A process for the preparation of a diesel anti-wear agent

Abstract

The application relates to the technical field of oil additives, and particularly discloses a preparation method of diesel anti-wear agent, which comprises the following steps: under an inert atmosphere, 20-40 parts by mass of conjugated unsaturated fatty acid, 60-80 parts by mass of non-conjugated unsaturated fatty acid, 13-19 parts by mass of polyhydric alcohol, 0.3-0.7 parts by mass of antioxidant and 30-40 parts by mass of cyclohexane are uniformly mixed, 4-6 parts by mass of a catalyst is added and uniformly mixed, the temperature is raised to 160-180 DEG C, reaction is carried out for 2-4 hours, the temperature is lowered to 100-120 DEG C, 1-2 parts by mass of boric acid is added, reaction is continuously carried out for 120-180 minutes, solid-liquid separation is carried out, and distillation is carried out to obtain the diesel anti-wear agent; the catalyst is a core-shell structure composite in which a rare earth metal oxide layer and a heteropoly acid metal salt are sequentially loaded on the surface of a porous metal carrier. The diesel anti-wear agent prepared by the application has good anti-wear performance and low-temperature fluidity.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of oil additives, in particular to a preparation method of diesel anti-wear agent. BACKGROUND

[0002] In diesel, the main factors affecting the anti-wear lubricity are polycyclic aromatic hydrocarbons, oxygen-containing impurities, nitrogen-containing impurities and sulfur compounds; the strength of diesel lubricity depends on the content of anti-wear substances; polycyclic aromatic hydrocarbons and nitrogen-containing compounds have good anti-wear effect, while sulfur compounds not only do not have anti-wear effect, but also promote wear.

[0003] However, most of the sulfur compounds in diesel exist in the form of heterocyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons, so in the early 20th century, the removal of sulfur compounds from diesel was vigorously advocated due to the serious environmental pollution caused by sulfur compounds, and at the same time, aromatic hydrocarbons and polycyclic aromatic hydrocarbons with lubricating properties and other components with lubricating properties were also removed. Therefore, as the sulfur content of diesel is reduced, the engines using diesel oil are constantly experiencing wear and damage, thereby shortening the service life. Therefore, it is an important topic to study how to improve the anti-wear property of low-sulfur diesel.

[0004] At present, adding anti-wear agents is the fundamental way to solve the problem of the decrease in the lubricity of low-sulfur diesel. Diesel anti-wear agents are mainly divided into acid type anti-wear agents and ester type anti-wear agents. The acid type anti-wear agents will cause the acid value of diesel to rise after being added to diesel, and will have negative effects on the basic additives in diesel. The ester type anti-wear agents are mainly synthesized by esterification of long-chain unsaturated fatty acids and polyols, and are the clean diesel anti-wear components with the most promising development prospects in the current research and use at home and abroad.

[0005] The patent application file with the publication number 105001924 A discloses a preparation method of low-condensation-point diesel anti-wear agent, which uses long-chain unsaturated fatty acids and polyols as raw materials, and uses an Al2O3 multi-element supported rare earth catalyst for catalysis, and the mass ratio of the raw materials is:

[0006] Xylene is used as a solvent, long-chain unsaturated fatty acids, polyols and Al2O3 multi-element supported rare earth catalysts are sequentially added to the solvent, and under the condition of a temperature of 140-160 DEG C, the xylene is refluxed to carry water, and low-temperature esterification reaction is carried out for 2-5 hours; then the temperature is raised to 220-260 DEG C to carry out high-temperature esterification reaction for 0.5-1.5 hours, while the solvent xylene is separated out, the Al2O3 multi-element supported rare earth catalyst is filtered out, and the low-condensation-point diesel anti-wear agent is obtained.

[0007] In the above technical solution, the thermal conductivity of Al2O3 is relatively low, and in the esterification reaction system, it is used as a carrier of a multi-element supported rare earth catalyst. When the reaction is heated from the low-temperature esterification stage of 140-160 DEG C to the high-temperature esterification stage of 220-260 DEG C, the poor thermal conductivity of Al2O3 easily leads to uneven heat distribution of the reaction system, and local overheating to a certain extent will cause carbonization of part of the long-chain unsaturated fatty acid, which will produce impurities, change the composition of the reaction system, and cause the anti-wear performance of the anti-wear agent to be poor. SUMMARY

[0008] In order to improve the anti-wear performance of the diesel anti-wear agent, the application provides a preparation method of a diesel anti-wear agent.

[0009] The preparation method of the diesel anti-wear agent provided by the application adopts the following technical solution:

[0010] The preparation method of the diesel anti-wear agent comprises the following steps:

[0011] In an inert atmosphere, 20-40 parts by mass of conjugated unsaturated fatty acid, 60-80 parts by mass of non-conjugated unsaturated fatty acid, 13-19 parts by mass of polyol, 0.3-0.7 parts by mass of antioxidant and 30-40 parts by mass of cyclohexane are uniformly mixed, 4-6 parts by mass of catalyst is added and uniformly mixed, heated to 160-180 DEG C, reacted for 2-4 h, cooled to 100-120 DEG C, 1-2 parts by mass of boric acid is added, and reacted for 120-180 min, then solid-liquid separation and distillation are performed to obtain the diesel anti-wear agent;

[0012] The catalyst is a core-shell structure composite in which a rare earth metal oxide layer and a heteropolyacid metal salt are sequentially loaded on the surface of a porous metal carrier.

[0013] In the above technical solution, the conjugated unsaturated fatty acid can quickly form a firm chemisorption film on the metal surface due to the double bond conjugation effect, effectively reducing the direct contact between metals and reducing wear. The non-conjugated unsaturated fatty acid has a stable molecular structure, which helps to improve the flexibility of the adsorption film at low temperature and improve the low-temperature fluidity of the anti-wear agent. At the same time, its good oxidation stability can inhibit the degradation of the film layer and improve the oxidation stability of the anti-wear agent. The synergistic effect of the two realizes the overall optimization of the anti-wear performance, low-temperature fluidity and oxidation stability. After the main reaction is cooled, boric acid is added to form a stable boric acid ester film, which significantly improves the high-temperature stability, anti-wear performance and oxidation life of the anti-wear agent.

[0014] The catalyst adopts a core-shell structure composite, and the three-dimensional pore network of the porous metal carrier provides an efficient mass transfer channel, which is beneficial to the adsorption and diffusion of the reactants. The rare earth metal oxide layer and the heteropolyacid metal salt form a double acid site, which significantly improves the rate and efficiency of the esterification reaction through synergistic catalysis. At the same time, the core-shell structure ensures the stability of the catalyst, so that it can still maintain good catalytic activity after being used for many times.

[0015] Preferably, the conjugated unsaturated fatty acid is at least one of conjugated linoleic acid and conjugated linolenic acid.

[0016] Preferably, the non-conjugated unsaturated fatty acid is at least one of oleic acid and palmitoleic acid.

[0017] Preferably, the polyol is any one of pentaerythritol and trimethylolpropane.

[0018] Preferably, the catalyst is pretreated before use by the following steps:

[0019] The catalyst is immersed in a silane coupling agent solution with a pH of 3-4 and a volume concentration of 1-3% at 40-60°C for 1-3h, then solid-liquid separation and drying are performed to obtain the pretreated catalyst.

[0020] The silane coupling agent solution comprises a silane coupling agent, ethanol and water.

[0021] Preferably, in the silane coupling agent, the volume ratio of ethanol to water is (5-7):(3-5).

[0022] In the above technical solution, the silane coupling agent constructs a double hydrophilic interface layer on the surface of the catalyst, the hydrophobic group of which combines with the fatty acid alkyl chain, and the hydrophilic group forms a hydrogen bond network with the polyol, significantly enhancing the interparticle repulsion and inhibiting agglomeration. The pretreated catalyst forms stable dispersed particles in the reaction system, effectively improving the contact efficiency of the reactants and active sites and promoting the esterification reaction process.

[0023] Preferably, the antioxidant is antioxidant 1010.

[0024] Preferably, the preparation method of the catalyst comprises the following steps:

[0025] (1) After acid etching of the porous metal carrier, washing, drying, a pretreated carrier is obtained;

[0026] (2) The pretreated carrier is immersed in a precursor solution, the pH is adjusted to 9-10, then the temperature is raised to 160-180°C, and the reaction is carried out for 6-10h, then washing, drying, a pre-loaded catalyst is obtained;

[0027] (3) the pre-loaded catalyst is immersed in a heteropolyacid metal salt solution for 30-60 min, solid-liquid separation is performed, drying is performed, and then calcination is performed under an inert atmosphere, and cooling is performed, thereby obtaining the catalyst;

[0028] The precursor solution comprises a rare earth metal salt, and the molar concentration of the rare earth metal salt is 0.15-0.25 mol / L; the molar concentration of the heteropolyacid metal salt solution is 0.05-0.2 mol / L.

[0029] Preferably, the mass-volume ratio of the porous metal carrier, the precursor solution and the heteropolyacid metal salt solution is 1 g:(15-25) mL:(15-25) mL.

[0030] In the above technical solution, the porous metal carrier is pretreated by acid etching, so that the surface of the carrier becomes rough, more micropores and grooves are formed, more active sites are provided for the subsequent loading of active components, and the uniform distribution of the active components on the surface of the carrier is promoted. The heteropolyacid metal salt has strong acidity and unique catalytic performance, and after being loaded on the surface of the rare earth metal oxide layer, it forms a double-acid site synergistic effect with the rare earth metal oxide. This synergistic effect can significantly improve the catalytic activity and selectivity of the catalyst for esterification reaction, accelerate the reaction rate, and improve the yield of diesel anti-wear agent. At the same time, the synergistic effect of the double-acid site can also inhibit the occurrence of side reactions to some extent, and improve the purity and quality of the product.

[0031] Preferably, the rare earth metal salt is any one of cerium nitrate and lanthanum nitrate.

[0032] Preferably, the precursor solution further comprises polyethylene glycol with a volume concentration of 0.8%-1.2%.

[0033] Preferably, in the precursor solution and the heteropolyacid metal salt solution, the solvent is prepared by mixing ethanol and water in a volume ratio of 1:(1-2).

[0034] Preferably, the porous metal carrier is any one of foamed nickel and foamed titanium.

[0035] Preferably, the heteropolyacid metal salt solution is any one of cesium phosphotungstate and potassium phosphotungstate.

[0036] Preferably, the acid solution used for acid etching comprises nitric acid and water, and the volume concentration of the nitric acid is 20%-25%.

[0037] Preferably, the acid solution used for acid etching further comprises hydrofluoric acid, and the volume concentration of the hydrofluoric acid is 3%-5%.

[0038] Preferably, the acid etching conditions are as follows: temperature 30-60 ℃, and time 15-35 min.

[0039] Preferably, the calcination conditions are: first heating to 200-240℃, sintering for 50-70min, then heating to 300-350℃, sintering for 60-120min.

[0040] Preferably, when the polyol is added, the step of adding 0.5-2 parts by mass of graphene oxide is also included.

[0041] Preferably, the graphene oxide is pretreated before use by the following steps:

[0042] After the graphene oxide and polyethylene glycol are mixed uniformly, oleic acid is added and mixed uniformly, and then ultrasonic treatment is performed for 30-40min, and the product is obtained.

[0043] The mass ratio of the graphene oxide, polyethylene glycol and oleic acid is 1: (1-2): (0.05-0.1).

[0044] Preferably, the frequency of the ultrasonic treatment is 20-40kHz, and the power is 300-500W.

[0045] In the above technical solution, after the graphene oxide is mixed with the polyethylene glycol, the hydroxyl groups of the polyethylene glycol can form hydrogen bonds with the hydroxyl groups on the surface of the graphene oxide, thereby playing a preliminary wrapping and dispersing role. After the addition of the oleic acid, the long-chain alkyl groups of the oleic acid are hydrophobic and can interact with the molecular chains of the polyethylene glycol, and at the same time, the carboxyl groups of the oleic acid can also interact with the groups on the surface of the graphene oxide, thereby further improving the dispersibility and compatibility of the graphene oxide in the oil phase.

[0046] The pretreated graphene oxide can form a relatively stable adsorption film with the metal surface through the residual hydroxyl groups on the surface and the polyethylene glycol and oleic acid on the surface, and the three can synergistically effectively reduce the friction coefficient and the wear scar diameter, thereby improving the anti-wear performance of the diesel anti-wear agent. In addition, the synergistic effect of the polyethylene glycol and the oleic acid not only enables the graphene oxide to have good dispersion stability in the diesel anti-wear agent system, but also enables the graphene oxide to maintain viscosity stability at high temperatures and improve low-temperature fluidity, thereby providing multi-dimensional protection for long-term lubrication under extreme working conditions.

[0047] Preferably, when the polyol is added, the step of adding 2-4 parts by mass of glycerol triglycidyl ether is also included.

[0048] In the above technical solution, in the esterification reaction system, the epoxy group of glycerol triglycidyl ether can undergo ring-opening reaction with the carboxyl group of fatty acid, and the generated product has multiple branched chains and polar groups, which can form a more dense and firm adsorption film on the metal surface. During friction, this adsorption film can effectively isolate the metal surface, reduce direct contact and wear between metals, thereby significantly reducing the wear scar diameter and improving the anti-wear performance of the diesel anti-wear agent. In addition, during the use of the diesel anti-wear agent, they can capture free radicals and inhibit the progress of oxidation reactions, thereby improving the oxidation stability of the anti-wear agent.

[0049] In summary, the present application has the following beneficial effects:

[0050] 1. The present application adopts gradient matching of conjugated / non-conjugated unsaturated fatty acids to construct a dynamic-stable double film layer system: conjugated fatty acids form a chemical adsorption layer on the metal surface through conjugated double bonds, providing long-acting anti-wear foundation; non-conjugated fatty acids continuously supplement film layer defects due to molecular flexibility, and the boronic acid added in the later reaction period reacts with fatty acid esters to form a boron-containing glassy film layer through condensation reaction, forming a double-layer anti-wear structure with the physical adsorption layer, thereby improving the anti-wear performance.

[0051] 2. The core-shell catalyst used in the present application uses rare earth metal oxides as the core and loaded heteropolyacid metal salts as the shell layer to construct a double-acid site synergistic catalytic system, which realizes efficient synergistic catalysis of the esterification reaction of conjugated / non-conjugated unsaturated fatty acids and polyol, not only reducing the activation energy of the reaction, but also improving the yield of the target product.

[0052] 3. The present application preferably uses pretreated graphene oxide to improve the dispersibility and stability of graphene oxide in the diesel anti-wear agent system and the lubricating performance. The pretreated graphene oxide forms a layered physical adsorption layer on the friction interface due to its ultra-low friction coefficient and ultra-high hardness, significantly reducing direct contact. At the same time, the surface oxygen-containing functional groups of the pretreated graphene oxide interact with polar molecules (such as fatty acid esters) in diesel through hydrogen bonds to construct a boundary lubrication synergistic network, enhancing the stability of the lubrication film. DETAILED DESCRIPTION

[0053] The present application is further described in detail below in conjunction with the examples.

[0054] The raw materials of the examples and comparative examples of the present application are all ordinary commercially available, except for special instructions.

[0055] In the preparation example, the pore size of the foamed nickel is 100-500 μm, and the porosity is ≥90%; the pore size of the foamed titanium is 50-200 μm, and the porosity is ≥85%; before use, the foamed nickel or foamed titanium is cut into a 0.5 cm×0.5 cm sheet, then immersed in a container containing acetone, and ultrasonically cleaned for 10 min at an ultrasonic frequency of 30 kHz and a power of 120 W; after cleaning, the foamed nickel or foamed titanium is naturally air-dried and ready for use; the thickness of the foamed nickel or foamed titanium is about 0.5-1 mm;

[0056] The polyethylene glycol is polyethylene glycol 2000.

[0057] Synthesis of catalysts in preparation examples 1-6

[0058] Preparation example 1

[0059] The preparation method of the catalyst in the present preparation example comprises the following steps:

[0060] (1) 10 g of foamed nickel is immersed in 100 mL of a 22% nitric acid solution, heated to 55°C, etched for 30 min, washed with deionized water until neutral, transferred to a vacuum drying oven and adjusted to a temperature of 60°C, and dried to a constant weight to obtain pretreated foamed nickel;

[0061] (2) The pretreated foamed nickel is immersed in 200 mL of a precursor solution, ammonia water with a molar concentration of 0.6 mol / L is slowly added dropwise under stirring at a speed of 200 r / min, the pH is adjusted to between 9 and 9.5, heated to 170°C, and reacted for 8 h; after natural cooling, the foamed nickel is washed with ethanol for 3 times, transferred to a vacuum drying oven and adjusted to a temperature of 60°C, and dried to a constant weight to obtain a pre-loaded catalyst;

[0062] (3) The pre-loaded catalyst is immersed in 200 mL of a cesium phosphotungstate solution with a molar concentration of 1 mol / L, treated under a vacuum of -0.1 MPa for 45 min, filtered, transferred to a vacuum drying oven and adjusted to a temperature of 60°C, dried to a constant weight, then transferred to a sintering furnace, replaced with nitrogen for 3 times, continuously introduced nitrogen at a speed of 50 mL / min, first heated to 220°C at a speed of 5°C / min, kept for 60 min, then heated to 320°C at a speed of 3°C / min, kept for 90 min, stopped introducing nitrogen, and cooled with the furnace to obtain the catalyst.

[0063] The precursor solution comprises cerium nitrate, polyethylene glycol and a solvent, the molar concentration of the cerium nitrate is 0.2 mol / L, the volume concentration of the polyethylene glycol is 1%, and the solvent is a mixture of ethanol and water in a volume ratio of 1:1.5;

[0064] The solvent of the cesium phosphotungstate solution is a mixture of ethanol and water in a volume ratio of 1:1.5.

[0065] Preparation example 2

[0066] The preparation method of the catalyst in the present preparation example comprises the following steps:

[0067] (1) 10 g of foamed nickel is immersed in 100 mL of a nitric acid solution with a volume concentration of 20%, heated to 60°C, etched for 35 min, washed with deionized water until neutral, transferred into a vacuum drying box and adjusted to a temperature of 60°C, and dried to a constant weight to obtain pretreated foamed nickel;

[0068] (2) The pretreated foamed nickel is immersed in 150 mL of a precursor solution, ammonia water with a molar concentration of 0.6 mol / L is slowly added dropwise at a stirring speed of 200 r / min, the pH is adjusted to between 9.5 and 10, heated to 180°C, and reacted for 10 h, then naturally cooled, washed with ethanol for 3 times, transferred into a vacuum drying box and adjusted to a temperature of 60°C, and dried to a constant weight to obtain a pre-loaded catalyst;

[0069] (3) The pre-loaded catalyst is immersed in 150 mL of a cesium phosphotungstate solution with a molar concentration of 0.05 mol / L, treated with a vacuum of -0.12 MPa for 60 min, filtered, transferred into a vacuum drying box and adjusted to a temperature of 60°C, dried to a constant weight, then transferred into a sintering furnace, replaced with nitrogen for 3 times, continuously passed nitrogen at a speed of 40 mL / min, first heated to 200°C at a speed of 5°C / min, kept for 70 min, then heated to 350°C at a speed of 3°C / min, kept for 120 min, stopped passing nitrogen, and cooled with the furnace to obtain the catalyst.

[0070] The precursor solution comprises cerium nitrate, polyethylene glycol and a solvent, the molar concentration of the cerium nitrate is 0.15 mol / L, the volume concentration of the polyethylene glycol is 0.8%, and the solvent is a mixture of ethanol and water in a volume ratio of 1:1;

[0071] The solvent of the cesium phosphotungstate solution is a mixture of ethanol and water in a volume ratio of 1:1.

[0072] Preparation Example 3

[0073] The preparation method of the catalyst in the present preparation example comprises the following steps:

[0074] (1) 10 g of foamed nickel is immersed in 100 mL of a nitric acid solution with a volume concentration of 25%, heated to 50°C, etched for 25 min, washed with deionized water until neutral, transferred into a vacuum drying box and adjusted to a temperature of 60°C, and dried to a constant weight to obtain pretreated foamed nickel;

[0075] (2) The pretreated foamed nickel is immersed in 250 mL of precursor solution, ammonia water with a molar concentration of 0.6 mol / L is slowly added under stirring at a speed of 200 r / min, the pH is adjusted to 9-9.5, the temperature is raised to 160°C, and the reaction is carried out for 6 h. After natural cooling, the foamed nickel is washed with ethanol for 3 times, is transferred into a vacuum drying box, and the temperature is adjusted to 60°C. The foamed nickel is dried to constant weight to obtain a pre-loaded catalyst;

[0076] (3) The pre-loaded catalyst is immersed in 250 mL of cesium phosphotungstate solution with a molar concentration of 0.2 mol / L, is treated under a vacuum of-0.08 MPa for 30 min, is filtered, is transferred into a vacuum drying box, and the temperature is adjusted to 60°C. The catalyst is dried to constant weight, is then transferred into a sintering furnace, is replaced with nitrogen for 3 times, and is continuously supplied with nitrogen at a speed of 60 mL / min. The temperature is raised to 240°C at a speed of 5°C / min, and the temperature is maintained for 50 min. Then the temperature is raised to 300°C at a speed of 3°C / min, and the temperature is maintained for 60 min. The supply of nitrogen is stopped, and the furnace is cooled to obtain the catalyst.

[0077] The precursor solution comprises cerium nitrate, polyethylene glycol, and a solvent. The molar concentration of cerium nitrate is 0.25 mol / L, the volume concentration of polyethylene glycol is 1.2%, and the solvent is a mixture of ethanol and water in a volume ratio of 1:2.

[0078] The solvent of the cesium phosphotungstate solution is a mixture of ethanol and water in a volume ratio of 1:2.

[0079] Preparation Example 4

[0080] The difference between the present preparation example and Preparation Example 1 is that:

[0081] Potassium phosphotungstate with the same molar concentration and volume is used to replace cesium phosphotungstate.

[0082] The other steps are the same as those in Preparation Example 1.

[0083] Preparation Example 5

[0084] The difference between the present preparation example and Preparation Example 1 is that:

[0085] In step (1), 10 g of foamed titanium is immersed in 100 mL of acid solution, the temperature is raised to 30°C, and etching is carried out for 20 min. The foamed titanium is washed with deionized water until neutral, is transferred into a vacuum drying box, and the temperature is adjusted to 60°C. The foamed titanium is dried to constant weight to obtain pretreated foamed nickel.

[0086] The acid solution comprises nitric acid, hydrofluoric acid, and water. The volume concentration of nitric acid is 20%, and the volume concentration of hydrofluoric acid is 3%.

[0087] The other steps are the same as those in Preparation Example 1.

[0088] Preparation Example 6

[0089] The preparation example is different from the preparation example 1 in that:

[0090] In step (1), 10 g of titanium foam is immersed in 100 mL of acid solution, heated to 40℃, etched for 15 min, washed with deionized water until neutral, transferred to a vacuum drying oven and adjusted to a temperature of 60℃, and dried to a constant weight to obtain a pretreated nickel foam;

[0091] The acid solution comprises nitric acid, hydrofluoric acid and water, the volume concentration of the nitric acid is 25%, and the volume concentration of the hydrofluoric acid is 5%.

[0092] The others are the same as in the preparation example 1.

[0093] Example 1

[0094] The preparation method of the diesel anti-wear agent of the example comprises the following steps:

[0095] In a reaction kettle equipped with a stirring device, a thermometer, a reflux condenser and a water separator, after 3 times of replacement with nitrogen, 30 g of conjugated linoleic acid, 70 g of oleic acid, 13 g of pentaerythritol and 30 g of cyclohexane are sequentially added, the stirrer is turned on, the mixture is uniformly stirred at a speed of 200 r / min, 4 g of a catalyst is added, and the stirring and mixing are continued for 10 min, then the temperature is raised to 170℃ at a rate of 3℃ / min, and the reaction is carried out for 3 h, during which water in the water separator is discharged every 30 min, the temperature is lowered to 110℃, 0.5 g of boric acid is added in three portions with an interval of 10 min, the stirring and reaction are continued for 150 min, then a small amount of sample is taken out from the reaction kettle for acid value detection, if the acid value is >1 mg KOH / g, the catalyst is supplemented, and the reaction is continued until the acid value is ≤1 mg KOH / g, the total supplemental amount of the catalyst is not higher than 10% of the mass of the added catalyst, the catalyst is filtered and separated, the filtered catalyst is washed with 15 mL of cyclohexane, the washing liquid and the filtrate are combined, and the combined liquid product is transferred to a distillation device, heated to 85℃, and subjected to normal pressure distillation to remove cyclohexane, then the pressure is adjusted to 8 kPa, heated to 130℃, and subjected to reduced pressure distillation, cooled to 80℃, 0.4 g of antioxidant 1010 is added, and the mixture is uniformly stirred to obtain a diesel anti-wear agent.

[0096] The catalyst is from the preparation example 1.

[0097] Before use, the catalyst is subjected to the following pretreatment steps:

[0098] The above catalyst is immersed in a silane coupling agent solution, heated to 50℃, reacted for 2 h, filtered, washed with deionized water for 3 times, transferred to a vacuum drying oven and adjusted to a temperature of 60℃, and dried to a constant weight.

[0099] The silane coupling agent solution comprises silane coupling agent KH550 and a solvent, the amount of the silane coupling agent solution is 100 mL, the volume concentration of the silane coupling agent KH550 is 2%, and the solvent is a mixture of ethanol and water in a volume ratio of 3:2.

[0100] Example 2

[0101] The preparation method of the diesel anti-wear agent of the example comprises the following steps:

[0102] After the reaction kettle equipped with a stirring device, a thermometer and a reflux condenser is replaced with nitrogen for 3 times, 20 g of conjugated linoleic acid, 80 g of oleic acid, 13.5 g of pentaerythritol and 40 g of cyclohexane are sequentially added, the stirrer is turned on, the mixture is uniformly stirred at a speed of 200 r / min, 5 g of a catalyst is added, and the stirring and mixing are continued for 10 min, then the temperature is increased to 160℃ at a rate of 3℃ / min, and the reaction is continued for 4 h, then the temperature is lowered to 100℃, 0.5 g of boric acid is added twice at an interval of 15 min, the stirring and reaction are continued for 180 min, then a small amount of sample is taken out from the reaction kettle for acid value detection, if the acid value is >1 mg KOH / g, the catalyst is supplemented, and the reaction is continued until the acid value is ≤1 mg KOH / g, the total amount of the supplemented catalyst is not higher than 10% of the mass of the added catalyst, the catalyst is filtered and separated, 15 mL of cyclohexane is used to wash the obtained catalyst, the washing liquid and the filtrate are combined, and the combined liquid product is transferred to a distillation device, the temperature is increased to 105℃, and the cyclohexane is removed by atmospheric distillation, then the pressure is adjusted to 8 kPa, the temperature is increased to 130℃, and the product is subjected to vacuum distillation, then the temperature is lowered to 80℃, 0.3 g of antioxidant 1010 is added, and the mixture is uniformly stirred to obtain the diesel anti-wear agent.

[0103] The catalyst is from Preparation Example 2.

[0104] Before use, the catalyst is subjected to the following pretreatment steps:

[0105] The above catalyst is immersed in a silane coupling agent solution, the temperature is increased to 40℃, the reaction is continued for 3 h, then the catalyst is filtered and washed with deionized water for 3 times, and then the catalyst is transferred to a vacuum drying oven and the temperature is adjusted to 60℃, and the catalyst is dried to constant weight.

[0106] The silane coupling agent solution comprises silane coupling agent KH550 and a solvent, the amount of the silane coupling agent solution is 100 mL, the volume concentration of the silane coupling agent KH550 is 1%, and the solvent is a mixture of ethanol and water in a volume ratio of 7:3.

[0107] Example 3

[0108] The preparation method of the diesel anti-wear agent of the example comprises the following steps:

[0109] In a reaction kettle equipped with stirring device, thermometer and reflux condenser, after purging 3 times with nitrogen, 40 g of conjugated linoleic acid, 60 g of oleic acid, 14 g of pentaerythritol and 35 g of cyclohexane were added in turn, then the stirrer was started and the mixture was stirred at a speed of 200 r / min until uniform, then 6 g of catalyst was added and the stirring was continued for 10 min, then the temperature was raised to 180℃ at a rate of 3℃ / min, and the reaction was carried out for 4 h, then the temperature was lowered to 120℃, 0.5 g of boric acid was added in four portions with an interval of 10 min, and the stirring was continued for 90 min, then a small amount of sample was taken from the reaction kettle for acid value detection, if the acid value was >1 mg KOH / g, the catalyst was supplemented, and the reaction was continued until the acid value was ≤1 mg KOH / g, the total amount of supplemented catalyst was not more than 10% of the mass of the catalyst added, then the catalyst was separated by filtration, the catalyst obtained by filtration was washed with 15 mL of cyclohexane, the washing liquid was combined with the filtrate, and the combined liquid product was transferred to a distillation device, the temperature was raised to 105℃, and normal pressure distillation was carried out to remove cyclohexane, then the pressure was adjusted to 8 kPa, the temperature was raised to 130℃, and vacuum distillation was carried out, then the temperature was lowered to 80℃, 0.5 g of antioxidant 1010 was added, and the mixture was stirred until uniform, to obtain the diesel anti-wear agent.

[0110] The catalyst was from Preparation Example 3.

[0111] Before use, the catalyst was pretreated by the following steps:

[0112] The above catalyst was immersed in a silane coupling agent solution, the temperature was raised to 60℃, and the reaction was carried out for 1 h, then the catalyst was filtered and washed with deionized water for 3 times, then it was transferred to a vacuum drying oven and the temperature was adjusted to 60℃, and dried to constant weight, to obtain the catalyst.

[0113] The silane coupling agent solution included silane coupling agent KH550 and solvent, the amount of the silane coupling agent solution was 100 mL, the volume concentration of the silane coupling agent KH550 was 3%, and the solvent was a mixture of ethanol and water in a volume ratio of 1:1.

[0114] Example 4

[0115] The preparation method of the diesel anti-wear agent of the present example included the following steps:

[0116] In a reaction kettle equipped with stirring device, thermometer, reflux condenser and water separator, after nitrogen was introduced to replace 3 times, 30 g of conjugated linolenic acid, 70 g of palmitoleic acid, 14.5 g of pentaerythritol and 35 g of cyclohexane were sequentially added, then the stirrer was started to stir at a speed of 200 r / min until the mixture was uniform, 6 g of catalyst was added, and the stirring was continued for 10 min, then the temperature was increased to 170℃ at a rate of 3℃ / min, and the reaction was carried out for 3 h, during which water in the water separator was discharged every 30 min, the temperature was decreased to 110℃, 0.5 g of boric acid was added in three times with an interval of 10 min, the stirring was continued for 150 min, then a small amount of sample was taken out from the reaction kettle for acid value detection, if the acid value was >1 mg KOH / g, the catalyst was supplemented, and the reaction was continued until the acid value was ≤1 mg KOH / g, the total supplemental amount of catalyst was not more than 10% of the mass of the catalyst added, the catalyst was separated by filtration, the catalyst obtained by filtration was washed with 15 mL of cyclohexane, the washing liquid and the filtrate were combined, and the combined liquid product was transferred to a distillation device, the temperature was increased to 85℃, and normal pressure distillation was carried out to remove cyclohexane, then the pressure was adjusted to 8 kPa, the temperature was increased to 130℃, and vacuum distillation was carried out, then the temperature was cooled to 80℃, 0.7 g of antioxidant 1010 was added, and the stirring was continued until the mixture was uniform, thereby diesel oil anti-wear agent was obtained.

[0117] The catalyst was from Preparation Example 4.

[0118] Before use, the catalyst was pretreated by the following steps:

[0119] The above catalyst was immersed in a silane coupling agent solution, the temperature was increased to 50℃, the reaction was carried out for 2 h, then the catalyst was filtered and washed with deionized water for 3 times, and then the catalyst was transferred to a vacuum drying oven and the temperature was adjusted to 60℃, and the catalyst was dried to constant weight.

[0120] The silane coupling agent solution included silane coupling agent KH550 and solvent, the amount of the silane coupling agent solution was 100 mL, the volume concentration of the silane coupling agent KH550 was 2%, and the solvent was a mixture of ethanol and water in a volume ratio of 3:2.

[0121] Example 5

[0122] The preparation method of the diesel oil anti-wear agent of the present example included the following steps:

[0123] In a reaction kettle equipped with stirring device, thermometer, reflux condenser and water separator, after nitrogen was introduced to replace 3 times, 20 g of conjugated linoleic acid, 10 g of conjugated linolenic acid, 70 g of palmitoleic acid, 15 g of pentaerythritol and 35 g of cyclohexane were sequentially added, then the stirrer was started to stir at a speed of 200 r / min until the mixture was uniform, 6 g of catalyst was added, and the stirring was continued for 10 min, then the temperature was increased to 170℃ at a rate of 3℃ / min, and the reaction was carried out for 3 h, during which water in the water separator was discharged every 30 min, the temperature was decreased to 110℃, and 0.5 g of boric acid was added in three portions with an interval of 10 min, the stirring was continued for 150 min, then a small amount of sample was taken out from the reaction kettle for acid value detection, if the acid value was >1 mg KOH / g, the catalyst was supplemented, and the reaction was continued until the acid value was ≤1 mg KOH / g, the total amount of the supplemented catalyst was not more than 10% of the mass of the added catalyst, the catalyst was separated by filtration, the catalyst obtained by filtration was washed with 15 mL of cyclohexane, the washing liquid and the filtrate were combined, and the combined liquid product was transferred to a distillation device, the temperature was increased to 85℃, and cyclohexane was removed by atmospheric distillation, then the pressure was adjusted to 8 kPa, the temperature was increased to 130℃, and vacuum distillation was carried out, then the temperature was cooled to 80℃, 0.7 g of antioxidant 1010 was added, and the stirring was continued until the mixture was uniform, thereby obtaining the diesel oil anti-wear agent.

[0124] The catalyst was from Preparation Example 5.

[0125] Before use, the catalyst was pretreated by the following steps:

[0126] The above catalyst was immersed in a silane coupling agent solution, the temperature was increased to 50℃, and the reaction was carried out for 2 h, then the catalyst was filtered and washed with deionized water for 3 times, and then the catalyst was transferred to a vacuum drying oven and the temperature was adjusted to 60℃, and the catalyst was dried to constant weight.

[0127] The silane coupling agent solution included silane coupling agent KH550 and solvent, the amount of the silane coupling agent solution was 100 mL, the volume concentration of the silane coupling agent KH550 was 2%, and the solvent was a mixture of ethanol and water in a volume ratio of 3:2.

[0128] Example 6

[0129] The preparation method of the diesel oil anti-wear agent of the present example included the following steps:

[0130] After the reaction kettle equipped with stirring device, thermometer, reflux condenser and water separator was replaced with nitrogen for 3 times, 30 g of conjugated linoleic acid, 40 g of palmitoleic acid, 30 g of oleic acid, 19 g of trimethylolpropane and 35 g of cyclohexane were sequentially added, then the stirrer was turned on and the mixture was stirred at a speed of 200 r / min until uniform, 6 g of catalyst was added and the stirring was continued for 10 min, then the temperature was raised to 170 ℃ at a rate of 3 ℃ / min, and the reaction was carried out for 3 h, during which water in the water separator was discharged every 30 min, the temperature was lowered to 110 ℃, and 0.5 g of boric acid was added in three portions with an interval of 10 min each time, the stirring was continued for 150 min, then a small amount of sample was taken out from the reaction kettle for acid value detection, if the acid value was >1 mg KOH / g, the catalyst was supplemented, and the reaction was continued until the acid value was ≤1 mg KOH / g, the total amount of the supplemented catalyst was not more than 10% of the mass of the added catalyst, the catalyst was separated by filtration, the catalyst obtained by filtration was washed with 15 mL of cyclohexane, the washing liquid and the filtrate were combined, and the combined liquid product was transferred to a distillation device, the temperature was raised to 85 ℃, and cyclohexane was removed by atmospheric distillation, then the pressure was adjusted to 8 kPa, the temperature was raised to 130 ℃, and vacuum distillation was carried out, then the temperature was lowered to 80 ℃, 0.7 g of antioxidant 1010 was added, and the mixture was stirred until uniform, to obtain the diesel anti-wear agent.

[0131] The catalyst was from Preparation Example 6.

[0132] Before use, the catalyst was pretreated by the following steps:

[0133] The above catalyst was immersed in a silane coupling agent solution, the temperature was raised to 50 ℃, and the reaction was carried out for 2 h, then the catalyst was filtered and washed with deionized water for 3 times, and then transferred to a vacuum drying oven and adjusted to a temperature of 60 ℃, and dried to constant weight.

[0134] The silane coupling agent solution included silane coupling agent KH550 and a solvent, the amount of the silane coupling agent solution was 100 mL, the volume concentration of the silane coupling agent KH550 was 2%, and the solvent was a mixture of ethanol and water in a volume ratio of 3:2.

[0135] Example 7

[0136] The difference between this example and Example 1 is that:

[0137] When pentaerythritol was added, 0.5 g of graphene oxide was also added.

[0138] Before use, the graphene oxide was pretreated by the following steps:

[0139] After 0.5 g of graphene oxide and 0.5 g of polyethylene glycol were stirred and mixed uniformly, 0.025 g of oleic acid was added, and the mixture was stirred and mixed uniformly, then ultrasonic treatment was carried out for 20 min, the ultrasonic frequency was 20 kHz, and the power was 300 W.

[0140] Other than Example 1.

[0141] Example 8

[0142] The difference between this example and Example 7 is that:

[0143] 1.5 g of graphene oxide was also added when adding pentaerythritol.

[0144] The graphene oxide was pretreated before use by the following steps:

[0145] After 1.5 g of graphene oxide and 3 g of polyethylene glycol were stirred and mixed evenly, 0.15 g of oleic acid was added, stirred and mixed evenly, and then ultrasonic treatment was performed for 30 min, with an ultrasonic frequency of 30 kHz and a power of 400 W.

[0146] Other than Example 7.

[0147] Example 9

[0148] The difference between this example and Example 8 is that:

[0149] 2 g of graphene oxide and 2 g of glycerol triglycidyl ether were also added when adding pentaerythritol.

[0150] The graphene oxide was pretreated before use by the following steps:

[0151] After 2 g of graphene oxide and 4 g of polyethylene glycol were stirred and mixed evenly, 0.2 g of oleic acid was added, stirred and mixed evenly, and then ultrasonic treatment was performed for 40 min, with an ultrasonic frequency of 40 kHz and a power of 500 W.

[0152] Other than Example 8.

[0153] Example 10

[0154] The difference between this example and Example 9 is that:

[0155] The amount of glycerol triglycidyl ether was 4 g.

[0156] Other than Example 9.

[0157] Comparative Example 1

[0158] The preparation method of the diesel oil anti-wear agent of this comparative example includes the following steps:

[0159] In a reaction kettle equipped with stirring device, thermometer, reflux condenser and water separator, after nitrogen was introduced for 3 times, 100 g of oleic acid, 13 g of pentaerythritol and 30 g of cyclohexane were added in turn, then the stirrer was started, the mixture was stirred uniformly at a speed of 200 r / min, 4 g of catalyst was added, the stirring and mixing was continued for 10 min, then the temperature was increased to 170℃ at a rate of 3℃ / min, the reaction was carried out for 3 h, during which water in the water separator was discharged every 30 min, the temperature was decreased to 110℃, 0.5 g of boric acid was added in three times, with an interval of 10 min each time, the stirring and reaction was continued for 150 min, then a small amount of sample was taken out from the reaction kettle for acid value detection, if the acid value was >1 mg KOH / g, the catalyst was supplemented, and the reaction was continued until the acid value was ≤1 mg KOH / g, the total supplemental amount of catalyst was not more than 10% of the mass of the catalyst added, the catalyst was separated by filtration, the catalyst obtained by filtration was washed with 15 mL of cyclohexane, the washing liquid and the filtrate were combined, and the combined liquid product was transferred to a distillation device, the temperature was increased to 85℃, and normal pressure distillation was carried out to remove cyclohexane, then the pressure was adjusted to 8 kPa, the temperature was increased to 130℃, and vacuum distillation was carried out, then the temperature was cooled to 80℃, 0.4 g of antioxidant 1010 was added, and the stirring and mixing was uniform, to obtain the diesel anti-wear agent.

[0160] The catalyst is from Preparation Example 1.

[0161] Before use, the catalyst is subjected to the following pretreatment steps:

[0162] The above catalyst is immersed in a silane coupling agent solution, the temperature is increased to 50℃, the reaction is carried out for 2 h, then it is filtered and washed with deionized water for 3 times, then it is transferred to a vacuum drying oven and the temperature is adjusted to 60℃, and dried to constant weight, to obtain the catalyst.

[0163] The silane coupling agent solution includes silane coupling agent KH550 and solvent, the amount of the silane coupling agent solution is 100 mL, the volume concentration of the silane coupling agent KH550 is 2%, and the solvent is a mixture of ethanol and water in a volume ratio of 3:2.

[0164] Comparative Example 2

[0165] The preparation method of the diesel anti-wear agent of the present comparative example includes the following steps:

[0166] In a reaction kettle equipped with stirring device, thermometer, reflux condenser and water separator, after nitrogen was introduced to replace 3 times, 100 g of conjugated linoleic acid, 13 g of pentaerythritol and 30 g of cyclohexane were added in turn, then the stirrer was started, the mixture was stirred uniformly at a speed of 200 r / min, 4 g of catalyst was added, and the stirring and mixing was continued for 10 min, then the temperature was raised to 170℃ at a rate of 3℃ / min, and the reaction was carried out for 3 h, during which water in the water separator was discharged every 30 min, the temperature was lowered to 110℃, and 0.5 g of boric acid was added in three portions with an interval of 10 min, the stirring and reaction was continued for 150 min, then a small amount of sample was taken out from the reaction kettle for acid value detection, if the acid value was >1 mg KOH / g, the catalyst was supplemented, and the reaction was continued until the acid value was ≤1 mg KOH / g, the total amount of supplemented catalyst was not more than 10% of the mass of the catalyst added, the catalyst was separated by filtration, the catalyst obtained by filtration was washed with 15 mL of cyclohexane, the washing liquid and the filtrate were combined, and the combined liquid product was transferred to a distillation device, the temperature was raised to 85℃, and cyclohexane was removed by atmospheric distillation, then the pressure was adjusted to 8 kPa, the temperature was raised to 130℃, and vacuum distillation was carried out, then the temperature was lowered to 80℃, 0.4 g of antioxidant 1010 was added, and the stirring and mixing was uniform, to obtain a diesel oil anti-wear agent.

[0167] The catalyst is from Preparation Example 1.

[0168] Before use, the catalyst is subjected to the following pretreatment steps:

[0169] The above catalyst is immersed in a silane coupling agent solution, the temperature is raised to 50℃, the reaction is carried out for 2 h, filtration is carried out, deionized water is used for washing 3 times, and then the catalyst is transferred to a vacuum drying oven and the temperature is adjusted to 60℃, and drying is carried out until the weight is constant, to obtain the catalyst.

[0170] The silane coupling agent solution includes silane coupling agent KH550 and solvent, the amount of the silane coupling agent solution is 100 mL, the volume concentration of the silane coupling agent KH550 is 2%, and the solvent is a mixture of ethanol and water in a volume ratio of 3:2.

[0171] Comparative Example 3

[0172] The preparation method of the diesel oil anti-wear agent of the present comparative example includes the following steps:

[0173] In a reaction kettle equipped with stirring device, thermometer, reflux condenser and water separator, after 3 times of nitrogen replacement, 100 g of conjugated linoleic acid, 13 g of pentaerythritol and 30 g of cyclohexane were sequentially added, then the stirrer was started, and the mixture was stirred at a speed of 200 r / min until uniform, then 4 g of catalyst was added, and the stirring was continued for 10 min, then the temperature was raised to 170℃ at a rate of 3℃ / min, and the reaction was carried out for 3 h, during which water in the water separator was discharged every 30 min, after the reaction was completed, a small amount of sample was taken out from the reaction kettle, and the acid value was detected, if the acid value was >1 mg KOH / g, the catalyst was supplemented, and the reaction was continued until the acid value was ≤1 mg KOH / g, the total amount of the supplemented catalyst was not more than 10% of the mass of the added catalyst, the temperature was lowered to 80℃, and the catalyst was separated by filtration, the catalyst obtained by filtration was washed with 15 mL of cyclohexane, the washing liquid and the filtrate were combined, and the combined liquid product was transferred to a distillation device, the temperature was raised to 85℃, and cyclohexane was removed by atmospheric distillation, then the pressure was adjusted to 8 kPa, the temperature was raised to 130℃, and vacuum distillation was carried out, then the temperature was lowered to 80℃, 0.4 g of antioxidant 1010 was added, and the mixture was stirred until uniform, to obtain a diesel anti-wear agent.

[0174] Before use, the catalyst is pretreated by the following steps:

[0175] The above catalyst is immersed in a silane coupling agent solution, the temperature is raised to 50℃, and the reaction is carried out for 2 h, then the catalyst is filtered and washed with deionized water for 3 times, and then transferred to a vacuum drying oven and adjusted to a temperature of 60℃, and dried to constant weight to obtain the catalyst.

[0176] The silane coupling agent solution includes silane coupling agent KH550 and a solvent, the amount of the silane coupling agent solution is 100 mL, the volume concentration of the silane coupling agent KH550 is 2%, and the solvent is a mixture of ethanol and water in a volume ratio of 3:2.

[0177] Comparative Example 4

[0178] The difference between this comparative example and Example 1 is that:

[0179] The amount of the catalyst used is the same.

[0180] The preparation method of the catalyst includes the following steps:

[0181] The preparation method of the catalyst of this preparation example includes the following steps:

[0182] (1) 10 g of foamed nickel is immersed in 100 mL of a nitric acid solution with a volume concentration of 22%, the temperature is raised to 55℃, and etching is carried out for 30 min, then the foamed nickel is washed with deionized water until neutral, and then transferred to a vacuum drying oven and adjusted to a temperature of 60℃, and dried to constant weight to obtain pretreated foamed nickel;

[0183] (2) The pretreated foamed nickel is immersed in 200 mL of precursor solution, ammonia water with a molar concentration of 0.6 mol / L is slowly added dropwise at a stirring speed of 200 r / min, the pH is adjusted to 9-9.5, the temperature is increased to 170°C, and the reaction is performed for 8 h. After natural cooling, the catalyst is washed with ethanol for 3 times, transferred into a vacuum drying box, and the temperature is adjusted to 60°C. After drying to a constant weight, the catalyst is transferred into a sintering furnace, nitrogen is introduced for replacement for 3 times, and then nitrogen is continuously introduced at a speed of 50 mL / min. The temperature is increased to 220°C at a speed of 5°C / min, and the temperature is maintained for 60 min. Then the temperature is increased to 320°C at a speed of 3°C / min, and the temperature is maintained for 90 min. Then the introduction of nitrogen is stopped, and the furnace is cooled to obtain the catalyst.

[0184] Other same as Example 1.

[0185] Performance test

[0186] The diesel anti-wear agents in Examples 1-10 and Comparative Examples 1-4 are added into low-sulfur diesel (sulfur content 10.0 mg / kg, kinematic viscosity at 40°C 3.2 mm 2 / s) to perform wear test of diesel. The wear test conditions are as follows: a high-frequency reciprocating testing machine is used, the temperature is 60±0.5°C, the normal load is 200±0.5N, the reciprocating frequency is 50 Hz (corresponding to a stroke of 1 mm), the single test duration is 75 min, each test is repeated for 3 times, the average value is taken, and a blank control group is set. The specific test results are shown in Table 1.

[0187] The diesel anti-wear agents in Examples 1-10 and Comparative Examples 1-4 are added into low-sulfur diesel (sulfur content 10.0 mg / kg, kinematic viscosity at 40°C 3.2 mm 2 / s) to perform pour point test of diesel. The test conditions are as follows: an automatic pour point tester is used, the pour point is tested at a cooling rate of 3°C / min, each test is repeated for 3 times, the average value is taken, and the specific test results are shown in Table 1.

[0188] The mixing ratio of the diesel anti-wear agent and the low-sulfur diesel is 40-100 μg / g. The diesel anti-wear agent is added into the low-sulfur diesel according to the ratio, the temperature is increased to 60°C, and the stirring speed is 600 r / min. The stirring and mixing are performed for 60 min to ensure uniform dispersion.

[0189] Table 1 Wear test data of the diesel anti-wear agents in Examples 1-10 and Comparative Examples 1-4

[0190]

[0191] The performance test data in Table 1 is analyzed as follows:

[0192] From Examples 1-3 and Comparative Examples 1-4, it can be seen that within a certain range, the higher the proportion of conjugated linoleic acid in the fatty acid combination, the better the anti-wear performance, but the pour point will slightly rise due to the regularity of the molecular structure of conjugated linoleic acid promoting crystallization. Although the use of conjugated linoleic acid alone has good anti-wear performance, it has poor low-temperature fluidity. On the contrary, the use of oleic acid alone has good low-temperature fluidity, but the anti-wear performance is insufficient. In addition, the boron-containing lubricating film generated by the reaction of boric acid and fatty acid cooperates with the adsorption film, reduces the wear scar diameter by enhancing the boundary lubrication effect.

[0193] From Examples 4-10, it can be seen that first, due to the adaptability of the conjugated double bond of conjugated linoleic acid to the metal surface, the anti-wear activity is significantly better than that of conjugated linolenic acid; second, the two-dimensional sheet layer of graphene oxide forms a continuous reinforced film layer through physical filling and chemical cross-linking of glycerol triglycidyl ether, and the performance shows a stepwise increase with the increase of the addition amount; third, the symmetrical structure of pentaerythritol can form a three-dimensional network film layer, and its hardness and load capacity are better than those of trimethylolpropane.

[0194] The specific embodiments are only an explanation of the present application, and are not a limitation of the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A process for the preparation of a diesel anti-wear agent, characterized in that, It comprises the following steps: Under inert atmosphere, 20-40 parts by mass of conjugated unsaturated fatty acid, 60-80 parts by mass of non-conjugated unsaturated fatty acid, 13-19 parts by mass of polyol, 0.3-0.7 parts by mass of antioxidant and 30-40 parts by mass of cyclohexane are uniformly mixed, 4-6 parts by mass of catalyst is added and uniformly mixed, the temperature is raised to 160-180℃, and the reaction is carried out for 2-4 hours, the temperature is lowered to 100-120℃, 1-2 parts by mass of boric acid is added, and the reaction is continued for 120-180 minutes, then solid-liquid separation and distillation are carried out to obtain diesel anti-wear agent; The catalyst is a core-shell structure composite of a rare earth metal oxide layer and a heteropoly acid metal salt sequentially loaded on the surface of a porous metal carrier; The conjugated unsaturated fatty acid is at least one of conjugated linoleic acid and conjugated linolenic acid; The non-conjugated unsaturated fatty acid is at least one of oleic acid and palmitoleic acid; The polyol is any one of pentaerythritol and trimethylolpropane; The heteropoly acid metal salt is any one of cesium phosphotungstate and potassium phosphotungstate.

2. The method of claim 1, wherein the diesel anti-wear agent is prepared by the steps of: The preparation method of the catalyst comprises the following steps: (1) The porous metal carrier is subjected to acid etching, washing, and drying to obtain a pretreated carrier; (2) The pretreated carrier is immersed in a precursor solution, the pH is adjusted to 9-10, the temperature is raised to 160-180℃, and the reaction is carried out for 6-10 hours, then the pretreated carrier is washed and dried to obtain a pre-loaded catalyst; (3) The pre-loaded catalyst is immersed in a heteropoly acid metal salt solution for 30-60 minutes, then solid-liquid separation and drying are carried out, and calcination is carried out under inert atmosphere to obtain the catalyst; The precursor solution comprises a rare earth metal salt, and the molar concentration of the rare earth metal salt is 0.15-0.25 mol / L; the molar concentration of the heteropoly acid metal salt solution is 0.05-0.2 mol / L.

3. The method of claim 2, wherein the anti-wear agent is prepared by the steps of: The catalyst is subjected to the following pretreatment steps before use: The catalyst is immersed in a silane coupling agent solution with a pH of 3-4 and a volume concentration of 1%-3% at 40-60℃ for 1-3 hours, then solid-liquid separation and drying are carried out to obtain the catalyst; The silane coupling agent solution comprises a silane coupling agent, ethanol and water.

4. The method of claim 2, wherein the anti-wear agent is prepared by the steps of: The rare earth metal salt is any one of cerium nitrate and lanthanum nitrate.

5. The method of claim 1, wherein the anti-wear agent is prepared by the steps of: The porous metal carrier is any one of foamed nickel and foamed titanium.

6. The method of claim 1, wherein the diesel anti-wear agent is prepared by the steps of: When the polyol is added, the step of adding 0.5-2 parts by mass of graphene oxide is further included.

7. The method of claim 6, wherein the diesel anti-wear agent is prepared by the steps of: The graphene oxide is subjected to the following pretreatment steps before use: The graphene oxide and polyethylene glycol are uniformly mixed, then oleic acid is added and uniformly mixed, and ultrasonic treatment is carried out for 30-40 minutes to obtain the graphene oxide; the mass ratio of the graphene oxide, polyethylene glycol and oleic acid is 1:(1-2):(0.05-0.1).

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