CN114507559A

CN114507559A - Diesel antiwear agent containing rare earth oxide and preparation method thereof

Info

Publication number: CN114507559A
Application number: CN202210182358.5A
Authority: CN
Inventors: 王寿瑞
Original assignee: Dalian Daping Oil Chemistry Co ltd
Current assignee: Dalian Daping Oil Chemistry Co ltd
Priority date: 2022-02-25
Filing date: 2022-02-25
Publication date: 2022-05-17

Abstract

The invention provides a rare earth oxide-containing diesel antiwear agent and a preparation method thereof, and relates to the technical field of oil additives. The diesel antiwear agent containing rare earth oxide comprises the following raw materials in parts by weight: 10-15 parts of surfactant, 10-20 parts of antirust agent, 0.9-1.5 parts of rare earth oxide, 1.3-1.8 parts of calcite, 10-20 parts of oleic acid, 15-25 parts of glycerol, 2-3.5 parts of silicon dioxide, 30-40 parts of toluene and 50-70 parts of base oil. The calcite can effectively improve the bearing capacity and the wear resistance of oil, mainly because the calcite is deposited on a friction surface, and the effects of bearing and wear resistance are achieved; the rare earth oxide is spherical in shape and can play a role in lubrication and bearing, so that the rare earth oxide can effectively play a role in wear resistance; the antirust agent can prevent the metal powder which is rubbed and dropped by a machine from rusting to influence the quality of oil in the using process, and the antiwear agent is ensured to be used for a long time.

Description

Diesel antiwear agent containing rare earth oxide and preparation method thereof

Technical Field

The invention relates to the technical field of oil additives, in particular to a diesel antiwear agent containing rare earth oxide and a preparation method thereof.

Background

With the increasing concern of various countries in the world on environmental problems, the production of high-quality clean energy has become the development direction of the modern oil refining industry, and the production standard of diesel oil is gradually improved. The clean diesel oil has the characteristics of low aromatic hydrocarbon content, high cetane number, light fraction, low sulfur and low nitrogen. Sulfur is the most harmful element that increases the level of pollutants in the atmosphere, and thus the level of sulfur-containing compounds in diesel fuel is tightly controlled. The clean diesel oil produced at present is mainly produced by adopting a hydrogenation process, and the method removes sulfur-containing compounds in the diesel oil and simultaneously reduces the content of nitrogen-containing compounds and oxygen-containing compounds in the diesel oil. It is known that the lubricity of diesel oil depends mainly on the content of anti-wear impurities in the diesel oil, and polycyclic aromatic hydrocarbons, oxygen-containing impurities and nitrogen-containing impurities are very effective anti-wear agents. The lower content of nitrogen compounds and oxygen compounds causes a decrease in the lubricating performance of diesel fuel itself, resulting in wear and failure of the fuel pump.

The antiwear agent is a high-tech additive for engine oil (lubricating oil), and the antiwear agents usually used in the lubricating oil include sulfur type antiwear agents, phosphorus type antiwear agents, sulfur and phosphorus type antiwear agents, halogen type antiwear agents, organic metal type antiwear agents and boron type antiwear agents, which can reduce the abrasion of an engine and increase the power of the engine.

Reducing the sulfur content of fuel can reduce the emission of pollutants such as sulfur oxides, hydrocarbons, carbon monoxide and the like of motor vehicles, especially inhalable Particulate Matters (PM) and the like, is particularly important for improving the atmospheric quality, and has become the development direction of clean fuel. Along with the removal of sulfur in the process of producing low-sulfur diesel oil by a hydrogenation process, the content of polar oxygen-containing and nitrogen-containing compounds, polycyclic aromatic hydrocarbon and other natural lubricating components in the diesel oil is reduced, the lubricating property of the diesel oil is weakened, and the addition of a lubricity improver (namely an antiwear agent) becomes an effective method for compensating the reduction of the lubricating property of the hydrogenated diesel oil. Along with the execution of the national IV and V automobile diesel standards, the application range of the diesel antiwear agent is continuously expanded. Different antiwear agents have different compositions and properties, which can affect the quality and the service performance of commercial diesel oil, such as emulsification, high acid value, excessive oxidation stability (calculated by total insoluble substances) and the like, and seriously threaten the stability of the quality of the diesel oil for vehicles.

The diesel oil used as the lubricant of an engine fuel, a fuel delivery pump and a high-pressure oil pump has proper polarity to ensure good lubricity so as to be beneficial to generating a compact monomolecular adsorption layer on the surface of the electron-deficient metal, avoid dry friction caused by direct contact between friction pairs and reduce friction resistance; proper viscosity and good viscosity-temperature performance should be kept so as to give full play to boundary lubrication and reduce wear. The low-sulfur and ultra-low-sulfur clean diesel produced by the hydrogenation process has the advantages that polar natural lubricants such as sulfur-containing compounds, oxygen-containing compounds, nitrogen-containing compounds, polycyclic aromatic hydrocarbons, olefins and the like in molecules are almost completely disappeared, a compact monomolecular adsorption layer is difficult to generate on the surface of metal, and the lubricity of the diesel is greatly reduced.

An effective oil film is formed between moving parts, dry friction caused by direct contact between the parts is avoided, and the method is the core for reducing friction between friction pairs, reducing friction resistance, improving lubricity, inhibiting abrasion and ensuring safe and effective work of an engine. The selection of a functional group structure with good lubricating effect is the basis of the selection of the antiwear agent, the good compatibility with diesel oil and additives is the basic requirement of the components of the antiwear agent, and the basic requirement of clean emission is to reduce or at least not increase the emission of pollutants of an engine. Therefore, the research on the antiwear agent is beneficial to reasonably selecting the diesel antiwear agent and can effectively solve the quality problem of additized diesel.

Disclosure of Invention

The invention aims to provide a diesel antiwear agent containing rare earth oxide, which has the advantages of high temperature resistance, good oil solubility and little pollution.

The invention also aims to provide a preparation method of the diesel antiwear agent containing rare earth oxide so as to obtain the diesel antiwear agent.

The technical problem to be solved by the invention is realized by adopting the following technical scheme.

On one hand, the embodiment of the application provides a diesel antiwear agent containing rare earth oxide, which comprises the following raw materials in parts by weight: 10-15 parts of surfactant, 10-20 parts of antirust agent, 0.9-1.5 parts of rare earth oxide, 1.3-1.8 parts of calcite, 10-20 parts of oleic acid, 15-25 parts of glycerol, 2-3.5 parts of silicon dioxide, 30-40 parts of toluene and 50-70 parts of base oil.

On the other hand, the embodiment of the application provides a preparation method of a diesel antiwear agent containing rare earth oxide, which comprises the following steps:

uniformly mixing oleic acid, silicon dioxide and glycerol, adding toluene, heating and filtering to obtain a treated substance 1;

heating the treated object 1 to obtain a treated object 2;

uniformly mixing the rare earth oxide and the calcite, adding a surfactant, and performing ultrasonic treatment at 75-83 ℃ for 30-40min to obtain a treated substance 3;

stirring the treated matter 3 and the base oil for 4-6 hours to obtain a treated matter 4;

and stirring the treated substance 2, the treated substance 4 and the antirust agent for 1-2 hours to obtain a finished diesel anti-wear agent.

Compared with the prior art, the embodiment of the invention has at least the following advantages or beneficial effects:

the calcite can effectively improve the bearing capacity and the wear resistance of oil, mainly because the calcite is deposited on a friction surface, and the effects of bearing and wear resistance are achieved; the rare earth oxide is spherical in shape and can play a role in lubrication and bearing, so that the rare earth oxide can effectively play a role in wear resistance; the antirust agent can prevent metal powder which is rubbed and dropped off by a machine from rusting to influence the quality of oil in the using process, and the long-time use of the antiwear agent is ensured; the product obtained by the reaction of the oleic acid and the glycerol is an ester-type substance, has excellent anti-wear effect and excellent surface activity, and is convenient to be uniformly mixed with the diesel oil; the base oil can provide sufficient lubrication.

According to the invention, oleic acid, silicon dioxide and glycerol are reacted, so that the prepared treated substance 1 has stronger surface activity, and the problem of solubility can be effectively solved; the rare earth oxide is spherical and nanoscale in size, so that the lubricating property can be effectively improved, in use, the friction surface can be effectively smoothed, pits on the friction surface can be filled up, and the effect of protecting the structure is achieved, the rare earth oxide and the calcite are nanoscale, the surfaces of particles have huge surface energy, the surface energy is mixed with a surfactant, the surface tension can be reduced, a layer of solvent film is formed on a solid-liquid interface, the particles are not easy to agglomerate, and the wettability and the lubricating property can be improved; under ultrasonic treatment, the rare earth oxide, the surfactant and the calcite can be better adsorbed, so that the solution is uniformly distributed and has stable performance, and the whole diesel antiwear agent can be uniformly mixed by stirring at last.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to specific examples.

The invention provides a diesel antiwear agent containing rare earth oxide, which comprises the following raw materials in parts by weight: 10-15 parts of surfactant, 10-20 parts of antirust agent, 0.9-1.5 parts of rare earth oxide, 1.3-1.8 parts of calcite, 10-20 parts of oleic acid, 15-25 parts of glycerol, 2-3.5 parts of silicon dioxide, 30-40 parts of toluene and 50-70 parts of base oil. The calcite can effectively improve the bearing capacity and the wear resistance of oil, mainly because the calcite is deposited on a friction surface, and the effects of bearing and wear resistance are achieved; the rare earth oxide is spherical in shape and can play a role in lubrication and bearing, so that the rare earth oxide can effectively play a role in wear resistance; the antirust agent can prevent metal powder which is rubbed and dropped off by a machine from rusting to influence the quality of oil in the using process, and the long-time use of the antiwear agent is ensured; the product obtained by the reaction of the oleic acid and the glycerol is an ester-type substance, has excellent anti-wear effect and excellent surface activity, and is convenient to be uniformly mixed with the diesel oil; the base oil can provide sufficient lubrication.

In some embodiments of the present invention, the surfactant comprises (2-3) by mass: (2-3): tween 80, span 80 and polyether of 1. The surfactant in the proportion can provide good lipophilicity and nanoparticle surface affinity, and has good stabilizing effect on rare earth oxide and calcite.

In some embodiments of the invention, the rust inhibitor is an alkenyl succinic acid half ester. The alkenyl succinic acid half ester has low acid value, good fluidity and good oil solubility, and can form a protective film on the surface of metal to prevent the corrosion and the rust of the surface of the metal and form a compact oil film with the metal.

In some embodiments of the invention, the rare earth oxide is lanthanum oxide.

In some embodiments of the present invention, the rare earth oxide has a particle size of 20 to 30nm, and the calcite has a particle size of 50 to 80 nm. The rare earth oxide and the calcite with the size have better stability and homodispersity.

In some embodiments of the invention, the base oil is a mineral oil or a synthetic oil.

The invention also provides a preparation method of the rare earth oxide-containing diesel antiwear agent, which comprises the following steps: uniformly mixing oleic acid, silicon dioxide and glycerol, adding toluene, heating and filtering to obtain a treated substance 1; heating the treated object 1 to obtain a treated object 2; uniformly mixing the rare earth oxide and the calcite, adding a surfactant, and performing ultrasonic treatment at 75-83 ℃ for 30-40min to obtain a treated substance 3; stirring the treated matter 3 and the base oil for 4-6 hours to obtain a treated matter 4; and stirring the treated substance 2, the treated substance 4 and the antirust agent for 1-2 hours to obtain a finished diesel anti-wear agent. According to the invention, oleic acid, silicon dioxide and glycerol are reacted, so that the prepared treated substance 1 has stronger surface activity, and the problem of solubility can be effectively solved; the rare earth oxide is spherical and nanoscale in size, so that the lubricating property can be effectively improved, in use, the friction surface can be effectively smoothed, pits on the friction surface can be filled up, and the effect of protecting the structure is achieved, the rare earth oxide and the calcite are nanoscale, the surfaces of particles have huge surface energy, the surface energy is mixed with a surfactant, the surface tension can be reduced, a layer of solvent film is formed on a solid-liquid interface, the particles are not easy to agglomerate, and the wettability and the lubricating property can be improved; under ultrasonic treatment, the rare earth oxide, the surfactant and the calcite can be better adsorbed, so that the solution is uniformly distributed and has stable performance, and the whole diesel antiwear agent can be uniformly mixed by stirring at last.

In some embodiments of the present invention, the treated material 1 is heated at 135-145 ℃ for 8-10 hours. Under the condition, the reaction of the oleic acid and the glycerol is convenient, so that the raw materials are fully reacted.

In some embodiments of the present invention, the heating condition of the treated material 2 is between-0.08 MPa and-0.12 MPa and between 100 ℃ and 110 ℃ for 2 to 3 hours. The heat treatment under these conditions can remove the moisture contained in the treated material 2.

In some embodiments of the present invention, the stirring condition of the processed object 4 is to stir at 78-89 ℃ and 1400-1600 r/min for 4-6 h. The treated material 4 can be dispersed uniformly and has stable properties.

In some embodiments of the invention, the treated object 2, the treated object 4 and the antirust agent are stirred at a speed of 800-1200 r/min. The treatment under the condition can ensure that the quality of the finished diesel antiwear agent is uniform and stable, and ensure the use effect of the diesel antiwear agent.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

A preparation method of a diesel antiwear agent containing rare earth oxide comprises the following steps:

raw materials: 100g of surfactant (Tween 80, span 80 and polyether in a mass ratio of 2: 2: 1), 100g of alkenyl succinic acid half ester, 9g of lanthanum oxide, 13g of calcite, 100g of oleic acid, 150g of glycerol, 20g of silicon dioxide, 300g of toluene and 500g of mineral oil.

Mixing oleic acid, silicon dioxide and glycerol uniformly, adding toluene, heating at 135 ℃ for 8 hours, and filtering to obtain a treated substance 1;

heating the treated object 1 for 2 hours under the conditions of 0.08MPa and 100 ℃ to obtain a treated object 2;

mixing lanthanum oxide and calcite uniformly, adding a surfactant, and performing ultrasonic treatment at 75 ℃ for 30min to obtain a treated substance 3;

stirring the treated substance 3 and mineral oil at 78 deg.C and 1400r/min for 4h to obtain treated substance 4;

and stirring the treated substance 2, the treated substance 4 and the alkenyl succinic acid half-ester for 1h under the condition of 800r/min to obtain a finished product of the diesel antiwear agent.

Example 2

raw materials: 130g of surfactant (Tween 80, span 80 and polyether in a mass ratio of 3: 2: 1), 150g of alkenyl succinic acid half ester, 12g of lanthanum oxide, 16g of calcite, 150g of oleic acid, 200g of glycerol, 28g of silicon dioxide, 350g of toluene and 600g of mineral oil.

Mixing oleic acid, silicon dioxide and glycerol uniformly, adding toluene, heating at 140 ℃ for 9 hours, and filtering to obtain a treated substance 1;

heating the treated substance 1 at-0.1 MPa and 105 deg.C for 2.5h to obtain treated substance 2;

mixing lanthanum oxide and calcite uniformly, adding a surfactant, and performing ultrasonic treatment at 79 ℃ for 35min to obtain a treated substance 3;

stirring the treated substance 3 and mineral oil at 83 deg.C and 1500r/min for 5h to obtain treated substance 4;

and stirring the treated substance 2, the treated substance 4 and the alkenyl succinic acid half-ester for 1.5 hours under the condition of 1000r/min to obtain a finished product of the diesel antiwear agent.

Example 3

raw materials: 130g of surfactant (Tween 80, span 80 and polyether in a mass ratio of 2: 3: 1), 150g of alkenyl succinic acid half ester, 12g of lanthanum oxide, 16g of calcite, 150g of oleic acid, 200g of glycerol, 28g of silicon dioxide, 350g of toluene and 600g of mineral oil.

Example 4

raw materials: 150g of surfactant (Tween 80, span 80 and polyether in a mass ratio of 3: 3: 1), 200g of alkenyl succinic acid half ester, 15g of lanthanum oxide, 18g of calcite, 200g of oleic acid, 250g of glycerol, 35g of silicon dioxide, 400g of toluene and 700g of mineral oil.

Mixing oleic acid, silicon dioxide and glycerol uniformly, adding toluene, heating at 145 ℃ for 10 hours, and filtering to obtain a treated substance 1;

heating the treated substance 1 at-0.12 MPa and 110 deg.C for 3h to obtain treated substance 2;

mixing lanthanum oxide and calcite uniformly, adding surfactant, and performing ultrasonic treatment at 83 deg.C for 30-40min to obtain treated substance 3;

stirring the treated substance 3 and mineral oil at 89 deg.C and 1600r/min for 6h to obtain treated substance 4;

and stirring the treated substance 2, the treated substance 4 and the alkenyl succinic acid half-ester for 2 hours at the speed of 1200r/min to obtain a finished product of the diesel antiwear agent.

Comparative example 1

This comparative example differs from example 3 in that: the surfactant is prepared from the following components in a mass ratio of 1: 1: tween 80, span 80 and polyether of 1.

raw materials: 130g of surfactant (Tween 80, span 80 and polyether in a mass ratio of 1: 1: 1), 150g of alkenyl succinic acid half ester, 12g of lanthanum oxide, 16g of calcite, 150g of oleic acid, 200g of glycerol, 28g of silicon dioxide, 350g of toluene and 600g of mineral oil.

Comparative example 2

This comparative example differs from example 3 in that: the surfactant is prepared from the following components in percentage by mass: 2: tween 80, span 80 and polyether of 3.

raw materials: 130g of surfactant (Tween 80, span 80 and polyether in a mass ratio of 5: 2: 3), 150g of alkenyl succinic acid half ester, 12g of lanthanum oxide, 16g of calcite, 150g of oleic acid, 200g of glycerol, 28g of silicon dioxide, 350g of toluene and 600g of mineral oil.

Examples of the experiments

First, wear Performance testing

According to the addition of 200 mug/g, the diesel antiwear agents prepared in examples 1-4 and comparative examples 1-2 are respectively added into diesel, the mixture is uniformly mixed, the performance of the diesel antiwear agent is detected, the detection method is that the paper towel with grinding marks is measured according to SH/T0765-200 in the Diesel lubricity assessment (high frequency reciprocating testing machine method), and the measurement results are shown in Table 1.

TABLE 1

As can be seen from the table 1, the antiwear agent prepared by the method has better antiwear performance on diesel oil, can effectively reduce the generation of grinding marks and prolong the service life of devices, and compared with the examples 1-4, the effect of the example 3 is optimal, and the effect of reducing the grinding marks is optimal; comparing example 3 with comparative examples 1 to 2, it can be seen that the proportion of the surfactant is very important and has a great influence on the anti-wear properties after adjustment.

Then the diesel oil antiwear agent prepared in example 3 is added into diesel oil according to the addition amounts of 20 mug/g, 40 mug/g, 80 mug/g and 100 mug/g respectively, the mixture is uniformly mixed, the performance of the diesel oil antiwear agent is detected, the detection method is that the paper towel with grinding marks is measured according to SH/T0765-200 which is the evaluation of diesel oil lubricity (high frequency reciprocating testing method), and the measurement results are shown in Table 2.

TABLE 2

According to the table 2, it can be known that the higher the addition amount of the diesel antiwear agent prepared by the method, the better the antiwear performance of the diesel, but after the addition amount is up to 80 mug/g, the antiwear effect is improved a little. This shows that the diesel antiwear agent prepared by the method is added in an optimal amount of 80 mu g/g.

In conclusion, the calcite provided by the invention can effectively improve the bearing capacity and the anti-wear capacity of oil, mainly because the calcite is deposited on a friction surface, and the effects of bearing and anti-wear are further achieved; the rare earth oxide is spherical in shape and can play a role in lubrication and bearing, so that the rare earth oxide can effectively play a role in wear resistance; the antirust agent can prevent metal powder which is rubbed and dropped off by a machine from rusting to influence the quality of oil in the using process, and the long-time use of the antiwear agent is ensured; the product obtained by the reaction of the oleic acid and the glycerol is an ester-type substance, has excellent anti-wear effect and excellent surface activity, and is convenient to be uniformly mixed with the diesel oil; the base oil can provide sufficient lubrication.

According to the invention, oleic acid, silicon dioxide and glycerol are reacted, so that the prepared treated substance 1 has stronger surface activity, and the problem of solubility can be effectively solved; the rare earth oxide is spherical and nanoscale in size, so that the lubricating property can be effectively improved, in use, the friction surface can be effectively smoothed, pits on the friction surface can be filled up, and the effect of protecting the structure is achieved, the rare earth oxide and the calcite are nanoscale, the surfaces of particles have huge surface energy, the surface energy is mixed with a surfactant, the surface tension can be reduced, a layer of solvent film is formed on a solid-liquid interface, the particles are not easy to agglomerate, and the wettability and the lubricating property can be improved; under ultrasonic treatment, the rare earth oxide, the surfactant and calcite can be better adsorbed, so that the solution is uniformly distributed, the performance is stable, and the whole diesel antiwear agent can be uniformly mixed by stirring at last.

The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims

1. The diesel antiwear agent containing rare earth oxide is characterized by comprising the following raw materials in parts by weight: 10-15 parts of surfactant, 10-20 parts of antirust agent, 0.9-1.5 parts of rare earth oxide, 1.3-1.8 parts of calcite, 10-20 parts of oleic acid, 15-25 parts of glycerol, 2-3.5 parts of silicon dioxide, 30-40 parts of toluene and 50-70 parts of base oil.

2. The diesel antiwear agent containing rare earth oxide according to claim 1, wherein the surfactant comprises the following components in a mass ratio of (2-3): (2-3): tween 80, span 80 and polyether of 1.

3. The diesel antiwear agent containing rare earth oxide according to claim 1, wherein the rust inhibitor is alkenyl succinic acid half ester.

4. The diesel antiwear agent containing rare earth oxide according to claim 1, wherein the rare earth oxide is lanthanum oxide.

5. The diesel antiwear agent containing rare earth oxide according to claim 1, wherein the particle size of the rare earth oxide is 20-30 nm, and the particle size of the calcite is 50-80 nm.

6. The diesel antiwear agent containing rare earth oxide according to claim 1, wherein the base oil is mineral oil or synthetic oil.

7. The preparation method of the rare earth oxide-containing diesel antiwear agent, as claimed in any one of claims 1 to 6, comprises the following steps:

heating the treated object 1 to obtain a treated object 2;

8. The preparation method of the rare earth oxide-containing diesel antiwear agent according to claim 7, wherein the treatment substance 1 is heated at 135-145 ℃ for 8-10 h.

9. The preparation method of the rare earth oxide-containing diesel anti-wear agent as claimed in claim 7, wherein the heating condition of the treatment substance 2 is heating for 2-3 h under the conditions of-0.08 to-0.12 MPa and 100-110 ℃.

10. The preparation method of the rare earth oxide-containing diesel anti-wear agent as claimed in claim 7, wherein the stirring condition of the treatment substance 4 is that the treatment substance is stirred for 4-6 hours at 78-89 ℃ and 1400-1600 r/min.