CN112625803A - Method for preparing higher fatty acid ester by using illegal cooking oil - Google Patents
Method for preparing higher fatty acid ester by using illegal cooking oil Download PDFInfo
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- CN112625803A CN112625803A CN202011487658.1A CN202011487658A CN112625803A CN 112625803 A CN112625803 A CN 112625803A CN 202011487658 A CN202011487658 A CN 202011487658A CN 112625803 A CN112625803 A CN 112625803A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
- C11C1/04—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by hydrolysis
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/12—Refining fats or fatty oils by distillation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/08—Refining
- C11C1/10—Refining by distillation
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/087—Boron oxides, acids or salts
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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
- 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
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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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
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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
- 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
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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
- 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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a method for preparing higher fatty acid ester by using illegal cooking oil, which comprises the following steps: the method comprises the steps of illegal cooking oil purification, catalytic hydrolysis, separation, two-stage distillation and esterification, wherein a complex ionic liquid catalyst is used in the catalytic hydrolysis step, and the mass part ratio of the catalyst to the illegal cooking oil is 1: (30-50).
Description
Technical Field
The invention belongs to the technical field of fatty acid ester preparation, and particularly relates to a method for preparing higher fatty acid ester by using illegal cooking oil and application of the prepared fatty acid ester.
Background
The illegal cooking oil generally refers to various inferior oils in life, and mainly comes from greasy floaters in sewers, garbage discharged from hotels, restaurants and other industries, waste oil from animal processing, residual oil after repeatedly frying food, and the like. The yield of the illegal cooking oil in China is very high, and the direct discharge of the illegal cooking oil not only causes huge waste of resources, but also has huge influence on the living environment of people. Therefore, how to fully excavate and utilize abundant illegal cooking oil resources and change waste into valuables is a problem which needs to be solved urgently.
The lubricating grease is grease-like semisolid consisting of base oil and a thickening agent, and mainly plays roles of lubricating, protecting and sealing when mechanical parts rub. The grease may be classified into vegetable oil, mineral oil, synthetic oil, and the like based on the base oil, and may be classified into lithium-based, calcium-based, sodium-based, complex-based, bentonite, and the like based on the thickener. Among them, biodegradable environment-friendly greases have a high biodegradation rate, using rapidly biodegradable greases as base oils, and are gradually drawing attention.
CN1206332C discloses a biodegradable grease, which comprises 70-94% of vegetable oil, thickener bentonite and amine antioxidant or mixed antioxidant of phenols and amines; CN100510031C discloses a biodegradable lubricating grease, which comprises vegetable oil, lithium-calcium fatty acid mixed soap, antioxidant, metal antirust agent, and the like; CN111560278A discloses an environment-friendly composite aluminum-based lubricating ester and a preparation method thereof, wherein, epoxy fatty acid polyol ester obtained by hydrolyzing and esterifying vegetable oil is taken as base oil; CN105505546 discloses a preparation method of lubricating grease containing nano rare earth oxide, wherein rapeseed oil or waste vegetable oil is used as base oil; CN102199471B discloses an environment-friendly lubricating grease composition, which comprises base oil and a composite lithium soap thickener, wherein the base oil is mixed oil of modified vegetable oil and poly alpha olefin oil. In many studies on environmentally friendly greases, studies on a base oil which is a mixture of an animal fat and a vegetable oil, particularly a drainage oil, are rarely made.
Therefore, the development and research of the environment-friendly grease using the illegal cooking oil as the base oil component of the grease are of great significance for the full utilization of illegal cooking oil resources and the reduction of environmental pollution.
Disclosure of Invention
An object of the present invention is to provide a method for preparing higher fatty acid esters using illegal cooking oil, which realizes substantially higher fatty acid ester production by a combination of ionic liquid catalysis and two-stage distillation, while avoiding corrosion of a reaction vessel by a strong acid or strong alkali solvent and environmental pollution caused by discharge of a strong acid or strong alkali solution, and realizing sufficient development and reuse of illegal cooking oil resources.
The invention also aims to provide the environment-friendly bio-based lubricating grease which takes the illegal cooking oil as a basic raw material, realizes the maximum utilization of illegal cooking oil resources, and has the advantages of low manufacturing cost, simple and convenient method and easy batch production; the compound of sulfurized fatty acid ester and inorganic borate is used as an extreme pressure agent, and the lubricating grease prepared by the compound has good wear resistance and extreme pressure resistance, good compatibility and environment-friendly effect through the synergistic effect of the compound with an antioxidant, a thickening agent and an antirust agent.
The purpose of the invention is realized by the following technical scheme:
a method for preparing saturated higher fatty acid ester from illegal cooking oil is characterized by comprising the following steps:
A. catalytic hydrolysis: placing the pretreated illegal cooking oil into a reaction container, adding water and an ionic liquid catalyst, heating and stirring, and reacting for 3-4 hours;
B. separation: cooling the waste oil after catalytic hydrolysis to room temperature, standing for layering, and removing the lower mixed liquid to obtain the upper crude fatty acid;
C. first distillation: distilling the crude fatty acid at a temperature ranging from 210 ℃ to 230 ℃ under vacuum to separate a lower fatty acid;
D. and (3) second distillation: under vacuum, distilling the residual crude fatty acid after the first distillation again at the temperature range of 270 ℃ and 290 ℃ and collecting fractions;
E. esterification reaction: reacting the collected fraction with methanol or ethanol to produce fatty acid ester.
The ionic liquid catalyst is a compound ionic liquid catalyst, and the mass part ratio of the catalyst to the illegal cooking oil is 1: (30-50). Preferably, the mass part ratio of the catalyst to the illegal cooking oil is 1: (35-45); more preferably, the mass part ratio of the catalyst to the illegal cooking oil is 1: 40.
wherein the complex ionic liquid catalyst consists of carboxyl functional ionic liquid and sulfonic acid functional ionic liquid, preferably, the carboxyl functional ionic liquid is selected from one or more of 1-carboxyethyl-3-methylimidazole nitrate, 1-carboxymethyl-3-methylimidazole nitrate, 1-carboxyethyl-3-methylimidazole chloride and 1-carboxymethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt; and the sulfonic acid functionalized ionic liquid is selected from one or more of N-sulfonyl butyl pyridine p-toluenesulfonate, sulfonic butyl pyridine lactone, sulfonic propyl pyridine lactone, 1-butyl sulfonic acid-3-methylimidazole bisulfate and 1-butyl sulfonic acid-3-methylimidazole trifluoroacetate.
Wherein the mass part ratio of the carboxyl functionalized ionic liquid to the sulfonic acid functionalized ionic liquid is (1-3): 1.
preferably, the mass part ratio of the carboxyl functionalized ionic liquid to the sulfonic acid functionalized ionic liquid is (1.5-2.5): 1, more preferably, the mass part ratio of the carboxyl functionalized ionic liquid to the sulfonic acid functionalized ionic liquid is 2: 1.
wherein, under the vacuum condition, the first distillation is carried out at the temperature range of 210-230 ℃ to separate out the low-carbon fatty acid; preferably, the crude fatty acid is subjected to a first distillation under vacuum at a temperature in the range of 215-225 ℃; more preferably, the first distillation is conducted at a temperature of 210 ℃, 212 ℃, 214 ℃, 216 ℃, 218 ℃, 220 ℃, 222 ℃, 224 ℃, 226 ℃, 228 ℃ and 230 ℃ or any value within any range therebetween.
Wherein, under the vacuum condition, the second distillation is carried out at the temperature range of 270-290 ℃ to separate most of stearic acid; preferably, the remaining crude fatty acid after the first distillation is subjected to a second distillation at a temperature within the range of 275-285 ℃ under vacuum conditions; more preferably, the second distillation is conducted at a temperature of 270 ℃, 272 ℃, 274 ℃, 276 ℃, 278 ℃, 280 ℃, 282 ℃, 284 ℃, 286 ℃, 288 ℃, and 290 ℃ or any value in any range between them.
Wherein, herein, the lower fatty acid means a fatty acid having a carbon number in the range of 1 to 12; preferably, the lower fatty acid is a fatty acid having a number of carbon atoms in the range of 1 to 12, 2-11, 3-10 or 4-8.
Herein, the higher fatty acid means a fatty acid having a carbon number in the range of 13 to 18.
Wherein, before the catalytic hydrolysis step, a purification step is also included. Wherein the purifying step comprises: weighing illegal cooking oil, centrifuging to remove suspended matters, adding appropriate amount of water to remove colloidal substances, drying and dehydrating, adding activated clay 1-5% of the mass of the illegal cooking oil, heating to 90-120 deg.C, stirring, keeping the temperature for 1.5-2.0 hr, and decolorizing to obtain pretreated illegal cooking oil.
Wherein, in the step of catalytic hydrolysis, the reaction is carried out for 3 to 4 hours at the reaction temperature of 90 to 150 ℃.
Use of a saturated higher fatty acid ester prepared according to the above process for the preparation of a grease for industrial use.
An environment-friendly bio-based grease comprising a saturated higher fatty acid ester prepared according to the above method.
Specifically, the environment-friendly bio-based lubricating grease comprises the following components in parts by weight: 60-100 parts of base grease, 20-40 parts of thickening agent, 5-15 parts of antioxidant, 1-5 parts of extreme pressure agent and 1-5 parts of antirust agent.
Wherein the base fat is the higher fatty acid ester prepared by the method.
Wherein the thickener is selected from one or more of atactic polypropylene, amorphous alpha-olefin copolymer, polymethacrylate bentonite, polyurethane and bentonite.
Wherein the antioxidant is selected from one or more of p, p-diisopropyl diphenylamine, N-diaryl butyl p-phenylenediamine, dioctyl diphenylamine, N-alkyl-alpha-naphthylamine, polytrimethyl dihydroquinoline and octylated diphenylamine.
Wherein the extreme pressure agent is a compound of sulfurized fatty acid ester and inorganic borate nanoparticles. Wherein the sulfurized fatty acid ester is selected from one or more of dimethyl dithiocarboxylate, distearyl thiodipropionate, methyl sulfurized fatty acid ester, and thioethyl stearate; the inorganic borate nanoparticles are selected from one or more of calcium borate nanoparticles, molybdenum borate nanoparticles, potassium borate nanoparticles and magnesium borate nanoparticles.
Wherein the inorganic borate nanoparticles are chemically modified borate nanoparticles. Specifically, the inorganic borate nanoparticles are oleic acid or stearic acid modified borate nanoparticles.
Wherein the chemical modification comprises the following steps: dissolving inorganic borate in water, heating to 50-80 ℃, stirring for 30-50 minutes, adding solvent xylene and modifier oleic acid or stearic acid, heating to 80-110 ℃, fully stirring for 2-4 hours, stopping reaction, standing for layering, and spray drying an organic layer at the temperature of 100-120 ℃ to obtain the borate nano-particles modified by the oleic acid or the stearic acid.
Wherein the nanoparticle has a particle size of 50-500nm, preferably the nanoparticle has a particle size of 50, 100, 150, 200, 250, 300, 350, 400, 450, 500nm or any value in any range therebetween.
Wherein the vulcanized fatty acid ester and the inorganic borate are prepared from (1-3) the following components in parts by weight: 1, preferably, the mass part ratio of the sulfurized fatty acid ester to the borate nanoparticles is (1-2): 1; more preferably, the ratio of the sulfurized fatty acid ester to the borate nanoparticles in parts by mass is 1.5: 1.
wherein, the environment-friendly bio-based grease comprises 60, 65, 70, 75, 80, 85, 90, 95, 100 parts of base grease or any value in any range therebetween by weight.
Wherein the kinematic viscosity of the base grease at 40 ℃ is 70-140mm2/s。
Wherein the grease comprises, in parts by weight, thickener 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40 parts or any value within any range therebetween.
Wherein the grease comprises, in parts by weight, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts of antioxidant or any value within any range therebetween.
Wherein the grease comprises, in parts by weight, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 parts of an extreme pressure agent or any value in any range therebetween.
Wherein the antirust agent is selected from one or more of sorbitan trioleate, sorbitan monooleate, zinc sulfonate, calcium sulfonate, sodium petroleum sulfonate and barium petroleum sulfonate.
Wherein, the lubricating grease also comprises 5-15 parts of ricefield eel mucus by weight. Preferably, the grease further comprises 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts of finless eel mucus or any value in any range therebetween.
The swamp eel mucus is a substance rich in mucin and polysaccharide, wherein the mucin is a highly glycosylated high molecular weight substance with gel forming capability, has extremely strong adhesiveness, is easy to adsorb and fix on the surface of a metal part to repair a concave-convex part which is invisible to naked eyes on the surface, and further forms an acid-resistant, oxidation-resistant and water vapor-resistant film structure.
The extraction method of the ricefield eel mucus comprises the following steps: placing the finless eel in a 80-100 mesh filter screen, enabling the finless eel to continuously creep due to water shortage, crowding mutually to generate a large amount of mucus, enabling the mucus to flow into a container with an oil-water separation function, and collecting to obtain the finless eel mucus.
A preparation method of environment-friendly bio-based lubricating grease comprises the following steps: adding the basic grease and the thickening agent into a reaction vessel, heating to 50-80 ℃, fully stirring for 20-40 minutes, continuously heating to 120-160 ℃, keeping the temperature for 5-8 minutes, stopping heating, adding the antioxidant, the extreme pressure agent and the antirust agent, fully stirring, cooling to room temperature, grinding, filtering and packaging.
Specifically, the preparation method of the environment-friendly bio-based lubricating grease comprises the following steps:
a) adding 60-100 parts of base grease and 20-40 parts of thickening agent into a reactor provided with a heating device and a stirring device, heating to 50-80 ℃, and stirring for 20-40 minutes at the speed of 300-;
b) continuously heating to 120 ℃ and 160 ℃, and keeping the temperature for 5-8 minutes;
c) stopping heating, adding 5-15 parts of antioxidant, 1-5 parts of extreme pressure agent and 1-5 parts of antirust agent, and fully stirring;
d) cooling to room temperature, grinding, filtering, and packaging.
Optionally, in step c), 5-15 parts of the eel mucus are added and fully stirred.
Specifically, the preparation method of the environment-friendly bio-based lubricating grease comprises the following steps:
1) catalytic hydrolysis: placing the pretreated illegal cooking oil into a reaction container, adding water and an ionic liquid catalyst, heating and stirring, and reacting for 3-4 hours;
2) separation: cooling the waste oil after catalytic hydrolysis to room temperature, standing for layering, and removing the lower mixed liquid to obtain the upper crude fatty acid;
3) first distillation: distilling the crude fatty acid at a temperature ranging from 210 ℃ to 230 ℃ under vacuum to separate a lower fatty acid;
4) and (3) second distillation: under vacuum, distilling the residual crude fatty acid after the first distillation again at the temperature range of 270 ℃ and 290 ℃ and collecting fractions;
5) esterification reaction: reacting the collected fraction with methanol or ethylene glycol to produce fatty acid ester;
6) adding 60-100 parts of the fatty acid ester prepared in the step 5) and 20-40 parts of the thickening agent into a reactor provided with a heating device and a stirring device, heating to 50-80 ℃, and stirring for 20-40 minutes at the speed of 300-;
7) continuously heating to 120 ℃ and 160 ℃, and keeping the temperature for 5-8 minutes;
8) adding 5-15 parts of antioxidant, 1-5 parts of extreme pressure agent and 1-5 parts of antirust agent, and fully stirring;
9) cooling to room temperature, grinding, filtering, and packaging.
In the method, the base fat includes a higher fatty acid ester derived from illegal cooking oil; specifically, the base grease comprises grease obtained by carrying out catalytic hydrolysis, two-stage distillation and esterification on the illegal cooking oil; more specifically, the base fat is higher fatty acid ester of illegal cooking oil after catalytic hydrolysis, two-stage distillation and esterification reaction.
In the method, a purification step is further included before the catalytic hydrolysis step. The purification step comprises: weighing illegal cooking oil, centrifuging to remove suspended matters, adding appropriate amount of water to remove colloidal substances, drying and dehydrating, adding activated clay 1-5% of the mass of the illegal cooking oil, heating to 90-120 deg.C, stirring, keeping the temperature for 1.5-2.0 hr, and decolorizing to obtain pretreated illegal cooking oil.
The environment-friendly bio-based lubricating grease disclosed by the invention realizes the following technical effects:
(1) the preparation method for preparing the higher fatty acid ester has simple steps and convenient material obtaining, successfully separates the low-carbon fatty acid and the higher fatty acid by the composite ionic liquid catalyst and the two-stage distillation and esterification process, reduces the corrosion of the traditional sulfuric acid catalytic hydrolysis to a reaction container, and avoids the environmental pollution caused by incomplete reaction of concentrated acid. Meanwhile, the inventor of the invention unexpectedly finds that the complex ionic liquid catalyst consisting of the carboxyl functional ionic liquid and the sulfonic acid functional ionic liquid is adopted to better match fatty acids with different molecular weights and structures in the illegal cooking oil, thereby achieving better integral separation effect.
(2) The environment-friendly bio-based lubricating grease disclosed by the invention takes the ubiquitous illegal cooking oil in life as a main raw material, so that a feasible way is provided for resource utilization and waste recycle of the illegal cooking oil, and the problems of environmental pollution and human health caused by improper treatment of the illegal cooking oil are further reduced.
(3) The environment-friendly bio-based lubricating grease disclosed by the invention takes biodegradable illegal cooking oil as a main raw material, and the synergistic effect among the biodegradable illegal cooking oil, the high-grade fatty acid ester, the compound extreme pressure agent, the antioxidant and the antirust agent is increased through the combination of the high-grade fatty acid ester prepared from the illegal cooking oil and the compound extreme pressure agent, the antioxidant and the antirust agent. In addition, the borate nano-particles modified by oleic acid or stearic acid are used as the thickening agent, so that the borate nano-particles have good compatibility with the base grease to a certain extent, and the nano-particles with tiny sizes realize good dispersibility in the base grease.
(4) The use of the sulfur-containing and boron-containing compound extreme pressure agent obviously improves the extreme pressure wear resistance of the lubricating grease, and simultaneously, as the sulfur in the sulfur-containing extreme pressure agent and the boron in the boron-containing extreme pressure agent can have the same action with the metal elements on the surface of a metal part, a vulcanized metal film and a boronized metal film are generated, the workpiece is protected from abrasion to a certain extent, and the sealing property between the two parts is improved.
(5) In the lubricating grease, the finless eel mucus is added to form a film with high viscosity and good waterproofness on the surface of a metal part, so that the sealing property and the waterproofness of the lubricating grease are improved, and the extreme pressure wear-resistant effect of the lubricating grease is improved.
Detailed Description
The technical solutions of the present invention will be described in detail and completely with reference to specific embodiments below, however, those skilled in the art will appreciate that the described embodiments are only for illustrative purposes and are not all the inventions. Based on the illustrated embodiments of the present invention, those skilled in the art will better understand and appreciate the technical solutions claimed in the present invention and the technical effects achieved thereby.
In this context, illegal cooking oil generally refers to various inferior oils in life, including oils resulting from processing and refining of inferior meat; the oil produced by simply processing and refining residues and leftovers (generally called swill) from the industries of hotels, restaurants and the like; and edible oil from repeated frying. Specifically, the illegal cooking oil refers to waste oil and fat which takes fatty acid glyceride as a main component, is turbid in appearance and opaque, wherein the illegal cooking oil has the moisture content of more than 1.0%, the acid value of more than 5.0mgKOH/g, the saponification value of more than 250mg/g and the conductivity of more than 4 pS/m.
Preparation of (mono) basic esters
The preparation method comprises the following steps: preparation of base fat 1 of the invention
(1) Purifying: weighing 1000 g of swill-cooked dirty oil, centrifuging to remove suspended matters, adding a proper amount of water to remove colloidal substances, heating to about 200 ℃, stirring, drying and dehydrating, cooling, adding about 40 g of activated clay, heating to 110 ℃, uniformly stirring, preserving heat for 2.0 hours, and decoloring;
(2) catalytic hydrolysis: placing the purified illegal cooking oil into a reaction container, adding deionized water, stirring, adding 16 g of 1-carboxyethyl-3-methylimidazole nitrate and 8 g of 1-butylsulfonic acid-3-methylimidazole hydrogen sulfate, slowly stirring, heating to the temperature of 125 ℃, and reacting for about 3 hours;
(3) separation: cooling the waste oil after catalytic hydrolysis to room temperature, standing for layering, and removing the lower mixed liquid to obtain the upper crude fatty acid;
(4) first distillation: distilling the crude fatty acid at a temperature of about 220 ℃ under vacuum to separate off lower fatty acids;
(5) and (3) second distillation: under vacuum, distilling the residual crude fatty acid after the first distillation at 280 ℃ again, condensing the steam escaping at high temperature, and collecting the fraction;
(6) esterification reaction: reacting the collected fraction with methanol at 60 ℃ for 2.5 hours, distilling under reduced pressure, removing excessive methanol, and drying under reduced pressure to generate fatty acid methyl ester, namely the basic ester 1 of the invention.
The preparation method 2 comprises the following steps: preparation of base fat 2 of the invention
The remaining components and contents and operation were the same as in preparation Process 1 except that 1-carboxyethyl-3-methylimidazole nitrate in the catalytic hydrolysis step (2) in preparation Process 1 was replaced with 1-carboxyethyl-3-methylimidazole chloride salt and 1-butylsulfonic acid-3-methylimidazole hydrogensulfate salt was replaced with sulfopropylpyridinolide.
The preparation method 3 comprises the following steps: preparation of base fat 3 of the invention
The remaining components and contents and operation were the same as in preparation Process 1 except that 16 g of 1-carboxyethyl-3-methylimidazole nitrate in the catalytic hydrolysis step (2) in preparation Process 1 was replaced with 18 g of 1-carboxymethyl-3-methylimidazole nitrate and 8 g of 1-butylsulfonic acid-3-methylimidazole hydrogensulfate was replaced with 6 g of 1-butylsulfonic acid-3-methylimidazole trifluoroacetate.
The preparation method 4 comprises the following steps: preparation of base fat 4 of the invention
The temperature of the first distillation, 220 ℃ was replaced by 210 ℃ and the temperature of the second distillation, 280 ℃, was replaced by 270 ℃, and the remaining components and contents and operation were the same as in preparation method 1.
The preparation method 5: preparation of base fat 5 of the invention
The remaining components and contents and operation were the same as in preparation method 1 except that the temperature of the first distillation was changed to 230 ℃ instead of 220 ℃ and the temperature of the second distillation was changed to 290 ℃.
The preparation method 6 comprises the following steps: preparation of base fat 6 for comparison
In the catalytic hydrolysis step (2) in preparation method 1, only 24 g of 1-carboxyethyl-3-methylimidazolium nitrate was added as an ionic liquid catalyst, and the remaining components and contents and operation were the same as in preparation method 1.
The preparation method 7 comprises the following steps: preparation of base fat 7 for comparison
In the catalytic hydrolysis step (2) in preparation Process 1, only 24 g of 1-butylsulfonic acid-3-methylimidazolium hydrogensulfate was added as an ionic liquid catalyst, and the remaining components and contents and operation were the same as in preparation Process 1.
The preparation method 8 comprises the following steps: preparation of base fat 8 for comparison
The remaining components and contents and operation were the same as in preparation method 1, except that the temperature of the second distillation was changed from 280 ℃ to 260 ℃.
The preparation method 9: preparation of base fat 9 for comparison
The remaining components and contents and operation were the same as in preparation Process 1, except that the first distillation and the second distillation were combined to be distilled at a temperature of 260 ℃.
Preparation of (II) grease
Greases of examples 1-11 and comparative examples 1-7 were prepared according to the following specific steps 1 and 2, and the specific components and contents (by weight) of each grease, which further contained 10 parts of the antioxidant octylated diphenylamine and 2 parts of the rust inhibitor sorbitan trioleate, are shown in table 1 below.
Step 1: dissolving inorganic borate in water, heating to 65 ℃, stirring for 35 minutes, adding xylene and oleic acid, heating to 105 ℃, fully stirring for 2.5 hours, stopping reaction, standing for layering, and spray-drying an organic layer at 110 ℃ to obtain the oleic acid modified borate nanoparticles (extreme pressure agent).
Step 2: adding the base grease and the thickening agent into a reaction vessel by weight, mixing, heating to 55 ℃, adding a proper amount of acetone, fully stirring, then adding the antioxidant, the sulfurized fatty acid ester, the inorganic borate nano-particles and the antirust agent, stirring, heating to 100 ℃, reacting at constant temperature for 6 hours, standing, cooling and grinding to obtain the lubricating grease.
TABLE 1
(II) test indexes
Measuring the dropping point of the lubricating grease by a GB/T3498 lubricating grease dropping point measuring method; measuring the working cone penetration according to GB/T269-91; according to GB/T12583-1998, the maximum non-seizing load PB value (N) is determined by a four-ball method; the greases of the examples and comparative examples were tested for wear scar diameter using a four ball friction wear tester. The specific detection results are shown in the following table 2:
TABLE 2
From the measurement results in table 2, it is understood that the dropping point temperature of the grease is affected by factors such as the thickener and the extreme pressure agent. The dropping point is greatest when the ratio of the fatty acid sulfate ester to the borate nanoparticles is 1.5: 1; borate modification and application of only the fatty acid ester of sulfuric acid or borate had no significant effect on the drop point. The dropping point temperature is continuously increased as the specific gravity of the thickener in the grease is gradually increased. In addition, as shown in comparative examples 3 to 4, distillation once and at a low temperature increased the dropping point temperature of the grease, which may be because the lower temperature was insufficient to separate out C18 fatty acids such as stearic acid, oleic acid, and the drop in the number of carbon atoms increased the dropping point temperature to some extent, and the wear scar diameter significantly increased.
Furthermore, as shown in comparative examples 3-4, the reduced distillation temperature and the reduced number of distillations significantly increased the working penetration of the grease, probably because the lower temperature made it difficult to separate the longer chain higher fatty acids with more carbon atoms, and the separated fatty acids contained more lower fatty acids as a result of one distillation, which softened the grease and increased the penetration. Extreme pressure agent type and modification affect cone penetration. In greases, a relative increase in the proportion of thickener reduces the penetration of the grease; and the penetration degree of the lubricating grease is reduced to a certain extent by adding the swamp eel mucus.
As shown in examples 1, 6 to 7 and comparative examples 5 to 7, the compounding of extreme pressure agents allows the grease to have a large PB value, and the oleic acid-modified borate allows the grease to be prepared to have better extreme pressure wear resistance and reduce wear of friction parts.
The reason why the performance of each index of the lubricating grease added with the swamp eel mucus is better than that of the lubricating grease without the swamp eel mucus is probably that the swamp eel mucus contains a large amount of mucin, the mucin is adhered to the surface of a part to form an adhesion layer with certain viscosity and thickness, and O and S elements contained in the adhesion layer react with metal to form a biological oxide or sulfide film, and the film can reduce the contact probability of the part and water vapor and oxygen in the air, so that the wear-resisting extreme pressure performance of the lubricating grease is improved.
From table 2 above, it can be seen that the overall performance of the greases of the present invention is the result of the synergistic effect of the base grease, thickener, extreme pressure agent and other additives.
The present invention is not limited to the embodiments listed above, and those skilled in the art will appreciate that various substitutions, modifications and combinations of the technical features of the present invention can be made by those skilled in the art without departing from the spirit and substance of the present invention, and the technical solutions of the various modifications, substitutions and combinations are covered by the scope of the claims of the present invention.
Claims (10)
1. A method for preparing higher fatty acid ester from illegal cooking oil is characterized by comprising the following steps:
A. catalytic hydrolysis: placing the pretreated illegal cooking oil into a reaction container, adding water and an ionic liquid catalyst, heating and stirring, and reacting for 3-4 hours;
B. separation: cooling the waste oil after catalytic hydrolysis to room temperature, standing for layering, and removing the lower mixed liquid to obtain an upper crude fatty acid layer;
C. first distillation: distilling the crude fatty acid at a temperature ranging from 210 ℃ to 230 ℃ under vacuum to separate a lower fatty acid;
D. and (3) second distillation: redistilling the remaining crude fatty acid after the first distillation at a temperature in the range of 270 ℃ and 290 ℃ under vacuum to separate most of the stearic acid;
E. esterification reaction: reacting the collected fraction with methanol or ethanol to produce fatty acid ester.
2. The method of claim 1, wherein the ionic liquid catalyst is a combination of a carboxyl-functionalized ionic liquid and a sulfonic acid-functionalized ionic liquid.
3. The method according to claim 1, wherein the mass part ratio of the catalyst to the illegal cooking oil is 1: (30-50).
4. The method of claim 2, wherein the carboxy-functionalized ionic liquid is selected from one or more of 1-carboxyethyl-3-methylimidazole nitrate, 1-carboxymethyl-3-methylimidazole nitrate, 1-carboxyethyl-3-methylimidazole chloride salt, and 1-carboxymethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt; the sulfonic acid functionalized ionic liquid is selected from one or more of N-sulfonyl butyl pyridine p-toluenesulfonate, sulfonic butyl pyridine lactone, sulfonic propyl pyridine lactone, 1-butyl sulfonic acid-3-methylimidazole bisulfate and 1-butyl sulfonic acid-3-methylimidazole trifluoroacetate.
5. The method according to claim 2, wherein the mass part ratio of the carboxyl functionalized ionic liquid to the sulfonic acid functionalized ionic liquid is (1-3): 1; preferably, the mass part ratio of the carboxyl functionalized ionic liquid to the sulfonic acid functionalized ionic liquid is (1.5-2.5): 1; more preferably, the mass part ratio of the carboxyl functionalized ionic liquid to the sulfonic acid functionalized ionic liquid is 2: 1.
6. the process as claimed in claim 1, characterized in that the crude fatty acid is subjected to the first distillation under vacuum at a temperature in the range of 215-225 ℃.
7. The process as claimed in claim 1, wherein the remaining crude fatty acid after the first distillation is subjected to a second distillation under vacuum at a temperature in the range of 275 ℃ and 285 ℃.
8. The method of claim 1, further comprising a purification step prior to the catalytic hydrolysis step.
9. The method of claim 8, wherein the purifying step comprises weighing the illegal cooking oil, centrifuging to remove suspended matter, adding water to remove colloidal substances, drying, adding activated clay, heating to 90-120 ℃, stirring, maintaining the temperature for 1.5-2.0 hours, and decolorizing to obtain pretreated illegal cooking oil.
10. The method as claimed in claim 1, wherein the catalytic hydrolysis step is carried out at a reaction temperature of 90 to 150 ℃ for 3 to 4 hours.
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