CN116144418A

CN116144418A - Gasoline and engine oil composition and preparation method thereof

Info

Publication number: CN116144418A
Application number: CN202310168953.8A
Authority: CN
Inventors: 关建平; 杨杰; 王扬
Original assignee: Liaoning Baite Lubrication Technology Co ltd
Current assignee: Liaoning Baite Lubrication Technology Co ltd
Priority date: 2023-02-27
Filing date: 2023-02-27
Publication date: 2023-05-23

Abstract

The invention relates to the field of production of gasoline and engine oil, in particular to a gasoline and engine oil composition and a preparation method thereof. The automobile oil composition comprises the following components in parts by weight: 20-50 parts of a first dispersing agent, 15-30 parts of an aromatic amine type soot ashless dispersing agent, 3-10 parts of calcium sulfonate, 3-10 parts of magnesium sulfonate, 2-10 parts of zinc dialkyl dithiophosphate, 2-15 parts of an amine antioxidant, 0.2-2 parts of molybdenum salt, 0.03-0.2 part of a silicon type anti-foaming agent and 2-5 parts of base oil. The gasoline and engine oil composition has the characteristics of long service life and low-speed pre-ignition frequency.

Description

Gasoline and engine oil composition and preparation method thereof

Technical Field

The invention relates to the field of production of gasoline and engine oil, in particular to a gasoline and engine oil composition and a preparation method thereof.

Background

Along with the increase of environmental protection, the control on recycling the used engine oil is more and more strict, so that the generation of the used engine oil is reduced, and the oil change period of the engine oil is required to be prolonged. The most commonly used antioxidants at present are phenolic, aminic, phosphorus-containing, sulfur-containing and other antioxidants, of which hindered phenols and aminic are the most effective two antioxidants. However, due to the relatively low molecular weight of conventional antioxidants, the environment is polluted by volatilizing, migrating and being extracted by solvents into the atmosphere, soil and water under high temperature environment or with the lapse of use time, thus potentially affecting human health. Meanwhile, after the loss of the antioxidant, the lubricating oil is easy to thicken, so that the service life of the lubricating oil is greatly reduced.

Compared with the air passage injection and natural air suction gasoline engine, the supercharged direct injection gasoline engine has the advantages of low energy consumption, strong dynamic property, flexible control and the like, and is increasingly applied to the market at present. However, with the continuous increase of the supercharging ratio, the power density and the in-cylinder thermal load of the engine are obviously increased, and an abnormal combustion phenomenon occurs in the supercharged direct injection gasoline engine, wherein the abnormal combustion phenomenon mainly occurs under the working condition of low rotation speed (less than or equal to 1750 r/min) and high load (BMEP (more than or equal to 15 bar), and the combustion starts to be ignited with spark at first, so that the abnormal combustion phenomenon is called low-speed pre-combustion at present. Studies have shown that lubricating oils are important reasons for inducing low-speed pre-ignition in gasoline engines, and that common lubricating oils have not been able to reduce the frequency of low-speed pre-ignition.

The antioxidants used in the technical scheme of the existing gasoline and engine oil composition are generally octyl butyl diphenylamine, dioctyl diphenylamine, di-tert-butyl p-cresol, shielding phenols, sulfur-containing antioxidants and the like, and the antioxidants are easy to volatilize at high temperature and cannot play a good role in antioxidation. The viscosity increase inhibiting ability is not good, so the oil change period is short. The detergent used in the technical scheme of the existing gasoline and engine oil composition is generally calcium salicylate sulfonate, calcium alkyl phenol sulfide, calcium sulfonate and the like, and researches show that the low-speed pre-combustion is influenced by the content of calcium in the gasoline and engine oil composition, and the low-speed pre-combustion frequency is obviously increased along with the increase of the content of the calcium.

In view of this, the present invention has been made.

Disclosure of Invention

The invention relates to a gasoline engine oil composition, which comprises the following components in parts by weight:

20-50 parts of a first dispersing agent, 15-30 parts of an aromatic amine type soot ashless dispersing agent, 3-10 parts of calcium sulfonate, 3-10 parts of magnesium sulfonate, 2-10 parts of zinc dialkyl dithiophosphate, 2-15 parts of an amine antioxidant, 0.2-2 parts of molybdenum salt, 0.03-0.2 part of a silicon type anti-foaming agent and 2-5 parts of base oil.

The automobile oil composition mainly comprises components of an amine antioxidant, an aromatic amine type soot ashless dispersant, magnesium sulfonate, calcium sulfonate and the like according to a certain proportion, and the components are synergistic, so that the service life of the automobile oil is prolonged, and the occurrence frequency of low-speed pre-ignition is reduced.

In another aspect, the invention also relates to a preparation method of the gasoline engine oil composition, which comprises the following steps:

mixing the above materials.

The preparation method of the gasoline and oil composition is simple, does not need a complex process method, and the obtained gasoline and oil has long service life, is not easy to cause the problem of low-speed pre-ignition and has excellent use performance.

Compared with the prior art, the invention has the beneficial effects that:

(1) The engine oil composition provided by the invention is mainly composed of amine antioxidants, aromatic amine type soot ashless dispersants, magnesium sulfonate, calcium sulfonate and the like according to a certain proportion, and the components are synergistic, so that the service life of the engine oil is prolonged, and the occurrence frequency of low-speed pre-ignition is reduced.

(2) The preparation method of the gasoline and oil composition provided by the invention is simple, does not need a complex process method, and the obtained gasoline and oil has long service life, is not easy to cause the problem of low-speed pre-ignition and has excellent use performance.

Detailed Description

The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

20 to 50 parts (e.g., 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts), 15 to 30 parts (e.g., 15 parts, 18 parts, 20 parts, 23 parts, 25 parts, 28 parts, or 30 parts) of an aromatic amine type soot ashless dispersant, 3 to 10 parts (e.g., 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts) of calcium sulfonate, 3 to 10 parts (e.g., 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts) of magnesium sulfonate, 2 to 10 parts (e.g., 2 parts, 3 parts, 4 parts) of zinc dialkyldithiophosphate 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts), 2 to 15 parts (e.g., 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts or 15 parts) of an amine antioxidant, 0.2 to 2 parts (e.g., 0.2 parts, 0.5 parts, 0.8 parts, 1.1 parts, 1.4 parts, 1.7 parts or 2 parts) of a molybdenum salt, 0.03 to 0.2 parts (e.g., 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.13 parts, 0.15 parts, 0.18 parts or 0.2 parts) of a base oil, and 2 to 5 parts (e.g., 2 parts, 3 parts, 4 parts or 5 parts) of a silicon-based antifoaming agent.

Sulfonate plays a major role in motor oil: the sulfonate has larger alkali reserve, can continuously neutralize oxo-acids generated by oxidation of lubricating oil and fuel oil in the use process, and organize further oxidative condensation of the oxo-acids, so that paint films are reduced; washing action: the sulfonate has strong adsorption performance on the produced paint film and carbon deposit, and can wash the paint film and carbon deposit adsorbed on the piston to disperse in oil; dispersing action: the sulfonate can adsorb and disperse solid small particles such as colloid and carbon particles which are generated in the oil, and the solid small particles can be gathered between the sulfonate and the oil to form large particles which are adhered to a cylinder or are settled into sludge; solubilization: sulfonate itself is a surfactant that can dissolve liquid solutes that are otherwise insoluble in oil.

The addition amount of calcium sulfonate can influence the problem of low-speed pre-ignition, the frequency of low-speed pre-ignition can be gradually increased along with the increase of the content of calcium in an oil product, the content of calcium in the oil product and the base number have a certain corresponding relation, and the higher the content of calcium, the larger the base number of the oil product. The base number is mainly used for neutralizing acidic substances generated in the use process of the oil product, so that a certain base number is needed in the oil product to achieve the effect of neutralizing the acidic substances. According to the invention, a certain amount of magnesium sulfonate is added to be matched with a certain amount of magnesium sulfonate, so that the frequency of low-speed pre-combustion can be reduced on the premise of keeping the same base number. Meanwhile, the lubricating oil can be inhibited from oxidative deterioration under the high-temperature condition, the generation of high-temperature sediments on the surface of a piston ring area (piston, piston ring, cylinder sleeve and ring groove) is reduced, and the oil change period can be prolonged under the same working condition.

The dispersant is compounded with the high-base number sulfonate, has a better synergistic effect, can obviously enhance the solubilization under the condition of keeping a better stabilizing effect, and particularly can neutralize the acidic oxides serving as the fatlute matrix in time due to the stronger neutralization capability of the high-base number metal detergent, so that the solubilization capability of the succinimide is protected from being rapidly consumed by the products, the succinimide is fully kept and plays the role of the succinimide as the dispersant, and meanwhile, the stronger dispersion capability of the succinimide is kept.

Compared with the traditional dispersing agent, the aromatic amine type soot ashless dispersing agent not only has better oxidation resistance and sludge dispersibility, but also has excellent soot dispersibility. Its soot dispersing property is better. In the traditional scheme, the dispersion performance of the oil product on soot is improved, the common method is to increase the consumption of a dispersing agent, but the use of excessive dispersing agent can affect the low-temperature fluidity, the wear resistance and other performances of the oil product.

The zinc dialkyl dithiosulfate can decompose peroxide generated in the use process of oil products, and capture free radicals and the decomposition effect of the free radicals. Less oil sludge is generated, the viscosity increase of the oil product is inhibited, a certain abrasion resistance is achieved, and some harm caused by great metal abrasion is reduced.

The amine antioxidant is a free radical terminator and can react with the transferred chain carrier to change the amine antioxidant into an inactive substance, so that the amine antioxidant has the function of stopping oxidation reaction. The molecular weight of the common antioxidant is relatively low, and the common antioxidant can be volatilized, migrated and extracted into the atmosphere, soil and water continuously along with the use time under a high-temperature environment, so that the environment pollution is caused, and the potential influence on human health is caused. Meanwhile, after the loss of the antioxidant, the lubricating oil is easy to thicken, so that the service life of the lubricating oil is greatly reduced. There is a potential for precipitation. The amine antioxidant used in the invention is a polymerization antioxidant, and is characterized by high temperature resistance, difficult volatilization, good antioxidation and viscosity increase inhibition at high temperature.

The molybdenum salt has better wear resistance and oxidation resistance, can form a complex protective film even friction polymer when added into lubricating oil, can reduce the friction coefficient of the oil product, ensures that the sliding of a machine part is smoother, and achieves the effect of saving fuel while enhancing the wear resistance and the load bearing capacity of the oil product. After being used in combination with an antioxidant, the oxidation induction period of lubricating oil can be prolonged.

The silicon anti-foaming agent can reduce the foaming generation amount of lubricating oil, improve the fluidity of an oil film on the surface of foam, thin the foaming oil film and accelerate the foaming to rise to the cracking speed of the surface of the oil.

The base oil serves to enhance the solubility of the composition, including at least one of constant force 150N, plateau model 150N, or Wheatstone 150N.

Preferably, the gasoline engine oil composition comprises the following components in parts by weight:

25-45 parts of a first dispersing agent, 18-25 parts of an aromatic amine type soot ashless dispersing agent, 5-8 parts of calcium sulfonate, 5-8 parts of magnesium sulfonate, 4-7 parts of zinc dialkyl dithiophosphate, 4-12 parts of an amine antioxidant, 0.05-0.15 part of a molybdenum salt, and 3-4 parts of a silicon type anti-foaming agent.

Preferably, the molecular weight of the amine antioxidant is 1000 to 1500 (e.g., 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, or 1500).

Preferably, the amine antioxidant is available from Van der Waals under the model number VaNLUBE9317.

Preferably, the calcium sulfonate comprises at least one of a first calcium sulfonate, a second calcium sulfonate, or a third calcium sulfonate.

Preferably, the first calcium sulfonate has a base number of 20 to 30mgKOH/g (e.g., 20mgKOH/g, 23mgKOH/g, 25mgKOH/g, 28mgKOH/g, or 30 mgKOH/g).

Preferably, the second calcium sulfonate has a base number of 285 to 315mgKOH/g (e.g., 285mgKOH/g, 290mgKOH/g, 295mgKOH/g, 300mgKOH/g, 305mgKOH/g, 310mgKOH/g, or 315 mgKOH/g).

Preferably, the third calcium sulfonate has a base number of 385 to 415mgKOH/g (e.g., 385mgKOH/g, 390mgKOH/g, 395mgKOH/g, 400mgKOH/g, 405mgKOH/g, 410mgKOH/g, or 415 mgKOH/g).

Preferably, the magnesium sulfonate has a base number of 385 to 415mgKOH/g (e.g., 385mgKOH/g, 390mgKOH/g, 395mgKOH/g, 400mgKOH/g, 405mgKOH/g, 410mgKOH/g, or 415 mgKOH/g).

Preferably, the molecular weight of the silicon-based anti-foaming agent is 100 to 12500 (e.g., 100, 200, 300, 500, or 12500). Available from dakangning corporation.

Preferably, the aromatic amine type soot ashless dispersant comprises: at least one of aromatic amine type, hetero atom ring type or graft type.

Preferably, the first dispersant comprises: at least one of a mono-polyisobutylene succinimide, a di-polyisobutylene succinimide, a multi-polyisobutylene succinimide, a boronated polyisobutylene succinimide, or a polymeric polyisobutylene succinimide.

Preferably, the molecular weight of the high molecular polyisobutylene succinimide is 2100-2400.

Preferably, the zinc dialkyldithiophosphate comprises at least one of a zinc primary alkyl zinc salt of phosphorus bis, a zinc primary alkyl zinc salt of phosphorus butyl, a zinc trioctyl salt of phosphorus or a zinc basic bis-octyl salt of phosphorus.

Preferably, the molybdenum salt comprises at least one of molybdenum dialkyldithiocarbamates, non-phosphorothioate organo molybdenum or molybdenum dialkyldithiophosphates.

mixing the above materials.

The preparation method is simple, does not need a complex process method, and the obtained gasoline and engine oil has long service life, is not easy to cause the problem of low-speed pre-combustion and has excellent use performance.

Preferably, the mixing specifically includes:

first mixing the first dispersing agent, the aromatic amine type soot ashless dispersing agent and the base oil to obtain a first mixed system; adding amine antioxidants, molybdenum salts, zinc dialkyl dithiophosphates and silicon anti-foaming agents into the first mixed system, and then carrying out second mixing to obtain a second mixed system; and adding calcium sulfonate and magnesium sulfonate into the second mixed system, and then carrying out third mixing.

Preferably, the temperature of the first mixing is 75-85 ℃, and the time of the first mixing is 25-35 min.

Preferably, the temperature of the second mixing is 70-75 ℃, and the time of the second mixing is 25-35 min.

Preferably, the temperature of the third mixing is 70-75 ℃, and the time of the third mixing is 50-60 min.

Embodiments of the present invention will be described in detail below with reference to specific examples and comparative examples.

Examples 1 to 5

The gasoline engine oil compositions provided in examples 1-5 include the components in parts by weight as shown in Table 1.

TABLE 1

Example 6

The preparation method of the gasoline engine oil composition provided by the embodiment comprises the following steps:

adding macromolecule polyisobutylene succinimide, boronated polyisobutylene succinimide, aromatic amine type soot ashless dispersant and base oil into a production kettle according to a proportion, stirring while heating, stirring at 80 ℃ for 30min, then adding amine antioxidant, molybdenum salt, zinc dialkyl dithiophosphate and silicon type anti-foaming agent, stirring at 73 ℃ for 30min at a constant temperature, finally adding calcium sulfonate and magnesium sulfonate, and stirring at 73 ℃ for 1 h.

Example 7

adding macromolecule polyisobutylene succinimide, boronated polyisobutylene succinimide, aromatic amine type soot ashless dispersant and base oil into a production kettle according to a proportion, stirring while heating, stirring at 75 ℃ for 35min, then adding amine antioxidant, molybdenum salt, zinc dialkyl dithiophosphate and silicon type anti-foaming agent, stirring at 70 ℃ for 35min at a constant temperature, finally adding calcium sulfonate and magnesium sulfonate, and stirring at 75 ℃ for hours.

Example 8

adding macromolecule polyisobutylene succinimide, boronated polyisobutylene succinimide, aromatic amine type soot ashless dispersant and base oil into a production kettle according to a proportion, stirring while heating, stirring at 85 ℃ for 25min, then adding amine antioxidant, molybdenum salt, zinc dialkyl dithiophosphate and silicon type anti-foaming agent, stirring at 75 ℃ for 25min, finally adding calcium sulfonate and magnesium sulfonate, and stirring at 70 ℃ for 50min.

Comparative examples 1 to 5

The gasoline engine oil compositions provided in comparative examples 1-5 include the components in parts by weight as shown in Table 2.

TABLE 2

Comparative example 6

This comparative example differs from example 1 only in that the molecular weight of the amine antioxidant is 350.

Comparative example 7

This comparative example differs from example 1 only in that the aromatic amine type soot ashless dispersant is replaced with a polymeric polyisobutylene succinimide.

Experimental example

The gasoline engine oil compositions of examples 1 to 5 and the gasoline engine oil compositions of comparative examples 1 to 7 were prepared by the preparation method provided in example 6.

Performance test oil product scheme: 59.5 parts of large continuous constant force 150N type base oil, 20 parts of PAO6 type base oil, 14 parts of gasoline engine oil composition, 0.5 part of G826P pour point depressant and 6 parts of LZ7067 finger sticking agent, adding the large continuous constant force 150N, PAO to a stirring kettle, stirring while heating to 70 ℃, stirring for 30 minutes, adding the gasoline engine oil composition prepared by the examples and the comparative examples, stirring G826P, LZ7067 at 70 ℃ for 1.5 hours, and obtaining ACEA C3 5W30 finished oil, wherein the viscosity change rate after the Dahler oxidation test, the oxidation value test, the KHT test and the PDSC test are carried out, and the test results are shown in Table 3.

TABLE 3 Table 3

Note that: the lower the viscosity change rate and oxidation number, the better the PDSC time, and the higher the KHT series.

As can be seen from the data in Table 3, the viscosity change rate and oxidation number of the gasoline and engine oil composition of the present invention after the oxidation are smaller, which means that the oxidation degree is smaller, and the mileage is longer as the oxidation degree is smaller under the same working conditions. The PDSC result of the gasoline and engine oil composition of the invention shows that the longer the oxidation induction period is, the better the antioxidation effect is, and the longer the driving mileage is. KHT represents the high-temperature cleaning performance of oil products, the higher the number of stages is, the better the cleaning performance is under the same working condition, and the longer the oil change mileage is.

Low speed pre-ignition problem: the related paper shows that the calcium element can increase the low-speed pre-ignition frequency, and the calcium element is derived from calcium sulfonate, and the calcium sulfonate mainly provides the base number of the product, and the base number is used for neutralizing the acid of the product in the use process of the oil product, so that the base number in the oil product is important. Magnesium salts are used instead of calcium salts, and the frequency of low-speed pre-ignition is reduced under the same base number.

In conclusion, the gasoline and oil composition provided by the invention has the characteristics of long service life and low occurrence frequency of low-speed pre-combustion.

While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.

Claims

1. The automobile oil composition is characterized by comprising the following components in parts by weight:

2. The gasoline engine oil composition of claim 1, comprising the following components in parts by weight:

3. The gasoline engine oil composition according to claim 1 or 2, characterized in that the molecular weight of the amine antioxidant is 1000-1500.

4. The motor oil composition of claim 1 or 2, wherein the calcium sulfonate comprises at least one of a first calcium sulfonate, a second calcium sulfonate, or a third calcium sulfonate;

preferably, the first calcium sulfonate has a base number of 20 to 30mgKOH/g;

preferably, the second calcium sulfonate has a base number of 285-315 mgKOH/g;

preferably, the third calcium sulfonate has a base number of 385 to 415mgKOH/g.

5. The gasoline engine oil composition according to claim 1 or 2, characterized in that the magnesium sulfonate has a base number of 385 to 415mgKOH/g.

6. The gasoline engine oil composition according to claim 1 or 2, wherein the molecular weight of the silicon-based anti-foaming agent is 100 to 12500.

7. The gasoline engine oil composition of claim 1 or 2, wherein the aromatic amine type soot ashless dispersant comprises: at least one of aromatic amine type, hetero atom ring type or graft type;

preferably, the first dispersant comprises: at least one of a mono-polyisobutylene succinimide, a di-polyisobutylene succinimide, a multi-polyisobutylene succinimide, a boronated polyisobutylene succinimide, or a polymeric polyisobutylene succinimide;

preferably, the zinc dialkyldithiophosphate comprises at least one of a zinc primary alkyl zinc salt of phosphorus bis, a zinc primary alkyl zinc salt of phosphorus butyl, a zinc trioctyl salt of phosphorus or a zinc basic bis-octyl salt of phosphorus;

8. The method for producing a gasoline engine oil composition as claimed in any one of claims 1 to 7, comprising the steps of:

mixing the above materials.

9. The method for preparing a gasoline engine oil composition according to claim 8, wherein the mixing specifically comprises:

10. The method for preparing a gasoline engine oil composition according to claim 9, wherein the temperature of the first mixing is 75-85 ℃, and the time of the first mixing is 25-35 min;

preferably, the temperature of the second mixing is 70-75 ℃, and the time of the second mixing is 25-35 min;