Hydrogen radical time sequence based low-temperature high-adaptation methanol composite modified fuel and preparation method thereof

Abstract

The application provides a low-temperature high-adaptation methanol composite modified fuel based on hydrogen radical timing mediation and a preparation method thereof, and belongs to the technical field of clean energy fuel preparation.The composite modified fuel is composed of 88-92 parts of refined methanol and 8-12 parts of a composite modified mother liquor;the composite modified mother liquor comprises a cyclic olefin ignition component, decalin, a cosolvent, triethanolamine, di-tert-butyl-p-cresol and n-octane;decalin is used as a hydrogen functional component, a fire core is established by the cyclic olefin low-temperature ignition in the combustion process, then the decalin is directionally cracked to release hydrogen radicals, and the methanol combustion reaction path is time-sequentially mediated.The composite modified fuel obtained by the application is superior to the national sixth b motor vehicle emission standard in terms of various tail gas emission indexes, and can fundamentally optimize the application performance of the methanol fuel, can be adapted to different application scenarios such as use in severe cold regions, global normalization popularization and low-cost popularization in the civil market and the like.

Description

Technical Field

[0001] This invention belongs to the field of clean energy fuel preparation technology, and particularly relates to a low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-series mediation and its preparation method. Background Technology

[0002] my country is rich in coal but poor in oil and natural gas, and its dependence on imported oil remains high, resulting in immense pressure on energy conservation, emission reduction, carbon reduction, and pollution control in the transportation sector. Methanol is a domestically produced, mature, and self-controllable clean liquid energy source with sufficient domestic production capacity and a mature industrial chain, possessing the foundation for large-scale replacement of refined oil products. However, pure methanol fuel has several inherent defects that restrict its large-scale application in the industry. Methanol has a high activation energy for combustion, making it difficult to form a stable flame core in low-temperature environments, resulting in poor cold-start performance and hindering its widespread adoption in frigid northern regions. Furthermore, the high proportion of oxygen atoms in the molecule and the low effective hydrocarbon content result in insufficient overall calorific value (pure methanol has a lower heating value of only about 4700 kcal / kg, less than half that of gasoline), leading to weak power output under heavy-load conditions. The combustion reaction path is simple, with a slow flame propagation rate, easily generating intermediate products such as formaldehyde, formyl groups, formic acid, and free carbon. Long-term use can easily cause internal engine corrosion, carbon deposits in the cylinder, fuel injector blockage, and swelling and aging of sealing components.

[0003] To overcome the aforementioned shortcomings, the industry has explored various methanol modification technologies, but existing solutions still have their own significant performance limitations and environmental risks. Specifically: Pure methanol M85 / M90 is a national standard fuel. This is the most basic methanol-gasoline blending scheme, without any deep combustion modification of the methanol fuel. Its core problems are: extremely poor low-temperature starting performance, typically failing to start properly when the ambient temperature is below -5℃, unstable idling, and easy stalling, making its widespread use difficult in the frigid regions of northern my country. Furthermore, due to the lack of combustion path control methods, incomplete combustion of methanol is a significant issue, leading to a risk of exceeding emission standards for unconventional pollutants such as formaldehyde in the exhaust, posing a potential hazard to human health and the environment.

[0004] This technology uses decahydronaphthalene as a single blending agent to blend methanol fuel. Recognizing the lack of active free radicals in methanol combustion, it attempts to improve combustion by adding hydrogen-rich components such as decahydronaphthalene, hoping to release hydrogen free radicals during combustion. However, its core drawback lies in the lack of a low-temperature ignition component. Decahydronaphthalene has a high pyrolysis initiation temperature (approximately 550°C). In the cold start phase without a low-temperature ignition nucleus, the in-cylinder temperature cannot reach its effective pyrolysis range quickly enough, resulting in initial combustion still primarily relying on the direct oxidation of methanol with high activation energy. Therefore, this approach cannot fundamentally solve the problem of low-temperature methanol start-up; its reliable cold start temperature is typically still above 0°C, and its adaptability to extremely cold environments remains insufficient. Furthermore, the single hydrogen source supplementation fails to create a continuous combustion-mediated combustion process, resulting in limited improvement in combustion efficiency.

[0005] Aromatic methanol-modified fuels. To compensate for the low calorific value of methanol, some solutions use aromatics to blend the fuel and improve its overall calorific value. While this approach can improve power performance to some extent, it may also present environmental challenges. Studies have shown that aromatic components readily generate unburned hydrocarbons and volatile organic compounds during combustion. If the formulation or operating conditions are not properly controlled, it may lead to high concentrations of benzene compounds and particulate matter (PM) in the exhaust gas, making it difficult to meet the stringent requirements of current China VI b emission standards for motor vehicles in some cases. Therefore, the unrestricted use of aromatics contradicts the environmentally friendly goal of clean energy substitution and poses compliance risks.

[0006] In summary, none of the existing technical solutions in the industry can simultaneously solve the integrated challenges of low-temperature start-up, power matching, clean combustion, and low emissions of methanol fuel. There is a lack of a disruptive technical solution that can leverage the clean properties of methanol, surpass the overall performance of gasoline under all operating conditions, and require no major vehicle modifications. Summary of the Invention

[0007] To address the shortcomings of existing methanol fuels, such as poor low-temperature starting performance, significant power loss, incomplete combustion, severe carbon buildup and corrosion, high levels of harmful exhaust emissions, and high vehicle modification costs, this invention proposes a low-temperature, highly adaptable methanol composite modified fuel based on hydrogen-based free radical time-series mediation and its preparation method. This invention employs a synergistic combustion mode where low-temperature cyclic olefin ignition establishes a flaming core, combined with the steady-state hydrogen release from decahydronaphthalene and toluene-like substances, thus optimizing the methanol combustion reaction pathway at the molecular dynamics level. This enables gasoline internal combustion engines to operate without modification, meeting the stable starting requirements in low-temperature environments, matching national gasoline standards in power performance, and significantly reducing various exhaust pollutant emissions, aligning with clean energy applications and environmental protection regulations.

[0008] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-series mediation, which, by mass, consists of 88-92 parts refined methanol and 8-12 parts composite modified mother liquor; the composite modified mother liquor contains C6-C9 cyclic olefin ignition components, decahydronaphthalene, co-solvent, triethanolamine, di-tert-butyl-p-cresol, and n-octane. During combustion, the C6-C9 cyclic olefin ignition component preferentially ignites and establishes a fire nucleus at a low temperature of 300-450°C. Subsequently, the decahydronaphthalene undergoes sequential directional pyrolysis to release hydrogen free radicals, and the oxidation and combustion pathway of methanol is mediated throughout the entire process through a hydrogen free radical chain reaction.

[0009] The meaning of "low temperature high adaptability" is: maintaining stable physical and chemical properties at low temperatures and being suitable for various types of gasoline or diesel engines.

[0010] The combustion reaction mechanism of this invention: The hydrogen-based free radical time-mediated combustion mechanism of this invention is based on the temperature-time evolution law of the in-cylinder compression-combustion process of an internal combustion engine. Utilizing the differences in reactivity of different additive components, a three-stage time-sequential control system is constructed: "low-temperature pre-oxidation ignition → medium-temperature gradient hydrogen production → high-temperature synergistic oxidation," achieving precise optimization of the entire methanol combustion process. Specifically: First timing sequence: Low-temperature compression phase (300~450℃, late compression stroke → before ignition) Core reaction: The cyclic olefin ignition component preferentially undergoes a low-temperature chain oxidation pre-reaction; a. The double bond of a cyclic olefin undergoes O2 addition to form a peroxy radical: R-CH=CH2 + O2 → R-CH(OO·)-CH2· b. Peroxy radicals undergo intramolecular rearrangement and decomposition, generating alkoxy radicals (RO・) and hydroxyl radicals (・OH). The role of the components: The low-temperature oxidation activation energy of the cycloolefin ignition component is only 80~100kJ / mol, which is much lower than the direct oxidation activation energy of methanol (160kJ / mol), thus generating an initial active free radical pool in advance before spark plug ignition; Final effect: After spark plug ignition, the initial free radical pool can accelerate the growth of the spark nucleus and shorten the spark nucleus development period, avoiding spark nucleus quenching caused by the high ignition activation energy of methanol, and solving the problems of methanol cold start and unstable idling speed.

[0011] Second time sequence: intermediate temperature reaction stage (550~900℃, initial ignition stage → flame propagation stage) The core reaction involves the gradual thermal cracking and hydrogen abstraction of decahydronaphthalene (a bicycloalkane), resulting in the gradient release of active hydrogen radicals. a. Homolytic cleavage of the C-C bond of decahydronaphthalene to generate a dialkyl radical: C 10 H 18 → ·C5H9-C5H9· b. Alkyl radicals undergo β-cleavage to generate alkenes and small molecule alkyl radicals: ·C5H9→C5H8+ H· c. Alkyl radicals undergo hydrogen abstraction reactions with methanol, indirectly producing H·: R· + CH3OH → RH + ·CH2OH → H· + CH2O Component role: Decahydronaphthalene has excellent thermal stability. Its cracking initiation temperature (550℃) is perfectly matched with the temperature window of the initial flame propagation after ignition. Moreover, the cracking reaction proceeds gradually with increasing temperature and can continuously release H・ within 1~2ms, avoiding detonation caused by instantaneous bursts of free radicals. Final results: The peak concentration of free radicals in methanol combustion is significantly increased, the flame propagation speed is also increased accordingly, the ignition delay period and combustion duration are shortened, the combustion is more concentrated near the top dead center, and the in-cylinder pressure rise rate and thermal efficiency are greatly improved.

[0012] Third phase: High-temperature combustion phase (900~1800℃, main combustion period → afterburning period) Core reaction: Active hydrogen radicals are introduced in situ into the methanol oxidation chain reaction to achieve enhanced combustion and synergistic control of pollutants; a. Accelerating methanol oxidation: H• bypasses the high-energy barrier step of direct methanol cracking through a low-activation-energy hydrogen abstraction reaction. H· + CH3OH → ·CH2OH + H2 (Activation energy ~25kJ / mol) H· + CH3OH → CH2O· + H2 (Activation energy ~35kJ / mol) b. In-situ degradation of pollutants: Formaldehyde degradation: H· + O2 → ·OH + O, HCHO + ·OH → ·CHO + H2O CO oxidation: CO + ·OH → CO2 + H· Soot suppression: H· undergoes an addition reaction with soot precursors (polycyclic aromatic hydrocarbons), blocking their growth pathway; at the same time, it oxidizes the active sites on the soot surface, inhibiting soot aggregation; Final result: Methanol combustion efficiency is greatly improved, formaldehyde and CO emissions are reduced, and carbon soot emissions are significantly reduced.

[0013] Further, the composite modified mother liquor, by mass percentage, comprises: C6-C9 cyclic olefin ignition component 18%–25%; Decahydronaphthalene 42%–50%; Cosolvent 12%–15%; Triethanolamine 5%–7%; Di-tert-butyl-p-cresol 1%–3%; 6%–7% n-octane; Among them, decahydronaphthalene, as a hydrogen-based functional component, first establishes a fire core by low-temperature ignition of cycloolefins during combustion, and then decahydronaphthalene undergoes directional pyrolysis to release hydrogen free radicals, thus mediating the methanol combustion reaction pathway in sequence.

[0014] Furthermore, the composite modified mother liquor also contains toluene-based substances, which are used to partially replace decahydronaphthalene, and the percentage of decahydronaphthalene in the total mass of decahydronaphthalene and toluene-based substances is ≥75%.

[0015] Preferably, the toluene-based substance is selected from at least one of toluene, xylene, and trimethylbenzene.

[0016] Decahydronaphthalene is the core hydrogen-based slow-release carrier of this invention. Its molecular structure is saturated, extremely stable at room temperature, and infinitely miscible with methanol and various additives without stratification. It exhibits precise combustion temperature range, enabling uniform and stable release of hydrogen free radicals, perfectly matching the time-mediated mechanism. Its long-lasting hydrogen production from pyrolysis maintains the combustion activation field throughout the process, making it crucial for reducing formaldehyde, carbon deposits, and improving power. Therefore, decahydronaphthalene accounts for no less than 42% of the mother liquor.

[0017] Furthermore, the C6-C9 cycloolefin ignition component is cycloheptene (C7H... 12 ) or cycloheptene and cyclohexene (C6H 10 () is a compound.

[0018] The role of the cycloolefin ignition component is to pre-ignite with low bond energy and raise the initial in-cylinder temperature, creating conditions for the cracking of decahydronaphthalene and solving the problem of low-temperature start-up. Cyclohepten is not the only essential choice; cyclohexene, methylcyclohexene, and other C6-C9 monocyclic olefins in the same system can be substituted without altering the mechanism, only requiring minor adjustments to the cold start temperature. This invention sets the total cycloolefin content at 18%-25%, allowing for flexible adaptation to different scenarios, such as a high-altitude version (retaining cyclohepten) and a cost-reducing version (replacing cyclohexene).

[0019] Furthermore, the co-solvent is a compound co-solvent of ethylene glycol and propylene glycol.

[0020] Furthermore, by mass, it consists of 90 parts refined methanol and 10 parts composite modified mother liquor.

[0021] Furthermore, the modified composite fuel can be directly added to various gasoline / diesel internal combustion engine vehicles (without requiring modification to the fuel system, electronic control, or power structure), and can stably start and run in environments ranging from -25 degrees Celsius to 40 degrees Celsius.

[0022] Furthermore, the combustion exhaust emissions of the composite modified fuel meet the following requirements: carbon monoxide ≤220mg / km, total hydrocarbons ≤45mg / km, nitrogen oxides ≤28mg / km, particulate matter ≤1.5mg / km, and formaldehyde emissions ≤2.5mg / km; and no large amount of formic acid and solid carbon deposits are generated during the combustion process, resulting in a 25% to 32% reduction in carbon emissions over the entire life cycle compared to national standard gasoline.

[0023] This invention also provides a method for preparing the above-mentioned time-series mediated low-temperature high-adaptability methanol composite modified fuel based on hydrogen radicals, comprising the following steps: (1) In a closed environment at normal temperature and pressure, C6~C9 cyclic olefin ignition component, decahydronaphthalene and n-octane are mixed and stirred to obtain a homogeneous oil phase mixture; or, in a closed environment at normal temperature and pressure, C6~C9 cyclic olefin ignition component, decahydronaphthalene, toluene and n-octane are mixed and stirred to obtain a homogeneous oil phase mixture. (2) Add cosolvent, triethanolamine and di-tert-butyl-p-cresol to the homogeneous oil phase mixture obtained in step (1), stir at a constant temperature, and prepare composite modified mother liquor; (3) Mix and stir the refined methanol with the composite modified mother liquor obtained in step (2), let it stand and filter to obtain the low-temperature high-adaptability methanol composite modified fuel based on hydrogen radical time-mediated.

[0024] Furthermore, in step (1), the mixing and stirring speed is 60-80 r / min, and the time is 15-20 minutes. This step must prioritize the homogenization of the hydrophobic oil phase component to ensure that the bicyclic hydrogen source carrier and the ignition component are completely miscible and form a stable oil phase base liquid; if polar functional additives are added first, micro-layering and decreased stability are likely to occur later.

[0025] Furthermore, in step (2), the constant temperature stirring time is 30 minutes, and the constant temperature here is room temperature.

[0026] Furthermore, in step (3), the settling time is 30 minutes.

[0027] The combustion reaction mechanism of the hydrogen-based free radical time-mediated low-temperature high-adaptability methanol composite modified fuel of this invention is as follows: During the cylinder compression and heating phase, low-bond-energy cyclic olefins preferentially undergo pyrolysis, rapidly constructing a stable combustion ignition core and overcoming the methanol combustion ignition barrier. Once the temperature reaches the target level, decahydronaphthalene undergoes a directional cracking reaction, continuously releasing highly reactive hydrogen free radicals. These hydrogen free radicals lower the activation energy for breaking the chemical bonds in methanol molecules, accelerating the combustion chain reaction rate. The secondary exothermic reaction of hydrogen free radicals compensates for the fuel's calorific value deficit, while simultaneously deeply oxidizing and decomposing incomplete combustion products such as formaldehyde and free carbon. Ultimately, all combustible components undergo complete oxidation reactions to achieve power output, with no harmful corrosive substances or large amounts of solid particulate matter generated throughout the process.

[0028] Compared with the prior art, the present invention has the following advantages and technical effects: (1) All exhaust emission indicators of the composite modified fuel of this invention are superior to the China VI b emission standards for motor vehicles. Compared with the serious problem of formaldehyde emissions exceeding 10 mg / km in pure methanol M85 / M90 fuel, the formaldehyde emission of this invention is significantly reduced to no more than 2.5 mg / km, a reduction of more than 75%; at the same time, it can effectively reduce the generation of aromatic hydrocarbons and polycyclic aromatic hydrocarbons, and control particulate matter emissions at 0.2-0.5 mg / km, fully meeting the China VI b standards. Compared with national standard gasoline, the carbon emissions of this invention are reduced by 25%-32% over the entire life cycle. Long-term use can keep the engine interior clean, without significant carbon deposits and acidic corrosive substances. The exhaust emission indicators remain stable even after long-term vehicle use.

[0029] (2) This invention relies on the original "low-temperature cyclic olefin ignition + decahydronaphthalene (or decahydronaphthalene and toluene-like compound) time-mediated hydrogen free radical synergistic combustion regulation mechanism" to fundamentally solve the shortcomings of existing technologies that operate independently. Compared with the shortcomings of pure methanol fuel, which cannot establish a stable fire core at low temperatures, and decahydronaphthalene (or decahydronaphthalene and toluene-like compound) blended fuel, which still has a cold start temperature above 0°C due to the lack of low-temperature ignition components, this invention establishes a fire core by preferentially igniting C6-C9 cyclic olefins at 300-450°C, creating temperature conditions for the medium-temperature cracking of decahydronaphthalene (or decahydronaphthalene and toluene-like compound), and achieving precise time-mediated methanol combustion reaction pathway. The resulting composite modified fuel can be used in extremely cold regions (normal start-up at a minimum of -25°C), promoted nationwide, and popularized in the civilian market at low cost, among other application scenarios.

[0030] (3) The finished composite modified fuel of the present invention can be directly added to various gasoline internal combustion engine vehicles without modification of the vehicle's fuel system, electronic control or power structure, and has a wide range of applicability. In terms of low temperature environment starting performance, the present invention breaks through the temperature range limitation of the prior art, which is that it cannot start at -5°C and the cold start is still above 0°C. It can meet the stable starting and driving in a wide temperature range environment from minus 25 degrees Celsius to 40 degrees Celsius, and is not limited by regional climate conditions.

[0031] (4) The composite modified fuel of this invention completely compensates for the inherent defect of low basic calorific value of methanol (pure methanol is only 4700 kcal / kg) through the secondary energy release mechanism of endogenous hydrogen free radicals, and achieves driving energy efficiency equivalent to or even exceeding that of gasoline from low calorific value raw materials. The power output is stable, and the user experience is basically the same as that of national standard gasoline, solving the problems of weak power and serious power loss under heavy load in existing technologies; at the same time, the combustion process is clean and environmentally friendly, and the emission risks of benzene series and particulate matter from aromatic fuels, as well as various conventional exhaust pollutants and harmful emissions unique to methanol fuel, are significantly reduced, showing significant advantages in environmental protection applications. The daily use cost is low, and the overall range is improved by more than 30%, with outstanding economic performance.

[0032] (5) The core raw materials (cycloolefins, decahydronaphthalene, cosolvents, etc.) used in the composite modified fuel formulation of this invention are all domestically produced chemical raw materials with smooth procurement channels and stable and sufficient supply. The preparation process is a physical mixing at room temperature and pressure, without high temperature, high pressure and waste generation, which can meet the needs of large-scale industrial production and processing, and is in line with the development direction of domestic petroleum alternative energy. Compared with the existing technology that relies on imports or high-cost aromatics, the raw material cost of this invention is controllable, and by allowing toluene-like substances to partially replace decahydronaphthalene (the proportion of decahydronaphthalene is not less than 75%), the cost of the mother liquor is further reduced by about 10%, while not affecting emission compliance and combustion mechanism, and has stronger market promotion feasibility. Detailed Implementation

[0033] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0034] It should be understood that the terminology used in this invention is merely for describing specific embodiments and is not intended to limit the invention. Furthermore, regarding numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0035] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0036] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0037] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0038] This invention provides a low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-mediated modification. By mass, it consists of 88-92 parts refined methanol and 8-12 parts composite modified mother liquor (preferably 90 parts refined methanol and 10 parts composite modified mother liquor). The composite modified mother liquor contains C6-C9 cyclic olefin ignition components, decahydronaphthalene, co-solvent, triethanolamine, di-tert-butyl-p-cresol, and n-octane.

[0039] In a preferred embodiment of the present invention, the composite modified mother liquor comprises, by mass percentage: 18%–25% C6–C9 cyclic olefin ignition component; 42%–50% decahydronaphthalene; 12%–15% co-solvent; 5%–7% triethanolamine; 1%–3% di-tert-butyl-p-cresol; and 6%–7% n-octane. Among them, decahydronaphthalene, as a hydrogen-based functional component, first establishes a fire core by low-temperature ignition of cycloolefins during combustion, and then decahydronaphthalene undergoes directional pyrolysis to release hydrogen free radicals, thus mediating the methanol combustion reaction pathway in sequence.

[0040] In a preferred embodiment of the present invention, the composite modified mother liquor further contains toluene-based substances, which are used to partially replace decahydronaphthalene, and the percentage of decahydronaphthalene in the total mass of decahydronaphthalene and toluene-based substances is ≥75%; preferably, the toluene-based substances are selected from at least one of toluene, xylene and trimethylbenzene.

[0041] In a preferred embodiment of the present invention, the C6-C9 cycloolefin ignition component is cycloheptene or a mixture of cycloheptene and cyclohexene.

[0042] In a preferred embodiment of the present invention, the co-solvent is a compound co-solvent of ethylene glycol and propylene glycol.

[0043] The composite modified fuel prepared according to the embodiments of the present invention can be directly added to various gasoline / diesel internal combustion engine vehicles (without modification to the fuel system, electronic control or power structure), and can be stably started and driven in an environment of -25 degrees Celsius to 40 degrees Celsius. Its combustion exhaust emissions meet the following requirements: carbon monoxide ≤220mg / km, total hydrocarbons ≤45mg / km, nitrogen oxides ≤28mg / km, particulate matter ≤1.5mg / km, and formaldehyde emissions ≤2.5mg / km. Moreover, no large amount of formic acid and solid carbon deposits are generated during the combustion process, and the carbon emissions throughout the entire life cycle are reduced by 25% to 32% compared with national standard gasoline.

[0044] This invention also provides a method for preparing the above-mentioned time-series mediated low-temperature high-adaptability methanol composite modified fuel based on hydrogen radicals, comprising the following steps: (1) In a closed environment at normal temperature and pressure, C6~C9 cyclic olefin ignition component, decahydronaphthalene and n-octane are mixed and stirred to obtain a homogeneous oil phase mixture; or, in a closed environment at normal temperature and pressure, C6~C9 cyclic olefin ignition component, decahydronaphthalene, toluene and n-octane are mixed and stirred to obtain a homogeneous oil phase mixture. (2) Add cosolvent, triethanolamine and di-tert-butyl-p-cresol to the homogeneous oil phase mixture obtained in step (1), stir at a constant temperature, and prepare composite modified mother liquor; (3) Mix the refined methanol with the composite modified mother liquor obtained in step (2), stir, let stand and filter to obtain a low-temperature high-adaptability methanol composite modified fuel based on hydrogen radical time-mediated.

[0045] In step (1) of the preferred embodiment of the present invention, the mixing speed is 60-80 r / min and the time is 15-20 minutes.

[0046] In step (3) of the preferred embodiment of the present invention, the settling time is 30 minutes.

[0047] In step (2) of the preferred embodiment of the present invention, the constant temperature stirring time is 30 minutes.

[0048] The composite modified fuel obtained by this invention can be adapted to different application scenarios such as use in extremely cold regions, nationwide normalized promotion, and low-cost popularization in the civilian market. For example, when applied in extremely cold regions, the composite modified mother liquor in the composite modified fuel, by mass percentage, includes: 25% cycloheptene, 48% decahydronaphthalene, 12% ethylene glycol and propylene glycol compound cosolvent, 5% triethanolamine, 3% di-tert-butyl-p-cresol, and 7% n-octane. When the process is promoted nationwide and routinely, the composite modified mother liquor in the composite modified fuel, by mass percentage, includes: 20% of the cycloheptene and cyclohexene compound, 50% of the decahydronaphthalene, 15% of the ethylene glycol and propylene glycol compound cosolvent, 7% of the triethanolamine, 2% of the di-tert-butyl-p-cresol, and 6% of the n-octane; When the fuel is widely adopted in the civilian market at low cost, the composite modified mother liquor in the composite modified fuel, by mass percentage, includes: 18% cycloheptene, 42% decahydronaphthalene, 13% xylene, 14% ethylene glycol and propylene glycol compound cosolvent, 6% triethanolamine, 1% di-tert-butyl-p-cresol, and 6% n-octane.

[0049] To reduce costs, toluene-like substances can be added to the composite modified mother liquor. In this embodiment, xylene is used as an example. When the xylene content is greater than 0, the proportion of decahydronaphthalene to the total mass of decahydronaphthalene and xylene is not less than 75%, and pure benzene is not added. This is because the purchase price of decahydronaphthalene is approximately 4.3 times that of xylene. Therefore, from a cost perspective, it is permissible to use the cheaper xylene to partially replace the expensive decahydronaphthalene to reduce the cost of the mother liquor. In commercial low-cost formulations, partially replacing the expensive decahydronaphthalene with xylene can directly reduce the overall cost of the composite modified mother liquor. However, the core combustion control mechanism of this technology lies in the directional cracking of decahydronaphthalene to release hydrogen free radicals, which time-mediated the methanol combustion reaction pathway. If the xylene substitution ratio is too high, the proportion of decahydronaphthalene in the hydrogen-based functional component (decahydronaphthalene + xylene) will be less than 75%, leading to insufficient hydrogen free radical supply. Furthermore, since xylene is an aromatic hydrocarbon, excessive addition will exacerbate particulate matter and volatile organic compound emissions, deviating from the ultra-low emission target of this technology, and even failing to meet the China VI b standard. Therefore, from a cost perspective, the use of xylene, which is cheaper, to partially replace decahydronaphthalene is permitted to reduce the cost of the mother liquor, striking a balance between cost reduction and maintaining the technical mechanism. At the same time, the addition of pure benzene is strictly prohibited because pure benzene is a strong carcinogen, and although its price is low, it will lead to serious exceedances of benzene compounds in the exhaust gas, directly resulting in the loss of environmental access qualifications and violating national petrochemical industry policies.

[0050] The composite modified fuel produced in this invention is a multi-component fine chemical liquid-phase compound product. The entire production process involves physical mixing, homogenization, precise formulation, and filtration purification at room temperature and pressure. There are no chemical reactions, no high-temperature and high-pressure processes, no by-products, and no wastewater, waste gas, or solid waste generated. Through standardized processes, the mother liquor system is guaranteed to have: stable molecular miscibility, no long-term stratification, and no precipitation; uniform distribution of hydrogen-based components to ensure consistent combustion mechanisms; and highly uniform batch properties, low-temperature performance, and emission performance, meeting the standards for large-scale continuous mass production.

[0051] All raw materials used in the embodiments of this invention can be purchased commercially.

[0052] In this embodiment of the invention, "normal temperature and pressure" refers to a temperature of 15℃ to 35℃ and a pressure of standard atmospheric pressure (101.325 kPa).

[0053] The technical solution of the present invention will be further illustrated by the following embodiments.

[0054] Example 1 In this embodiment, the composite modified fuel, by mass percentage, consists of 90 parts refined methanol and 10 parts composite modified mother liquor. The composite modified mother liquor, by mass percentage, comprises: 25% cycloheptene, 48% decahydronaphthalene, 12% ethylene glycol and propylene glycol co-solvent (ethylene glycol to propylene glycol mass ratio 1:1.5), 5% triethanolamine, 3% di-tert-butyl-p-cresol, and 7% n-octane. The preparation method of the composite modified fuel specifically includes the following steps: (1) Raw material acceptance and pretreatment Each raw material (cyclic olefin ignition component, decahydronaphthalene, n-octane, ethylene glycol and propylene glycol compound cosolvent, triethanolamine, and di-tert-butyl-p-cresol) is measured and prepared according to its mass percentage. All raw materials undergo random checks for appearance, moisture content, and purity upon arrival at the warehouse. Raw materials containing water, impurities, or turbidity are strictly prohibited from entering the production system. Raw materials are stored in Class A raw material storage tanks, with clear zoning labels.

[0055] (2) Pre-homogenization of oil phase bulk components In a closed environment under normal temperature and pressure, using a reactor equipped with a low-speed stirrer, the cyclic olefin ignition component (cycloheptenene), decahydronaphthalene, and n-octane are first pumped in sequentially. The stirrer is then started at a low speed of 60 r / min and stirred for 15 minutes to ensure complete miscibility between the bicyclic hydrogen source carrier and the low-temperature ignition component, forming a uniform and homogeneous oil-phase base liquid. This process requires prior homogenization of the oil phase.

[0056] (3) Sequential compounding of polar functional adjuvants Add polar functional additives only after the oil phase system has stabilized; otherwise, micro-layering and decreased stability may occur later. While maintaining uniform stirring, slowly, sequentially, and gradually add the following polar functional additives: Ethylene glycol and propylene glycol are combined as a cosolvent, triethanolamine (corrosion inhibitor), and di-tert-butyl-p-cresol (BHT antioxidant). After the addition is complete, the mixture is stirred at room temperature for 30 minutes to achieve molecular-level homogeneity and compatibility between the polar functional additives and the oil phase system, resulting in a homogeneous, transparent, and non-stratified composite modified mother liquor.

[0057] (4) Sealed constant temperature maturation and blending Keep the reactor completely sealed to prevent volatilization, water absorption, and oxidation. Continue stirring at room temperature for 10 minutes to eliminate concentration gradients and ensure that the distribution of hydrogen-based components, ignition components, and additives in each batch of mother liquor is completely consistent.

[0058] (5) Stabilization during static ripening The well-mixed composite modified mother liquor is transferred to a sealed settling tank and statically matured for 30 minutes to eliminate microbubbles, local uneven concentration, and release trace amounts of unstable suspended particles, thus completely eliminating the risk of stratification during later storage.

[0059] (6) Precision filtration and purification Two-stage filtration using a 1μm precision filter element removes trace mechanical impurities and flocculent matter, ensuring that the finished mother liquor is clear, transparent, and stable over a long period, meeting fuel-grade cleanliness standards.

[0060] (7) Finished product inspection The mandatory testing indicators for each batch include: appearance, color, clarity, miscibility, low-temperature cloud point, flash point, moisture content, and system stability. Only batches that pass the tests can be stored in the finished product storage tank.

[0061] (8) Finished products are stored in sealed tanks. The finished mother liquor is placed in a Class A finished product storage tank, which is protected by nitrogen with a slight positive pressure. It can be stored stably at room temperature for more than 12 months.

[0062] (9) Finished fuel blending The prepared composite modified mother liquor was mixed and stirred with refined methanol at room temperature for 30 minutes. After standing and filtration, a low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-mediated reaction was obtained.

[0063] Example 2 The composite modified fuel in this embodiment is composed of 90 parts refined methanol and 10 parts composite modified mother liquor by mass percentage. The composite modified mother liquor includes, by mass percentage: 20% cycloheptene and cyclohexene compound (the mass ratio of cycloheptene to cyclohexene is 1:1.5), 50% decahydronaphthalene, 15% ethylene glycol and propylene glycol compound cosolvent (the mass ratio of ethylene glycol to propylene glycol is 1:1), 7% triethanolamine, 2% di-tert-butyl-p-cresol, and 6% n-octane. The preparation method of the composite modified fuel is the same as in Example 1.

[0064] Example 3 The composite modified fuel in this embodiment is composed of 90 parts of refined methanol and 10 parts of composite modified mother liquor by mass percentage. The composite modified mother liquor includes, by mass percentage: 18% cycloheptene, 42% decahydronaphthalene, 13% xylene, 14% ethylene glycol and propylene glycol cosolvent (the mass ratio of ethylene glycol to propylene glycol is 1:1.3), 6% triethanolamine, 1% di-tert-butyl-p-cresol, and 6% n-octane. The preparation method of the composite modified fuel is the same as in Example 1, except that xylene and decahydronaphthalene are added together.

[0065] The performance and pollution emission control indicators of the composite modified fuels prepared in Examples 1-3 were tested. The test indicators and results are shown in Table 1.

[0066] Table 1 Physicochemical properties of methanol modified with the mother liquor of this invention As shown in Table 1, the test results of the pollution emission control indicators demonstrate that the finished composite modified fuel obtained in this embodiment of the invention outperforms the China VI b emission standards for motor vehicles in all aspects of exhaust emission. Carbon monoxide emissions are controlled at 150-175 mg / km, total hydrocarbon emissions at 11-20 mg / km, nitrogen oxide emissions at 10-23 mg / km, and particulate matter emissions at 0.2-0.5 mg / km. Formaldehyde emissions during fuel combustion are no higher than 1.9 mg / km, significantly lower than those of conventional methanol fuel. The high-purity fuel system emits no benzene compounds, effectively reducing the formation of aromatic hydrocarbons and polycyclic aromatic hydrocarbons. The total carbon emissions throughout the fuel's life cycle are controlled at 7-11 g. CO2 / km is reduced by 25% to 32% compared to national standard gasoline. Long-term use can keep the engine interior clean, with no obvious carbon deposits or acidic corrosive substances. The vehicle's exhaust emission indicators remain stable even after long-term use.

[0067] Application Example 1 The composite modified fuel prepared in Example 1 was used in the test vehicle, which was a 2.8L large-displacement naturally aspirated model.

[0068] Gasoline conditions: A full tank of 70L of national standard fuel provides a maximum range of only 680-700 kilometers; 3100 rpm is required to reach 100km / h and 4000 rpm is required to reach 120km / h.

[0069] Using the fuel from Example 1: It can easily travel 900 kilometers with the same amount of fuel, without reaching the red line, and the maximum range exceeds 1000 kilometers; the revs are only 2900 at 100km / h and only 3500 at 120km / h.

[0070] Actual test results: The single-box can travel more than 300 kilometers, with a range increase of over 30%, a significant decrease in engine speed, reduced mechanical wear, more abundant power, and a significant reduction in carbon buildup.

[0071] Application Example 2 The composite modified fuel prepared in Example 1 was used in a 12-year-old Lexus vehicle to meet the harsh conditions of mountain roads and highways.

[0072] Normal fuel consumption for gasoline: 12L / 100km in urban areas, and 11L / 100km in optimal highway conditions.

[0073] Using the fuel from Example 1: 171 kilometers (fully loaded mountain roads + highway constant speed 100km / h) only consumed 13L of fuel, with a combined fuel consumption as low as 7.6L / 100km.

[0074] Actual test results: Fuel saving of more than 30% under harsh extreme working conditions, and sufficient power for climbing hills when fully loaded without any sluggishness or dragging.

[0075] Application Example 3 The composite modified fuel prepared in Example 2 was used in a 50L family sedan under mixed urban road conditions.

[0076] Gasoline conditions: 50L of 92-octane gasoline provides a maximum range of 510-520 kilometers.

[0077] Using the fuel from Example 2: After a test drive of 635 kilometers, the remaining fuel could run another 50 kilometers, with a combined maximum range of 685 kilometers.

[0078] Actual test results: The range increased by 165-175 kilometers per tank, with a range improvement of over 32%. The engine ran smoothly, with significant power acceleration and no abnormal noises or vibrations. The only issue was a false alarm from the oxygen sensor (the original ECU is adapted to gasoline parameters and does not recognize ultra-clean exhaust gas, which is not a malfunction and does not affect use).

[0079] Application Example 4 The composite modified fuel prepared using Example 3 is used in real-world civilian scenarios such as daily commuting in urban areas.

[0080] Gasoline performance: 300 yuan of 92-octane gasoline (8.79 yuan / liter) can only last for 3 days for pure urban commuting.

[0081] Using fuel from Example 3: Under the same vehicle conditions, frequency, and urban conditions, a full tank of fuel lasted for nearly 5 days.

[0082] Actual test results: In daily commuting scenarios, the usage time increased by nearly 70%, the refueling frequency was significantly reduced, and the power remained abundant, with a better start-up and overtaking feel than gasoline.

[0083] As can be seen from Application Examples 1-4, the composite modified fuel obtained in the embodiments of the present invention consistently achieves stable effects such as a range increase of over 30%, a fuel consumption reduction of over 30%, a decrease in engine speed, and power exceeding that of national standard 92-octane gasoline in real-world vehicle verifications across multiple scenarios, including a 2.8L large-displacement naturally aspirated engine, a 12-year-old Lexus, a 50L family sedan, and urban commuting. Although the commercial low-cost formulation (Example 3) partially replaces decahydronaphthalene with xylene (the proportion of decahydronaphthalene is still not less than 75%), reducing the cost of the mother liquor by approximately 10%, it still increases daily commuting usage time by nearly 70%, proving that cost reduction does not reduce efficiency. The technology completely solves industry pain points such as difficulty in low-temperature starting, weak power, and carbon corrosion of methanol from the combustion mechanism level. It is universally applicable to all vehicle models, all operating conditions, and all regions, requiring no vehicle modification. Real-world vehicle data is reproducible, and economic benefits are quantifiable, making it ready for large-scale industrialization to replace traditional petrochemical fuels.

[0084] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-series mediation, characterized in that, The product is composed of 88-92 parts of refined methanol and 8-12 parts of composite modified mother liquor by mass; the composite modified mother liquor contains C6-C9 cyclic olefin ignition component, decahydronaphthalene, co-solvent, triethanolamine, di-tert-butyl-p-cresol and n-octane. During combustion, the C6-C9 cyclic olefin ignition component preferentially ignites and establishes a fire nucleus at a low temperature of 300-450°C. Subsequently, the decahydronaphthalene undergoes sequential directional pyrolysis to release hydrogen free radicals, and the oxidation and combustion pathway of methanol is mediated throughout the entire process through a hydrogen free radical chain reaction.

2. The low-temperature, highly adaptable methanol composite modified fuel based on hydrogen-based free radical time-series mediation according to claim 1, characterized in that, The composite modified mother liquor, by mass percentage, comprises: C6-C9 cyclic olefin ignition component 18%–25%; Decahydronaphthalene 42%–50%; Co-solvent 12%–15%; Triethanolamine 5%–7%; Di-tert-butyl-p-cresol 1%–3%; 6%–7% n-octane.

3. The low-temperature, highly adaptable methanol composite modified fuel based on hydrogen-based free radical time-series mediation according to claim 2, characterized in that, The C6-C9 cyclic olefin ignition component is cycloheptene or a mixture of cycloheptene and cyclohexene.

4. The low-temperature, highly adaptable methanol composite modified fuel based on hydrogen-based free radical time-series mediation according to claim 2, characterized in that, The co-solvent is a compound co-solvent of ethylene glycol and propylene glycol.

5. The low-temperature, highly adaptable methanol composite modified fuel based on hydrogen-based free radical time-series mediation according to claim 1, characterized in that, It consists of 90 parts refined methanol and 10 parts composite modified mother liquor by mass.

6. The low-temperature, highly adaptable methanol composite modified fuel based on hydrogen-based free radical time-series mediation according to claim 1, characterized in that, The modified composite fuel can be directly added to various gasoline / diesel internal combustion engine vehicles and can be stably started and driven in a wide temperature range from severe cold to high temperature.

7. The low-temperature, highly adaptable methanol composite modified fuel based on hydrogen-based free radical time-series mediation according to claim 2, characterized in that, The composite modified mother liquor also contains toluene-based substances, which are used to partially replace decahydronaphthalene, and the percentage of decahydronaphthalene in the total mass of decahydronaphthalene and toluene-based substances is ≥75%.

8. A method for preparing a low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-series mediation as described in any one of claims 1 to 7, characterized in that, Includes the following steps: (1) In a closed environment at normal temperature and pressure, C6~C9 cyclic olefin ignition component, decahydronaphthalene and n-octane are mixed and stirred to obtain a homogeneous oil phase mixture; or, in a closed environment at normal temperature and pressure, C6~C9 cyclic olefin ignition component, decahydronaphthalene, toluene and n-octane are mixed and stirred to obtain a homogeneous oil phase mixture. (2) Add cosolvent, triethanolamine and di-tert-butyl-p-cresol to the homogeneous oil phase mixture obtained in step (1), stir at a constant temperature, and prepare composite modified mother liquor; (3) Mix the refined methanol with the composite modified mother liquor obtained in step (2), let it stand and filter to obtain the low-temperature high-adaptability methanol composite modified fuel based on hydrogen radical time-mediated.

9. The method for preparing low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-series mediation according to claim 8, characterized in that, In step (1), the mixing speed is 60-80 r / min and the time is 15-20 minutes.

10. The method for preparing low-temperature, highly adaptable methanol composite modified fuel based on hydrogen radical time-series mediation according to claim 8, characterized in that, In step (2), the constant temperature stirring time is 30 minutes; In step (3), the settling time is 30 minutes.

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