a distillation residue generated in production of biodiesel, a silica gel thickener, a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer.
  • Table 5 Composition and Properties of Grease using Fumed Silica Gel as Thickener Amount (%) Name 1 2 3 Fumed Silica Gel 16.0 13.0 10.0 Biodiesel Distillation Residue 72.0 74.0 77.0 Pour Point Depressant 1.0 1.0 1.0 1.0 Lubricating Additive 1.0 1.0 1.0 1.0 Water-Resistance Additive 1.0 1.0 1.0 Thickener 8.0 9.0 9.0 Etc.
  • the present invention uses a biodiesel distillation residue as base oil of grease so as to provide environmentally friendly grease and obtain recycling benefits of the biodiesel distillation residue, and the environmentally friendly grease may having good lubrication compared to conventional petroleum base oil and be cheaper than a product using vegetable oil or synthetic ester as base oil.

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Abstract

A grease composition using lubricating base oil that is biodegradable by microorganisms in nature and has an affinity to the human body is provided. More particularly, a distillation residue secondarily generated in production of biodiesel from vegetable oil (soybean oil and canola oil) is used as the lubricating base oil. The grease composition is produced by adding 1 to 20wt% of additives to 100 to 95wt% of distillation residues, which is generated in production of biodiesel, and 1 to 30wt% of thickeners.

Description

    BACKGROUND OF THE INVENTION 1. Field of the Invention
  • The present invention relates to a grease for lubricating machinery, equipment or instruments used in general industry, and more particularly, to a grease composition produced using, as base oil, 10 to 95wt% of final residues which is generated in production of biodiesel using deodorized distillates of soybean oil and canola oil.
    • 2. Description of the Related Art <Components and Classification of Common Grease>
  • Component Content Subject 1 Subject 2 Subject 3
    C Base Oil 50-95% Petroleum Petroleum Distilled For central refueling
    O Hydrocarbon Mineral Oil For multi-purposes
    M -Paraffin-based, For high-weight
    P Naphthene-based, etc.
    S
    I Synthetic Oil PAO-based, Ester-based, Synthetic Oil Grease,
    T Poly Glycol-based, Low Temperature
    I Silicone-based, Fluorine- Grease (Dewax)
    O based, etc.
    N Thickener 3-30% Soap Formation of soap by Lithium and Lithium
    reaction between metal Complex Grease,
    O hydroxide such as Ca, Li, Aluminum Complex
    F Al, etc. and fatty acid Grease,
    Calcium Complex
    G Grease
    R Non-Soap Urea, Silica Gel, Bentone Urea Grease, Bentone
    E Grease,
    A Silica Gel Grease
    S Additive 3-30% Additive Anti-Oxidation,
    E Lubrication improvement
    Rust Inhibitor, Structure
    Stabilizer
    Filler Carbon Black, Zinc
    Oxide
    Solid Lubricant Graphite, Molybdenum Molybdenum Paste,
    Disulfide, etc. Fluoro (silicone) Grease
  • The lubricating grease is classified into a metal soap grease such as Ca, Na, Li, Al, Ba or its complex grease and a non-soap grease such as bentone, silica, urea, graphite or PTFE according to the kind of the thickener, and classified into a mineral oil grease and a synthetic oil grease according to the kind of a base oil.
  • The greases preserve performance and lifespan of lubricating units and equipment by reducing a friction between units in a lubricating region, reducing wear in metals, enhancing characteristics of a lubricating surface, reducing adhesion to a metal surface and melting, preventing deformation due to heat by removing the heat, and maximizing prevention of impurity injection and sealing effect. The petroleum hydrocarbon lubricating base oil, which is produced in the final step of the common crude oil refining process, is generally used as base oil for grease. However, grease using the petroleum hydrocarbon may cause environmental damage, and may threaten the health of a human who uses the grease.
  • Recently, as interest in the importance of environmental protection and the health and safety of workers has been increasing, research on environmentally acceptable lubricating base oils which will substitute for the hydrocarbon lubricating base oil of this grease is progressing in North American and Western European nations.
  • According to this trend, the present invention is directed to developing a grease composition using a distillation residue generated in the 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. In general, 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.
    Figure imgb0001
  • 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.
  • When methyl ester made from vegetable oil, that is, biodiesel, is spilled on soil, the soil is less polluted than by hydrocarbon-base lubricating base oil, because of lower toxicity and higher biodegradation. Also, corresponding to United Nations Framework Convention on Climate Change (UNFCCC) (Life cycle CO2: 1/4 of gasoline), one(1) ton of the methyl ester from vegetable oil cuts 2.2 tons of CO2, which contributes to an increase in global competitiveness. 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.
    • CH3-(CH2)14-COO-CH3 : Methyl Palmitate
    • CH3-(CH2)6-CH2-CH=CH-CH2-(CH2)6-COO-CH3 : Methyl Oleate
    • CH3-(CH2)3-CH2-CH=CH-CH2-CH=CH-CH2-(CH2)6-COO-CH3: Methyl Linoleate
  • The methyl ester from vegetable oil is made by the following processes.
    Figure imgb0002
  • Here, R, R' and R" are saturated or unsaturated hydrocarbons with alkyl groups.
    • <Compositions of Fatty Acids of Canola Oil and Soybean Oil for Producing Biodiesel>
  • Fatty Acid
    Fatty Oil and Oils    		 C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 C20:0
    C22:0    		 C20:1 C22:1
    Canola Oil - 2-5% 0.2% 1-2% 10% 10% 5-10% 0.9% 50%
    Soybean Oil 0.3% 7-10% 0-1% 3-6% 22-34% 50-60% 2-10% 5-10% -
    • <Chemical Structure of Fatty Acid Used in Production of Grease>
  • Name of Fatty Acid Carbon Number Double Bond Number Chemical Structure
    Palmitic Acid 16 0 COCH3(CH2)14COOH
    Palmitoleic Acid 16 1 CH3(CH2)5CH=CH(CH2)7COOH
    Stearic Acid 18 0 CH3(CH2)16COOH
    Oleic Acid 18 1 CH3(CH2)7CH=CH(CH2)7COOH
    Linoleic Acid 18 2 CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH
    Linolenic Acid 18 3 CH3(CH2)2CH=CHCH2CH= CH(CH2)CH=CH(CH2)7COOH
    Arachldic Acid 20 0 CH3(CH2)18COOH
    Eicosenoic Acid 20 1 CH3(CH2)7CH=CH(CH2)9COOH
    Behenic Acid 22 0 CH3(CH2)20COOH
    Erucic Acid 22 1 CH3(CH2)7CH=CH(CH2)11COOH
    • <Comparison of Biodegradation of Vegetable Oil and Synthetic Ester Base Oil, CEL-L-33-A-93 Method>
  • Order Soybean Oil Rapeseed Oil Synthetic Ester Petroleum Hydrocarbon
    (Mineral oil)
    1 96.5% 97.0% 96.4% 19.7%
    2 97.2% 99.0% 97.2% 18.9%
    Average 96.9% 97.5% 96.8% 19.3%
  • Components and ratios of vegetable oil methyl ester depend on components and composition ratios of fatty acid of the vegetable oil. The methyl ester of the fatty acid listed in Table 1 is a component of the vegetable oil methyl ester.
    • <Chemical Structure of Fatty Acid Used in Biodegradable Grease Made From Vegetable Oil>
  • Name of Fatty Acid Carbon Number/ Double Bond Number Chemical Structure
    Caprylic C8 CH3(CH2)6COOH
    Capric C10 CH3(CH2)8COOH
    Lauric C12 CH3(CH2)10COOH
    Myristric C14 CH3(CH2)12COOH
    Palmitic C16:0 CH3(CH2)14COOH
    Palmitoleic C16:1 CH3(CH2)5CH=CH(CH2)7COOH
    Stearic C18:0 CH3(CH2)16COOH
    Oleic C18:1 CH3(CH2)7CH=CH(CH2)7COOH
    Linoleic C18:2 CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH
    Linolenic C18:3 CH3(CH2)2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH
    Arachidic C20:0 CH3(CH2)18COOH
    Eicosenoic C20:1 CH3(CH2)7CH=CH(CH2)9COOH
    Behenic C22:0 CH3(CH2)20COOH
    Erucic C22:1 CH3(CH2)7CH=CH(CH2)11COOH
  • 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.
    • <Fatty Acid Components of Vegetable Oil Used in Formation of Biodiesel>
  • Fatty acid, Fatty oil and oil C8:0 C10:0 C14:0 C16:0 C16:1 C18:0 C18:1 C18:2 C18:3 C20:0
    C22:0    		 C20:1
    C22:1
    Coconut oil 5-9 4-10 44-51 13-18 7-10 - 1-4 5-8 1-3 - - -
    Palm Kernal Oil 2-4 3-7 45-52 14-19 6-9 0-1 1-3 10-18 1-2 - 1-2 -
    Palm Oil - - - 1-6 32-47 - 1-6 40-52 2-11 - - -
    Soybean Oil - - - 0.3 7-11 0-1 3-6 22-34 50-60 2-10 5-10 -
    Jatropha Oil - - - 35-50 - 0-10 30-40 5-15 - - - -
    Canola Oil - - - - 2-5 0.2 1-2 10-15 10-20 5-10 0.9 50-60
  • 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, and 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 (CO2), and low emission of air pollutants. Recently, 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. Europe recognizes that 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). In the 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. According to the active announcement of the government, 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. 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. Although biodiesel also emits the greenhouse gas CO2, when viewed from an overall cycle of the process (from production to consumption) it yields very low amounts of CO2, 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. Also, in the aspect of infrastructure, diesel engine or gas station networks may be used, and thus less additional cost is required. However, although such advantages can be expected, 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.
  • For these reasons, high purity products 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.
    • SUMMARY OF THE INVENTION
  • An embodiment of the invention provides a grease composition produced by adding additives to distillation residues, which are generated in production of biodiesel by distillation of a reaction mixture obtained by transesterification of vegetable or animal oil with an alcohol, and thickeners.
  • The thickener includes lithium soap, urea, aluminum complex soap or bentonite, and the additive includes a pour point depressant, a lubricating additive, a structure stabilizer, an oxidation inhibitor, or a corrosion inhibitor. Here, the additives are those having less effect the environment and not including any of components with restrictions in use such as nitrite, formaldehyde and derivatives thereof, and petroleum hydrocarbon.
  • In one aspect, the present invention is directed to an industrial lubricating grease for machinery and equipment, and more particularly, to a grease composition produced by adding 3 to 30wt% additives to 10 to 95wt% distillation residues, which is generated in production of biodiesel 10a and 3 to 30wt% thickeners.
  • The distillation residue of biodiesel of the present invention is generated from soybean oil or rapeseed oil.
  • The thickener used in the present invention includes at least one selected from the group consisting of lithium soap, aluminum soap, diurea, bentone and silica gel.
  • The lithium and aluminum soaps include lithium and aluminum metals, and soaps formed by soponification between 12-hydroxy stearic acid, stearic acid, boric acid or benzoic acid and H2O.
  • The urea thickener includes a diurea product, formed by a reaction between one selected from the group consisting of a tolylene diisocyanate compound, diisocyanate compounds such as diphenylmethane diisocyanate and naphthalene diisocyanate, and one selected from the group consisting of monoamines such as benzylamine, toluidine and chloroaniline, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonyldecylamine and eicosylamine.
  • The bentone thickener includes bentonite and a self-activator such as alcohol or by distillation of a reaction mixture obtained by transesterification of vegetable or animal oil with an alcohol water.
  • The silica gel thickener is fumed silica which includes hydrophobic and hydrophilic silicas.
  • The additive used in the present invention includes at least one selected from the group consisting of a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor, a structure stabilizer and a thickener.
  • The pour point depressant used in the present invention includes polymethacrylate, aromatic synthetic base oil or derivatives thereof.
  • The lubricating additive includes metal salts of dithiocarbamate, aryl phosphate and phosphoric ester, sulfide or derivatives thereof.
  • The corrosion inhibitor includes benzotriazole, tolyltriazole, mercaptobenzothiazole or derivatives thereof.
  • The oxidation inhibitor includes tetrabutylmethylphenol, a quinoline compound or derivatives thereof.
  • The structure stabilizer includes a copolymer such as ethylene propylene or derivatives thereof.
  • The thickener includes derivatives of polybutene or polyisobutylene.
    • DETAILED DESCRIPTION OF THE INVENTION
  • Greases were formed using a distillation residue of biodiesel as lubricating base oil by four thickeners, and then their properties and performances were measured.
    • Exemplary Embodiment 1 (Lithium Thickener)
  • A lithium soap grease was produced using a distillation residue generated in production of biodiesel, lithium soap (a soponification product of lithium hydroxide and fatty acid such as 12-hydroxy stearic acid, stearic acid, azelaic acid or boric acid), a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor, a structure stabilizer and a thickener. Table 1. Composition and Properties of Lithium Soap Grease
    Amount (%) Name 1 2 3
    Fatty Acid 6.0 4.0 2.0
    Lithium Hydroxide 0.9 0.6 0.3
    Biodiesel distillation residue 82.0 83.0 85.0
    Pour Point depressant 1.0 1.0 1.0
    Lubricating Additive 1.0 1.0 1.0
    Thickener 8.0 9.0 9.0
    Etc. Proper quantity Proper quantity Proper quantity
    Property Categories
    Worked Penetration 330 367 421
    Dropping Point (°C) 170 162 159
    4-ball Test (Shell Method), mm 0.6 or less 0.6 or less 0.6 or less
    Oil Separation % (100°C, 24h) 4.5 6.5 9.0
    Copper Corrosion (100°C, 24h) No color change No color change No color change
    • Exemplary Embodiment 2 (Urea Thickener)
  • A urea grease was produced using a distillation residue generated in production of biodiesel, a urea thickener (diurea, a tolylene diisocyanate compound, a diisocyanate compound of diphenylmethane diisocyanate or naphthalene diisocyanate, monoamine of benzylamine, toluidine or chloroaniline, or an aromaticamine such as tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonyldecylamine or eicosylamine), a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer. Table 2. Composition and Properties of Urea Grease
    Amount (%) Name 1 2 3
    Diisocyanate 10.0 8.0 6.0
    Aromatic amine 10.0 8.0 6.0
    Biodiesel Distillation Residue 68.0 70.0 74.0
    Pour Point Depressant 1.0 1.0 1.0
    Lubricating Additive 1.0 1.0 1.0
    Water-Resistance Additive 1.0 1.0 1.0
    Thickener 8.0 9.0 9.0
    Etc. Proper quantity Proper quantity Proper quantity
    Property Categories
    Worked Penetration 290 335 360
    Dropping Point (°C) 260 255 252
    4-ball Test (Shell Method), mm 0.6 or less 0.6 or less 0.6 or less
    Oil Separation % (100°C, 24h) 3.0 4.3 5.8
    Copper Corrosion (100°C, 24h) No color change No color change No color change
    • Exemplary Embodiment 3 (Aluminum Thickener)
  • An aluminum complex grease was produced using a distillation residue generated in production of biodiesel, an aluminum complex thickener (an aluminum metal compound, and a fatty acid such as benzoic, palmitic, palmitoleic, stearic, oleic or linoleic acid), a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer. Table 3. Composition and Properties of Aluminum Grease
    Amount (%) Name 1 2 3
    Aluminum Isopropoxide 8.0 6.0 4.0
    Stearic Acid 11.0 8.3 5.6
    Benzoic Acid 4.8 3.6 2.4
    Water (H2O) 0.7 0.5 0.3
    Biodiesel Distillation Residue 63.5 68.6 74.7
    Pour Point Depressant 1.0 1.0 1.0
    Lubricating Additive 1.0 1.0 1.0
    Water-Resistance Additive 1.0 1.0 1.0
    Thickener 8.0 9.0 9.0
    Etc. Proper quantity Proper quantity Proper quantity
    Property Categories
    Worked Penetration 275 312 363
    Dropping Point (°C) 261 258 247
    4-ball Test (Shell Method), mm 0.6 or less 0.6 or less 0.6 or less
    Oil Separation % (100°C, 24h) 2.5 3.7 4.1
    Copper Corrosion (100°C, 24h) No color change No color change No color change
    • Exemplary Embodiment 4 (Bentone Thickener)
  • A bentone grease was produced using a distillation residue generated in production of biodiesel, a bentone thickener, a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer. Table 4. Composition and Properties of Bentone Grease
    Amount (%) Name 1 2 3
    Bentonite 10.0 8.0 6.0
    Methanol 0.1 0.1 0.1
    Biodiesel Distillation Residue 78.0 79.0 81.0
    Pour Point Depressant 1.0 1.0 1.0
    Lubricating Additive 1.0 1.0 1.0
    Water-Resistance Additive 1.0 1.0 1.0
    Thickener 8.0 9.0 9.0
    Etc. Proper quantity Proper quantity Proper quantity
    Property Categories
    Worked Penetration 288 317 356
    Dropping Point (°C) None None None
    4-ball Test (Shell Method), mm 0.7 or less 0.7 or less 0.7 or less
    Oil Separation % (100°C, 24h) 1.8 2.9 3.5
    Copper Corrosion (100°C, 24h) No color change No color change No color change
    • Exemplary Embodiment 5 (Silica Thickener)
  • A silica grease was produced using a distillation residue generated in production of biodiesel, a silica gel thickener, a pour point depressant, a lubricating additive, a corrosion inhibitor, an oxidation inhibitor and a structure stabilizer. Table 5. Composition and Properties of Grease using Fumed Silica Gel as Thickener
    Amount (%) Name 1 2 3
    Fumed Silica Gel 16.0 13.0 10.0
    Biodiesel Distillation Residue 72.0 74.0 77.0
    Pour Point Depressant 1.0 1.0 1.0
    Lubricating Additive 1.0 1.0 1.0
    Water-Resistance Additive 1.0 1.0 1.0
    Thickener 8.0 9.0 9.0
    Etc. Proper quantity Proper quantity Proper quantity
    Property Categories
    Worked Penetration 316 361 405
    Dropping Point (°C) None None None
    4-ball Test (Shell Method), mm 0.8 or less 0.8 or less 0.8 or less
    Oil Separation % (100°C, 24h) 3.3 4.2 7.8
    Copper Corrosion (100°C, 24h) No color change No color change No color change
  • The present invention uses a biodiesel distillation residue as base oil of grease so as to provide environmentally friendly grease and obtain recycling benefits of the biodiesel distillation residue, and the environmentally friendly grease may having good lubrication compared to conventional petroleum base oil and be cheaper than a product using vegetable oil or synthetic ester as base oil.

Claims (8)

  1. A grease composition produced by adding 3 to 20wt% of additives to 50 to 95wt% of distillation residues, which are generated in production of biodiesel by distillation of a reaction mixture obtained by transesterification of vegetable or animal oil with an alcohol, and 3 to 30wt% of thickeners.
  2. The composition according to claim 1, wherein the vegetable oil is selected from the group comprising rice bran oil, waste cooking oil, soybean oil or canola oil and wherein the distillation residue has a base oil kinematic viscosity of 20 to 400 cSt at 40°C.
  3. The composition according to claim 1, wherein the thickener comprises at least one selected from the group consisting of lithium soap, diurea, an aluminum complex, a bentone thickener and a silica gel thickener.
  4. The composition according to claim 3, wherein the lithium soap thickener comprises at least one selected from the group consisting of a lithium hydroxide metal compound, 12-hydroxy stearic, stearic, boric, azelaic, and sebacic acids
  5. The composition according to claim 3, wherein the diurea thickener comprises at least one selected from the group consisting of a diisocyanate compound, monoamines such as benzylamine, toluidine and chloroaniline, and aromatic amines such as tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonyldecylamine, and eicosylamine.
  6. The composition according to claim 3, wherein the aluminum complex soap thickener is formed of an aluminum metal compound, and at least one selected from the group consisting of benzoic, stearic, palmitic, palmitoleic, and oleic acids.
  7. The composition according to claim 3, wherein the silica gel thickener is formed of fumed silica, which comprises hydrophobic and hydrophilic silicas and dispersed in the base oil to be used as the grease thickener.
  8. The composition according to claim 1, wherein the additive comprises at least one selected from the group consisting of: a pour point depressant comprising polymethacrylate, aromatic synthetic base oil and derivates thereof; a lubricating additive comprising metal salt of dithiocarbamate, aryl phosphate or phosphoric ester, sulfide and derivates thereof; a corrosion inhibitor comprising benzotriazole, tolyltriazole, mercaptothiazole and derivates thereof; an oxidation inhibitor comprising tetrabutyl methylphenol, a quinoline compound and derivates thereof; and a structure stabilizer comprising a copolymer such as ethylene propylene and derivates thereof.
EP07118302A 2007-01-12 2007-10-11 Biodegradable grease composition using distillation residue generated in production of biodiesel Not-in-force EP1944352B1 (en)

Applications Claiming Priority (1)

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KR1020070003691A KR100721600B1 (en) 2007-01-12 2007-01-12 Composition of grease prodnced from distillated residuum

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EP1944352A1 EP1944352A1 (en) 2008-07-16
EP1944352B1 true EP1944352B1 (en) 2010-08-11

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JP (1) JP4776603B2 (en)
KR (1) KR100721600B1 (en)
AT (1) ATE477317T1 (en)
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ES (1) ES2352982T3 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG154349A1 (en) * 2008-01-11 2009-08-28 Cheng Kit Yew Composition and process of manufacturing of biodiesel grease by gelling biodiesel, anti-wear additives, extreme pressure additives, water repellent additives and anti-oxidant additives.
DE102009026396A1 (en) * 2009-08-18 2011-04-07 Green Finance Ag Flux additive for bituminous compounds
KR101340007B1 (en) 2010-11-17 2013-12-10 (주) 토탈방재 Manufacturing method of emulsifier using by-product biodiesel
DE102019134330A1 (en) * 2019-12-13 2021-06-17 Klüber Lubrication München Se & Co. Kg Use of a grease composition with a high upper service temperature
JP2023171713A (en) * 2023-05-29 2023-12-05 協同油脂株式会社 Biomass grease composition

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Publication number Priority date Publication date Assignee Title
CH654020A5 (en) * 1982-07-19 1986-01-31 Sp K Byuro Analit Priborostr Lubricant for cold-forming of metals
AU626014B2 (en) * 1988-10-21 1992-07-23 Malaysian Palm Oil Board Production of alkyl esters from oils and fats
JPH0586389A (en) * 1991-09-27 1993-04-06 Showa Shell Sekiyu Kk Biodegradable grease composition
BR9304049A (en) * 1992-11-12 1994-05-17 Lubrizol Corp Grease composition and method for increasing the drip point of a grease.
US5595965A (en) * 1996-05-08 1997-01-21 The Lubrizol Corporation Biodegradable vegetable oil grease
JP2002265986A (en) * 2001-03-15 2002-09-18 Akio Kobayashi Method for producing fatty acid alkyl ester and glycerin
FR2824331B1 (en) * 2001-05-04 2004-01-16 Total Raffinage Distribution LUBRICATING GREASE, ITS PREPARATION AND ITS USE, PARTICULARLY FOR LUBRICATING CONTACTS INVOLVING ELASTOMERS
WO2003018729A1 (en) * 2001-08-31 2003-03-06 Abcon Aps Non-toxic biodegradable grease
JP2003277780A (en) * 2002-03-26 2003-10-02 Nsk Ltd Biodegradable grease composition and rolling device
EP1529828A1 (en) * 2003-10-31 2005-05-11 Malaysian Palm Oil Board Lubricant base oil of palm fatty acid origin
US20060225341A1 (en) * 2004-12-20 2006-10-12 Rodolfo Rohr Production of biodiesel

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DE602007008350D1 (en) 2010-09-23
ES2352982T3 (en) 2011-02-24
KR100721600B1 (en) 2007-05-23
ATE477317T1 (en) 2010-08-15
JP2008169370A (en) 2008-07-24
EP1944352A1 (en) 2008-07-16
JP4776603B2 (en) 2011-09-21

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