A diesel fuel additive and a method for its preparation

Abstract

The application relates to the technical field of diesel oil additives, and discloses a diesel oil additive and a preparation method thereof, which comprises the following raw materials in parts by mass: t-butyl peroxy benzoate 15-20 parts, polyether amine 10-15 parts, isooctyl nitrate 25-30 parts, antioxidant 2-4 parts, preservative 3-5 parts, dispersant 6-8 parts and composite anti-wear agent 6-8 parts. The composite anti-wear agent is added into the mixture of t-butyl peroxy benzoate, polyether amine and isooctyl nitrate to serve as the diesel oil additive. The polyether amine chain segment contained on the surface of the composite anti-wear agent can form a steric hindrance or electrostatic stabilization system with the diesel oil additive, prevents the agglomeration of the composite anti-wear agent, and improves the combustion performance of diesel oil.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of diesel oil additives, in particular to a diesel oil additive and a preparation method thereof. BACKGROUND

[0002] The diesel engine is characterized by oxygen-rich and non-uniform combustion of diesel in the combustion chamber, resulting in pollutants in the exhaust mainly being nitrogen oxides and PM particulate matter. In order to reduce the generation of particulate matter PM and improve the combustion efficiency of biodiesel, a diesel oil additive is added to diesel (including biodiesel and ordinary diesel), which can improve the quality of biodiesel, promote the combustion of biodiesel, and thus improve the economy of fuel and reduce the generation of particulate matter. The diesel oil additive is composed of oxygen-containing organic matter, nanomaterials, cleaning activation factors, antioxidants, and preservative materials, and is developed for harmful components such as sulfur, gum and engine carbon in oil, which can improve the cetane number, enhance the power, and promote the performance of combustion work.

[0003] Metal nanoparticles as a component of diesel oil additives have small size effect, quantum effect, surface effect and interface effect, which can improve oil quality, promote diesel combustion, improve combustion efficiency and atomization quality, and reduce carbon monoxide, nitrogen oxides and other emissions. However, metal nanoparticles are prone to agglomeration and other problems, which affect the combustion performance of diesel. In addition, the current diesel has low sulfur content, poor lubricity, which easily causes nozzle blockage, sticking wear of fuel injection pump and other problems, affecting the combustion performance of diesel. SUMMARY

[0004] The present application provides a diesel oil additive and a preparation method thereof, which solves the problem of poor lubricity and incomplete combustion of diesel oil.

[0005] The technical scheme of the present application is as follows:

[0006] A diesel oil additive comprises the following raw materials by mass: 15-20 parts of t-butyl peroxybenzoate, 10-15 parts of polyether amine, 25-30 parts of isooctyl nitrate, 2-4 parts of antioxidant, 3-5 parts of preservative, 6-8 parts of dispersant, and 6-8 parts of composite anti-wear agent.

[0007] The composite anti-wear agent is obtained by mixing and reacting pretreated graphene oxide nanosheets, polyether amine, isocyanate and t-butyl hydroquinone, and then mixing with modified molybdenum disulfide nanosheets.

[0008] The modified molybdenum disulfide nanosheet is obtained by intercalating the molybdenum disulfide nanosheet with an intercalating agent, and then mixing and reacting with cerium nitrate hexahydrate, dispersant and ammonia.

[0009] A preparation method of a diesel oil additive comprises the following preparation steps:

[0010] Tert-butyl perbenzoate and isooctyl nitrate are mixed, stirred at 45-55° C. for 20-30 minutes, a dispersant and polyetheramine are added, nitrogen is introduced, ultrasonic mixing is performed at 20-30 kHz for 10-15 minutes, the mixture is allowed to stand at 2-3 MPa and 65-75° C. for 45-55 minutes, an antioxidant, a preservative and a composite anti-wear agent are added, the mixture is stirred and mixed for 20-30 minutes, and the mixture is cooled to room temperature to obtain a diesel additive.

[0011] Furthermore, the dispersant is prepared by mixing octadecyl amide and polyethylene glycol-200 in a mass ratio of (1-1.2):1.

[0012] Furthermore, the antioxidant is zinc dialkyl dithiophosphate.

[0013] Furthermore, the preservative is selected from diisooctylamine or octylbutyldiphenylamine.

[0014] Furthermore, the composite anti-wear agent is specifically prepared by the following steps:

[0015] A1. MoS2 nanosheets and an intercalant were added to n-hexane, stirred evenly, heated to 75-85°C, stirred for 3-5 hours, filtered, washed, and dried to obtain a solid. The solid was added to deionized water and sonicated at 40-60 kHz for 1-2 hours. The solid was centrifuged, washed, and dried to obtain exfoliated MoS2 nanosheets.

[0016] A2. The exfoliated molybdenum disulfide nanosheets and cerium nitrate hexahydrate were added to deionized water and stirred uniformly. Ammonia was added to adjust the pH to 9-11. Ethylene glycol was then added and stirred at 200-300 rpm for 1-2 hours. After standing, the mixture was filtered, washed, dried, calcined at 280-320°C for 3-5 hours, and cooled to room temperature to obtain modified molybdenum disulfide nanosheets.

[0017] A3. Add polyetheramine and tert-butylhydroquinone to tetrahydrofuran and stir until completely dissolved. Maintain the temperature at 0-4°C. Add isocyanate and stir for 30-35 minutes. Raise the temperature to 55-65°C and add pretreated graphene oxide nanosheets. Continue stirring for 5-6 hours. Cool to room temperature, centrifuge, wash, and dry to obtain modified graphene oxide nanosheets.

[0018] A4. Add modified graphene oxide nanosheets and modified molybdenum disulfide nanosheets to ethanol, stir at 60-70°C for 1-2 hours, let stand, filter, wash, and dry to obtain a composite anti-wear agent.

[0019] Further, in the above A1 reaction process, the intercalation agent can be intercalated into the interlayer of the molybdenum disulfide nanosheet, and after ultrasonic treatment, the exfoliated molybdenum disulfide nanosheet is formed, avoiding the weak van der Waals force between adjacent sulfur atom layers of the molybdenum disulfide nanosheet, and the layers are easy to separate, which affects the anti-wear performance of diesel, further reduces the combustion performance, and causes the generation of carbon deposition.

[0020] Further, in the above A2 reaction process, the hydroxyl group contained on the surface of the exfoliated molybdenum disulfide nanosheet can be combined with cerium ions in cerium nitrate hexahydrate, and ammonia water can be used as a precipitant and ethylene glycol as a dispersant to form a complex on the surface of the exfoliated molybdenum disulfide nanosheet. After high-temperature calcination, the complex is decomposed by heat to form nanometer cerium oxide with a size of 2-5 nm on the surface of the exfoliated molybdenum disulfide nanosheet, and the modified exfoliated molybdenum disulfide nanosheet is obtained.

[0021] Further, in the above A3 reaction process, in the organic solvent tetrahydrofuran, the amino group of the polyether amine can react with toluene diisocyanate, and toluene diisocyanate can also react with the hydroxyl group of 2,5-di-tert-butyl hydroquinone to form an anti-carbon deposition agent; the formed anti-carbon deposition agent can be attached to the surface of the pretreated graphene oxide nanosheet to obtain a modified graphene oxide nanosheet.

[0022] Further, in the above A4 reaction process, the amino, aliphatic, and hydroxyl groups contained on the surface of the modified graphene oxide nanosheet can be combined with the hydroxyl groups on the surface of the modified exfoliated molybdenum disulfide nanosheet through chemical bonds, so that the modified graphene oxide nanosheet is coated on the modified exfoliated molybdenum disulfide nanosheet to form a layered composite material as a composite anti-wear agent.

[0023] Further, in step A1, the amount ratio of the molybdenum disulfide nanosheet, the intercalation agent, and n-hexane is (1-2) g:(1-1.2) g:(35-45) mL.

[0024] Further, in step A1, the amount ratio of the solid and deionized water is (1-3) g:(90-110) mL.

[0025] Further, in step A2, the amount ratio of the exfoliated molybdenum disulfide nanosheet, cerium nitrate hexahydrate, deionized water, and ethylene glycol is (2-3) g:(8.2-8.4) g:(65-75) mL:(0.6-1) g.

[0026] Further, in step A3, the amount ratio of the polyether amine, tert-butyl hydroquinone, tetrahydrofuran, isocyanate, and pretreated graphene oxide nanosheet is (7-9) g:(3.1-3.5) g:(45-55) mL:(3-4) g:(5-6) g.

[0027] Further, in step A4, the modified graphene oxide nanosheet, modified molybdenum disulfide nanosheet and ethanol are used in a ratio of (1-2) g:(1-1.2) g:(90-110) mL.

[0028] Further, the isocyanate is toluene-2,4-diisocyanate.

[0029] Further, the molybdenum disulfide nanosheet has a size of 100-130 nm and a thickness of 5-7 nm.

[0030] Further, the intercalation agent is n-butyllithium.

[0031] Further, the pretreated graphene oxide nanosheet is prepared by the following steps:

[0032] The graphene oxide nanosheet is added to the Tris-HCl buffer solution, stirred uniformly, and dopamine is added, and after continuous stirring, the pretreated graphene oxide nanosheet is obtained by filtering, washing and drying.

[0033] Further, in the above reaction process, in the Tris-HCl buffer solution, dopamine can self-polymerize on the surface of the graphene oxide nanosheet to form polydopamine, forming a polydopamine-modified graphene oxide nanosheet.

[0034] Further, the graphene oxide nanosheet, Tris-HCl buffer solution and dopamine are used in a ratio of (1-2) g:(90-110) mL:(0.4-0.6) g.

[0035] Further, the graphene oxide nanosheet is a single-layer graphene oxide nanosheet, has a size of 100-150 nm and a thickness of 0.8-1.2 nm.

[0036] The present application has the following beneficial effects:

[0037] (1) In the technical scheme of the present application, the intercalation agent can be intercalated into the interlayer of the molybdenum disulfide nanosheet, and after ultrasonic treatment, the exfoliated molybdenum disulfide nanosheet is formed, which avoids the weak van der Waals force between adjacent sulfur atom layers of the molybdenum disulfide nanosheet, and the layers are easy to separate, which affects the anti-wear performance of the biodiesel, and further reduces the combustion performance, and is conducive to the synthesis of nano cerium oxide on the exfoliated molybdenum disulfide nanosheet, which is more easy to form a layered composite material, improve the anti-wear performance, and improve the combustion performance of the biodiesel; the nano cerium oxide is formed on the surface of the exfoliated molybdenum disulfide nanosheet, on the one hand, the synthesized nano cerium oxide as a biodiesel additive can promote the combustion of biodiesel, and enhance the mixing of oil mist and air, so that the combustion is more complete, and the complete combustion of unburned hydrocarbons is promoted, on the other hand, the exfoliated molybdenum disulfide nanosheet as a carrier of nano cerium oxide avoids the agglomeration of small size nano cerium oxide in the biodiesel, which affects the combustion performance of the biodiesel, in addition, the nano cerium oxide forms a concave-convex structure on the exfoliated molybdenum disulfide nanosheet, forms a lubricating film on the metal surface, reduces the friction loss of the engine, improves the wear resistance, and increases the combustion performance of the biodiesel.

[0038] (2) In the technical scheme of the present application, dopamine can be self-polymerized on the surface of the graphene oxide nanosheet to form polydopamine, and the polydopamine modified graphene oxide nanosheet is formed, which is conducive to the synthesis of an anti-carbon deposition agent on the surface of the graphene oxide nanosheet, improves the anti-carbon deposition performance of the biodiesel, and further improves the combustion performance of the biodiesel, the anti-carbon deposition agent formed by polyetheramine, isocyanate and tert-butyl hydroquinone is attached to the surface of the pretreated graphene oxide nanosheet, on the one hand, the amine group, ether bond and hydroxyl group contained in the formed anti-carbon deposition agent can adsorb carbon particles through polar action to form micelles to prevent soot agglomeration and deposition, improve the anti-carbon deposition performance of the biodiesel, and further improve the combustion efficiency of the biodiesel, on the other hand, the pretreated graphene oxide nanosheet forms an anti-carbon deposition agent, which further improves the high temperature resistance of the anti-carbon deposition agent, and the anti-carbon deposition agent improves the dispersion performance of the pretreated graphene oxide nanosheet in the biodiesel, as a biodiesel additive, improves the anti-carbon deposition and anti-wear performance of the biodiesel.

[0039] (3) In the technical scheme of the present application, the modified graphene oxide nanosheet is coated on the modified exfoliated molybdenum disulfide nanosheet to form a layered composite material. On the one hand, the nanometer cerium oxide contained in the layered composite material interlayer serves as a lubricating component, so that the layered composite material moves back and forth between the layers, generates a micro ball bearing effect, increases the buffer distance of the layered composite material, has excellent wear resistance, and the surface of the layered composite material contains a polar functional group, which can be adsorbed on the metal surface to form a wear-resistant coating, thereby improving the wear resistance of the biodiesel. On the other hand, the adsorbed carbon particles act between the layers of the layered composite material, together with the nanometer cerium oxide as a lubricating component, to further enhance the wear resistance of the biodiesel. In addition, the nanometer cerium oxide has excellent redox performance and can promote the oxidation reaction of the carbon particles at a lower temperature, so that the carbon particles are converted into carbon dioxide and water more quickly, thereby reducing the deposition of carbon on the surface of the engine.

[0040] (4) In the technical scheme of the present application, the composite anti-wear agent is added to the mixture of tert-butyl benzene peroxide, polyether amine and isooctyl nitrate as a diesel additive. The polyether amine segment contained on the surface of the composite anti-wear agent can form a steric hindrance or electrostatic stabilization system with the diesel additive to prevent the agglomeration of the composite anti-wear agent and improve the combustion performance of the diesel. DETAILED DESCRIPTION

[0041] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0042] The raw materials used in the embodiments of the present application are shown below, and all the reagents used are analytical grade.

[0043] The polyether amine has a molecular weight of 400 and is purchased from Merck Investment (China) Co., Ltd.

[0044] The preservative is diisooctylamine, and the antioxidant is zinc dialkyldithiophosphate.

[0045] The polyethylene glycol-200 is purchased from Haian Petroleum Chemical Plant in Jiangsu Province.

[0046] The isocyanate is toluene-2,4-diisocyanate.

[0047] The molybdenum disulfide nanosheet has a sheet diameter of 120 nm and a thickness of 6 nm, and the intercalation agent is n-butyl lithium.

[0048] The graphene oxide nanosheet is a single-layer graphene oxide nanosheet with a sheet diameter of 130 nm and a thickness of 1 nm.

[0049] The pretreated graphene oxide nanosheets are prepared by the following steps:

[0050] 1.5 g of graphene oxide nanosheets is added to 100 mL of Tris-HCl buffer solution with pH of 8.5, stirred at 25℃ and 2000 r / min for 20 min, 0.5 g of dopamine is added, stirred at 30℃ and 2000 r / min for 2 h, filtered, washed with deionized water for 3 times, dried in an oven at 70℃ for 10 min, and the pretreated graphene oxide nanosheets are obtained. Embodiment

[0051] A diesel oil additive, comprising the following raw materials in mass parts: 15 parts of t-butyl peroxy benzoate, 10 parts of polyether amine, 25 parts of isooctyl nitrate, 2 parts of zinc dialkyldithiophosphate, 3 parts of diisooctylamine, 6 parts of dispersant, and 6 parts of composite anti-wear agent.

[0052] A preparation method of a diesel oil additive, comprising the following preparation steps:

[0053] The t-butyl peroxy benzoate and the isooctyl nitrate are mixed, stirred at 45℃ for 20 min, the dispersant and the polyether amine are added, nitrogen is introduced, ultrasonic mixing is performed at 20 KHz for 10 min, the mixture is statically placed at 2 MPa and 65℃ for 45 min, the zinc dialkyldithiophosphate, the diisooctylamine and the composite anti-wear agent are added, and the stirring is continued for 20 min, and the diesel oil additive is obtained after cooling to room temperature.

[0054] The dispersant is prepared by mixing octadecanamide and polyethylene glycol-200 in a mass ratio of 1:1.

[0055] The composite anti-wear agent is prepared by the following steps:

[0056] A1. 1 g of molybdenum disulfide nanosheets and 1 g of n-butyllithium are added to 35 mL of n-hexane, stirred uniformly, heated to 75℃, stirred for 3 h, filtered, washed with deionized water for 3 times, dried in an oven at 70℃ for 10 min, 1 g of the solid is added to 90 mL of deionized water, ultrasonic treated at 40 KHz for 1 h, the product is collected by centrifugation at 6000 r / min, the product is washed with deionized water for 3 times, and dried in an oven at 70℃ for 10 min to obtain exfoliated molybdenum disulfide nanosheets;

[0057] A2. 2 g of exfoliated molybdenum disulfide nanosheets and 8.2 g of cerium nitrate hexahydrate are added to 65 mL of deionized water, stirred uniformly, ammonia water is added to adjust the pH to 9, 0.6 g of ethylene glycol is further added, stirred at 200 r / min for 1 h, statically placed for 1 h, filtered, washed with deionized water for 3 times, dried in an oven at 100℃ overnight, placed in a muffle furnace, calcined at 280℃ for 3 h, and cooled to room temperature to obtain modified molybdenum disulfide nanosheets.

[0058] A3. 7 g of polyether amine and 3.1 g of tert-butyl hydroquinone were added to 45 mL of tetrahydrofuran, stirred until completely dissolved, the temperature was kept at 0°C, 3 g of toluene-2,4-diisocyanate was added, stirred for 30 min, the temperature was raised to 55°C, 5 g of pretreated graphene oxide nanosheet was added, and the stirring reaction was continued for 5 h, and then cooled to room temperature. The solid was collected by centrifugation at 5000 r / min, the solid was washed with deionized water for 3 times, and dried in an oven at 80°C for 10 min to obtain modified graphene oxide nanosheet;

[0059] A4. 1 g of modified graphene oxide nanosheet and 1 g of modified molybdenum disulfide nanosheet were added to 90 mL of ethanol, stirred at 60°C for 1 h, and then filtered and washed with deionized water for 3 times. Dried in an oven at 70°C for 10 min to obtain a composite anti-wear agent. Embodiment

[0060] A diesel oil additive, comprising the following raw materials in mass parts: tert-butyl peroxy benzoate 18 parts, polyether amine 13 parts, isooctyl nitrate 28 parts, zinc dialkyldithiophosphate 3 parts, diisooctylamine 4 parts, dispersant 7 parts, and composite anti-wear agent 7 parts.

[0061] A method for preparing a diesel oil additive, comprising the following preparation steps:

[0062] Tert-butyl peroxy benzoate and isooctyl nitrate were mixed and stirred at 50°C for 25 min, then the dispersant and polyether amine were added, nitrogen was introduced, and ultrasonic mixing was carried out at 25 KHz for 13 min. The mixture was placed at 2.5 MPa and 70°C for 50 min, then zinc dialkyldithiophosphate, diisooctylamine and composite anti-wear agent were added, and the stirring was continued for 25 min. The mixture was cooled to room temperature to obtain the diesel oil additive.

[0063] The dispersant is prepared by mixing octadecanamide and polyethylene glycol-200 in a mass ratio of 1.1:1.

[0064] The composite anti-wear agent is prepared by the following steps:

[0065] A1. 1.5 g of molybdenum disulfide nanosheet and 1.1 g of n-butyllithium were added to 40 mL of n-hexane, stirred until uniform, and then the temperature was raised to 80°C and stirred for 4 h. The mixture was filtered and washed with deionized water for 3 times. The solid was dried in an oven at 70°C for 10 min to obtain a solid. 2 g of the solid was added to 100 mL of deionized water, and ultrasonic treatment was carried out at 50 KHz for 1.5 h. The product was collected by centrifugation at 6000 r / min, washed with deionized water for 3 times, and dried in an oven at 70°C for 10 min to obtain exfoliated molybdenum disulfide nanosheet.

[0066] A2. 2.5 g of exfoliated molybdenum disulfide nanosheets and 8.3 g of cerium nitrate hexahydrate were added to 70 mL of deionized water, stirred uniformly, ammonia water was added to adjust the pH to 10, 0.8 g of ethylene glycol was added, stirred at 250 r / min for 1.5 h, and then left to stand for 1 h. After filtration, deionized water was used for washing 3 times, and then the sample was dried in an oven at 100℃ overnight. The sample was placed in a muffle furnace and calcined at 300℃ for 4 h, and then cooled to room temperature to obtain modified molybdenum disulfide nanosheets;

[0067] A3. 8 g of polyether amine and 3.3 g of tert-butyl hydroquinone were added to 50 mL of tetrahydrofuran, stirred until completely dissolved, and then the temperature was maintained at 2℃. Then, 3.5 g of toluene-2,4-diisocyanate was added, and the reaction was stirred for 33 min. The temperature was then increased to 60℃, and 5.5 g of pretreated graphene oxide nanosheets was added. The reaction was continued to stir for 5.5 h, and then the sample was cooled to room temperature. The solid was collected by centrifugation at 5000 r / min, and then the solid was washed with deionized water 3 times. The sample was dried in an oven at 80℃ for 10 min to obtain modified graphene oxide nanosheets;

[0068] A4. 1.5 g of modified graphene oxide nanosheets and 1.1 g of modified molybdenum disulfide nanosheets were added to 100 mL of ethanol, and then the sample was stirred at 65℃ for 1.5 h. After standing for 1 h, the sample was filtered, washed with deionized water 3 times, and then dried in an oven at 70℃ for 10 min to obtain a composite anti-wear agent. Embodiment

[0069] A diesel oil additive, comprising the following raw materials in mass parts: 20 parts of tert-butyl peroxy benzoate, 15 parts of polyether amine, 30 parts of isooctyl nitrate, 4 parts of zinc dialkyldithiophosphate, 5 parts of diisooctylamine, 8 parts of dispersant, and 8 parts of composite anti-wear agent;

[0070] A preparation method of a diesel oil additive, comprising the following preparation steps:

[0071] Tert-butyl peroxy benzoate and isooctyl nitrate were mixed, and then the mixture was stirred at 55℃ for 30 min. Then, a dispersant and polyether amine were added, and then nitrogen was introduced. The mixture was subjected to ultrasonic mixing at 30 KHz for 15 min, and then the mixture was left to stand at 3 MPa and 75℃ for 55 min. Then, zinc dialkyldithiophosphate, diisooctylamine, and a composite anti-wear agent were added, and then the mixture was continuously stirred for 30 min. The mixture was cooled to room temperature to obtain a diesel oil additive.

[0072] The dispersant was prepared by mixing octadecanamide and polyethylene glycol-200 in a mass ratio of 1.2:1.

[0073] The composite anti-wear agent was prepared by the following steps:

[0074] A1. 2 g of molybdenum disulfide nanosheets and 1.2 g of n-butyllithium were added to 45 mL of n-hexane, stirred uniformly, heated to 85°C, stirred for 5 h, filtered, washed with deionized water 3 times, dried in a 70°C oven for 10 min, 3 g of solid was added to 110 mL of deionized water, ultrasonic treated at 60 KHz for 2 h, the product was collected by centrifugation at 6000 r / min, the product was washed with deionized water 3 times, dried in a 70°C oven for 10 min, to obtain exfoliated molybdenum disulfide nanosheets;

[0075] A2. 3 g of exfoliated molybdenum disulfide nanosheets and 8.4 g of cerium nitrate hexahydrate were added to 75 mL of deionized water, stirred uniformly, ammonia water was added to adjust the pH to 11, 1 g of ethylene glycol was added, stirred at 300 r / min for 2 h, stood for 1 h, filtered, washed with deionized water 3 times, dried in a 100°C oven overnight, placed in a muffle furnace, calcined at 320°C for 5 h, cooled to room temperature, to obtain modified molybdenum disulfide nanosheets;

[0076] A3. 9 g of polyether amine and 3.5 g of tert-butyl hydroquinone were added to 55 mL of tetrahydrofuran, stirred until completely dissolved, the temperature was maintained at 4°C, 4 g of toluene-2,4-diisocyanate was added, stirred for 35 min, heated to 65°C, 6 g of pretreated graphene oxide nanosheets was added, continue to stir for 6 h, cooled to room temperature, the solid was collected by centrifugation at 5000 r / min, the solid was washed with deionized water 3 times, dried in an 80°C oven for 10 min, to obtain modified graphene oxide nanosheets;

[0077] A4. 2 g of modified graphene oxide nanosheets and 1.2 g of modified molybdenum disulfide nanosheets were added to 110 mL of ethanol, stirred at 70°C for 2 h, stood for 1 h, filtered, washed with deionized water 3 times, dried in a 70°C oven for 10 min, to obtain a composite anti-wear agent.

[0078] Comparative Example 1

[0079] A diesel oil additive, comprising the following mass parts of raw materials: tert-butyl peroxybenzoate 20 parts, polyether amine 15 parts, isooctyl nitrate 30 parts, zinc dialkyldithiophosphate 4 parts, diisooctylamine 5 parts, dispersant 8 parts, composite anti-wear agent 8 parts;

[0080] A preparation method of a diesel oil additive, comprising the following preparation steps:

[0081] Mixing t-butyl peroxy benzoate and isooctyl nitrate, stirring at 55℃ for 30 min, adding dispersant and polyether amine, nitrogen blowing, mixing ultrasonic at 30KHz for 15 min, standing at 3MPa, 75℃ for 55 min, adding zinc dialkyldithiophosphate, diisooctylamine and complex anti-wear agent, continuing stirring and mixing for 30 min, cooling to room temperature, to obtain diesel oil additive;

[0082] The dispersant is prepared by mixing octadecanamide and polyethylene glycol-200 in a mass ratio of 1.2:1.

[0083] The complex anti-wear agent is prepared by the following steps:

[0084] A1. 3g of molybdenum disulfide nanosheets and 8.4g of cerium nitrate hexahydrate were added to 75mL of deionized water, stirred uniformly, ammonia water was added to adjust the pH to 11, 1g of ethylene glycol was added, stirred at 300r / min for 2h, stood for 1h, filtered, washed with deionized water for 3 times, dried in a 100℃ oven overnight, placed in a muffle furnace, calcined at 320℃ for 5h, cooled to room temperature, to obtain modified molybdenum disulfide nanosheets;

[0085] A2. 9g of polyether amine and 3.5g of t-butyl hydroquinone were added to 55mL of tetrahydrofuran, stirred until completely dissolved, the temperature was kept at 4℃, 4g of toluene-2,4-diisocyanate was added, stirred for 35min, the temperature was raised to 65℃, 6g of pretreated graphene oxide nanosheets were added, continued to stir for 6h, cooled to room temperature, the solid was collected by centrifugation at 5000r / min, the solid was washed with deionized water for 3 times, dried in an 80℃ oven for 10min, to obtain modified graphene oxide nanosheets;

[0086] A3. 2g of modified graphene oxide nanosheets and 1.2g of modified molybdenum disulfide nanosheets were added to 110mL of ethanol, stirred at 70℃ for 2h, stood for 1h, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10min, to obtain complex anti-wear agent.

[0087] Comparative Example 2

[0088] A diesel oil additive, comprising the following raw materials in mass parts: t-butyl peroxy benzoate 20 parts, polyether amine 15 parts, isooctyl nitrate 30 parts, zinc dialkyldithiophosphate 4 parts, diisooctylamine 5 parts, dispersant 8 parts, complex anti-wear agent 8 parts;

[0089] A preparation method of a diesel oil additive, comprising the following preparation steps:

[0090] The tert-butyl peroxy benzoate and isooctyl nitrate are mixed, stirred at 55℃ for 30 min, the dispersant and polyether amine are added, nitrogen is introduced, mixed ultrasonic is carried out at 30KHz for 15 min, the zinc dialkyldithiophosphate, diisooctylamine and composite anti-wear agent are added, continue to stir and mix for 30 min, cool to room temperature, diesel oil additive is obtained;

[0091] The dispersant is prepared by mixing octadecanamide and polyethylene glycol-200 in a mass ratio of 1.2:1.

[0092] The composite anti-wear agent is prepared by the following steps:

[0093] A1. 2g of molybdenum disulfide nanosheets and 1.2g of n-butyllithium are added to 45mL of n-hexane, stirred uniformly, heated to 85℃, stirred for 5h, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10min, 3g of solid is added to 110mL of deionized water, ultrasonic treatment is carried out at 60KHz for 2h, the product is collected by centrifugation at 6000r / min, the product is washed with deionized water for 3 times, dried in a 70℃ oven for 10min, to obtain exfoliated molybdenum disulfide nanosheets;

[0094] A2. 9g of polyether amine and 3.5g of tert-butyl hydroquinone are added to 55mL of tetrahydrofuran, stirred until completely dissolved, the temperature is maintained at 4℃, 4g of toluene-2,4-diisocyanate is added, stirred for 35min, heated to 65℃, 6g of pretreated graphene oxide nanosheets is added, continue to stir for 6h, cool to room temperature, the solid is collected by centrifugation at 5000r / min, the solid is washed with deionized water for 3 times, dried in a 80℃ oven for 10min, to obtain modified graphene oxide nanosheets;

[0095] A3. 2g of modified graphene oxide nanosheets and 1.2g of exfoliated molybdenum disulfide nanosheets are added to 110mL of ethanol, stirred at 70℃ for 2h, after standing for 1h, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10min, to obtain a composite anti-wear agent.

[0096] Comparative example 3

[0097] A diesel oil additive, including the following mass parts of raw materials: tert-butyl peroxy benzoate 20 parts, polyether amine 15 parts, isooctyl nitrate 30 parts, zinc dialkyldithiophosphate 4 parts, diisooctylamine 5 parts, dispersant 8 parts, composite anti-wear agent 8 parts;

[0098] A preparation method of a diesel oil additive, including the following preparation steps:

[0099] Mixing t-butyl peroxybenzoate and isooctyl nitrate, stirring at 55℃ for 30 min, adding dispersant and polyether amine, nitrogen blowing, mixing ultrasonic at 30KHz for 15 min, standing at 3MPa, 75℃ for 55 min, adding zinc dialkyldithiophosphate, diisooctylamine and composite anti-wear agent, continuing to stir and mix for 30 min, cooling to room temperature to obtain diesel oil additive;

[0100] The dispersant is prepared by mixing octadecanamide and polyethylene glycol-200 in a mass ratio of 1.2:1.

[0101] The composite anti-wear agent is prepared by the following steps:

[0102] A1. 2g of molybdenum disulfide nanosheets and 1.2g of n-butyllithium were added to 45mL of n-hexane, stirred uniformly, heated to 85℃, stirred for 5h, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10min, 3g of solid was added to 110mL of deionized water, ultrasonic treated at 60KHz for 2h, the product was collected by centrifugation at 6000r / min, the product was washed with deionized water for 3 times, dried in a 70℃ oven for 10min to obtain exfoliated molybdenum disulfide nanosheets;

[0103] A2. 3g of exfoliated molybdenum disulfide nanosheets and 8.4g of cerium nitrate hexahydrate were added to 75mL of deionized water, stirred uniformly, ammonia water was added to adjust the pH to 11, 1g of ethylene glycol was added, stirred at 300r / min for 2h, stood for 1h, filtered, washed with deionized water for 3 times, dried in a 100℃ oven overnight, placed in a muffle furnace, calcined at 320℃ for 5h, cooled to room temperature to obtain modified molybdenum disulfide nanosheets;

[0104] A3. 9g of polyether amine and 3.5g of t-butyl hydroquinone were added to 55mL of tetrahydrofuran, stirred until completely dissolved, the temperature was maintained at 4℃, 4g of toluene-2,4-diisocyanate was added, stirred for 35min, heated to 65℃, 6g of graphene oxide nanosheets was added, continued to stir for 6h, cooled to room temperature, the solid was collected by centrifugation at 5000r / min, the solid was washed with deionized water for 3 times, dried in a 80℃ oven for 10min to obtain modified graphene oxide nanosheets;

[0105] A4. 2g of modified graphene oxide nanosheets and 1.2g of modified molybdenum disulfide nanosheets were added to 110mL of ethanol, stirred at 70℃ for 2h, stood for 1h, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10min to obtain composite anti-wear agent.

[0106] Comparative Example 4

[0107] A diesel oil additive, comprising the following raw materials in parts by mass: 20 parts of t-butyl peroxy benzoate, 15 parts of polyether amine, 30 parts of isooctyl nitrate, 4 parts of zinc dialkyldithiophosphate, 5 parts of diisooctylamine, 8 parts of dispersant, and 8 parts of composite anti-wear agent.

[0108] A preparation method of a diesel oil additive, comprising the following preparation steps:

[0109] The t-butyl peroxy benzoate and the isooctyl nitrate are mixed, stirred at 55℃ for 30 min, the dispersant and the polyether amine are added, nitrogen is introduced, mixed ultrasonically at 30KHz for 15 min, and then the zinc dialkyldithiophosphate, the diisooctylamine and the composite anti-wear agent are added, and the stirring is continued for 30 min, and then the diesel oil additive is obtained after cooling to room temperature.

[0110] The dispersant is prepared by mixing octadecanamide and polyethylene glycol-200 in a mass ratio of 1.2:1.

[0111] The composite anti-wear agent is prepared by the following steps:

[0112] A1. 2g of molybdenum disulfide nanosheets and 1.2g of n-butyllithium are added to 45mL of n-hexane, stirred uniformly, heated to 85℃, stirred for 5h, filtered, washed with deionized water for 3 times, dried in a 70℃ oven for 10min, 3g of the solid is added to 110mL of deionized water, ultrasonically treated at 60KHz for 2h, the product is collected by centrifugation at 6000r / min, the product is washed with deionized water for 3 times, and dried in a 70℃ oven for 10min to obtain exfoliated molybdenum disulfide nanosheets;

[0113] A2. 3g of exfoliated molybdenum disulfide nanosheets and 8.4g of cerium nitrate hexahydrate are added to 75mL of deionized water, stirred uniformly, ammonia water is added to adjust the pH to 11, 1g of ethylene glycol is added, stirred at 300r / min for 2h, and then left to stand for 1h, filtered, washed with deionized water for 3 times, dried in a 100℃ oven overnight, placed in a muffle furnace, calcined at 320℃ for 5h, and then cooled to room temperature to obtain modified molybdenum disulfide nanosheets;

[0114] A3. 2g of pretreated graphene oxide nanosheets and 1.2g of modified molybdenum disulfide nanosheets are added to 110mL of ethanol, stirred at 70℃ for 2h, left to stand for 1h, filtered, washed with deionized water for 3 times, and dried in a 70℃ oven for 10min to obtain the composite anti-wear agent.

[0115] The diesel oil additives prepared in Examples 1-3 and Comparative Examples 1-4 are subjected to performance detection.

[0116] The diesel oil additive prepared above and the biomass diesel oil are mixed, and the mass ratio of the diesel oil additive to the biomass diesel oil is 1.5:98.5.

[0117] Diesel oil combustion heat value test: the combustion heat value of the biomass diesel oil containing the diesel oil additive is determined by using a low-pressure oxygen bomb combustion method, and the test is performed according to GB 384-1981 petroleum product heat value determination method, and the test conditions are as follows: the test is performed at an altitude of 70 m, and the corresponding oxygen bomb oxygen charging pressure is 0.89 MPa; the combustion heat value of the 0# diesel oil without adding the diesel oil additive is 27.1 KJ;

[0118] Lubricating property test: the tribological property of the diesel oil is tested by using a high-frequency reciprocating friction and wear testing machine (HFRR), the test is performed according to SHT 0765-200 diesel oil lubricating evaluation standard method, the wear scar size (steel ball wear scar diameter) is determined by using a three-dimensional scanner, and the test conditions are as follows: four-ball friction and wear testing machine, load 39.2 N, rotation speed 600 r / min, temperature 25℃, and test time 40 min; the steel ball wear scar diameter of the 0# diesel oil without adding the diesel oil additive is 0.54 mm;

[0119] Anti-carbon deposition property test: the gum of the biomass diesel oil added with the diesel oil additive prepared above is determined by using an actual gum method GBT 509-1988, and the method is as follows: 25 mL of the biomass diesel oil added with the diesel oil additive is added to a beaker without a nozzle, and is placed in an oil bath groove at 250℃, a tee joint is arranged at the central part of the bath cover, the tee joint is adjusted so that the lower end of the joint is 3 cm away from the sample liquid surface, air is supplied to the beaker, the air flow speed is increased from 20 L / min to 50 L / min within the first 20 min, the air supply is kept, when the oil gas is no longer emitted, there is dry residue at the bottom of the beaker, the sample is evaporated, and is cooled for 30 min under dry conditions; the gum produced by the biomass diesel oil without adding the diesel oil additive is 2511 mg / 100 mL.

[0120] The test results are shown in Table 1.

[0121] Table 1: Performance test of the diesel oil additive prepared in Examples 1-3 and Comparative Examples 1-4

[0122]

[0123] As shown by the data in Table 1, the diesel oil additive prepared in Examples 1-3 can improve the combustion property, the lubricating property and the anti-carbon deposition property of the diesel oil.

[0124] The combustion, anti-wear and anti-carbon deposition performance of the diesel fuel additive mixed with the biodiesel is reduced, which proves that the intercalation of the intercalation agent into the layers of the molybdenum disulfide nanosheet forms the exfoliated molybdenum disulfide nanosheet, avoids the weak van der Waals force between the adjacent sulfur atom layers of the molybdenum disulfide nanosheet, and the layers are easy to separate, which affects the anti-wear performance of the diesel fuel, and further reduces the combustion performance. The exfoliated molybdenum disulfide nanosheet is conducive to the synthesis of nano cerium oxide on the exfoliated molybdenum disulfide nanosheet, and more easily forms a layered composite material, improves the anti-wear performance, and improves the combustion performance of the diesel fuel.

[0125] The combustion, anti-wear and anti-carbon deposition performance of the diesel fuel additive mixed with the biodiesel is reduced, which proves that the intercalation of the intercalation agent into the layers of the molybdenum disulfide nanosheet forms the exfoliated molybdenum disulfide nanosheet, avoids the weak van der Waals force between the adjacent sulfur atom layers of the molybdenum disulfide nanosheet, and the layers are easy to separate, which affects the anti-wear performance of the diesel fuel, and further reduces the combustion performance. The exfoliated molybdenum disulfide nanosheet is conducive to the synthesis of nano cerium oxide on the exfoliated molybdenum disulfide nanosheet, and more easily forms a layered composite material, improves the anti-wear performance, and improves the combustion performance of the diesel fuel.

[0126] The combustion, anti-wear and anti-carbon deposition performance of the diesel fuel additive mixed with the biodiesel is reduced, which proves that the intercalation of the intercalation agent into the layers of the molybdenum disulfide nanosheet forms the exfoliated molybdenum disulfide nanosheet, avoids the weak van der Waals force between the adjacent sulfur atom layers of the molybdenum disulfide nanosheet, and the layers are easy to separate, which affects the anti-wear performance of the diesel fuel, and further reduces the combustion performance. The exfoliated molybdenum disulfide nanosheet is conducive to the synthesis of nano cerium oxide on the exfoliated molybdenum disulfide nanosheet, and more easily forms a layered composite material, improves the anti-wear performance, and improves the combustion performance of the diesel fuel.

[0127] The combustion, anti-wear and anti-carbon deposition performance of the diesel fuel additive mixed with the biodiesel is reduced, which proves that the intercalation of the intercalation agent into the layers of the molybdenum disulfide nanosheet forms the exfoliated molybdenum disulfide nanosheet, avoids the weak van der Waals force between the adjacent sulfur atom layers of the molybdenum disulfide nanosheet, and the layers are easy to separate, which affects the anti-wear performance of the diesel fuel, and further reduces the combustion performance. The exfoliated molybdenum disulfide nanosheet is conducive to the synthesis of nano cerium oxide on the exfoliated molybdenum disulfide nanosheet, and more easily forms a layered composite material, improves the anti-wear performance, and improves the combustion performance of the diesel fuel.

[0128] In the description, references to "one embodiment," "an example," "certain examples" etc. mean that the particular feature, structure, material, or characteristic being described is included in at least one embodiment or example of the application. The appearances of an item in various examples or embodiments is not necessarily indicative of a frequency of occurrence in the various examples or embodiments. Moreover, descriptions of well-known methods associated are omitted so as not to obscure the disclosure.

[0129] The foregoing merely illustrates the principles of the application. Various modifications and adaptations will occur to those skilled in the art after consideration of the preceding description. All such modifications and adaptations employing the principles of the application are intended to be within the scope of the claims.

Claims

1. A diesel fuel additive characterised in that, The composite anti-wear agent is obtained by mixing and reacting pretreated graphene oxide nanosheets, polyether amine, isocyanate and tert-butyl hydroquinone, and then mixing with modified molybdenum disulfide nanosheets. The modified molybdenum disulfide nanosheets are obtained by intercalating molybdenum disulfide nanosheets with an intercalating agent, and then mixing and reacting with cerium nitrate hexahydrate, ethylene glycol and ammonia water. The modified molybdenum disulfide nanosheets are obtained by intercalating molybdenum disulfide nanosheets with an intercalating agent, and then mixing and reacting with cerium nitrate hexahydrate, ethylene glycol and ammonia water. The composite anti-wear agent is obtained by mixing and reacting pretreated graphene oxide nanosheets, polyether amine, isocyanate and tert-butyl hydroquinone, and then mixing with modified molybdenum disulfide nanosheets. A1. The molybdenum disulfide nanosheets and the intercalating agent are added to n-hexane, stirred uniformly, heated to 75-85℃, stirred for 3-5h, filtered, washed, dried, and the solid is added to deionized water, ultrasonic treated for 1-2h at 40-60kHz, centrifuged, washed, and dried to obtain exfoliated molybdenum disulfide nanosheets; A2. The exfoliated molybdenum disulfide nanosheets and cerium nitrate hexahydrate are added to deionized water, stirred uniformly, ammonia water is added to adjust the pH to 9-11, and then ethylene glycol is added, stirred at 200-300r / min for 1-2h, and after standing, filtered, washed, dried, and calcined at 280-320℃ for 3-5h to obtain modified molybdenum disulfide nanosheets; A3. The polyether amine and tert-butyl hydroquinone are added to tetrahydrofuran, stirred until completely dissolved, the temperature is maintained at 0-4℃, isocyanate is added, stirred and reacted for 30-35min, heated to 55-65℃, pretreated graphene oxide nanosheets are added, and the stirring is continued for 5-6h, and then cooled to room temperature, centrifuged, washed, and dried to obtain modified graphene oxide nanosheets; A4. The modified graphene oxide nanosheets and modified molybdenum disulfide nanosheets are added to ethanol, stirred at 60-70℃ for 1-2h, and after standing, filtered, washed, and dried to obtain the composite anti-wear agent.

2. A diesel additive according to claim 1, characterised in that, In step A1, the amount ratio of the molybdenum disulfide nanosheets, the intercalating agent and n-hexane is (1-2)g:(1-1.2)g:(35-45)mL; The amount ratio of the solid and deionized water is (1-3)g:(90-110)mL.

3. The diesel fuel additive of claim 1, wherein In step A2, the amount ratio of the exfoliated molybdenum disulfide nanosheets, cerium nitrate hexahydrate, deionized water and ethylene glycol is (2-3)g:(8.2-8.4)g:(65-75)mL:(0.6-1)g.

4. The diesel fuel additive of claim 1, wherein, In step A3, the amount ratio of the polyether amine, tert-butyl hydroquinone, tetrahydrofuran, isocyanate and pretreated graphene oxide nanosheets is (7-9)g:(3.1-3.5)g:(45-55)mL:(3-4)g:(5-6)g.

5. The diesel fuel additive of claim 1, wherein, In step A4, the amount ratio of the modified graphene oxide nanosheets, modified molybdenum disulfide nanosheets and ethanol is (1-2)g:(1-1.2)g:(90-110)mL.

6. The diesel fuel additive of claim 1, wherein, The pretreated graphene oxide nanosheets are obtained by the following steps: The graphene oxide nanosheet is added into Tris-HCl buffer solution, stirred uniformly, dopamine is added, after continuous stirring, the pretreated graphene oxide nanosheet is obtained through filtration, washing and drying.

7. A diesel fuel additive according to claim 6, characterised in that, The dosage ratio of the graphene oxide nanosheet, Tris-HCl buffer solution and dopamine is (1-2) g:(90-110) mL:(0.4-0.6) g.

8. A process for the preparation of the diesel additive according to any one of claims 1 to 7, characterized in that, The preparation steps include the following steps: The t-butyl peroxybenzoate and isooctyl nitrate are mixed, stirred at 45-55 DEG C for 20-30 min, the dispersant and polyether amine are added, nitrogen is introduced, mixed ultrasonic is carried out at 20-30 kHz for 10-15 min, the antioxidant, preservative and composite anti-wear agent are added, the stirring is continuously carried out for 20-30 min, and the diesel oil additive is obtained after cooling to room temperature.

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