Process for preparing additive for lubricating oil of internal combustion engine and lubricating oil containing said additive
阅读说明：本技术 内燃机润滑油添加剂的制备方法及含有该添加剂的润滑油 (Process for preparing additive for lubricating oil of internal combustion engine and lubricating oil containing said additive ) 是由 丁永萍 刘旭东 韩伟 张旭 郭玉玮 于 2020-12-14 设计创作，主要内容包括：本发明属于内燃机润滑油领域,具体涉及一种内燃机润滑油添加剂的制备方法及含有该添加剂的润滑油。蓖麻油修饰碳酸稀土化合物润滑油添加剂的制备方法如下：a、在蒸馏水中加入10～30g的稀土卤化物,搅拌至澄清透明液体；b、在剧烈搅拌下逐滴滴加含有20～60g蓖麻油酸和20～40g碳酸钠的乙醇溶液,溶液立即呈白色浑浊状,恒温反应1～3h,反应完全；c、静置沉化,过滤,沉淀用蒸馏水洗剂数次,再用无水乙醇洗涤数次,干燥得样品,研细备用。本发明合成了能够在基础油中具有较好溶解分散性的蓖麻油修饰碳酸稀土化合物润滑油添加剂,具有较好的氧化稳定性,属于绿色环保型极压抗磨添加剂。(The invention belongs to the field of lubricating oil for internal combustion engines, and particularly relates to a preparation method of an additive for lubricating oil for internal combustion engines and lubricating oil containing the additive. The preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive comprises the following steps: a. adding 10-30 g of rare earth halide into distilled water, and stirring to obtain clear and transparent liquid; b. dropwise adding an ethanol solution containing 20-60 g of ricinoleic acid and 20-40 g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 1-3 h at constant temperature, and the reaction is complete; c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for several times, drying to obtain sample, and grinding. The castor oil modified rare earth carbonate compound lubricating oil additive which can be well dissolved and dispersed in base oil is synthesized, has good oxidation stability, and belongs to a green environment-friendly extreme pressure anti-wear additive.)
1. The preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive is characterized by comprising the following steps of:
a. adding 10-30 g of rare earth halide into distilled water, and stirring to obtain clear and transparent liquid;
b. dropwise adding an ethanol solution containing 20-60 g of ricinoleic acid and 20-40 g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 1-3 h at constant temperature, and the reaction is complete;
c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for several times, drying to obtain sample, and grinding.
2. The method of claim 1, wherein the rare earth halide is neodymium chloride or lanthanum chloride.
3. An energy-saving and environment-friendly lubricating oil for internal combustion engines, which is characterized by comprising the castor oil modified rare earth carbonate compound lubricating oil additive prepared by the preparation method of claim 1 or 2, wherein the energy-saving and environment-friendly lubricating oil for internal combustion engines specifically comprises the following components in parts by mass:
4. the energy-saving and environment-friendly lubricating oil for internal combustion engines as claimed in claim 3, wherein the antiwear agent is zinc dialkyl dithiophosphate.
5. The energy-saving and environment-friendly lubricating oil for internal combustion engines as claimed in claim 3, wherein the high-temperature antioxidant is alkylated diphenylamine.
6. The energy-saving and environment-friendly lubricating oil for internal combustion engines as claimed in claim 3, wherein the viscosity index improver is an ethylene-propylene copolymer.
7. The energy-saving and environment-friendly lubricating oil for internal combustion engines as claimed in claim 3, wherein the detergent is any two of synthetic calcium sulfonate, alkyl salicylic acid or sulfurized calcium alkyl phenate.
8. The energy-saving and environment-friendly lubricating oil for internal combustion engines as claimed in claim 3, wherein the dispersant is succinimide protected engine oil.
9. The energy-saving and environment-friendly lubricating oil for internal combustion engines as claimed in claim 3, wherein the pour point depressant is one of polymethyl acrylate, polyalphaolefin or T803B.
10. The energy-saving and environment-friendly lubricating oil for internal combustion engines as claimed in claim 3, wherein the defoaming agent is one of silicone emulsion, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether or polyoxyethylene polyoxypropylene amine ether.
Technical Field
The invention belongs to the field of lubricating oil for internal combustion engines, and particularly relates to a preparation method of an additive for lubricating oil for internal combustion engines and lubricating oil containing the additive.
Background
It is known that automobile exhaust emissions contain many substances, such as CO, which are harmful to the ecological environment and human health2、NO2、SO3NO, floating particulate matter, and the like. At present, the standard requirements for the automobile pollution emission are increasingly strict in China.
The development of engine hardware technology is directly driven by the discharge method size which is hard to handle in order to meet the requirements of the bad protection. The new technology adopted by the engine at present can better improve the pollution emission of the automobile to a certain extent, but also brings some problems. For example, a particle trap is adopted to control particle discharge, a reduction device is adopted to control incomplete combustion product discharge, a NOx removal device or an exhaust gas recycling system is adopted to reduce NOx discharge, and the like. These hardware developments directly impose new requirements on the lubricating oil, such as the requirement of reducing ash content in the particulate trap to avoid blockage, which limits the use of some metal elements such as Zn, etc. which are easy to generate ash content; the redox catalyst is required to reduce the sulfur content, because sulfur easily causes failure in the redox catalyst, and because the engine has the phenomenon of lubricating oil burning, the sulfur content of the Jian lubricating oil is higher, the carbon deposition during burning is more, and the sulfur-containing substances are more discharged; straightening of NOx removal devices, three-way catalysis, selective reduction catalysis and the like also requires reduction of sulfur and phosphorus content because phosphorus affects a three-way catalytic converter, poisons a catalyst, reduces catalytic effect, and analyzes combustion products adhered to a valve to find that the main component is Ca3(PO40)2It is not only engine oilThe gasoline engine oil for the vehicle has the advantages that the acetylene products are combusted, and abnormal combustion such as ignition and the like is caused by the combustion products, so that the function of the engine oil for the vehicle is to protect engine, prolong engine service life and extend engine to protect engine, save fuel and reduce exhaust pollutant emission, namely, the step of accelerating the upgrading and upgrading of engine oil and improving quality is needed. China is based on the situation of the country, and the gasoline lubricating oil equivalently adopts the American API standard. It is known from the upgrading and updating of the specifications of the American gasoline engine oil that in order to greatly reduce the emission of exhaust pollutants, the content of phosphorus elements which are easy to poison a catalyst in an automobile exhaust treatment device is reduced to be not more than 0.08% at most in a clear specification of the specifications of the gasoline engine oil GF-4. This has greatly expanded the use of zinc dialkyldithiophosphates (ZDDP) and conventional extreme pressure anti-grinding in motor oils, which are important components with an excellent combination of properties.
Because the traditional extreme pressure anti-wear cutting faces various environmental problems while spool is being held, and has the defects of poor multifunctionality, poor anti-emulsification, anti-cleaning and repairing functions and the like, more eyes are projected to rare earth and compounds thereof in recent years. Rare earth is a general name of 17 elements in scandium, iridium and lanthanide series, is used as a novel inactive extreme pressure anti-wear additive, and is more and more valued by the properties that the rare earth has a unique 4f electronic structure, strong chemical activity, low electronegativity, large atom half diameter, small atom radius after ionization, low melting point on a friction surface, a plurality of rare earth compounds have a hexagonal crystal structure system layered structure and the like. Because the extreme pressure antiwear additive does not react with metal chemically, the extreme pressure antiwear additive does not react with the traditional extreme pressure antiwear additive (containing P, S, Cl and other elements, the extreme pressure antiwear additive has corrosivity and selectivity for friction side materials, does not influence the environment, meets the requirement of environmental protection on a novel lubricating oil additive, and draws wide attention of researchers in the field of lubricating friction.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of an additive for lubricating oil of an internal combustion engine and lubricating oil containing the additive.
In order to achieve the above object, the present invention is realized by:
the preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive comprises the following steps:
a. adding 10-30 g of rare earth halide into distilled water, and stirring to obtain clear and transparent liquid;
b. dropwise adding an ethanol solution containing 20-60 g of ricinoleic acid and 20-40 g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 1-3 h at constant temperature, and the reaction is complete;
c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for several times, drying to obtain sample, and grinding.
Preferably, the rare earth halide is neodymium chloride or lanthanum chloride.
The energy-saving and environment-friendly lubricating oil for the internal combustion engine comprises a castor oil modified rare earth carbonate compound lubricating oil additive prepared by the preparation method, and specifically comprises the following components in parts by mass:
preferably, the antiwear agent is zinc dialkyldithiophosphate.
Preferably, the high-temperature antioxidant is alkylated diphenylamine.
Preferably, the viscosity index improver is an ethylene-propylene copolymer.
Preferably, the detergent is any two of synthetic calcium sulfonate, alkyl salicylic acid or sulfurized calcium alkyl phenate. .
Preferably, the dispersant is a succinimide engine oil.
Preferably, the pour point depressant is one of polymethyl acrylate, polyalphaolefin or T803B. .
Preferably, the defoaming agent is one of emulsified silicone oil, a higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether or polyoxyethylene polyoxypropylene amine ether:
compared with the prior art, the invention has the advantages and positive effects that:
(1) the invention utilizes the raw materials of rare earth chloride, castor oil, sodium carbonate and the like to synthesize the lubricating oil additive which can be well dissolved and dispersed in base oil, and the lubricating oil additive is a castor oil modified rare earth carbonate compound lubricating oil additive.
(2) The lubricating oil additive has better oxidation stability, belongs to a green environment-friendly extreme pressure antiwear additive, and has better extreme antiwear property.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described with reference to the following examples. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
The lubricating oil additive provided by the embodiment of the invention is a rare earth element-based lubricating oil extreme pressure antiwear agent, namely a castor oil modified rare earth carbonate compound lubricating oil additive to be prepared, so as to overcome the defects of the traditional action process of the extreme pressure antiwear agent containing elements such as chlorine, sulfur, phosphorus and the like, and particularly reduce the emission of tail gas of an internal combustion engine and contain CO2、NO2、SO3、SO2And pollutants such as floating particulate matters, thereby avoiding the pollution of the exhaust emission of the internal combustion engine to the urban air.
The internal combustion engine lubricating oil obtained in the embodiment of the invention is prepared by using zinc dialkyl dithiophosphate as an antiwear agent, alkylated diphenylamine as a high-temperature antioxidant, an ethylene-propylene copolymer as a viscosity index improver, synthetic calcium sulfonate, alkyl salicylic acid or sulfurized calcium alkyl phenate as a detergent, succinimide as a dispersant, polymethyl acrylate, poly-alpha-olefin or T803B pour point depressant as one of the following concrete embodiments, wherein the concrete embodiments are implemented according to the above requirements, so that the lubricating oil additive, the high-temperature antioxidant, the viscosity index improver, the detergent, the dispersant, the pour point depressant and the defoamer are uniformly called in the embodiments without detailed description.
The following embodiments mainly comprise two parts, wherein one part is the preparation of the castor oil modified rare earth carbonate compound lubricating oil additive, and the other part is the energy-saving and environment-friendly lubricating oil for the internal combustion engine prepared by using the castor oil modified rare earth carbonate compound lubricating oil additive.
Example 1
The embodiment provides a preparation method of a castor oil modified rare earth carbonate compound lubricating oil additive and internal combustion engine lubricating oil containing the lubricating oil additive.
The preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive specifically comprises the following steps:
a. adding 15.36g of neodymium chloride into distilled water, and stirring to obtain a clear and transparent liquid;
b. dropwise adding an ethanol solution containing 30g of ricinoleic acid and 30g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 1 hour at constant temperature until the reaction is complete;
c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for 10 times, drying to obtain sample, and grinding to obtain lubricant additive.
The internal combustion engine lubricating oil prepared by using the lubricating oil additive specifically comprises the following components in parts by mass: 95 parts of base oil, 0.5 part of antiwear agent, 0.5 part of lubricating oil additive, 0.3 part of thiophosphoric ammonium salt, 1 part of sulfurized isobutylene, 0.5 part of detergent, 0.4 part of dispersant, 0.2 part of pour point depressant and 0.0001 part of defoaming agent; the internal combustion engine lubricating oil prepared in the above parts is referred to as internal combustion engine lubricating oil A.
Example 2
The embodiment provides a preparation method of a castor oil modified rare earth carbonate compound lubricating oil additive and internal combustion engine lubricating oil containing the lubricating oil additive.
The preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive specifically comprises the following steps:
a. adding 19.2g of neodymium chloride into distilled water, and stirring to obtain a clear and transparent liquid;
b. dropwise adding an ethanol solution containing 40g of ricinoleic acid and 35g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 2 hours at constant temperature to complete the reaction;
c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for 15 times, drying to obtain sample, and grinding to obtain lubricant additive.
The internal combustion engine lubricating oil prepared by using the lubricating oil additive specifically comprises the following components in parts by mass: 95 parts of base oil, 0.5 part of antiwear agent, 1 part of lubricating oil additive, 0.3 part of thiophosphoric acid ammonium salt, 1 part of sulfurized isobutylene, 0.5 part of detergent, 0.4 part of dispersant, 0.2 part of pour point depressant and 0.0001 part of defoaming agent; the internal combustion engine lubricating oil prepared in the above portion is referred to as internal combustion engine lubricating oil B.
Example 3
The embodiment provides a preparation method of a castor oil modified rare earth carbonate compound lubricating oil additive and internal combustion engine lubricating oil containing the lubricating oil additive.
The preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive specifically comprises the following steps:
a. adding 20.48g of neodymium chloride into distilled water, and stirring to obtain a clear and transparent liquid;
b. dropwise adding an ethanol solution containing 50g of ricinoleic acid and 40g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 2.5 hours at constant temperature to complete the reaction;
c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for 20 times, drying to obtain sample, and grinding to obtain lubricant additive.
The internal combustion engine lubricating oil prepared by using the lubricating oil additive specifically comprises the following components in parts by mass: 95 parts of base oil, 0.5 part of antiwear agent, 1.2 parts of lubricating oil additive, 0.3 part of thiophosphoric ammonium salt, 1 part of sulfurized isobutylene, 0.5 part of detergent, 0.4 part of dispersant, 0.2 part of pour point depressant and 0.0001 part of defoaming agent; the internal combustion engine lubricating oil prepared in the above portions is referred to as internal combustion engine lubricating oil C.
Example 4
The embodiment provides a preparation method of a castor oil modified rare earth carbonate compound lubricating oil additive and internal combustion engine lubricating oil containing the lubricating oil additive.
The preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive specifically comprises the following steps:
a. adding 25.6g of neodymium chloride into distilled water, and stirring to obtain a clear and transparent liquid;
b. dropwise adding an ethanol solution containing 55g of ricinoleic acid and 40g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 3 hours at constant temperature until the reaction is complete;
c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for 20 times, drying to obtain sample, and grinding to obtain lubricant additive.
The internal combustion engine lubricating oil prepared by using the lubricating oil additive specifically comprises the following components in parts by mass: 95 parts of base oil, 0.5 part of antiwear agent, 1.5 parts of lubricating oil additive, 0.3 part of thiophosphoric ammonium salt, 1 part of sulfurized isobutylene, 0.5 part of detergent, 0.4 part of dispersant, 0.2 part of pour point depressant and 0.0001 part of defoaming agent; the internal combustion engine lubricating oil prepared in the above portion is referred to as internal combustion engine lubricating oil D.
Example 5
The embodiment provides a preparation method of a castor oil modified rare earth carbonate compound lubricating oil additive and internal combustion engine lubricating oil containing the lubricating oil additive.
The preparation method of the castor oil modified rare earth carbonate compound lubricating oil additive specifically comprises the following steps:
a. adding 18.38g of lanthanum chloride into distilled water, and stirring to obtain a clear and transparent liquid;
b. dropwise adding an ethanol solution containing 40g of ricinoleic acid and 30g of sodium carbonate under vigorous stirring, wherein the solution is immediately white and turbid, and reacting for 3 hours at constant temperature until the reaction is complete;
c. standing for precipitation, filtering, washing the precipitate with distilled water for several times, washing with anhydrous ethanol for 20 times, drying to obtain sample, and grinding to obtain lubricant additive.
The internal combustion engine lubricating oil prepared by using the lubricating oil additive specifically comprises the following components in parts by mass: 95 parts of base oil, 0.5 part of antiwear agent, 1.2 parts of lubricating oil additive, 0.3 part of thiophosphoric ammonium salt, 1 part of sulfurized isobutylene, 0.5 part of detergent, 0.4 part of dispersant, 0.2 part of pour point depressant and 0.0001 part of defoaming agent; the internal combustion engine lubricating oil prepared in the above portion is referred to as internal combustion engine lubricating oil E.
The engine lubricating oils of examples 1-4 above were added to an internal combustion engine and the sintering load and maximum seizure-free load were measured for the internal combustion engine as specified in table 1 below:
TABLE 1 sintering load and maximum non-seizing load test results
As can be seen from the above table, the lubricating oil for internal combustion engines prepared by using the lubricating oil additive of the present invention, when added to internal combustion engines, has much higher sintering load and maximum seizure-free load than the conventional lubricating oil for internal combustion engines.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.