High-stability composite additive of M100 green methanol fuel for vehicles and ships as well as preparation method and application of high-stability composite additive

Abstract

The invention relates to the field of clean energy additives, in particular to a high-stability composite additive of M100 green methanol fuel for vehicles and ships as well as a preparation method and application of the high-stability composite additive. Xylene; isoparaffin having a carbon number of 12 to 16; triethanolamine oleate; dimer acid glycol ester; benzotriazole; isooctyl nitrate; dimethyl carbonate; nano cerium dioxide; a terminated polyether amine; 2, 6-butylated hydroxytoluene is used as a raw material; 2, 2, 2-octylbutyldiphenylamine; triethyl hydroxylamine; propylene glycol monomethyl ether; isobutanol; an ether improver; polyethylene glycol dimethyl ether; sorbitan monostearate is added; an alkylate oil; the composite additive is green, high in calorific value and good in stability, can meet-25 DEG C cold start for vehicles, and can guarantee 60 DEG C high-temperature stability for ships.

Description

Technical Field

[0001] This invention relates to the field of clean energy additives, specifically to a highly stable composite additive for M100 green methanol fuel used in vehicles and ships, its preparation method, and its application. Background Technology

[0002] The large-scale and commercial application of M100 methanol fuel in both vehicle and marine sectors has accelerated significantly. In the vehicle sector, leading companies such as China National Petroleum Corporation (CNPC) have built and operate dozens of M100 methanol refueling stations in provinces including Guizhou, Shanxi, Liaoning, and Heilongjiang, forming a regional service network. Daily sales are stable at tens of tons, and market-based promotions are underway. Vehicle operation data shows that the low-temperature starting problem of M100 methanol vehicles in cold regions (such as Heilongjiang) has been resolved, and operation is stable. In the marine sector, significant breakthroughs have been achieved in commercial application. In July 2025, domestically produced green methanol successfully refueled the first methanol-powered container ship, achieving a seamless "production-transportation-refueling-use" process. Management departments such as the Shandong Maritime Safety Administration have issued special management measures, providing a standardized regulatory framework for the maritime refueling operations of new fuels, including methanol (alcohol fuel), and removing obstacles to safe operation.

[0003] However, the direct application of M100 fuel still faces inherent technical bottlenecks, and there are significant differences in performance requirements between automotive and marine applications: First, its low calorific value (approximately 22.7 MJ / kg, only 54% of diesel) results in insufficient engine power and short driving range, particularly limiting the high-load driving range of ships; second, it is highly corrosive, with methanol and its combustion products having a strong chemical and electrochemical corrosive effect on the metal components and rubber seals of the engine fuel system; third, it has poor compatibility with high-energy hydrocarbon additives, as hydrocarbon components introduced to increase calorific value are difficult to form a stable homogeneous system with polar methanol, easily resulting in stratification, turbidity, and narrow temperature adaptability; fourth, it has insufficient long-term storage stability, especially under high water content or high temperature (such as in marine engine room environments), it is prone to oxidation to generate acidic substances, exacerbating corrosion and producing gum.

[0004] Existing additive technologies mostly employ simple compounding of functional components, failing to systematically address the aforementioned contradictions: To enhance calorific value, some products rely on polycyclic aromatic hydrocarbons (PAHs) such as naphthalene, which, while effective to some extent, pose environmental toxicity, risks of combustion carbon buildup, and potential restrictions under international environmental regulations (such as IMO and REACH), contradicting the sustainable development core of "green methanol"; in terms of corrosion protection, most are single-metal corrosion inhibitors, lacking a synergistic and long-lasting protection system for the frequent start-stop cycles in vehicles and the high-temperature, high-humidity, and high-salt environments in marine applications; regarding stability, there is a lack of effective solutions to the compatibility issues between high proportions of non-polar components and methanol, making it difficult to guarantee long-term uniformity and stability of the product across the entire temperature range from -25℃ to 60℃. These deficiencies severely restrict the large-scale market application of high-performance M100 green methanol fuel, creating a stark contrast with current strong policy drivers and market demand.

[0005] Therefore, for different application scenarios in vehicles and ships, there is an urgent need to develop a composite additive that can completely eliminate environmentally controversial components, has high calorific value, strong corrosion protection, ultra-wide temperature range stability, and full compliance, in order to unlock the full potential of M100 green methanol fuel, respond to national strategies, and seize international market share. Summary of the Invention

[0006] The purpose of this invention is to provide a highly stable composite additive for M100 green methanol fuel used in vehicles and ships. It has a high closed-cup flash point (≥62℃), meeting the cold start requirements at -25℃ for vehicles and ensuring high-temperature stability at 60℃ for ships; a corrosion rate ≤0.0009mm / a, and rubber swelling ≤2.0%. Adding 5%-8% can increase the calorific value of M100 fuel by 11%-14%, and it also has advantages such as superior corrosion protection, wide temperature range stability, and green compliance.

[0007] Another objective of this invention is to provide a method for preparing a highly stable composite additive for M100 green methanol fuel used in vehicles and ships. The process is simple, involving mixing the raw materials in sequence to ensure uniform mixing.

[0008] The technical problem solved by this invention is achieved by the following technical solution.

[0009] On one hand, embodiments of the present invention provide a highly stable composite additive for M100 green methanol fuel used in vehicles and ships, comprising, by mass parts: 8-12 parts tetrahydrodicyclopentadiene or decahydronaphthalene; 7-10 parts xylene; 30-40 parts C12-C16 isoalkanes; 4-10 parts triethanolamine oleate; 4-6 parts polyethylene glycol dimerate; 0.005-0.015 parts benzotriazole; 3-5 parts isooctyl nitrate; 0.1-0.5 parts dimethyl carbonate; 3-4.5 parts nano-cerium dioxide; 0.2-0.5 parts terminal polyetheramine; 0.2-0 4 parts 2,6-di-tert-butyl-p-cresol; 0.1-0.2 parts octylbutyl diphenylamine; 0.05-0.1 parts triethylhydroxylamine; 4-7 parts propylene glycol methyl ether; 3-6 parts isobutanol; 1.5-3 parts ether modifier; 3-5 parts polyethylene glycol dimethyl ether; 2-4 parts sorbitan monostearate; 0.05-0.5 parts alkylated oil; wherein the ether modifier is at least one of tert-butyl ether or ethylene glycol tert-butyl ether.

[0010] In some embodiments of the present invention, a methanol fuel composite additive for vehicles is provided, comprising, by weight parts: Tetrahydrodicyclopentadiene or decahydronaphthalene 9-11 parts, xylene 8-10 parts, C12-C16 isoalkanes 33-38 parts, triethanolamine oleate 8-10 parts, polyethylene glycol dimer 4.5-5.5 parts, benzotriazole 0.008-0.012 parts, isooctyl nitrate 3.8-4.5 parts, dimethyl carbonate 0.3-0.6 parts, nano-cerium dioxide 3.2-3.8 parts, terminal polyetheramine 0.25- 0.35 parts, 0.25-0.35 parts of 2,6-di-tert-butyl-p-cresol, 0.12-0.18 parts of octylbutyl diphenylamine, 0.04-0.06 parts of triethylhydroxylamine, 5-7 parts of propylene glycol methyl ether, 4-6 parts of isobutanol, 1.8-2.2 parts of ethylene glycol tert-butyl ether, 3.5-4.5 parts of polyethylene glycol dimethyl ether, 2.5-3.5 parts of sorbitan monostearate, and 0.3-0.7 parts of alkylated oil. Preferred, by parts by weight, it includes: 10 parts tetrahydrodicyclopentadiene, 9 parts xylene, 36.5 parts C12-C16 isoalkanes, 9.5 parts triethanolamine oleate, 5 parts polyethylene glycol dimer, 0.01 parts benzotriazole, 4.2 parts isooctyl nitrate, 0.5 parts dimethyl carbonate, 3.5 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.15 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6.5 parts propylene glycol methyl ether, 5 parts isobutanol, 2 parts ethylene glycol tert-butyl ether, 4 parts polyethylene glycol dimethyl ether, 3 parts sorbitan monostearate, and 0.5 parts alkylated oil.

[0011] In some embodiments of the present invention, a marine methanol fuel composite additive is provided, comprising, by mass parts: Tetrahydrodicyclopentadiene or decahydronaphthalene 9-11 parts, xylene 6-8 parts, C12-C16 isoalkanes 38-42 parts, triethanolamine oleate 8-9 parts, polyethylene glycol dimer 5.2-5.8 parts, benzotriazole 0.008-0.012 parts, isooctyl nitrate 3.5-4.2 parts, dimethyl carbonate 0.1-0.3 parts, nano-cerium dioxide 3.8-4.3 parts, terminal polyetheramine 0.25-0 0.35 parts, 0.25-0.35 parts of 2,6-di-tert-butyl-p-cresol, 0.15-0.25 parts of octylbutyl diphenylamine, 0.04-0.06 parts of triethylhydroxylamine, 5-7 parts of propylene glycol methyl ether, 3-5 parts of isobutanol, 2.3-2.7 parts of ethylene glycol tert-butyl ether, 4.5-5.5 parts of polyethylene glycol dimethyl ether, 1.5-2.5 parts of sorbitan monostearate, and 0.3-0.6 parts of alkylated oil.

[0012] Preferred, by parts by weight, it includes: 10 parts tetrahydrodicyclopentadiene, 7 parts xylene, 40 parts C12-C16 isoalkanes, 8.5 parts triethanolamine oleate, 5.5 parts polyethylene glycol dimer, 0.01 parts benzotriazole, 4 parts isooctyl nitrate, 0.2 parts dimethyl carbonate, 4 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.2 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6 parts propylene glycol methyl ether, 4 parts isobutanol, 2.5 parts ethylene glycol tert-butyl ether, 5 parts polyethylene glycol dimethyl ether, 2 parts sorbitan monostearate, and 0.45 parts alkylated oil.

[0013] On the other hand, embodiments of the present invention provide a method for preparing a highly stable composite additive for M100 green methanol fuel used in vehicles and ships, comprising the following steps: S1. Mix C12-C16 isoalkanes, xylene, tetrahydrodicyclopentadiene or decahydronaphthalene, and stir at 500-600 r / min for 10-15 minutes to obtain the base material; S2. While stirring, add propylene glycol methyl ether, isobutanol, ether modifier and polyethylene glycol dimethyl ether, and stir for 5-8 minutes; S3. Adjust the speed to 400-500 r / min, add triethanolamine oleate, polyethylene glycol dimerate and benzotriazole, and stir for 8-10 minutes; S4. Add isooctyl nitrate, dimethyl carbonate, nano-cerium dioxide, terminal polyetheramine, alkylated oil and dehydrated sorbitan monostearate in sequence, and stir at 500-600 r / min for 12-15 minutes; S5. Finally, add 2,6-di-tert-butyl-p-cresol, octylbutyldiphenylamine and triethylhydroxylamine, stir for 5 minutes and let stand for 20-30 minutes to degas, thus obtaining the composite additive.

[0014] Thirdly, this invention provides an application of a highly stable composite additive for M100 green methanol fuel used in vehicles and ships. The composite additive is added to M100 methanol fuel as a methanol fuel for vehicles and ships, and the amount of the composite additive added is 5-8% of the mass of M100 methanol fuel.

[0015] Compared with the prior art, the embodiments of the present invention have at least the following advantages or beneficial effects: The composite additive provided by this invention has a green and high calorific value: it abandons naphthalene and uses high-energy saturated hydrocarbons, which increases the calorific value by 11%-14%.

[0016] Good stability: The core reinforcing agent has an extremely low iodine value (tetrahydrodicyclopentadiene ≤1, decahydronaphthalene ≤0.5 g I2 / 100g), ensuring storage stability from the source.

[0017] Excellent wide temperature range compatibility: Unique solvent network design ensures stability across the entire temperature range from -25℃ to 60℃, with no layering or crystallization.

[0018] Intrinsically safe with high flash point: High flash point components are selected, and the closed-cup flash point of the product is ≥62℃ (can be optimized to ≥65℃), ensuring safe storage and transportation.

[0019] For automotive applications, it meets the cold start requirement of -25℃; for marine applications, it ensures high-temperature stability at 60℃; corrosion rate ≤0.0009 mm / a, rubber swelling ≤2.0%. Sulfur and phosphorus content are far below national standards, complying with IMO environmental regulations and domestic green standards. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0021] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other. The present invention will now be described in detail with reference to specific embodiments.

[0022] This invention provides a highly stable composite additive for M100 green methanol fuel used in vehicles and ships, comprising, by weight: Highly stable basic reinforcing agent: 8-12 parts of tetrahydrodicyclopentadiene or decahydronaphthalene; Aromatic solvent: 7-10 parts xylene; High flash point isoalkanes support: 30-40 parts of C12-C16 isoalkanes.

[0023] Main corrosion inhibitor: 4-10 parts of triethanolamine oleate; Rubber protective agent: 4-6 parts of polyethylene dimerate; Corrosion inhibitor for copper-based metals: 0.005-0.015 parts of benzotriazole; Anti-knock agent: 3-5 parts of isooctyl nitrate; Oxygen-containing power enhancer: 0.1-0.5 parts of dimethyl carbonate; Nano-combustion catalyst: 3-4.5 parts of nano-cerium dioxide; Fuel system cleaner: 0.2-0.5 parts of terminal polyetheramine; Main antioxidant: 0.2-0.4 parts of 2,6-di-tert-butyl-p-cresol; Co-antioxidant: 0.1-0.2 parts of octylbutyldiphenylamine; Oxidation inducer: 0.05-0.1 parts of triethylhydroxylamine; Alcohol ether cosolvent: 4-7 parts propylene glycol methyl ether; Low-carbon alcohol regulator: 3-6 parts isobutanol; High flash point ether octane number improver: 1.5-3 parts, selected from at least one of tert-butyl ether or ethylene glycol tert-butyl ether; High temperature stability and co-solvent: 3-5 parts polyethylene glycol dimethyl ether; Nonionic surfactant: 2-4 parts of dehydrated sorbitan monostearate; Distillation range regulator: 0.05-0.5 parts of alkylated oil.

[0024] This composite additive is naphthalene-free, has a closed-cup flash point ≥62℃, sulfur content ≤15 mg / kg, and phosphorus content ≤1 mg / kg, meeting the requirements of GB / T 42436-2023 "M100 Methanol Fuel Additive for Vehicles".

[0025] When used as a methanol fuel additive for vehicles, it includes, by weight parts: Tetrahydrodicyclopentadiene or decahydronaphthalene 9-11 parts, xylene 8-10 parts, C12-C16 isoalkanes 33-38 parts, triethanolamine oleate 8-10 parts, polyethylene glycol dimer 4.5-5.5 parts, benzotriazole 0.008-0.012 parts, isooctyl nitrate 3.8-4.5 parts, dimethyl carbonate 0.3-0.6 parts, nano-cerium dioxide 3.2-3.8 parts, terminal polyetheramine 0.25- 0.35 parts, 0.25-0.35 parts of 2,6-di-tert-butyl-p-cresol, 0.12-0.18 parts of octylbutyl diphenylamine, 0.04-0.06 parts of triethylhydroxylamine, 5-7 parts of propylene glycol methyl ether, 4-6 parts of isobutanol, 1.8-2.2 parts of ethylene glycol tert-butyl ether, 3.5-4.5 parts of polyethylene glycol dimethyl ether, 2.5-3.5 parts of sorbitan monostearate, and 0.3-0.7 parts of alkylated oil. Preferred, by parts by weight, it includes: 10 parts tetrahydrodicyclopentadiene, 9 parts xylene, 36.5 parts C12-C16 isoalkanes, 9.5 parts triethanolamine oleate, 5 parts polyethylene glycol dimer, 0.01 parts benzotriazole, 4.2 parts isooctyl nitrate, 0.5 parts dimethyl carbonate, 3.5 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.15 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6.5 parts propylene glycol methyl ether, 5 parts isobutanol, 2 parts ethylene glycol tert-butyl ether, 4 parts polyethylene glycol dimethyl ether, 3 parts sorbitan monostearate, and 0.5 parts alkylated oil.

[0026] When used as a composite additive for marine methanol fuel, it includes, by mass parts: Tetrahydrodicyclopentadiene or decahydronaphthalene 9-11 parts, xylene 6-8 parts, C12-C16 isoalkanes 38-42 parts, triethanolamine oleate 8-9 parts, polyethylene glycol dimer 5.2-5.8 parts, benzotriazole 0.008-0.012 parts, isooctyl nitrate 3.5-4.2 parts, dimethyl carbonate 0.1-0.3 parts, nano-cerium dioxide 3.8-4.3 parts, terminal polyetheramine 0.25-0 0.35 parts, 0.25-0.35 parts of 2,6-di-tert-butyl-p-cresol, 0.15-0.25 parts of octylbutyl diphenylamine, 0.04-0.06 parts of triethylhydroxylamine, 5-7 parts of propylene glycol methyl ether, 3-5 parts of isobutanol, 2.3-2.7 parts of ethylene glycol tert-butyl ether, 4.5-5.5 parts of polyethylene glycol dimethyl ether, 1.5-2.5 parts of sorbitan monostearate, and 0.3-0.6 parts of alkylated oil.

[0027] Preferred, by parts by weight, it includes: 10 parts tetrahydrodicyclopentadiene, 7 parts xylene, 40 parts C12-C16 isoalkanes, 8.5 parts triethanolamine oleate, 5.5 parts polyethylene glycol dimer, 0.01 parts benzotriazole, 4 parts isooctyl nitrate, 0.2 parts dimethyl carbonate, 4 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.2 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6 parts propylene glycol methyl ether, 4 parts isobutanol, 2.5 parts ethylene glycol tert-butyl ether, 5 parts polyethylene glycol dimethyl ether, 2 parts sorbitan monostearate, and 0.45 parts alkylated oil.

[0028] The preparation method of the above-mentioned high-stability composite additive for M100 green methanol fuel for vehicles and ships includes the following steps: S1. Mix C12-C16 isoalkanes, xylene, tetrahydrodicyclopentadiene or decahydronaphthalene, and stir at 500-600 r / min for 10-15 minutes to obtain the base material; S2. While stirring, add propylene glycol methyl ether, isobutanol, ether modifier and polyethylene glycol dimethyl ether, and stir for 5-8 minutes; S3. Adjust the speed to 400-500 r / min, add triethanolamine oleate, polyethylene glycol dimerate and benzotriazole, and stir for 8-10 minutes; S4. Add isooctyl nitrate, dimethyl carbonate, nano-cerium dioxide, terminal polyetheramine, alkylated oil and dehydrated sorbitan monostearate in sequence, and stir at 500-600 r / min for 12-15 minutes; S5. Finally, add 2,6-di-tert-butyl-p-cresol, octylbutyldiphenylamine and triethylhydroxylamine, stir for 5 minutes and let stand for 20-30 minutes to degas, thus obtaining the composite additive.

[0029] The application of a highly stable composite additive for M100 green methanol fuel for vehicles and ships, wherein the composite additive is added to M100 methanol fuel as methanol fuel for vehicles and ships, and the amount of the composite additive added is 5-8% of the mass of M100 methanol fuel.

[0030] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0031] Example 1 This embodiment provides a methanol fuel composite additive for vehicles, the raw material ratio and preparation method of which are shown below: Weigh the raw materials (parts by weight): 10 parts tetrahydrodicyclopentadiene, 9 parts xylene, 36.5 parts isododecane, 9.5 parts triethanolamine oleate, 5 parts polyethylene glycol dimer, 0.01 parts benzotriazole, 4.2 parts isooctyl nitrate, 0.5 parts dimethyl carbonate, 3.5 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.15 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6.5 parts propylene glycol methyl ether, 5 parts isobutanol, 2 parts ethylene glycol tert-butyl ether, 4 parts polyethylene glycol dimethyl ether, 3 parts sorbitan monostearate, and 0.5 parts alkylated oil.

[0032] Preparation method: S1. Mix isododecane, xylene, and tetrahydrodicyclopentadiene, and stir at 600 r / min for 15 minutes to obtain the base material; S2. While stirring, add propylene glycol methyl ether, isobutanol, ether modifier and polyethylene glycol dimethyl ether, and stir for 8 minutes; S3. Adjust the speed to 500 r / min, add triethanolamine oleate, polyethylene glycol dimerate and benzotriazole, and stir for 10 minutes; S4. Add isooctyl nitrate, dimethyl carbonate, nano-cerium dioxide, terminal polyetheramine, alkylated oil and dehydrated sorbitan monostearate in sequence, and stir at 600 r / min for 15 minutes; S5. Finally, add 2,6-di-tert-butyl-p-cresol, octylbutyldiphenylamine and triethylhydroxylamine, stir for 5 minutes and let stand for 30 minutes to degas, thus obtaining the composite additive.

[0033] The composite additive prepared according to the above formula and method has a closed-cup flash point of 66℃, sulfur content of 10 mg / kg, and phosphorus content of 0.8 mg / kg.

[0034] Add 6 parts to 100 parts of M100 methanol. The mixed fuel has a closed-cup flash point of 15.2℃, a calorific value of 25.6 MJ / kg, no crystallization at -25℃, 4.5 mg / 100mL of gum after 90 days of storage at 60℃, a steel corrosion rate of 0.0007 mm / a, a rubber swelling rate of 1.6%, and a CO emission reduction of 54%.

[0035] Example 2 This embodiment provides a vehicle-grade version, the raw material ratio and preparation method of which are shown below: The difference from Example 1 is that the key components were adjusted to the lower limit of the range: 9 parts tetrahydrodicyclopentadiene, 8 parts xylene, 33 parts isododecane, 8 parts triethanolamine oleate, 1.8 parts ethylene glycol tert-butyl ether, and 3.5 parts polyethylene glycol dimethyl ether.

[0036] The preparation method is the same as in Example 1.

[0037] The composite additive prepared by the above formula and method has a closed-cup flash point of 63℃, and its performance fully meets the standards, proving the effectiveness of the lower limit.

[0038] Example 3 This embodiment provides a marine-grade version, the raw material ratio and preparation method of which are shown below: Weigh the raw materials (parts by weight): 10 parts tetrahydrodicyclopentadiene, 7 parts xylene, 40 parts isohexadecane, 8.5 parts triethanolamine oleate, 5.5 parts polyethylene glycol dimerate, 0.01 parts benzotriazole, 4 parts isooctyl nitrate, 0.2 parts dimethyl carbonate, 4 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.2 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6 parts propylene glycol methyl ether, 4 parts isobutanol, 2.5 parts ethylene glycol tert-butyl ether, 5 parts polyethylene glycol dimethyl ether, 2 parts sorbitan monostearate, and 0.45 parts alkylated oil.

[0039] Preparation method: S1. Mix isohexadecane, xylene, tetrahydrodicyclopentadiene or decahydronaphthalene, and stir at 500 r / min for 15 minutes to obtain the base material; S2. While stirring, add propylene glycol methyl ether, isobutanol, ether modifier and polyethylene glycol dimethyl ether, and stir for 8 minutes; S3. Adjust the speed to 400 r / min, add triethanolamine oleate, polyethylene glycol dimerate and benzotriazole, and stir for 10 minutes; S4. Add isooctyl nitrate, dimethyl carbonate, nano-cerium dioxide, terminal polyetheramine, alkylated oil and dehydrated sorbitan monostearate in sequence, and stir at 500 r / min for 15 minutes; S5. Finally, add 2,6-di-tert-butyl-p-cresol, octylbutyldiphenylamine and triethylhydroxylamine, stir for 5 minutes and let stand for 30 minutes to degas, thus obtaining the composite additive.

[0040] The product prepared by the above proportions and methods has a closed-cup flash point of 68℃.

[0041] The compound additive was added at a ratio of 7 parts to 100 parts of M100 methanol, and its performance met the high-load requirements for marine applications.

[0042] Example 4 The difference from Example 3 is that the amount of benzotriazole was increased to 0.015 parts, while the remaining raw materials and preparation method were the same as in Example 3. This composite additive showed significant protection against copper corrosion.

[0043] When the amount of benzotriazole was reduced to 0.005 parts, and the remaining raw materials and preparation methods were the same as in Example 3, the preservative effect of the composite additive decreased, demonstrating the effective range of the component.

[0044] Comparative Example The difference from Example 1 is that the composite additive does not contain a simple mixture of xylene and polyethylene glycol dimethyl ether. The preparation method is the same as in Example 1. The composite additive separates into layers after standing at 25°C for 2 hours.

[0045] In summary, the composite additive provided in this embodiment of the invention has a green and high calorific value: it abandons naphthalene and uses high-energy saturated hydrocarbons, which increases the calorific value by 11%-14%.

[0046] Excellent stability: The core reinforcing agent has extremely low iodine values ​​(tetrahydrodicyclopentadiene ≤1, decahydronaphthalene ≤0.5 g I2 / 100g), ensuring storage stability from the source. Superior wide temperature range compatibility: Unique solvent network design ensures stability across the entire temperature range from -25℃ to 60℃, with no layering or crystallization. High flash point inherently safe: Optimized high flash point components ensure a closed-cup flash point ≥62℃ (optimizable to ≥65℃), guaranteeing safe storage and transportation. Meets automotive cold-start requirements at -25℃ and marine high-temperature stability at 60℃; corrosion rate ≤0.0009mm / a, rubber swelling ≤2.0%. Sulfur and phosphorus content are far below national standards, complying with IMO environmental regulations and domestic green standards.

[0047] The embodiments described above are some, but not all, embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A highly stable composite additive for M100 green methanol fuel used in vehicles and ships, characterized in that, By weight, including: 8-12 parts tetrahydrodicyclopentadiene or decahydronaphthalene; 7-10 parts xylene; 30-40 parts C12-C16 isoalkanes; 4-10 parts triethanolamine oleate; 4-6 parts polyethylene glycol dimerate; 0.005-0.015 parts benzotriazole; 3-5 parts isooctyl nitrate; 0.1-0.5 parts dimethyl carbonate; 3-4.5 parts nano-cerium dioxide; 0.2-0.5 parts terminal polyetheramine; 0.2-0 4 parts 2,6-di-tert-butyl-p-cresol; 0.1-0.2 parts octylbutyl diphenylamine; 0.05-0.1 parts triethylhydroxylamine; 4-7 parts propylene glycol methyl ether; 3-6 parts isobutanol; 1.5-3 parts ether modifier; 3-5 parts polyethylene glycol dimethyl ether; 2-4 parts sorbitan monostearate; 0.05-0.5 parts alkylated oil; wherein the ether modifier is at least one of tert-butyl ether or ethylene glycol tert-butyl ether.

2. The high-stability composite additive for M100 green methanol fuel for vehicles and ships according to claim 1, characterized in that, By weight, including: Tetrahydrodicyclopentadiene or decahydronaphthalene 9-11 parts, xylene 8-10 parts, C12-C16 isoalkanes 33-38 parts, triethanolamine oleate 8-10 parts, polyethylene glycol dimer 4.5-5.5 parts, benzotriazole 0.008-0.012 parts, isooctyl nitrate 3.8-4.5 parts, dimethyl carbonate 0.3-0.6 parts, nano-cerium dioxide 3.2-3.8 parts, terminal polyetheramine 0.25- 0.35 parts, 0.25-0.35 parts of 2,6-di-tert-butyl-p-cresol, 0.12-0.18 parts of octylbutyl diphenylamine, 0.04-0.06 parts of triethylhydroxylamine, 5-7 parts of propylene glycol methyl ether, 4-6 parts of isobutanol, 1.8-2.2 parts of ethylene glycol tert-butyl ether, 3.5-4.5 parts of polyethylene glycol dimethyl ether, 2.5-3.5 parts of sorbitan monostearate, and 0.3-0.7 parts of alkylated oil.

3. The high-stability composite additive for vehicle and marine M100 green methanol fuel according to claim 2, characterized in that, By weight, including: 10 parts tetrahydrodicyclopentadiene, 9 parts xylene, 36.5 parts C12-C16 isoalkanes, 9.5 parts triethanolamine oleate, 5 parts polyethylene glycol dimer, 0.01 parts benzotriazole, 4.2 parts isooctyl nitrate, 0.5 parts dimethyl carbonate, 3.5 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.15 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6.5 parts propylene glycol methyl ether, 5 parts isobutanol, 2 parts ethylene glycol tert-butyl ether, 4 parts polyethylene glycol dimethyl ether, 3 parts sorbitan monostearate, and 0.5 parts alkylated oil.

4. The high-stability composite additive for vehicle and marine M100 green methanol fuel according to claim 1, characterized in that, By weight, including: Tetrahydrodicyclopentadiene or decahydronaphthalene 9-11 parts, xylene 6-8 parts, C12-C16 isoalkanes 38-42 parts, triethanolamine oleate 8-9 parts, polyethylene glycol dimer 5.2-5.8 parts, benzotriazole 0.008-0.012 parts, isooctyl nitrate 3.5-4.2 parts, dimethyl carbonate 0.1-0.3 parts, nano-cerium dioxide 3.8-4.3 parts, terminal polyetheramine 0.25-0 0.35 parts, 0.25-0.35 parts of 2,6-di-tert-butyl-p-cresol, 0.15-0.25 parts of octylbutyl diphenylamine, 0.04-0.06 parts of triethylhydroxylamine, 5-7 parts of propylene glycol methyl ether, 3-5 parts of isobutanol, 2.3-2.7 parts of ethylene glycol tert-butyl ether, 4.5-5.5 parts of polyethylene glycol dimethyl ether, 1.5-2.5 parts of sorbitan monostearate, and 0.3-0.6 parts of alkylated oil.

5. The high-stability composite additive for vehicle and marine M100 green methanol fuel according to claim 4, characterized in that, By weight, including: 10 parts tetrahydrodicyclopentadiene, 7 parts xylene, 40 parts C12-C16 isoalkanes, 8.5 parts triethanolamine oleate, 5.5 parts polyethylene glycol dimer, 0.01 parts benzotriazole, 4 parts isooctyl nitrate, 0.2 parts dimethyl carbonate, 4 parts nano-cerium dioxide, 0.3 parts terminal polyetheramine, 0.3 parts 2,6-di-tert-butyl-p-cresol, 0.2 parts octylbutyl diphenylamine, 0.05 parts triethylhydroxylamine, 6 parts propylene glycol methyl ether, 4 parts isobutanol, 2.5 parts ethylene glycol tert-butyl ether, 5 parts polyethylene glycol dimethyl ether, 2 parts sorbitan monostearate, and 0.45 parts alkylated oil.

6. A method for preparing a highly stable composite additive for M100 green methanol fuel for vehicles and ships as described in any one of claims 1-5, characterized in that, Includes the following steps: S1. Mix C12-C16 isoalkanes, xylene, tetrahydrodicyclopentadiene or decahydronaphthalene, and stir at 500-600 r / min for 10-15 minutes to obtain the base material; S2. While stirring, add propylene glycol methyl ether, isobutanol, ether modifier and polyethylene glycol dimethyl ether, and stir for 5-8 minutes; S3. Adjust the speed to 400-500 r / min, add triethanolamine oleate, polyethylene glycol dimerate and benzotriazole, and stir for 8-10 minutes; S4. Add isooctyl nitrate, dimethyl carbonate, nano-cerium dioxide, terminal polyetheramine, alkylated oil and dehydrated sorbitan monostearate in sequence, and stir at 500-600 r / min for 12-15 minutes; S5. Finally, add 2,6-di-tert-butyl-p-cresol, octylbutyldiphenylamine and triethylhydroxylamine, stir for 5 minutes and let stand for 20-30 minutes to degas, thus obtaining the composite additive.

7. The application of a highly stable composite additive for M100 green methanol fuel used in vehicles and ships, characterized in that, The high-stability composite additive described in claim 2 or 3 is added to M100 methanol fuel to serve as a vehicle methanol fuel, wherein the amount of the composite additive added is 5-6% of the mass of the M100 methanol fuel; Alternatively, the high-stability composite additive described in claim 4 or 5 may be added to M100 methanol fuel as marine methanol fuel, wherein the amount of the composite additive added is 6-8% of the mass of M100 methanol fuel.