CN112824503A - Nano soap-based thickener precursor for lubricating grease and preparation method and application thereof - Google Patents
Nano soap-based thickener precursor for lubricating grease and preparation method and application thereof Download PDFInfo
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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
- C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
- C10M123/02—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a non-macromolecular compound
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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
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
- C10M2201/0626—Oxides; Hydroxides; Carbonates or bicarbonates 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
- 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
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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
- C10M2207/10—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
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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
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
- C10M2219/0445—Sulfonic acids, Derivatives thereof, e.g. neutral salts used as thickening agents
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention belongs to the technical field of lubricating grease, and particularly relates to a nano soap-based thickener precursor for lubricating grease as well as a preparation method and application thereof. The precursor of the nano soap-based thickener for the lubricating grease is a dispersion composed of nano metal hydroxide particles, a surfactant and a liquid solvent. The application of the precursor of the nano soap-based thickening agent for the lubricating grease is to prepare the lubricating grease by adopting fatty acid, the precursor of the nano soap-based thickening agent, base oil and an additive. The precursor of the nano soap-based thickener participates in saponification in the preparation process of the lubricating grease, so that a good reaction effect is obtained, and the existing process for preparing the lubricating grease is not changed at all, so that the equipment transformation and investment required by the lubricating grease production factory due to product upgrading are avoided, and the product performance can be improved.
Description
Technical Field
The invention belongs to the technical field of lubricating grease, and particularly relates to a nano soap-based thickener precursor for lubricating grease as well as a preparation method and application thereof.
Background
The lubricating grease is used as an independent industrial part in the lubricant, and is widely applied to the fields of industrial machinery, agricultural machinery, transportation industry, electronic information industry and the like due to the characteristics of excellent water resistance, colloid stability, abrasion resistance, wide working temperature range and the like. Greases are mainly prepared by thickening a base oil with a thickener and adding an additive, and can be classified into metal soap-based greases, organic greases, hydrocarbon-based greases, and inorganic greases according to the type of the thickener used.
In recent years, global grease production has remained substantially stable. The global grease yield in 2017 is 116.7 ten thousand tons, and the Chinese grease yield accounts for 34.97% of the global yield. According to statistics, the yield of Chinese lithium grease reaches 23.34 ten thousand tons, and accounts for 55.35% of all greases. However, with the recent explosion of the new energy automobile market, the demand for secondary batteries has rapidly increased, and lithium hydroxide, which is an important raw material, has a rapidly increasing price, and the cost of lithium grease products has rapidly increased. And the price of the calcium hydroxide is kept stable for many years, which brings opportunity for the development of the calcium-based lubricating grease. The calcium-based lubricating grease is produced in large quantities in some small and medium-sized enterprises due to the reasons of simple production equipment and process, low price of raw materials, low investment and the like, and the production mode is to adopt a normal pressure kettle saponification reaction process for production.
Chinese patent CN109797032A discloses a novel anhydrous calcium-based lubricating grease and a preparation method thereof. The preparation method comprises the following steps: thickening, namely putting fatty acid, calcium hydroxide and 1/3-2/3 base oil into a pressure kettle, adding water, stirring and mixing, wherein the reaction time is 1.5-2.5 h, and the pressure in the pressure kettle is 0.11-0.20 Mpa; dehydrating, heating to 110-120 ℃, keeping the pressure in the pressure kettle at 0.21-0.35 Mpa, and continuously stirring for 30-50 min; fat forming, continuously heating to 125-140 ℃, keeping the temperature for 4-8 min, and stopping heating; and adding the residual base oil into the pressure kettle, continuously stirring for 25-35 min, and saponifying into grease.
High space navigation and the like (development and performance evaluation of anhydrous calcium-based lubricating grease, petroleum commercial technology, 4 th 2017) disclose a preparation method of anhydrous calcium-based lubricating grease, which comprises the following steps of: firstly, 3/4 base oil is added into an autoclave, then 12-hydroxystearic acid, calcium hydroxide and a certain amount of water are added into the autoclave, the mixture is heated to (100 +/-1) DEG C and continuously pressurized to start saponification reaction. Heating and refining: continuously slowly pressurizing and heating to 140 +/-1 ℃, and then keeping a certain pressure and time to ensure that the acid and the alkali completely react and the non-uniform or the agglomerate is dispersed and opened. And (3) decompressing and cooling, adding residual quenching oil to cool to a certain temperature after decompression, and keeping the temperature for 30min to control the stable formation of the soap fiber structure. Adding a reagent and performing post-treatment: when the temperature is reduced to below (80 +/-1) DEG C, the additive is added, and then the mixture is treated by a homogenizer and degassed by a degassing kettle to complete the production.
Zhao Shi Min (control of hydration process of calcium-based lubricating grease, Hunan chemical industry, volume 28, No. 5, and 10 months in 1998) discloses a preparation method and a formation principle of calcium-based lubricating grease, and discusses and analyzes problems of no water addition, grease softening and the like which are easy to occur in the hydration process and a solution thereof. It is emphasized that the grease formed is extremely unstable and tends not to form grease without the presence of water, so water is called a stabilizer, which is an essential component for the formation of calcium-based grease. The hydration process is one of the most important steps in the preparation of calcium-based fats, and must be carefully carried out as required to prepare a product with satisfactory quality.
Several key problems are highlighted in the production process of the above-mentioned document: because of the production raw material Ca (OH) of the calcium-based lubricating grease2The solid particles are slightly soluble in water, and the solubility is reduced along with the temperature rise, so that water needs to be added to participate in saponification reaction; in the saponification reaction, undissolved calcium hydroxide solid can not participate in the reaction, soap particles are easily formed, and the filtration is difficult; on the other hand, the saponification reaction of calcium hydroxide and fatty acid in base oil needs to be carried out at a temperature of more than 100 ℃, acid-base neutralization is an exothermic reaction, and the water generated in the reaction is vaporized to cause a tank expansion phenomenon; meanwhile, in order to prevent soap particles from forming, a large amount of water needs to be added, so that the pressure is difficult to release and soap runs out; the energy consumption is increased in the drainage process, and the working hours are prolonged; furthermore, the phenomenon of soft or non-fat grease of the grease is often caused by poor water or water drainage in the product.
The production process of the above documents has a common step, that is, water must be added in the production process, and the problems of unstable product quality, increased energy consumption and the like caused by the addition of water cannot be solved well all the time.
Also, since lithium hydroxide and calcium hydroxide are both bases, their saponification to fats is similar, and the production of lithium-based greases suffers more or less from the process problems and product quality problems encountered in the production of calcium-based greases.
The nano material is a material with the geometrical size reaching the nano scale and special performance, and the main types of the nano material comprise zero-dimensional nano particles and powder, one-dimensional carbon nano tubes and nano wires, two-dimensional nano films, three-dimensional nano crystal block materials and the like. The particularity of the structure of the nano material (such as large specific surface, small size effect, interface effect, quantum effect and quantum tunneling effect) endows the nano material with various unique properties different from the traditional material, particularly the specific electrical, thermal, magnetic, optical and mechanical properties and the like are most remarkable, and the nano material has important application and development values, and the tribological application of the nano material is also based on the unique properties of the nano material.
At present, the traditional lubricating grease still occupies the leading position of the current lubricating grease market, but the application limitation of the traditional lubricating grease in the aspects of high bearing capacity, environmental friendliness and the like is not negligible. For this reason, research and development of novel lubricating grease are receiving wide attention from domestic and foreign tribologists and lubricating oil research and development personnel, and research of nano-particle materials as lubricating oil additives becomes one of the focus of domestic and foreign attention. However, the preparation of the grease by using a nanomaterial as a thickener which is a main component of the grease to participate in saponification has hardly been reported.
In view of the above problems, it is necessary to provide a soap-based thickener precursor with high reactivity, so as to overcome the technical problems and product quality problems in the above grease production process.
Disclosure of Invention
The invention aims to provide a nano soap-based thickening agent precursor for lubricating grease, which can greatly improve the saponification speed in the production process of the lubricating grease and ensure complete saponification reaction without changing the production process of the lubricating grease and shorten the reaction time when applied to the preparation of the lubricating grease; the problems of soap leakage and tank expansion in the saponification reaction process are solved; meanwhile, as the soap base grease can be directly generated without adding water for reaction in the reaction process, the energy consumption in the production process is reduced, and the performance of the prepared lubricating grease product is greatly improved; the invention also provides a preparation method and application of the precursor of the nano soap-based thickener for lubricating grease.
The precursor of the nano soap-based thickener for the lubricating grease is a dispersion composed of nano metal hydroxide particles, a surfactant and a liquid solvent.
The nano metal hydroxide particles are one or two of nano calcium hydroxide particles or nano lithium hydroxide particles.
The particle size of the nano metal hydroxide particles is less than or equal to 2000nm, preferably 5-500nm, and more preferably 5-100 nm.
The nano metal hydroxide particles are prepared by grinding metal hydroxide particles by a sand mill, a ball mill, a colloid mill or a homogenizer until the particle size of the metal hydroxide reaches the nanometer level or directly purchasing nano metal hydroxide powder in the market.
The surfactant is one or more of fatty acid-based modifier, sulfonic acid-based modifier, silane coupling agent or titanate coupling agent, preferably one or more of fatty acid-based modifier, sulfonic acid-based modifier or titanate coupling agent.
The fatty acid modifier is one or more of palmitic acid, oleic acid, linoleic acid or stearic acid.
The liquid solvent is one or more of mineral base oil, synthetic base oil or vegetable oil base oil, and preferably mineral base oil.
The mass of the nano metal hydroxide particles is 10-60% of the total mass of the precursor of the nano soap-based thickening agent, the mass of the surfactant is 0.1-10% of the total mass of the precursor of the nano soap-based thickening agent, and the mass of the liquid solvent is 30-85% of the total mass of the precursor of the nano soap-based thickening agent.
The mass of the nano metal hydroxide particles is preferably 30-50% of the total mass of the precursor of the nano soap-based thickening agent.
The mass of the surfactant is preferably 0.5-5% of the total mass of the precursor of the nano soap-based thickening agent.
The preparation method of the precursor of the nano soap-based thickener for the lubricating grease is to emulsify nano metal hydroxide particles, a surfactant and a liquid solvent to prepare a dispersion.
The preparation method of the precursor of the nano soap-based thickener for the lubricating grease can also be used for preparing a dispersion by reacting metal oxide particles with water in a liquid solvent under a high shear condition to generate nano metal hydroxide particles, and simultaneously modifying and emulsifying the nano metal hydroxide particles by using a surfactant.
The metal oxide particles are one or both of calcium oxide particles or lithium oxide particles.
The preparation method of the precursor of the nano soap-based thickener for lubricating grease can also be obtained by emulsifying superfine metal oxide particles, water and a surfactant in a liquid solvent and reacting.
The preparation method of the precursor of the nano soap-based thickener for lubricating grease can also be prepared by emulsifying and reacting metal oxide particles, water, a surfactant and a liquid solvent in a closed high-temperature high-pressure environment under a high-shear condition.
The reaction under high shear conditions in the present invention means that high shear force is applied to the reaction system during the reaction process, so that the Reynolds number of the reaction system is in the range of 2000-. The high reynolds number provides a higher degree of mixing in the reaction zone to achieve a degree of micromixing. As the means for providing a high shear environment, a device for applying high-speed stirring and shearing force in the reaction step, such as a commercially available high shear emulsifying machine, a high shear homogenizer, or a high gravity reactor, may be used.
Emulsification may be an action between a liquid and a liquid, and specifically, an action in which one liquid is uniformly dispersed in another liquid that is not mutually soluble in the other liquid as minute droplets by an emulsification apparatus. Emulsification can also be an action between solid particles and a liquid, and particularly, hydrophilic solid particles are dispersed in oil in the form of extremely tiny particles through an emulsification device after being modified by a proper surfactant; or the lipophilic particles are dispersed in water in the form of very tiny particles by an emulsifying device after being modified by a proper surfactant; an emulsion is formed, a process called emulsification. Emulsification is generally achieved by emulsification equipment.
Emulsification equipment: the mechanical equipment for preparing the emulsion is mainly an emulsifying machine which enables oil and water to be in two phases; or oil, hydrophilic particles; or equipment for uniformly mixing water and lipophilic particles to form emulsion, wherein the types of the emulsifying machine are mainly three: an emulsifying mixer, a colloid mill and a homogenizer. The emulsifying device may also be a ball mill or a sand mill, which modifies and effects emulsification while grinding the particles to finer particles.
The emulsification mentioned in the invention refers to that the hydrophilic metal hydroxide and metal oxide particles are dispersed in the base oil in the form of tiny particles after being modified by a proper surfactant in an emulsification device.
The application of the nano soap-based thickener precursor for the lubricating grease is to prepare the lubricating grease by adopting fatty acid, the nano soap-based thickener precursor, base oil and an additive.
The invention adopts the nanometer soap-based thickener precursor to synthesize the lubricating grease, and the raw materials specifically comprise: in terms of mass percentage, the weight percentage of the alloy is,
the fatty acid is one or more of palmitic acid, oleic acid, sebacic acid, linoleic acid or stearic acid.
The base oil is one or more of mineral base oil, synthetic base oil or vegetable oil base oil.
The additive is the additive type commonly used in the field of lubricating grease, and comprises one or more of a rust inhibitor, an antioxidant or an extreme pressure antiwear agent.
The antirust agent, the antioxidant and the extreme pressure antiwear agent used in the invention are the antirust agent, the antioxidant and the extreme pressure antiwear agent commonly used in the field of lubricating grease.
The application of the nano soap-based thickener precursor refers to that the nano soap-based thickener precursor participates in saponification reaction in the synthesis process of the lubricating grease and thickens the base oil, so that the high-performance nano soap-based lubricating grease is prepared.
The application of the nano soap-based thickening agent precursor for the lubricating grease is specifically that base oil, fatty acid and the nano soap-based thickening agent precursor are added into a reaction kettle, mixed and heated to 80-110 ℃ to start saponification, the temperature is slowly and continuously raised to 115-180 ℃ for refining, so that acid and alkali are completely reacted, cold base oil is added to cool and lower the temperature to be below 80 ℃, the pH value of the system is adjusted, an additive is added, and a homogenizer is used for homogenization treatment, so that the production is completed.
The precursor of the nano soap-based thickener provided by the invention can be used for preparing calcium-based lubricating grease, lithium-based lubricating grease, composite calcium-based lubricating grease, composite lithium-based lubricating grease, composite calcium sulfonate-based lubricating grease and mixed soap-based lubricating grease containing metal calcium and lithium.
The invention has the following beneficial effects:
the precursor of the nano soap-based thickener participates in saponification in the preparation process of the lubricating grease, so that a good reaction effect is obtained, and the existing process for preparing the lubricating grease is not changed at all, so that the equipment transformation and investment required by the lubricating grease production factory due to product upgrading are avoided, and the product performance can be improved.
Compared with the conventional method that calcium hydroxide and/or lithium hydroxide powder is used as a reactant of the saponification reaction, the method can complete the saponification reaction without adding water, and the reaction activity is greatly improved because the calcium hydroxide and/or the lithium hydroxide participate in the reaction in a nano-scale form during the saponification reaction, so that the saponification reaction time is shortened, and the tank expansion phenomenon caused by water vaporization of the water participating in the reaction is avoided; and the generation of soap particles in the reaction process of calcium hydroxide and/or lithium hydroxide and the large energy consumption brought by the later drainage process are avoided. In addition to the benefits brought by the process aspect, the performance of the lubricating grease produced by the precursor of the nano calcium-containing soap-based thickening agent is far better than that of the commercial calcium-containing lubricating grease, and the use temperature is greatly improved. Through market application verification, the nano calcium-containing lubricating grease prepared by the nano soap-based thickener precursor can partially or completely replace lithium-based lubricating grease to become new universal lubricating grease, has higher cost performance, and has wider market prospect in the future.
Drawings
Fig. 1 is an SEM electron micrograph of calcium hydroxide particles in the nano soap-based thickener precursor prepared in example 1.
Fig. 2 is an SEM electron micrograph of calcium hydroxide particles in the nano soap-based thickener precursor prepared in example 5.
Fig. 3 is an SEM electron micrograph of calcium hydroxide particles in the nano soap-based thickener precursor prepared in example 6.
Fig. 4 is an SEM electron micrograph of calcium hydroxide particles in the nano soap-based thickener precursor prepared in example 7.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
680 g of base oil (SN500), 300 g of commercial high-purity calcium hydroxide powder, 9 g of oleic acid and 11 g of 12-hydroxystearic acid are prepared.
After 600g of base oil and calcium hydroxide powder are mixed evenly by a high-speed shearing emulsifying machine, oleic acid is added to continue stirring at high speed for 0.5hr, and the temperature of the system is slightly raised. Stopping high-speed stirring, transferring the oil phase suspension to planetary ball mill, coarse grinding for 2hr, fine grinding for 2hr, and selecting 0.2mm zirconium beads during fine grinding with loading coefficient of 60%. Taking out the modified calcium hydroxide dispersoid, transferring the dispersoid into a kettle provided with a high-speed shearing emulsifying machine, adding the mixed solution of 80g of base oil and 12-hydroxystearic acid which are preheated to 85 ℃ into the kettle under the condition that the emulsifying machine operates at a high speed, and continuing to emulsify for 0.5hr at a high speed to obtain the precursor of the calcium-containing soap-based thickening agent. The precursor of the thickening agent has good stability, and does not settle after standing for 2 months at room temperature. A few drops of the thickening agent precursor are taken to be ultrasonically cleaned in cyclohexane, base oil on particles is washed away, then a few drops of a cyclohexane system which is washed away from the base oil and contains calcium hydroxide particles are taken to be dropped on a copper net for SEM electron microscope analysis and test, the result is shown in figure 1, the content of the calcium hydroxide in the thickening agent precursor is 30 wt%, the particle size is about 500nm, and the particles are irregular flaky particles.
Example 2
680 g of base oil (SN500), 300 g of commercially available high-purity calcium hydroxide powder, 11 g of 12-hydroxystearic acid, 9 g of benzenesulfonic acid and 700g of cyclohexane are prepared.
300 g of calcium hydroxide powder, 700g of cyclohexane and 9 g of benzenesulfonic acid are subjected to ball milling for 2.0 hours in a planetary ball mill (0.2 mm zirconium beads are selected in the ball mill, the filling coefficient is 60%), then 600g of base oil is added into the suspension system after ball milling, and all cyclohexane is evaporated out through rotary evaporation. Then the mixed system without cyclohexane is transferred to a high speed shearing emulsifying machine for high speed stirring, 91g of the mixture of the base oil which is heated to 80 ℃ and fully mixed and the 12-hydroxystearic acid is added into the system of the calcium hydroxide and the base oil while the high speed stirring is carried out, and the high speed stirring is continued for 1.0 hour. And taking out the modified calcium hydroxide dispersoid to obtain the precursor of the calcium-containing soap-based thickening agent. The precursor of the thickening agent has good stability, and does not settle after standing for 3 months at room temperature. The thickening agent precursor contains 30 wt% of calcium hydroxide, the particle size is about 200nm, and the particles are irregular flaky particles.
Example 3
580g of base oil (SN150), 400 g of commercially available high-purity lithium hydroxide monohydrate, 20 g of benzenesulfonic acid and 700g of cyclohexane were prepared.
400 g of lithium hydroxide monohydrate, 700g of cyclohexane and 20 g of benzenesulfonic acid are subjected to ball milling for 3.0 hours in a planetary ball mill (0.2 mm zirconium beads are selected in the ball mill, the filling factor is 60%), 580g of base oil is added into the suspension system after ball milling, and rotary evaporation is carried out to remove all cyclohexane and part of crystal water of lithium hydroxide. And taking out the modified lithium hydroxide dispersoid to obtain the precursor of the lithium-containing soap-based thickening agent. The precursor of the thickening agent has good stability, and does not settle after standing for 3 months at room temperature. The lithium hydroxide content in the thickener precursor is 35 wt%, the particle size is about 300nm, and the particles are irregular flaky particles.
Example 4
Soap-based thickener precursors were prepared using the method and procedure described in example 1. The differences are as follows:
the method is characterized in that 300 g of the commercially available high-purity calcium hydroxide powder is changed into 250 g of the commercially available high-purity calcium hydroxide powder and 50 g of the commercially available high-purity lithium hydroxide monohydrate. The particle size of the mixed calcium-lithium hydroxide in the thickener precursor prepared in the embodiment is about 400nm, and the particles are irregular flaky particles. The calcium hydroxide content in the thickener precursor is 30 wt%. The thickener precursor is kept standing for 2 months at room temperature without any sedimentation.
Example 5
680 g of base oil (SN500), 227 g of high-purity calcium oxide powder with 3000 meshes sold in the market, 73 g of deionized water, 9 g of oleic acid and 11 g of 12-hydroxystearic acid are prepared. Mixing 9 g of oleic acid, 11 g of 12-hydroxystearic acid and 180 g of base oil, heating to 80 ℃ for standby, adding 500 g of base oil and 227 g of calcium oxide powder into a reactor provided with a high-speed shearing emulsifying machine for mixing and emulsifying, quickly adding 200 g of mixed oleic acid, stearic acid and base oil mixture (180 g of base oil, 9 g of oleic acid and 11 g of stearic acid) and 73 g of water into a mixed system of the base oil and the calcium oxide, quickly raising the temperature of the system after the temperature slowly rises for a short time, and then, continuously shearing and emulsifying at high speed for 2 hours; stopping the reaction, and obtaining the final reaction product, namely the precursor of the calcium-containing soap-based thickening agent. SEM electron microscopy analysis of the particles in the calcium-containing soap-based thickener precursor was performed in the same manner as in example 1, and the results are shown in fig. 2, in which the calcium hydroxide particles in the thickener precursor were flocculent particles smaller than 1 μm. The calcium hydroxide content in the thickener precursor is 30 wt%. The thickener precursor is kept standing for 2 months at room temperature without any sedimentation.
Example 6
Soap-based thickener precursors were prepared using the method and procedure as described in example 5. The differences are as follows:
the reactor with the high-speed shearing emulsifying machine is a closed reactor capable of bearing high temperature and high pressure. The oleic acid in the modifier is changed into 9 g of benzenesulfonic acid. SEM analysis and test results of particles in the calcium-containing soap-based thickener precursor are shown in figure 3, and calcium hydroxide particles in the thickener precursor prepared in the example are 30-40nm in size and are spherical-like particles. The calcium hydroxide content in the thickener precursor is 30 wt%. The thickener precursor is kept standing for 3 months at room temperature without any sedimentation.
Example 7
Soap-based thickener precursors were prepared using the method and procedure as described in example 5. The differences are as follows:
the reactor with the high-speed shearing emulsifying machine is a closed reactor capable of bearing high temperature and high pressure. The reaction raw materials are as follows: 477.5 g of base oil (SN500), 375 g of calcium oxide powder, 122.5 g of deionized water and 25 g of benzene sulfonic acid. The thickener precursor prepared in this example had a calcium hydroxide content of about 49.5 wt%, and SEM electron microscopy analysis tests performed on the particles in the calcium-containing soap-based thickener precursor showed that the particles had a particle size of 30-50nm, and were flaky irregular particles, as shown in fig. 4. The thickener precursor is kept standing for 2 months at room temperature without any sedimentation.
Example 8
A glass three-neck flask with a stirrer is used as a reaction kettle. Adding 240 g of SN500 base oil and 70 g of 12-hydroxystearic acid into a reaction kettle, heating to 80-90 ℃ while stirring, adding 36g of the precursor of the calcium-containing nano soap-based thickening agent prepared according to the embodiment 1 when the 12-hydroxystearic acid is completely melted in the base oil, continuing stirring and heating to about 110 ℃ to start saponification for 30 minutes. Adding 100 g of SN500 base oil, continuously slowly heating to about 140 ℃ for refining, keeping the temperature at about 140 ℃ for 3-5 minutes to ensure that acid and alkali completely react, adding 160 g of cold SN500 base oil, cooling to below 80 ℃, adjusting the pH value of the system, adding 18g of additives (wherein 3g of benzotriazole serving as an antirust agent, 3g of octyl butyl diphenylamine serving as an antioxidant and 12g of dibutyl phosphite serving as an extreme pressure antiwear agent), further cooling, pressing oil for 3 times by using a three-roller machine, and finishing the production. The performance test data of the prepared nano soap-based lubricating grease are shown in table 1.
Examples 9 to 12
A nano soap-based grease was prepared using the material ratios, methods and procedures as described in example 8. The differences are as follows:
the nano soap-based thickener precursors of examples 9-12 were prepared using the methods and steps of examples 4, 5, 6, and 7, respectively. In addition, in example 11, the addition amount of the precursor of the calcium-containing nano soap-based thickener was changed to 36g and 22 g. The performance test data of the prepared nano soap-based lubricating grease are shown in table 1.
Comparative example 1
A glass three-neck flask with a stirrer is used as a reaction kettle. 265 g of SN500 base oil and 70 g of 12-hydroxystearic acid are added, the temperature is raised to 80-90 ℃ while stirring, 10.7 g of calcium hydroxide is added when the 12-hydroxystearic acid is completely melted in the base oil, the stirring is continued and the temperature is raised to about 110 ℃, the stirring is continued for 30 minutes under the condition of keeping the temperature unchanged, and the saponification reaction does not occur. In order to ensure the saponification reaction to be complete, water is added dropwise according to the proportion of 4 times of the water and the calcium hydroxide in example 1 in Chinese patent CN109797032A, and the water addition process lasts for 30 minutes. And (2) after stopping adding water for 10 minutes, adding 100 g of base oil, continuously slowly heating to about 140 ℃ for refining, keeping the temperature at about 140 ℃ for 20 minutes to ensure that acid and alkali completely react, adding 160 g of cold base oil, cooling to below 80 ℃, adjusting the pH value of the system, adding 18g of additives (wherein 3g of benzotriazole serving as an antirust agent, 3g of octyl butyl diphenylamine serving as an antioxidant and 12g of dibutyl phosphite serving as an extreme pressure antiwear agent), further cooling, pressing oil for 3 times by using a three-roller machine, and finishing the production. The grease prepared by the comparative example is soft and dull. No further grease performance tests were performed.
Comparative example 2
The anhydrous calcium-based grease was prepared according to the method of example 1 in chinese patent CN109797032 a. The performance test data of the prepared anhydrous calcium-based lubricating grease are shown in table 1.
TABLE 1 comparison of product Performance test data for examples 7-11 and comparative example 2
The greases prepared in examples 8-12 were evaluated for performance and found: the dropping point and other performances of the lubricating grease prepared in the examples 8-12 are obviously higher than the requirements of GB/T491-. Compared with the standard GB/T7324-. The service life test results of the greases showed that the greases prepared in examples 8-12 can meet the service requirements at 120 ℃. The rheological property shows that compared with the common lithium-based lubricating grease, the lithium-based lubricating grease has stronger deformation control force, better lubricating property and more stable structure retention force. Compared with the anhydrous calcium-based grease in the comparative example 2, the performance of the anhydrous calcium-based grease is partially equivalent, and the performance of the anhydrous calcium-based grease is partially superior to that of the anhydrous calcium-based grease in the comparative example 2.
At present, the alkali amount used for producing the universal lithium-based lubricating grease and the calcium-based lubricating grease produced by the invention is 1-2%, and the price of lithium hydroxide is 70-80 times higher than that of calcium hydroxide, so that the price difference between the raw materials of the finished lubricating grease is 1500-3000 yuan/t, therefore, under the condition of equivalent product performance, the nano soap-based lubricating grease produced by using the precursor of the soap-based thickening agent produced by the invention has higher cost performance than that of the universal lithium-based lubricating grease, the production period is shortened, and the production energy consumption is reduced. The invention can save energy and improve the production efficiency in the process, and the product performance and the price are superior to the prior similar products.
Claims (10)
1. A precursor of a nano soap-based thickener for lubricating grease is characterized by being a dispersion composed of nano metal hydroxide particles, a surfactant and a liquid solvent.
2. The nano soap-based thickener precursor for grease according to claim 1, wherein the nano metal hydroxide particles are one or both of nano calcium hydroxide particles or nano lithium hydroxide particles.
3. The nano soap-based thickener precursor for grease according to claim 1, wherein the nano metal hydroxide particles have a particle size of 2000nm or less.
4. The precursor of the nano soap-based thickener for the grease lubricant according to claim 1, wherein the surfactant is one or more of a fatty acid-based modifier, a sulfonic acid-based modifier, a silane coupling agent or a titanate coupling agent.
5. The nano soap-based thickener precursor for lubricating grease according to claim 1, wherein the liquid solvent is one or more of mineral base oil, synthetic base oil or vegetable oil base oil.
6. The nano soap-based thickener precursor for lubricating grease as claimed in claim 1, wherein the mass of the nano metal hydroxide particles is 10-60% of the total mass of the nano soap-based thickener precursor, the mass of the surfactant is 0.1-10% of the total mass of the nano soap-based thickener precursor, and the mass of the liquid solvent is 30-85% of the total mass of the nano soap-based thickener precursor.
7. A method for preparing a nano soap-based thickener precursor for lubricating grease as claimed in any one of claims 1 to 6, wherein nano metal hydroxide particles, a surfactant and a liquid solvent are emulsified to form a dispersion.
8. A method for preparing a precursor of a nano soap-based thickener for greases according to any of claims 1 to 6, characterized in that under high shear conditions, metal oxide particles and water are reacted in a liquid solvent to generate nano metal hydroxide particles, and simultaneously, the nano metal hydroxide particles are modified by a surfactant and emulsified to form a dispersion.
9. Use of a nano soap-based thickener precursor according to any of claims 1 to 6 for a grease, characterized in that a grease is prepared using a fatty acid, a nano soap-based thickener precursor, a base oil and an additive.
10. Use of a nano-soap based thickener precursor for greases according to claim 9, characterized in that, in mass percent,
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| CN113736542A (en) * | 2021-08-31 | 2021-12-03 | 江苏澳润新材料有限公司 | Method for improving fineness of high-base-number calcium sulfonate-based lubricating grease |
| CN113789211A (en) * | 2021-09-28 | 2021-12-14 | 中国石油化工股份有限公司 | Lubricating grease composition for hoisting machinery and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060100292A1 (en) * | 2002-10-01 | 2006-05-11 | Nolan Stephen J | Metal hydroxide desiccated emulsions used to prepare grease |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060100292A1 (en) * | 2002-10-01 | 2006-05-11 | Nolan Stephen J | Metal hydroxide desiccated emulsions used to prepare grease |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736542A (en) * | 2021-08-31 | 2021-12-03 | 江苏澳润新材料有限公司 | Method for improving fineness of high-base-number calcium sulfonate-based lubricating grease |
| CN113736542B (en) * | 2021-08-31 | 2022-09-09 | 江苏澳润新材料有限公司 | Method for improving fineness of high-base-number calcium sulfonate-based lubricating grease |
| CN113789211A (en) * | 2021-09-28 | 2021-12-14 | 中国石油化工股份有限公司 | Lubricating grease composition for hoisting machinery and preparation method thereof |
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